Co-reporter:Rui Tang, Ming Wang, Moumita Ray, Ying Jiang, Ziwen Jiang, Qiaobing Xu, and Vincent M. Rotello
Journal of the American Chemical Society June 28, 2017 Volume 139(Issue 25) pp:8547-8547
Publication Date(Web):June 9, 2017
DOI:10.1021/jacs.7b02801
Active intracellular transport is a central mechanism in cell biology, directed by a limited set of naturally occurring signaling peptides. Here, we report the first nonpeptide moiety that recruits intracellular transport machinery for nuclear targeting. Proteins synthetically modified with a simple aromatic boronate motif are actively trafficked to the nucleus via the importin α/β pathway. Significantly, proteins too large to passively diffuse through nuclear pores were readily imported into the nucleus through this boronate-mediated pathway. The use of this simple motif to provide active intracellular targeting provides a promising strategy for directing subcellular localization for therapeutic and fundamental applications.
Co-reporter:Rubul Mout, Moumita Ray, Tristan Tay, Kanae Sasaki, Gulen Yesilbag Tonga, and Vincent M. Rotello
ACS Nano June 27, 2017 Volume 11(Issue 6) pp:6416-6416
Publication Date(Web):June 14, 2017
DOI:10.1021/acsnano.7b02884
Endosomal entrapment is a key hurdle for most intracellular protein-based therapeutic strategies. We report a general strategy for efficient delivery of proteins to the cytosol through co-engineering of proteins and nanoparticle vehicles. The proteins feature an oligo(glutamate) sequence (E-tag) that binds arginine-functionalized gold nanoparticles, generating hierarchical spherical nanoassemblies. These assemblies fuse with cell membranes, releasing the E-tagged protein directly into the cytosol. Five different proteins with diverse charges, sizes, and functions were effectively delivered into cells, demonstrating the generality of our method. Significantly, the engineered proteins retained activity after cytosolic delivery, as demonstrated through the delivery of active Cre recombinase, and granzyme A to kill cancer cells.Keywords: cytosolic protein delivery; hierarchical nanoassembly; membrane fusion; nanoparticles; protein engineering;
Co-reporter:Ngoc D. B. Le, Gulen Yesilbag Tonga, Rubul Mout, Sung-Tae Kim, Marcos E. Wille, Subinoy Rana, Karen A. Dunphy, D. Joseph Jerry, Mahdieh Yazdani, Rajesh Ramanathan, Caren M. Rotello, and Vincent M. Rotello
Journal of the American Chemical Society June 14, 2017 Volume 139(Issue 23) pp:8008-8008
Publication Date(Web):May 23, 2017
DOI:10.1021/jacs.7b03657
We report a nanosensor that uses cell lysates to rapidly profile the tumorigenicity of cancer cells. This sensing platform uses host–guest interactions between cucurbit[7]uril and the cationic headgroup of a gold nanoparticle to non-covalently modify the binding of three fluorescent proteins of a multi-channel sensor in situ. This approach doubles the number of output channels to six, providing single-well identification of cell lysates with 100% accuracy. Significantly, this classification could be extended beyond the training set, determining the invasiveness of novel cell lines. The unique fingerprint of these cell lysates required minimal sample quantity (200 ng, ∼1000 cells), making the methodology compatible with microbiopsy technology.
Co-reporter:Juhong Chen, Samuel D. Alcaine, Angelyca A. Jackson, Vincent M. Rotello, and Sam R. Nugen
ACS Sensors April 28, 2017 Volume 2(Issue 4) pp:484-484
Publication Date(Web):March 14, 2017
DOI:10.1021/acssensors.7b00021
T7 bacteriophages (phages) have been genetically engineered to carry the lacZ operon, enabling the overexpression of beta-galactosidase (β-gal) during phage infection and allowing for the enhanced colorimetric detection of Escherichia coli (E. coli). Following the phage infection of E. coli, the enzymatic activity of the released β-gal was monitored using a colorimetric substrate. Compared with a control T7 phage, our T7lacZ phage generated significantly higher levels of β-gal expression following phage infection, enabling a lower limit of detection for E. coli cells. Using this engineered T7lacZ phage, we were able to detect E. coli cells at 10 CFU·mL–1 within 7 h. Furthermore, we demonstrated the potential for phage-based sensing of bacteria antibiotic resistance profiling using our T7lacZ phage, and subsequent β-gal expression to detect antibiotic resistant profile of E. coli strains.Keywords: antibiotic resistance profiling; bacteria detection; beta-galactosidase; colorimetry; engineered bacteriophages;
Co-reporter:Rubul Mout, Moumita Ray, Yi-Wei Lee, Federica Scaletti, and Vincent M. Rotello
Bioconjugate Chemistry April 19, 2017 Volume 28(Issue 4) pp:880-880
Publication Date(Web):March 6, 2017
DOI:10.1021/acs.bioconjchem.7b00057
The successful use of clustered regularly interspaced short palindromic repeat (CRISPR)/Cas9-based gene editing for therapeutics requires efficient in vivo delivery of the CRISPR components. There are, however, major challenges on the delivery front. In this Topical Review, we will highlight recent developments in CRISPR delivery, and we will present hurdles that still need to be overcome to achieve effective in vivo editing.
Co-reporter:Ngoc D. B. Le;Xian Wang;Yingying Geng;Rui Tang;Gulen Yesilbag Tonga;Ziwen Jiang
Chemical Communications 2017 vol. 53(Issue 62) pp:8794-8797
Publication Date(Web):2017/08/01
DOI:10.1039/C7CC04561A
Endocrine disrupting chemicals (EDCs) interact with estrogen receptors (ERs), causing a broad range of adverse health effects. Current assays for EDC activity are slow and often lack sensitivity. We report here an ultra-sensitive nanosensor that can detect estrogenic cellular changes in ER(+) MCF-7 cells rapidly (minutes) at several orders of magnitude lower than the generally used assays. Notably, the sensor responses at these ultra-low EDC levels correlated with an increased synthesis phase (S-phase) cell population of EDC-treated cells. The nanosensor was also able to detect binary EDC mixture effects, with synergism observed for bisphenol A (BPA) – 17β-estradiol (E2), and antagonism for dicyclohexylphthalate (DCHP) – E2 and benzo(a)pyrene (BaP) – E2.
Co-reporter:Puspam Keshri, Vincent M. Rotello
Chem 2017 Volume 2, Issue 6(Volume 2, Issue 6) pp:
Publication Date(Web):8 June 2017
DOI:10.1016/j.chempr.2017.05.005
In this issue of Chem, Bunz and colleagues present an array-based sensor for the identification and classification of whiskies.
Co-reporter:Juhong Chen;Stephanie M. Andler;Julie M. Goddard;Sam R. Nugen
Chemical Society Reviews 2017 vol. 46(Issue 5) pp:1272-1283
Publication Date(Web):2017/03/06
DOI:10.1039/C6CS00313C
Pathogenic bacterial contamination is a major threat to human health and safety. In this review, we summarize recent strategies for the integration of recognition elements with nanomaterials for the detection and sensing of pathogenic bacteria. Nanoprobes can provide sensitive and specific detection of bacterial cells, which can be applied across multiple applications and industries.
Co-reporter:Roberto Cao-Milán;Luke D. He;Spencer Shorkey;Gulen Y. Tonga;Li-Sheng Wang;Xianzhi Zhang;Imad Uddin;Riddha Das;Mine Sulak
Molecular Systems Design & Engineering (2016-Present) 2017 vol. 2(Issue 5) pp:624-628
Publication Date(Web):2017/12/04
DOI:10.1039/C7ME00055C
The inclusion of transition metal catalysts into nanoparticle scaffolds permits the creation of catalytic nanosystems (nanozymes) able to imitate the behaviour of natural enzymes. Here we report the fabrication of a family of nanozymes comprised of bioorthogonal ruthenium catalysts inserted in the protective monolayer of gold nanoparticles. By introducing simple modifications to the functional groups at the surface of the nanozymes, we have demonstrated control over the kinetic mechanism of our system. Cationic nanozymes with hydrophobic surface functionalities tend to replicate the classical Michaelis Menten model, while those with polar groups display substrate inhibition behaviour, a key mechanism present in 20% of natural enzymes. The structural parameters described herein can be used for creating artificial nanosystems that mimic the complexity observed in cell machinery.
Co-reporter:Young-Kwan Kim;Li-Sheng Wang;Ryan Landis;Chang Soo Kim;Richard W. Vachet
Nanoscale (2009-Present) 2017 vol. 9(Issue 30) pp:10854-10860
Publication Date(Web):2017/08/03
DOI:10.1039/C7NR02949G
A chip-based platform for laser desorption/ionization mass spectrometry (LDI-MS) analysis of small molecules was developed by utilizing layer-by-layer (LBL) assembly of MoS2 nanoflakes and polyallylamine on an arbitrary substrate. The LDI-MS efficiency of small molecules on MoS2 films increased as a function of LBL assembly cycles until reaching a saturation point. The optimized MoS2 nanoflake film exhibits high LDI-MS efficiency, salt tolerance, reusability and uniform ionic signal distribution, and its performance was further enhanced by surface modification with perfluoroalkanes mimicking a clathrate nanostructure.
Co-reporter:Young-Kwan Kim;Li-Sheng Wang;Ryan Landis;Chang Soo Kim;Richard W. Vachet
Nanoscale (2009-Present) 2017 vol. 9(Issue 30) pp:10854-10860
Publication Date(Web):2017/08/03
DOI:10.1039/C7NR02949G
A chip-based platform for laser desorption/ionization mass spectrometry (LDI-MS) analysis of small molecules was developed by utilizing layer-by-layer (LBL) assembly of MoS2 nanoflakes and polyallylamine on an arbitrary substrate. The LDI-MS efficiency of small molecules on MoS2 films increased as a function of LBL assembly cycles until reaching a saturation point. The optimized MoS2 nanoflake film exhibits high LDI-MS efficiency, salt tolerance, reusability and uniform ionic signal distribution, and its performance was further enhanced by surface modification with perfluoroalkanes mimicking a clathrate nanostructure.
Co-reporter:Ryan F. Landis, Akash Gupta, Yi-Wei Lee, Li-Sheng Wang, Bianka Golba, Brice Couillaud, Roxane Ridolfo, Riddha Das, and Vincent M. Rotello
ACS Nano 2017 Volume 11(Issue 1) pp:
Publication Date(Web):December 22, 2016
DOI:10.1021/acsnano.6b07537
Infections caused by bacterial biofilms are an emerging threat to human health. Conventional antibiotic therapies are ineffective against biofilms due to poor penetration of the extracellular polymeric substance secreted by colonized bacteria coupled with the rapidly growing number of antibiotic-resistant strains. Essential oils are promising natural antimicrobial agents; however, poor solubility in biological conditions limits their applications against bacteria in both dispersed (planktonic) and biofilm settings. We report here an oil-in-water cross-linked polymeric nanocomposite (∼250 nm) incorporating carvacrol oil that penetrates and eradicates multidrug-resistant (MDR) biofilms. The therapeutic potential of these materials against challenging wound biofilm infections was demonstrated through specific killing of bacteria in a mammalian cell–biofilm coculture wound model.Keywords: biofilms; cross-linked; multidrug-resistant bacteria; nanocomposite; phytochemicals;
Co-reporter:Li-Sheng Wang, Bradley Duncan, Rui TangYi-Wei Lee, Brian Creran, Sukru Gokhan Elci, Jiaxin Zhu, Gülen Yesilbag Tonga, Jesse Doble, Matthew Fessenden, Mahin Bayat, Stephen Nonnenmann, Richard W. Vachet, Vincent M. Rotello
ACS Applied Materials & Interfaces 2017 Volume 9(Issue 1) pp:
Publication Date(Web):December 23, 2016
DOI:10.1021/acsami.6b13815
Protein-based biomaterials provide versatile scaffolds for generating functional surfaces for biomedical applications. However, tailoring the functional and biological properties of protein films remains a challenge. Here, we describe a high-throughput method to designing stable, functional biomaterials by combining inkjet deposition of protein inks with a nanoimprint lithography based methodology. The translation of the intrinsically charged proteins into functional materials properties was demonstrated through controlled cellular adhesion. This modular strategy offers a rapid method to produce customizable biomaterials.Keywords: biomaterial; cell patterning; inkjet printing; nanoimprint lithography; thin films;
Co-reporter:Yuanchang Liu, Joseph Hardie, Xianzhi Zhang, Vincent M. Rotello
Seminars in Immunology 2017 Volume 34(Volume 34) pp:
Publication Date(Web):1 December 2017
DOI:10.1016/j.smim.2017.09.011
•Physicochemical properties of NPs affect interactions with innate immune system.•Engineered NPs are effective for immunomodulation.•Immunotoxicity assays of NPs are challenging.Engineered nanoparticles (NPs) have broad applications in industry and nanomedicine. When NPs enter the body, interactions with the immune system are unavoidable. The innate immune system, a non-specific first line of defense against potential threats to the host, immediately interacts with introduced NPs and generates complicated immune responses. Depending on their physicochemical properties, NPs can interact with cells and proteins to stimulate or suppress the innate immune response, and similarly activate or avoid the complement system. NPs size, shape, hydrophobicity and surface modification are the main factors that influence the interactions between NPs and the innate immune system. In this review, we will focus on recent reports about the relationship between the physicochemical properties of NPs and their innate immune response, and their applications in immunotherapy.
Co-reporter:Shazia Mumtaz;Li-Sheng Wang;Syed Zajif Hussain;Muhammad Abdullah;Zille Huma;Zafar Iqbal;Brian Creran;Irshad Hussain
Chemical Communications 2017 vol. 53(Issue 91) pp:12306-12308
Publication Date(Web):2017/11/14
DOI:10.1039/C7CC07149C
We report a simple and economical colorimetric bacterial sensing strategy with catalytic amplification using dopamine-capped iron oxide (Dop-Fe3O4) nanoparticles. These nanoparticles catalyse the oxidation of a chromogenic substrate in the presence of H2O2 into a green colored product. The catalytic activity of the nanoparticles is inhibited in the presence of bacteria, providing naked eye detection of bacteria at 104 cfu mL−1 and by spectrophotometric detection down to 102 cfu mL−1.
Co-reporter:Subinoy Rana; S. Gokhan Elci; Rubul Mout; Arvind K. Singla; Mahdieh Yazdani; Markus Bender; Avinash Bajaj; Krishnendu Saha; Uwe H. F. Bunz; Frank R. Jirik
Journal of the American Chemical Society 2016 Volume 138(Issue 13) pp:4522-4529
Publication Date(Web):March 11, 2016
DOI:10.1021/jacs.6b00067
Supramolecular complexes of a family of positively charged conjugated polymers (CPs) and green fluorescent protein (GFP) create a fluorescence resonance energy transfer (FRET)-based ratiometric biosensor array. Selective multivalent interactions of the CPs with mammalian cell surfaces caused differential change in FRET signals, providing a fingerprint signature for each cell type. The resulting fluorescence signatures allowed the identification of 16 different cell types and discrimination between healthy, cancerous, and metastatic cells, with the same genetic background. While the CP-GFP sensor array completely differentiated between the cell types, only partial classification was achieved for the CPs alone, validating the effectiveness of the ratiometric sensor. The utility of the biosensor was further demonstrated in the detection of blinded unknown samples, where 121 of 128 samples were correctly identified. Notably, this selectivity-based sensor stratified diverse cell types in minutes, using only 2000 cells, without requiring specific biomarkers or cell labeling.
Co-reporter:Akash Gupta, Daniel F. Moyano, Attasith Parnsubsakul, Alexander Papadopoulos, Li-Sheng Wang, Ryan F. Landis, Riddha Das, and Vincent M. Rotello
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 22) pp:14096-14101
Publication Date(Web):May 18, 2016
DOI:10.1021/acsami.6b02548
Gold nanoparticles provide an excellent platform for biological and material applications due to their unique physical and chemical properties. However, decreased colloidal stability and formation of irreversible aggregates while freeze-drying nanomaterials limit their use in real world applications. Here, we report a new generation of surface ligands based on a combination of short oligo (ethylene glycol) chains and zwitterions capable of providing nonfouling characteristics while maintaining colloidal stability and functionalization capabilities. Additionally, conjugation of these gold nanoparticles with avidin can help the development of a universal toolkit for further functionalization of nanomaterials.
Co-reporter:Singyuk Hou, Kristen N. Sikora, Rui Tang, Yuanchang Liu, Yi-Wei Lee, Sung Tae Kim, Ziwen Jiang, Richard W. Vachet, and Vincent M. Rotello
ACS Nano 2016 Volume 10(Issue 7) pp:6731
Publication Date(Web):June 23, 2016
DOI:10.1021/acsnano.6b02105
Differentiation between cell surface-bound and internalized nanoparticles is challenging yet essential for accurately quantifying cellular uptake. Here, we describe a versatile mass spectrometry-based method that allows separate quantification of both cell surface-bound and internalized nanoparticles. This rapid method uses tuned laser fluencies to selectively desorb and ionize cell surface-bound cationic gold nanoparticles from intact cells, providing quantification of external particles. Overall nanoparticle quantities are obtained from the cell lysates, with subtraction of external particles from the total amount providing quantification of taken-up nanoparticles. The utility of this strategy was demonstrated through simultaneous quantitative determination of how cell-surface proteoglycans influence nanoparticle binding and uptake into cells.Keywords: cellular delivery; gold; mass spectrometry; nanoparticle
Co-reporter:Shuaidong Huo, Ying Jiang, Akash Gupta, Ziwen Jiang, Ryan F. Landis, Singyuk Hou, Xing-Jie Liang, and Vincent M. Rotello
ACS Nano 2016 Volume 10(Issue 9) pp:8732
Publication Date(Web):September 13, 2016
DOI:10.1021/acsnano.6b04207
Zwitterionic nanoparticles are generally considered nontoxic and noninteracting. Here, we report effective and selective antimicrobial activity of zwitterionic gold nanoparticles (AuNP) through modulation NP size and surface charge orientation. Using a set of 2, 4, and 6 nm core AuNPs, increasing particle size increased antimicrobial efficiency through bacterial membrane disruption. Further improvement was observed through control of the ligand structure, generating antimicrobial particles with low hemolytic activity and demonstrating the importance of size and surface structure in dictating the bioactivity properties of nanomaterials.Keywords: antimicrobial activity; charge orientation; size; zwitterionic gold nanoparticles
Co-reporter:Li-Sheng Wang, Akash Gupta, and Vincent M. Rotello
ACS Infectious Diseases 2016 Volume 2(Issue 1) pp:3
Publication Date(Web):October 21, 2015
DOI:10.1021/acsinfecdis.5b00116
Treatment of biofilm-associated infections is challenging, requiring the development of new therapeutic strategies. In this viewpoint, we discuss the use of nanoparticle-based systems as active therapeutic agents and as vehicles to transport drugs to the site of infection. These applications require understanding of the surface interactions of nanoparticles with bacteria/biofilms, an aspect that we likewise summarize.
Co-reporter:Krishnendu Saha, Mehran Rahimi, Mahdieh Yazdani, Sung Tae Kim, Daniel F. Moyano, Singyuk Hou, Ridhha Das, Rubul Mout, Farhad Rezaee, Morteza Mahmoudi, and Vincent M. Rotello
ACS Nano 2016 Volume 10(Issue 4) pp:4421
Publication Date(Web):April 3, 2016
DOI:10.1021/acsnano.6b00053
Using a family of cationic gold nanoparticles (NPs) with similar size and charge, we demonstrate that proper surface engineering can control the nature and identity of protein corona in physiological serum conditions. The protein coronas were highly dependent on the hydrophobicity and arrangement of chemical motifs on NP surface. The NPs were uptaken in macrophages in a corona-dependent manner, predominantly through recognition of specific complement proteins in the NP corona. Taken together, this study shows that surface functionality can be used to tune the protein corona formed on NP surface, dictating the interaction of NPs with macrophages.Keywords: complement system; gold nanoparticles; macrophages; protein corona; surface functionality
Co-reporter:Li-Sheng Wang, Akash Gupta, Bradley Duncan, Rajesh Ramanathan, Mahdieh Yazdani, and Vincent M. Rotello
ACS Biomaterials Science & Engineering 2016 Volume 2(Issue 11) pp:1862
Publication Date(Web):September 6, 2016
DOI:10.1021/acsbiomaterials.6b00464
Bacteria attach to the surfaces of medical devices and implants, resulting in life-threatening infections. Nonfouling coatings can be used to prevent adhesion of bacteria on the surface, while biocidal coatings kill the microbes. Combining nonfouling and biocidal properties can yield highly effective antimicrobial coatings. We demonstrate here a nanoimprint lithography (NIL)-based method to generate antibacterial coatings that both resist bacterial attachment and kill bacteria. In this strategy nanoimprint lithography was used to create water-stable films of bovine serum albumin (BSA) that are nonadhesive toward bacteria because of their negative/zwitterionic surface potential. Biocidal activity was then imparted through chlorination of cysteine sulfurs, providing slow release of chlorine and potent antimicrobial activity against pathogenic bacteria.Keywords: antifouling; antimicrobial; biomaterials; chlorination; coatings; nanoimprint lithography
Co-reporter:Tsukasa Mizuhara, Daniel F. Moyano, Vincent M. Rotello
Nano Today 2016 Volume 11(Issue 1) pp:31-40
Publication Date(Web):February 2016
DOI:10.1016/j.nantod.2015.11.002
•Surface properties are a key determinant of the biological properties of nanomaterials.•Organic synthesis provides atom-by-atom control over nanomaterial surfaces.•The control of nanoparticle surfaces is an important tool for the creation of diagnostics and therapeutics.The surface properties of nanoparticles (NPs) dictate their interaction with the outside world. The use of precisely designed molecular ligands to control NP surface properties provides an important toolkit for modulating their interaction with biological systems, facilitating their use in biomedicine. In this review we will discuss the application of the atom-by-atom control provided by organic synthesis to the generation of engineered nanoparticles, with emphasis on how the functionalization of NPs with these “small” organic molecules (Mw <1000) can be used to engineer NPs for a wide range of applications.
Co-reporter:William J. Peveler, Mahdieh Yazdani, and Vincent M. Rotello
ACS Sensors 2016 Volume 1(Issue 11) pp:1282
Publication Date(Web):September 30, 2016
DOI:10.1021/acssensors.6b00564
Sensing using specific and selective receptors provides two very different but complementary strategies. This Sensor Issues article will discuss the merits and challenges of specific sensors, and selective sensors based on synthetic arrays. We will examine where each has been successfully applied to a sensing challenge, and then look at how a combined approach could take elements of both to provide new sensor platforms.Keywords: antibodies; array-based sensing; chemical sensors; selectivity; specificity
Co-reporter:Ziwen Jiang, Ngoc D. B. Le, Akash Gupta and Vincent M. Rotello
Chemical Society Reviews 2015 vol. 44(Issue 13) pp:4264-4274
Publication Date(Web):08 Apr 2015
DOI:10.1039/C4CS00387J
Metallic nanoparticles provide versatile scaffolds for biosensing applications. In this review, we focus on the use of metallic nanoparticles for cell surface sensings. Examples of the use of both specific recognition and array-based “chemical nose” approaches to cell surface sensing will be discussed.
Co-reporter:Eunhee Jeoung;Bradley Duncan;Li-Sheng Wang;Krishnendu Saha;Chramouleeswaran Subramani;Peijian Wang;Yi-Cheun Yeh;Takashi Kushida;Yoni Engel;Michael D. Barnes
Advanced Materials 2015 Volume 27( Issue 40) pp:6251-6255
Publication Date(Web):
DOI:10.1002/adma.201502457
Co-reporter:Xiaoning Li, Yi-Cheun Yeh, Karuna Giri, Rubul Mout, Ryan F. Landis, Y. S. Prakash and Vincent M. Rotello
Chemical Communications 2015 vol. 51(Issue 2) pp:282-285
Publication Date(Web):10 Nov 2014
DOI:10.1039/C4CC07737G
Quantum dots were used as fluorescent probes to investigate nanoparticle penetration into biofilms. The particle penetration behavior was found to be controlled by surface chemical properties.
Co-reporter:Juhong Chen, Samuel D. Alcaine, Ziwen Jiang, Vincent M. Rotello, and Sam R. Nugen
Analytical Chemistry 2015 Volume 87(Issue 17) pp:8977
Publication Date(Web):July 14, 2015
DOI:10.1021/acs.analchem.5b02175
In this study, we demonstrate a bacteriophage (phage)-based magnetic separation scheme for the rapid detection of Escherichia coli (E. coli) in drinking water. T7 phage is a lytic phage with a broad host range specificity for E. coli. Our scheme was as follows: (1) T7 bacteriophage-conjugated magnetic beads were used to capture and separate E. coli BL21 from drinking water; (2) subsequent phage-mediated lysis was used to release endemic β-galactosidase (β-gal) from the bound bacterial cells; (3) the release of β-gal was detected using chlorophenol red-β-d-galactopyranoside (CRPG), a colorimetric substrate which changes from yellow to red in the presence of β-gal. Using this strategy, we were able to detect E. coli at a concentration of 1 × 104 CFU·mL–1 within 2.5 h. The specificity of the proposed magnetic probes toward E. coli was demonstrated against a background of competing bacteria. By incorporating a pre-enrichment step in Luria–Bertani (LB) broth supplemented with isopropyl β-d-thiogalactopyranoside (IPTG), we were able to detect 10 CFU·mL–1 in drinking water after 6 h of pre-enrichment. The colorimetric change can be determined either by visual observation or with a reader, allowing for a simple, rapid quantification of E. coli in resource-limited settings.
Co-reporter:Moumita Ray, Rui Tang, Ziwen Jiang, and Vincent M. Rotello
Bioconjugate Chemistry 2015 Volume 26(Issue 6) pp:1004
Publication Date(Web):May 26, 2015
DOI:10.1021/acs.bioconjchem.5b00141
We describe a method for quantitative monitoring of subcellular protein trafficking using nanoparticle-stabilized nanocapsules for protein delivery. This method provides rapid delivery of the protein into the cytosol, eliminating complications from protein homeostasis processes found with cellularly expressed proteins. After delivery, nuclear protein trafficking was followed by real time microscopic imaging. Quantitative analyses of the accumulation percentage and the import dynamics of the nuclear protein trafficking, demonstrate the utility of this method for studying intracellular trafficking systems.
Co-reporter:Chang Soo Kim, Rubul Mout, Yunlong Zhao, Yi-Cheun Yeh, Rui Tang, Youngdo Jeong, Bradley Duncan, Jeanne A. Hardy, and Vincent M. Rotello
Bioconjugate Chemistry 2015 Volume 26(Issue 5) pp:950
Publication Date(Web):April 20, 2015
DOI:10.1021/acs.bioconjchem.5b00146
Combination therapy employing proteins and small molecules provides access to synergistic treatment strategies. Co-delivery of these two payloads is challenging due to the divergent physicochemical properties of small molecule and protein cargos. Nanoparticle-stabilized nanocapsules (NPSCs) are promising for combination treatment strategies since they have the potential to deliver small molecule drugs and proteins simultaneously into the cytosol. In this study, we loaded paclitaxel into the hydrophobic core of the NPSC and self-assembled caspase-3 and nanoparticles on the capsule surface. The resulting combination NPSCs showed higher cytotoxicity than either of the single agent NPSCs, with synergistic action established using combination index values.
Co-reporter:Eunhee Jeoung;Yi-Cheun Yeh;Tyler Nelson;Takashi Kushida;Li-Sheng Wang;Rubul Mout;Xiaoning Li;Krishnendu Saha;Akash Gupta;Gülen Y. Tonga;John J. Lannutti
Macromolecular Rapid Communications 2015 Volume 36( Issue 7) pp:678-683
Publication Date(Web):
DOI:10.1002/marc.201400744
Co-reporter:Chaekyu Kim, Gulen Yesilbag Tonga, Bo Yan, Chang Soo Kim, Sung Tae Kim, Myoung-Hwan Park, Zhengjiang Zhu, Bradley Duncan, Brian Creran and Vincent M. Rotello
Organic & Biomolecular Chemistry 2015 vol. 13(Issue 8) pp:2474-2479
Publication Date(Web):23 Dec 2014
DOI:10.1039/C4OB02433H
Prolonged retention of internalized nanoparticulate systems inside cells improves their efficacy in imaging, drug delivery, and theranostic applications. Especially, regulating exocytosis of the nanoparticles is a key factor in the fabrication of effective nanocarriers for chemotherapeutic treatments but orthogonal control of exocytosis in the cellular environment is a major challenge. Herein, we present the first example of regulating exocytosis of gold nanoparticles (AuNPs), a model drug carrier, by using a simple host–guest supramolecular system. AuNPs featuring quaternary amine head groups were internalized into the cells through endocytosis. Subsequent in situ treatment of a complementary cucurbit[7]uril (CB[7]) to the amine head groups resulted in the AuNP-CB[7] complexation inside cells, rendering particle assembly. This complexation induced larger particle assemblies that remained sequestered in the endosomes, inhibiting exocytosis of the particles without any observed cytotoxicity.
Co-reporter:Juhong Chen, Ziwen Jiang, Jonathan D. Ackerman, Mahdieh Yazdani, Singyuk Hou, Sam R. Nugen and Vincent M. Rotello
Analyst 2015 vol. 140(Issue 15) pp:4991-4996
Publication Date(Web):15 May 2015
DOI:10.1039/C5AN00637F
Traditional plating and culturing methods used to quantify bacteria commonly require hours to days from sampling to results. We present here a simple, sensitive and rapid electrochemical method for bacterial detection in drinking water based on gold nanoparticle–enzyme complexes. The gold nanoparticles were functionalized with positively charged quaternary amine headgroups that could bind to enzymes through electrostatic interactions, resulting in inhibition of enzymatic activity. In the presence of bacteria, the nanoparticles were released from the enzymes and preferentially bound to the bacteria, resulting in an increase in enzyme activity, releasing a redox-active phenol from the substrate. We employed this strategy for the electrochemical sensing of Escherichia coli and Staphylococcus aureus, resulting in a rapid detection (<1 h) with high sensitivity (102 CFU mL−1).
Co-reporter:Ying Jiang;Rui Tang;Bradley Duncan;Ziwen Jiang;Dr. Bo Yan;Rubul Mout ;Dr. Vincent M. Rotello
Angewandte Chemie 2015 Volume 127( Issue 2) pp:516-520
Publication Date(Web):
DOI:10.1002/ange.201409161
Abstract
The use of nanoparticle-stabilized nanocapsules (NPSCs) for the direct cytosolic delivery of siRNA is reported. In this approach, siRNA is complexed with cationic arginine-functionalized gold nanoparticles by electrostatic interactions, with the resulting ensemble self-assembled onto the surface of fatty acid nanodroplets to form a NPSC/siRNA nanocomplex. The complex rapidly delivers siRNA into the cytosol through membrane fusion, a mechanism supported by cellular uptake studies. Using destabilized green fluorescent protein (deGFP) as a target, 90 % knockdown was observed in HEK293 cells. Moreover, the delivery of siRNA targeting polo-like kinase 1 (siPLK1) efficiently silenced PLK1 expression in cancer cells with concomitant cytotoxicity.
Co-reporter:Tsukasa Mizuhara;Krishnendu Saha;Daniel F. Moyano;Chang Soo Kim;Bo Yan;Young-Kwan Kim; Vincent M. Rotello
Angewandte Chemie 2015 Volume 127( Issue 22) pp:6667-6670
Publication Date(Web):
DOI:10.1002/ange.201411615
Abstract
A nanoparticle design featuring pH-responsive alkoxyphenyl acylsulfonamide ligands is reported herein. As a result of ligand structure, this nanoparticle is neutral at pH 7.4, becoming positively charged at tumor pH (<6.5). The particle uptake and cytotoxicity increase over this pH range. This pH-controlled uptake and toxicity makes this particle a promising tool for tumor selective therapy.
Co-reporter:Ying Jiang;Rui Tang;Bradley Duncan;Ziwen Jiang;Dr. Bo Yan;Rubul Mout ;Dr. Vincent M. Rotello
Angewandte Chemie International Edition 2015 Volume 54( Issue 2) pp:506-510
Publication Date(Web):
DOI:10.1002/anie.201409161
Abstract
The use of nanoparticle-stabilized nanocapsules (NPSCs) for the direct cytosolic delivery of siRNA is reported. In this approach, siRNA is complexed with cationic arginine-functionalized gold nanoparticles by electrostatic interactions, with the resulting ensemble self-assembled onto the surface of fatty acid nanodroplets to form a NPSC/siRNA nanocomplex. The complex rapidly delivers siRNA into the cytosol through membrane fusion, a mechanism supported by cellular uptake studies. Using destabilized green fluorescent protein (deGFP) as a target, 90 % knockdown was observed in HEK293 cells. Moreover, the delivery of siRNA targeting polo-like kinase 1 (siPLK1) efficiently silenced PLK1 expression in cancer cells with concomitant cytotoxicity.
Co-reporter:Tsukasa Mizuhara;Krishnendu Saha;Daniel F. Moyano;Chang Soo Kim;Bo Yan;Young-Kwan Kim; Vincent M. Rotello
Angewandte Chemie International Edition 2015 Volume 54( Issue 22) pp:6567-6570
Publication Date(Web):
DOI:10.1002/anie.201411615
Abstract
A nanoparticle design featuring pH-responsive alkoxyphenyl acylsulfonamide ligands is reported herein. As a result of ligand structure, this nanoparticle is neutral at pH 7.4, becoming positively charged at tumor pH (<6.5). The particle uptake and cytotoxicity increase over this pH range. This pH-controlled uptake and toxicity makes this particle a promising tool for tumor selective therapy.
Co-reporter:Subinoy Rana, Ngoc D. B. Le, Rubul Mout, Bradley Duncan, S. Gokhan Elci, Krishnendu Saha, and Vincent M. Rotello
ACS Central Science 2015 Volume 1(Issue 4) pp:191
Publication Date(Web):June 8, 2015
DOI:10.1021/acscentsci.5b00126
Cell surface glycosylation serves a fundamental role in dictating cell and tissue behavior. Cell surface glycomes differ significantly, presenting viable biomarkers for identifying cell types and their states. Glycoprofiling is a challenging task, however, due to the complexity of the constituent glycans. We report here a rapid and effective sensor for surface-based cell differentiation that uses a three-channel sensor produced by noncovalent conjugation of a functionalized gold nanoparticle (AuNP) and fluorescent proteins. Wild-type and glycomutant mammalian cells were effectively stratified using fluorescence signatures obtained from a single sensor element. Blinded unknowns generated from the tested cell types were identified with high accuracy (44 out of 48 samples), validating the robustness of the multichannel sensor. Notably, this selectivity-based high-throughput sensor differentiated between cells, employing a nondestructive protocol that required only a single well of a microplate for detection.
Co-reporter:Ying Jiang, Shuaidong Huo, Tsukasa Mizuhara, Riddha Das, Yi-Wei Lee, Singyuk Hou, Daniel F. Moyano, Bradley Duncan, Xing-Jie Liang, and Vincent M. Rotello
ACS Nano 2015 Volume 9(Issue 10) pp:9986
Publication Date(Web):October 5, 2015
DOI:10.1021/acsnano.5b03521
Correlation of the surface physicochemical properties of nanoparticles with their interactions with biosystems provides key foundational data for nanomedicine. We report here the systematic synthesis of 2, 4, and 6 nm core gold nanoparticles (AuNP) featuring neutral (zwitterionic), anionic, and cationic headgroups. The cellular internalization of these AuNPs was quantified, providing a parametric evaluation of charge and size effects. Contrasting behavior was observed with these systems: with zwitterionic and anionic particles, uptake decreased with increasing AuNP size, whereas with cationic particles, uptake increased with increasing particle size. Through mechanistic studies of the uptake process, we can attribute these opposing trends to a surface-dictated shift in uptake pathways. Zwitterionic NPs are primarily internalized through passive diffusion, while the internalization of cationic and anionic NPs is dominated by multiple endocytic pathways. Our study demonstrates that size and surface charge interact in an interrelated fashion to modulate nanoparticle uptake into cells, providing an engineering tool for designing nanomaterials for specific biological applications.Keywords: endocytosis pathway; passive fusion; size-dependent; sub-10 nm gold nanoparticles; surface charge;
Co-reporter:Bradley Duncan, Xiaoning Li, Ryan F. Landis, Sung Tae Kim, Akash Gupta, Li-Sheng Wang, Rajesh Ramanathan, Rui Tang, Jeffrey A. Boerth, and Vincent M. Rotello
ACS Nano 2015 Volume 9(Issue 8) pp:7775
Publication Date(Web):June 17, 2015
DOI:10.1021/acsnano.5b01696
Bacterial biofilms are widely associated with persistent infections. High resistance to conventional antibiotics and prevalent virulence makes eliminating these bacterial communities challenging therapeutic targets. We describe here the fabrication of a nanoparticle-stabilized capsule with a multicomponent core for the treatment of biofilms. The peppermint oil and cinnamaldehyde combination that comprises the core of the capsules act as potent antimicrobial agents. An in situ reaction at the oil/water interface between the nanoparticles and cinnamaldehyde structurally augments the capsules to efficiently deliver the essential oil payloads, effectively eradicating biofilms of clinically isolated pathogenic bacteria strains. In contrast to their antimicrobial action, the capsules selectively promoted fibroblast proliferation in a mixed bacteria/mammalian cell system making them promising for wound healing applications.Keywords: biofilm; phytochemicals; Pickering emulsion; self-assembly; silica nanoparticles;
Co-reporter:Rui Tang;Daniel F. Moyano;Chramouleeswaran Subramani;Bo Yan;Eunhee Jeoung;Gülen Yesilbag Tonga;Bradley Duncan;Yi-Cheun Yeh;Ziwen Jiang;Chaekyu Kim
Advanced Materials 2014 Volume 26( Issue 20) pp:3310-3314
Publication Date(Web):
DOI:10.1002/adma.201306030
Co-reporter:Youngdo Jeong;Yu-Cheng Chen;Merve K. Turksoy;Subinoy Rana;Gulen Yesilbag Tonga;Brian Creran;Amitav Sanyal;Alfred J. Crosby
Advanced Materials 2014 Volume 26( Issue 29) pp:5056-5061
Publication Date(Web):
DOI:10.1002/adma.201401226
Co-reporter:Gulen Yesilbag Tonga;Krishnendu Saha
Advanced Materials 2014 Volume 26( Issue 3) pp:359-370
Publication Date(Web):
DOI:10.1002/adma.201303001
The exterior surface of nanoparticles (NPs) dictates the behavior of these systems with the outside world. Understanding the interactions of the NP surface functionality with biosystems enables the design and fabrication of effective platforms for therapeutics, diagnostics, and imaging agents. In this review, we highlight the role of chemistry in the engineering of nanomaterials, focusing on the fundamental role played by surface chemistry in controlling the interaction of NPs with proteins and cells.
Co-reporter:Krishnendu Saha, Daniel F. Moyano and Vincent M. Rotello
Materials Horizons 2014 vol. 1(Issue 1) pp:102-105
Publication Date(Web):27 Sep 2013
DOI:10.1039/C3MH00075C
The role of nanoparticle surface hydrophobicity on hemolytic properties is established in the absence and presence of plasma proteins. Significantly, the formation of a plasma protein corona on the NP surface protects red blood cells from both hydrophilic and hydrophobic NP-mediated hemolysis.
Co-reporter:Yi-Cheun Yeh, Sung Tae Kim, Rui Tang, Bo Yan and Vincent M. Rotello
Journal of Materials Chemistry A 2014 vol. 2(Issue 29) pp:4610-4614
Publication Date(Web):21 May 2014
DOI:10.1039/C4TB00608A
Effective regulation of nanoparticle (NP) uptake facilitates the NP-based therapeutics and diagnostics. Here, we report the use of insulin and 2-deoxyglucose (2-DG) to modulate the cellular uptake of glucose-functionalized quantum dots (Glc-QDs) in C2C12 muscle cells. The cellular uptake of Glc-QDs can be modulated up to almost two-fold under insulin stimulation while be down-regulated in the presence of 2-DG. These results demonstrate the use of secondary regulators to control the cellular uptake of NPs through membrane protein recognition in a specific and fine-tunable fashion.
Co-reporter:Takashi Kushida, Krishnendu Saha, Chandramouleeswaran Subramani, Vikas Nandwana and Vincent M. Rotello
Nanoscale 2014 vol. 6(Issue 23) pp:14484-14487
Publication Date(Web):02 Oct 2014
DOI:10.1039/C4NR04128C
The intrinsic coagulation activity of silica nanoparticles strongly depends on their surface curvature. Nanoparticles with higher surface curvature do not denature blood coagulation factor XII on its surface, providing a coagulation ‘silent’ surface, while nanoparticles with lower surface curvature show denaturation and concomitant coagulation.
Co-reporter:Rubul Mout, Gulen Yesilbag Tonga, Moumita Ray, Daniel F. Moyano, Yuqing Xing and Vincent M. Rotello
Nanoscale 2014 vol. 6(Issue 15) pp:8873-8877
Publication Date(Web):10 Jun 2014
DOI:10.1039/C4NR02097A
Interfacing synthetic materials with biomacromolecules provides new systems for biological applications. We report the creation of a reversible multivalent supramolecular “zipper” recognition motif between gold nanoparticles and proteins. In this assembly, carboxylate-functionalized nanoparticles interact strongly with oligohistidine tags. This interaction can be tuned through His-tag length, and offers unique binding profiles based on the pH and electrolyte concentration of the medium.
Co-reporter:Kaimin Chen, Subinoy Rana, Daniel F. Moyano, Yisheng Xu, Xuhong Guo and Vincent M. Rotello
Nanoscale 2014 vol. 6(Issue 12) pp:6492-6495
Publication Date(Web):30 Apr 2014
DOI:10.1039/C4NR01085J
We demonstrate that ligand hydrophobicity can be used to increase affinity and selectivity of binding between monolayer-protected cationic gold nanoparticles and β-lactoglobulin protein isoforms containing two amino acid mutations.
Co-reporter:Brian Creran, Xiaoning Li, Bradley Duncan, Chang Soo Kim, Daniel F. Moyano, and Vincent M. Rotello
ACS Applied Materials & Interfaces 2014 Volume 6(Issue 22) pp:19525
Publication Date(Web):October 15, 2014
DOI:10.1021/am505689g
Low-cost diagnostics for drinking water contamination have the potential to save millions of lives. We report a method that uses inkjet printing to copattern an enzyme–nanoparticle sensor and substrate on a paper-based test strip for rapid detection of bacteria. A colorimetric response is generated on the paper substrate that allows visual detection of contamination without the need for expensive instrumentation. These strips demonstrate a viable nanomanufacturing strategy for low-cost bacterial detection.Keywords: bacteria; enzymes; gold nanoparticles; inkjet printing; sensing
Co-reporter:Yi-Cheun Yeh, Subinoy Rana, Rubul Mout, Bo Yan, Felix S. Alfonso and Vincent M. Rotello
Chemical Communications 2014 vol. 50(Issue 42) pp:5565-5568
Publication Date(Web):14 Apr 2014
DOI:10.1039/C4CC01257G
Supramolecular modification of nanoparticle surfaces through threading of cucurbit[7]uril (CB[7]) onto surface ligands is used to regulate protein–nanoparticle interactions.
Co-reporter:Ryan F. Landis, Mahdieh Yazdani, Brian Creran, Xi Yu, Vikas Nandwana, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2014 vol. 50(Issue 35) pp:4579-4581
Publication Date(Web):17 Mar 2014
DOI:10.1039/C4CC00805G
Hydrogen bonding heavily influences conformations, rate of reactions, and chemical equilibria. The development of a method to monitor hydrogen bonding interactions independent of polarity is challenging as both are linked. We have developed two solvatochromic dyes that detect hydrogen-bond-donating solvents. The unique solvatochromism of the triazine architecture has allowed the development of probes that monitor hydrogen-bond-donating species including water.
Co-reporter:Chang Soo Kim;Ngoc D. B. Le;Yuqing Xing;Bo Yan;Gulen Yesilbag Tonga;Chaekyu Kim;Richard W. Vachet
Advanced Healthcare Materials 2014 Volume 3( Issue 8) pp:1200-1202
Publication Date(Web):
DOI:10.1002/adhm.201400001
Co-reporter:Bo Yan, Gulen Yesilbag Tonga, Singyuk Hou, Patrick W. Fedick, Yi-Cheun Yeh, Felix S. Alfonso, Tsukasa Mizuhara, Richard W. Vachet, and Vincent M. Rotello
Analytical Chemistry 2014 Volume 86(Issue 13) pp:6710
Publication Date(Web):May 29, 2014
DOI:10.1021/ac501682y
Synthetic host–guest chemistry is a versatile tool for biomedical applications. Characterization and detection of host–guest complexes in biological systems, however, is challenging due to the complexity of the biological milieu. Here, we describe and apply a mass spectrometric method to monitor the association and dissociation of nanoparticle (NP)-based host–guest interactions that integrates NP-assisted laser desorption/ionization (LDI) and matrix assisted laser desoption/ionization (MALDI) mass spectrometry. This LDI/MALDI approach reveals how NP surface functionality affects host–guest interactions in cells, information difficult to achieve using other techniques.
Co-reporter:Gulen Yesilbag Tonga, Daniel F. Moyano, Chang Soo Kim, Vincent M. Rotello
Current Opinion in Colloid & Interface Science 2014 Volume 19(Issue 2) pp:49-55
Publication Date(Web):April 2014
DOI:10.1016/j.cocis.2014.03.004
•Inorganic nanoparticles provide platforms for biomedicine.•Numerous nanoparticle systems with useful properties have been developed.•Characterization is a very important but often neglected topic in nanomedicine.•We do not have an integrated understanding of nanobiosystems yet.•Lack of fundamental understanding means limited predictive capabilities.Inorganic nanomaterials have a wide array of physical and structural properties that make them attractive candidates for imaging and therapeutic delivery. Nanoparticle platforms have been intensely studied for these applications, and examples are starting to enter the clinic. This review looks at why inorganic particles provide promising platforms for biomedicine, and what issues need to be addressed for them to reach their potential.
Co-reporter:Ailing Fu, Rui Tang, Joseph Hardie, Michelle E. Farkas, and Vincent M. Rotello
Bioconjugate Chemistry 2014 Volume 25(Issue 9) pp:1602
Publication Date(Web):August 18, 2014
DOI:10.1021/bc500320j
The direct delivery of functional proteins into the cell cytosol is a key issue for protein therapy, with many current strategies resulting in endosomal entrapment. Protein delivery to the cytosol is challenging due to the high molecular weight and the polarity of therapeutic proteins. Here we review strategies for the delivery of proteins into cells, including cell-penetrating peptides, virus-like particles, supercharged proteins, nanocarriers, polymers, and nanoparticle-stabilized nanocapsules. The advantages and disadvantages of these approaches including cytosolar delivery are compared and contrasted, with promising pathways forward identified.
Co-reporter:Daniel F. Moyano, Krishnendu Saha, Gyan Prakash, Bo Yan, Hao Kong, Mahdieh Yazdani, and Vincent M. Rotello
ACS Nano 2014 Volume 8(Issue 7) pp:6748
Publication Date(Web):June 27, 2014
DOI:10.1021/nn5006478
A protein corona is formed at the surface of nanoparticles in the presence of biological fluids, masking the surface properties of the particle and complicating the relationship between chemical functionality and biological effects. We present here a series of zwitterionic NPs of variable hydrophobicity that do not adsorb proteins at moderate levels of serum protein and do not form hard coronas at physiological serum concentrations. These particles provide platforms to evaluate nanobiological behavior such as cell uptake and hemolysis dictated directly by chemical motifs at the nanoparticle surface.Keywords: cellular uptake; corona-free NPs; dynamic light scattering; hemolysis; hydrophobicity; interfacial tension; sedimentation
Co-reporter:Xiaoning Li, Hao Kong, Rubul Mout, Krishnendu Saha, Daniel F. Moyano, Sandra M. Robinson, Subinoy Rana, Xinrong Zhang, Margaret A. Riley, and Vincent M. Rotello
ACS Nano 2014 Volume 8(Issue 12) pp:12014
Publication Date(Web):December 2, 2014
DOI:10.1021/nn505753s
Identification of infectious bacteria responsible for biofilm-associated infections is challenging due to the complex and heterogeneous biofilm matrix. To address this issue and minimize the impact of heterogeneity on biofilm identification, we developed a gold nanoparticle (AuNP)-based multichannel sensor to detect and identify biofilms based on their physicochemical properties. Our results showed that the sensor can discriminate six bacterial biofilms including two composed of uropathogenic bacteria. The capability of the sensor was further demonstrated through discrimination of biofilms in a mixed bacteria/mammalian cell in vitro wound model.Keywords: biofilms; biosensor design; fluorescent proteins; gold nanoparticles; multichannel sensor; uropathogen;
Co-reporter:Joey N. Talbert, Li-Sheng Wang, Bradley Duncan, Youngdo Jeong, Stephanie M. Andler, Vincent M. Rotello, and Julie M. Goddard
Biomacromolecules 2014 Volume 15(Issue 11) pp:
Publication Date(Web):September 24, 2014
DOI:10.1021/bm500970b
Nanostructure-enabled hierarchical assembly holds promise for efficient biocatalyst immobilization for improved stability in bioprocessing. In this work we demonstrate the use of a hierarchical assembly immobilization strategy to enhance the physicochemical properties and stability of lipase B from Candida antarctica (CaLB). CaLB was complexed with iron oxide nanoparticles followed by interfacial assembly at the surface of an oil-in-water emulsion. Subsequent ring opening polymerization of the oil provided cross-linked microparticles that displayed an increase in catalytic efficiency when compared to the native enzyme and Novozym 435. The hierarchical immobilized enzyme assembly showed no leakage from the support in 50% acetonitrile and could be magnetically recovered across five cycles. Immobilized lipase exhibited enhanced thermal and pH stability, providing 72% activity retention after 24 h at 50 °C (pH 7.0) and 62% activity retention after 24 h at pH 3.0 (30 °C); conditions resulting in complete deactivation of the native lipase.
Co-reporter:Xiaoning Li, Sandra M. Robinson, Akash Gupta, Krishnendu Saha, Ziwen Jiang, Daniel F. Moyano, Ali Sahar, Margaret A. Riley, and Vincent M. Rotello
ACS Nano 2014 Volume 8(Issue 10) pp:10682
Publication Date(Web):September 18, 2014
DOI:10.1021/nn5042625
We present the use of functionalized gold nanoparticles (AuNPs) to combat multi-drug-resistant pathogenic bacteria. Tuning of the functional groups on the nanoparticle surface provided gold nanoparticles that were effective against both Gram-negative and Gram-positive uropathogens, including multi-drug-resistant pathogens. These AuNPs exhibited low toxicity to mammalian cells, and bacterial resistance was not observed after 20 generations. A strong structure–activity relationship was observed as a function of AuNP functionality, providing guidance to activity prediction and rational design of effective antimicrobial nanoparticles.Keywords: antimicrobial agents; gold nanoparticles; MDR E. coli; mode of action; MRSA; structure−activity relationship; uropathogens;
Co-reporter:Yi-Cheun Yeh;Rui Tang;Rubul Mout;Youngdo Jeong ; Vincent M. Rotello
Angewandte Chemie 2014 Volume 126( Issue 20) pp:5237-5241
Publication Date(Web):
DOI:10.1002/ange.201400559
Abstract
Multifunctional self-assembled systems present platforms for fundamental research and practical applications as they provide tunability of structure, functionality, and stimuli responsiveness. Pragmatic structures for biological applications have multiple design requirements, including control of size, stability, and environmental response. Here we present the fabrication of multifunctional nanoparticle-stabilized capsules (NPSCs) by using a set of orthogonal supramolecular interactions. In these capsules, fluorescent proteins are attached to quantum dots through polyhistidine coordination. These anionic assemblies interact laterally with cationic gold nanoparticles that are anchored to the fatty acid core through guanidinium–carboxylate interactions. The lipophilic core then provides a reservoir for hydrophobic endosome-disrupting agents, thereby generating a system featuring stimuli-responsive release of a payload into the cytosol with fluorescence monitoring.
Co-reporter:Yi-Cheun Yeh;Rui Tang;Rubul Mout;Youngdo Jeong ; Vincent M. Rotello
Angewandte Chemie International Edition 2014 Volume 53( Issue 20) pp:5137-5141
Publication Date(Web):
DOI:10.1002/anie.201400559
Abstract
Multifunctional self-assembled systems present platforms for fundamental research and practical applications as they provide tunability of structure, functionality, and stimuli responsiveness. Pragmatic structures for biological applications have multiple design requirements, including control of size, stability, and environmental response. Here we present the fabrication of multifunctional nanoparticle-stabilized capsules (NPSCs) by using a set of orthogonal supramolecular interactions. In these capsules, fluorescent proteins are attached to quantum dots through polyhistidine coordination. These anionic assemblies interact laterally with cationic gold nanoparticles that are anchored to the fatty acid core through guanidinium–carboxylate interactions. The lipophilic core then provides a reservoir for hydrophobic endosome-disrupting agents, thereby generating a system featuring stimuli-responsive release of a payload into the cytosol with fluorescence monitoring.
Co-reporter:Vikas Nandwana, Ifor Samuel, Graeme Cooke, and Vincent M. Rotello
Accounts of Chemical Research 2013 Volume 46(Issue 4) pp:1000
Publication Date(Web):November 19, 2012
DOI:10.1021/ar300132r
Flavins feature multiple attributes that explain their widespread occurrence in nature, including photostability, reversible electrochemistry, and especially the tunability of their optical, electronic, and redox properties by supramolecular interactions and modification of their chemical structure. Flavins are important redox cofactors for enzymatic catalysis and are central to a wide variety of processes, including biosynthesis, electron transport, photosynthesis, and DNA repair. The wide range of processes catalyzed by flavins makes them promising leads for synthetic catalysts. Their properties are also relevant to organic electronic and optoelectronic devices, where they have the potential to serve as photoactive electron carriers, a very uncommon property in current photovoltaic systems.In flavoenzymes, the flavin cofactor binds to the active site of the apoenzyme through noncovalent interactions. These interactions regulate cofactor recognition and tune the redox behavior of the flavin cofactor. In this Account, we describe the creation of host–guest systems based on small molecule, polymer, and nanoparticle scaffolds that explore the role of aromatic stacking on the redox properties of the flavin and provide insight into flavoenzyme function. We also describe the creation of synthetic flavin-based interlocked structures featuring aromatic stacking interactions, along with the use of aromatic stacking to direct self-assembly of flavin-based materials.The interplay between redox events and aromatic stacking interactions seen in these synthetic models is important for fundamental understanding of biological systems including the flavoenzymes. The precise control of aromatic interactions and binding of flavins not only underpins their biological activity but gives them the potential to be developed into novel organic optoelectronic materials based on tuned synthetic flavin–receptor assemblies. In a broader context, the redox properties of the flavin provide a very concise tool for looking at the role of electronics in aromatic stacking, an issue of general importance in biological and supramolecular chemistry.
Co-reporter:Sung Tae Kim, Krishnendu Saha, Chaekyu Kim, and Vincent M. Rotello
Accounts of Chemical Research 2013 Volume 46(Issue 3) pp:681
Publication Date(Web):January 7, 2013
DOI:10.1021/ar3000647
Surface properties dictate the behavior of nanomaterials in vitro, in vivo, and in the environment. Such properties include surface charge and hydrophobicity. Also key are more complex supramolecular interactions such as aromatic stacking and hydrogen bonding, and even surface topology from the structural to the atomic level. Surface functionalization of nanoparticles (NPs) provides an effective way to control the interface between nanomaterials and the biological systems they are designed to interact with. In medicine, for instance, proper control of surface properties can maximize therapeutic or imaging efficacy while minimizing unfavorable side effects. Meanwhile, in environmental science, thoughtful choice of particle coating can minimize the impact of manufactured nanomaterials on the environment.A thorough knowledge of how NP surfaces with various properties affect biological systems is essential for creating NPs with such useful therapeutic and imaging properties as low toxicity, stability, biocompatibility, favorable distribution throughout cells or tissues, and favorable pharmacokinetic profiles—and for reducing the potential environmental impact of manufactured nanomaterials, which are becoming increasingly prominent in the marketplace.In this Account, we discuss our research and that of others into how NP surface properties control interactions with biomolecules and cells at many scales, including the role the particle surface plays in determining in vivo behavior of nanomaterials. These interactions can be benign, beneficial, or lead to dysfunction in proteins, genes and cells, resulting in cytotoxic and genotoxic responses. Understanding these interactions and their consequences helps us to design minimally invasive imaging and delivery agents.We also highlight in this Account how we have fabricated nanoparticles to act as therapeutic agents via tailored interactions with biomacromolecules. These particles offer new therapeutic directions from traditional small molecule therapies, and with potentially greater versatility than is possible with proteins and nucleic acids.
Co-reporter:Bo Yan ; Sung Tae Kim ; Chang Soo Kim ; Krishnendu Saha ; Daniel F. Moyano ; Yuqing Xing ; Ying Jiang ; Amy L. Roberts ; Felix S. Alfonso ; Vincent M. Rotello ;Richard W. Vachet
Journal of the American Chemical Society 2013 Volume 135(Issue 34) pp:12564-12567
Publication Date(Web):August 9, 2013
DOI:10.1021/ja406553f
Imaging of nanomaterials in biological tissues provides vital information for the development of nanotherapeutics and diagnostics. Multiplexed imaging of different nanoparticles (NPs) greatly reduces costs, the need to use multiple animals, and increases the biodistribution information that can enhance diagnostic applications and accelerate the screening of potential therapeutics. Various approaches have been developed for imaging NPs; however, the readout of existing imaging techniques relies on specific properties of the core material or surface ligands, and these techniques are limited because of the relatively small number of NPs that can be simultaneously measured in a single experiment. Here, we demonstrate the use of laser desorption/ionization mass spectrometry (LDI-MS) in an imaging format to investigate surface chemistry dictated intraorgan distribution of NPs. This new LDI-MS imaging method enables multiplexed imaging of NPs with potentially unlimited readouts and without additional labeling of the NPs. It provides the capability to detect and image attomole levels of NPs with almost no interferences from biomolecules. Using this new imaging approach, we find that the intraorgan distributions of same-sized NPs are directly linked to their surface chemistry.
Co-reporter:S. Gokhan Elci, Daniel F. Moyano, Subinoy Rana, Gulen Yesilbag Tonga, Ronnie L. Phillips, Uwe H. F. Bunz and Vincent M. Rotello
Chemical Science 2013 vol. 4(Issue 5) pp:2076-2080
Publication Date(Web):01 Mar 2013
DOI:10.1039/C3SC22279A
A sensor array composed of eight functionalized gold nanoparticles and a fluorescent polymer was utilized to identify 11 glycosaminoglycans (GAGs) by their chemical signatures. Particle ligand structure was key in differentiating analytes, with aromatic and specific sugar functionalities recognizing GAG structural parameters including sulfonation, acetylation, epimeric structure, size, and charge.
Co-reporter:Yisheng Xu, Yoni Engel, Yunfeng Yan, Kaimin Chen, Daniel F. Moyano, Paul L. Dubin and Vincent M. Rotello
Journal of Materials Chemistry A 2013 vol. 1(Issue 39) pp:5230-5234
Publication Date(Web):30 Apr 2013
DOI:10.1039/C3TB20377H
Two β-lactoglobulin (BLG) isoforms, BLGA and BLGB, were used as a test bed for the differentiation of proteins using electrostatics. In these studies, the BLGA and BLGB binding to a highly charged, cationic gold nanoparticle (GNP) modified surface was investigated by atomic force microscopy (AFM) and surface plasmon resonance (SPR) spectroscopy. The binding affinity, and more importantly, the selectivity of this surface towards these two almost identical protein isoforms were both significantly increased on the cationic GNP surface array relative to the values measured with the same free cationic GNP in solution. While protein recognition is traditionally achieved almost exclusively via orientation dependent short-range interactions such as hydrogen bonds and hydrophobic interactions, our results show the potential of protein recognition platforms based on enhanced electrostatic interactions.
Co-reporter:Yi-Cheun Yeh, Krishnendu Saha, Bo Yan, Oscar R. Miranda, Xi Yu and Vincent M. Rotello
Nanoscale 2013 vol. 5(Issue 24) pp:12140-12143
Publication Date(Web):14 Oct 2013
DOI:10.1039/C3NR04037B
The effect of ligand structure on the cytotoxicity of cationic CdSe/ZnS quantum dots (QDs) was systematically investigated using mono- and bidentate ligands. Monothiol-functionalized QDs are more cytotoxic than dithiol-functionalized QDs.
Co-reporter:Bo Yan, Youngdo Jeong, Luiza A. Mercante, Gülen Yesilbag Tonga, Chaekyu Kim, Zheng-Jiang Zhu, Richard W. Vachet and Vincent M. Rotello
Nanoscale 2013 vol. 5(Issue 11) pp:5063-5066
Publication Date(Web):18 Apr 2013
DOI:10.1039/C3NR01384G
Functionalized magnetic nanoparticles (MNPs) have been characterized by laser desorption/ionization mass spectrometry (LDI-MS). Quantitative information about surface ligand composition and structure for monolayer and mixed monolayer protected Fe3O4 and FePt NPs can be obtained rapidly with very little sample consumption.
Co-reporter:Rubul Mout
Israel Journal of Chemistry 2013 Volume 53( Issue 8) pp:521-529
Publication Date(Web):
DOI:10.1002/ijch.201300026
Abstract
Surface engineering of nanoparticles controls the interaction of these materials with proteins and other biomolecules. These interactions provide an important tool for integrating synthetic and biological systems. We will discuss the use of nanoparticles to modulate the structure and function of proteins, the self-assembly of proteins and nanoparticles to create multifunctional materials, and the construction of nanoparticle-based sensors for the detection and identification of proteins and cells.
Co-reporter:Vikas Nandwana, Luis A. Serrano, Kyril M. Solntsev, Bernd Ebenhoch, Qian Liu, Gulen Y. Tonga, Ifor D. W. Samuel, Graeme Cooke, and Vincent M. Rotello
Langmuir 2013 Volume 29(Issue 24) pp:7534-7537
Publication Date(Web):March 13, 2013
DOI:10.1021/la4007372
We have demonstrated controlled assembly between CdSe quantum dots (QDs) and a fullerene (C60) derivative via complementary three-point hydrogen bonding interactions. The recognition-mediated assembly facilitated an interpenetrated network morphology and hence efficient charge transfer from QD to C60.
Co-reporter:Rui Tang, Chang Soo Kim, David J. Solfiell, Subinoy Rana, Rubul Mout, Elih M. Velázquez-Delgado, Apiwat Chompoosor, Youngdo Jeong, Bo Yan, Zheng-Jiang Zhu, Chaekyu Kim, Jeanne A. Hardy, and Vincent M. Rotello
ACS Nano 2013 Volume 7(Issue 8) pp:6667
Publication Date(Web):July 1, 2013
DOI:10.1021/nn402753y
Intracellular protein delivery is an important tool for both therapeutic and fundamental applications. Effective protein delivery faces two major challenges: efficient cellular uptake and avoiding endosomal sequestration. We report here a general strategy for direct delivery of functional proteins to the cytosol using nanoparticle-stabilized capsules (NPSCs). These NPSCs are formed and stabilized through supramolecular interactions between the nanoparticle, the protein cargo, and the fatty acid capsule interior. The NPSCs are ∼130 nm in diameter and feature low toxicity and excellent stability in serum. The effectiveness of these NPSCs as therapeutic protein carriers was demonstrated through the delivery of fully functional caspase-3 to HeLa cells with concomitant apoptosis. Analogous delivery of green fluorescent protein (GFP) confirmed cytosolic delivery as well as intracellular targeting of the delivered protein, demonstrating the utility of the system for both therapeutic and imaging applications.Keywords: intracellular protein delivery; nanocapsule; nanoparticle; organelle targeting; supramolecular assembly
Co-reporter:Chang Soo Kim, Bradley Duncan, Brian Creran, Vincent M. Rotello
Nano Today 2013 Volume 8(Issue 4) pp:439-447
Publication Date(Web):August 2013
DOI:10.1016/j.nantod.2013.07.004
•Triggered nanoparticles provide therapeutic benefits.•Exogenously mediated release of therapeutics from nanoparticle surfaces using external stimuli is discussed.•Endogenously mediated release using environmental differences in living systems is overviewed.•Developing multifunctional nanoparticles allows for theragnostic applications.Drug delivery systems (DDSs) face several challenges including site-specific delivery, stability, and the programmed release of drugs. Engineered nanoparticle (NP) surfaces with responsive moieties can enhance the efficacy of DDSs for in vitro and in vivo systems. This triggering process can be achieved through both endogenous (biologically controlled release) and exogenous (external stimuli controlled release) activation. In this review, we will highlight recent examples of the use of triggered release strategies of engineered nanomaterials for in vitro and in vivo applications.
Co-reporter:Krishnendu Saha, Sarit S. Agasti, Chaekyu Kim, Xiaoning Li, and Vincent M. Rotello
Chemical Reviews 2012 Volume 112(Issue 5) pp:2739-2779
Publication Date(Web):February 2, 2012
DOI:10.1021/cr2001178
Co-reporter:Rubul Mout, Daniel F. Moyano, Subinoy Rana and Vincent M. Rotello
Chemical Society Reviews 2012 vol. 41(Issue 7) pp:2539-2544
Publication Date(Web):06 Feb 2012
DOI:10.1039/C2CS15294K
Control of interactions between nanoparticles and biosystems is essential for the effective utilization of these materials in biomedicine. A wide variety of nanoparticle surface structures have been developed for imaging, sensing, and delivery applications. In this research Highlight, we will emphasize advances in tailoring nanoparticle interfaces for implementation in nanomedicine.
Co-reporter:Xi Yu;Jonathan T. Pham;Chramouleeswaran Subramani;Brian Creran;Yi-Cheun Yeh;Kan Du;Debabrata Patra;Oscar R. Mira;Alfred J. Crosby
Advanced Materials 2012 Volume 24( Issue 47) pp:6330-6334
Publication Date(Web):
DOI:10.1002/adma.201202776
Co-reporter:Myoung-Hwan Park;Chramouleeswaran Subramani;Subinoy Rana
Advanced Materials 2012 Volume 24( Issue 43) pp:5862-5866
Publication Date(Web):
DOI:10.1002/adma.201201863
Co-reporter:Yoni Engel, Jessica D. Schiffman, Julie M. Goddard, Vincent M. Rotello
Materials Today 2012 Volume 15(Issue 11) pp:478-485
Publication Date(Web):November 2012
DOI:10.1016/S1369-7021(12)70217-1
In this review, we present a few of the many important objectives in the area of biomedical engineering that could open new pathways for next-generation biomaterials. We also provide examples of how materials for these goals can be created in an economically viable means through recent advances in high throughput production. These strategies highlight the potential for nanomanufacturing in a variety of areas of importance for human health and safety.
Co-reporter:Daniel F. Moyano ; Meir Goldsmith ; David J. Solfiell ; Dalit Landesman-Milo ; Oscar R. Miranda ; Dan Peer
Journal of the American Chemical Society 2012 Volume 134(Issue 9) pp:3965-3967
Publication Date(Web):February 17, 2012
DOI:10.1021/ja2108905
Understanding the interactions of nanomaterials with the immune system is essential for the engineering of new macromolecular systems for in vivo applications. Systematic study of immune activation is challenging due to the complex structure of most macromolecular probes. We present here the use of engineered gold nanoparticles to determine the sole effect of hydrophobicity on the immune response of splenocytes. The gene expression profile of a range of cytokines (immunological reporters) was analyzed against the calculated log P of the nanoparticle headgroups, with an essentially linear increase in immune activity with the increase in hydrophobicity observed in vitro. Consistent behavior was observed with in vivo mouse models, demonstrating the importance of hydrophobicity in immune system activation.
Co-reporter:Brian Creran, Bo Yan, Daniel F. Moyano, Michael M. Gilbert, Richard W. Vachet and Vincent M. Rotello
Chemical Communications 2012 vol. 48(Issue 38) pp:4543-4545
Publication Date(Web):01 Mar 2012
DOI:10.1039/C2CC30499F
Patterns created by the inkjet printing of functionalized gold nanoparticles (NPs) can be selectively detected by laser desorption/ionization imaging mass spectrometry (LDI-IMS). These patterns can only be visualized by mass, providing a robust yet tunable system for potential anti-counterfeiting applications.
Co-reporter:Vikas Nandwana, Brian Fitzpatrick, Qian Liu, Kyril M. Solntsev, Xi Yu, Gülen Yesilbag Tonga, Serkan Eymur, Murat Tonga, Graeme Cooke and Vincent M. Rotello
Polymer Chemistry 2012 vol. 3(Issue 11) pp:3072-3076
Publication Date(Web):13 Jun 2012
DOI:10.1039/C2PY20353G
We have demonstrated fluorescence resonance energy transfer facilitated by recognition mediated assembly of quantum dots and a tailor-made fluorescent polymer.
Co-reporter:Zheng-Jiang Zhu, Rui Tang, Yi-Cheun Yeh, Oscar R. Miranda, Vincent M. Rotello, and Richard W. Vachet
Analytical Chemistry 2012 Volume 84(Issue 10) pp:4321
Publication Date(Web):April 20, 2012
DOI:10.1021/ac203408v
Monolayer stability of core–shell nanoparticles is a key determinant of their utility in biological studies such as imaging and drug delivery. Intracellular thiols (e.g., cysteine, cysteamine, and glutathione) can trigger the release of thiolate-bound monolayers from nanoparticles, a favorable outcome for controllable drug release applications but an unfavorable outcome for imaging agents. Here, we describe a method to quantify the monolayer release of gold nanoparticles (AuNPs) in living cells using parallel measurements by laser desorption/ionization (LDI) and inductively coupled plasma (ICP) mass spectrometry. This combination of methods is tested using AuNPs with structural features known to influence monolayer stability and on cells types with varying concentrations of glutathione. On the basis of our results, we predict that this approach should help efforts to engineer nanoparticle surface monolayers with tunable stability, providing stable platforms for imaging agents and controlled release of therapeutic monolayer payloads.
Co-reporter:Mottakin M. Abul Kashem, Debabrata Patra, Jan Perlich, André Rothkirch, Adeline Buffet, Stephan V. Roth, Vincent M. Rotello, and Peter Müller-Buschbaum
ACS Macro Letters 2012 Volume 1(Issue 3) pp:396
Publication Date(Web):February 27, 2012
DOI:10.1021/mz200141q
We show a route to produce a two- and three-dimensional network of nanoparticles via polymer-mediated self-assembly. A negatively charged polymer, CO2-functionalized poly (para-phenyleneethylene) (PPE-CO2), is used to build this network of iron–platinum (Fe–Pt) nanoparticles. The nanoparticles arrange locally in hexagonal and cubic lattice type network structures. The size and form of the networks are characterized with atomic force microscopy (AFM), transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and grazing incidence small-angle X-ray scattering (GISAXS). In thin film the network is perturbed due to the force field acting during spin coating.
Co-reporter:Zheng-Jiang Zhu, Huanhua Wang, Bo Yan, Hao Zheng, Ying Jiang, Oscar R. Miranda, Vincent M. Rotello, Baoshan Xing, and Richard W. Vachet
Environmental Science & Technology 2012 Volume 46(Issue 22) pp:12391
Publication Date(Web):October 26, 2012
DOI:10.1021/es301977w
Small (6–10 nm) functionalized gold nanoparticles (AuNPs) featuring different, well-defined surface charges were used to probe the uptake and distribution of nanomaterials in terrestrial plants, including rice, radish, pumpkin, and perennial ryegrass. Exposure of the AuNPs to plant seedlings under hydroponic conditions for a 5-day period was investigated. Results from these studies indicate that AuNP uptake and distribution depend on both nanoparticle surface charge and plant species. The experiments show that positively charged AuNPs are most readily taken up by plant roots, while negatively charged AuNPs are most efficiently translocated into plant shoots (including stems and leaves) from the roots. Radish and ryegrass roots generally accumulated higher amounts of the AuNPs (14–900 ng/mg) than rice and pumpkin roots (7–59 ng/mg). Each of the AuNPs used in this study were found to accumulate to statistically significant extents in rice shoots (1.1–2.9 ng/mg), while none of the AuNPs accumulated in the shoots of radishes and pumpkins.
Co-reporter:Xi Yu, Serkan Eymur, Vijay Singh, Boqian Yang, Murat Tonga, Amarnath Bheemaraju, Graeme Cooke, Chandramouleeswaran Subramani, Dhandapani Venkataraman, Robert J. Stanley and Vincent M. Rotello
Physical Chemistry Chemical Physics 2012 vol. 14(Issue 19) pp:6749-6754
Publication Date(Web):20 Mar 2012
DOI:10.1039/C2CP40073A
A donor–acceptor dyad model system using a flavin moiety as a photo-active acceptor has been synthesized for an energy and photo-induced electron transfer study. The photophysical investigations of the dyad revealed a multi-path energy and electron transfer process with a very high transfer efficiency. The photo-activity of flavin was believed to play an important role in the process, implying the potential application of flavin as a novel acceptor molecule for photovoltaics.
Co-reporter:Brian Fitzpatrick;Brian Creran;Graeme Cooke
Macromolecular Chemistry and Physics 2012 Volume 213( Issue 17) pp:1758-1767
Publication Date(Web):
DOI:10.1002/macp.201200225
Abstract
The synthesis of flavin-containing amphiphilic block copolymers using atom transfer radical polymerisation (ATRP) is described. In these systems, a flavin moiety is engineered into the ATRP initiator unit as an environmental probe and is subsequently used to produce three block copolymers featuring a hydrophobic methacrylate block and a DMAEM block. The dimethylamino unit of the latter is converted to a trimethylammonium unit to afford three amphiphilic block copolymers. Rheological measurements show that these materials form gels in dilute aqueous solution that can be disrupted upon irradiation with ultrasound. The disruption of the gel can be conveniently monitored by exploiting the solvatochromic nature of the S0–S2 absorption in the UV-vis spectrum in response to its changing environment.
Co-reporter:Brian Fitzpatrick;Brian Creran;Graeme Cooke
Macromolecular Chemistry and Physics 2012 Volume 213( Issue 17) pp:
Publication Date(Web):
DOI:10.1002/macp.201290052
Co-reporter:Subinoy Rana, Arvind K. Singla, Avinash Bajaj, S. Gokhan Elci, Oscar R. Miranda, Rubul Mout, Bo Yan, Frank R. Jirik, and Vincent M. Rotello
ACS Nano 2012 Volume 6(Issue 9) pp:8233
Publication Date(Web):August 26, 2012
DOI:10.1021/nn302917e
Rapid and sensitive methods of discriminating between healthy tissue and metastases are critical for predicting disease course and designing therapeutic strategies. We report here the use of an array of gold nanoparticle–green fluorescent protein elements to rapidly detect metastatic cancer cells (in minutes), as well as to discriminate between organ-specific metastases and their corresponding normal tissues through their overall intracellular proteome signatures. Metastases established in a new preclinical non-small-cell lung cancer metastasis model in athymic mice were used to provide a challenging and realistic testbed for clinical cancer diagnosis. Full differentiation between the analyte cell/tissue was achieved with as little as 200 ng of intracellular protein (∼1000 cells) for each nanoparticle, indicating high sensitivity of this sensor array. Notably, the sensor created a distinct fingerprint pattern for the normal and metastatic tumor tissues. Moreover, this array-based approach is unbiased, precluding the requirement of a priori knowledge of the disease biomarkers. Taken together, these studies demonstrate the utility of this sensor for creating fingerprints of cells and tissues in different states and present a generalizable platform for rapid screening amenable to microbiopsy samples.Keywords: array-based sensing; gold nanoparticle; lysates; metastasis; tissue
Co-reporter:Subinoy Rana, Xi Yu, Debabrata Patra, Daniel F. Moyano, Oscar R. Miranda, Irshad Hussain, and Vincent M. Rotello
Langmuir 2012 Volume 28(Issue 4) pp:2023-2027
Publication Date(Web):December 13, 2011
DOI:10.1021/la204017z
Subtle changes in the monolayer structure of nanoparticles (NPs) influence the interfacial behavior of both NPs and NP–protein conjugates. In this study, we use a series of monolayer-protected gold NPs to explore the role of particle hydrophobicity on their dynamic behavior at the toluene–water interface. Using dynamic surface tension measurements, we observed a linear decrease in the meso-equilibrium surface tension (γ) and faster dynamics as the hydrophobicity of the ligands increases. Further modulation of γ is observed for the corresponding NP–protein complexes at the charge-neutralization point.
Co-reporter:Bradley Duncan, S. Gokhan Elci, Vincent M. Rotello
Nano Today 2012 Volume 7(Issue 4) pp:228-230
Publication Date(Web):August 2012
DOI:10.1016/j.nantod.2012.06.001
Traditional cell detection based on biomarkers relies on specific lock-and-key recognition. However, many diseases either do not have obvious biomarkers or these markers are currently unknown. Unbiased sensor arrays based on nanoparticles use selective interactions to generate bioprofiles capable of identifying cell type and state. As a result, these arrays can differentiate subtle variations on the cell surfaces, presenting a potential approach for personalized diagnostics.Graphical abstractHighlights► Description of the unbiased array-based sensing method is presented. ► Selective interactions of sensors allow detection of subtle variations on cell surfaces. ► Unbiased array-based sensors have been used to discriminate cell states.
Co-reporter:Myoung-Hwan Park;Sarit S. Agasti;Brian Creran;Chaekyu Kim
Advanced Materials 2011 Volume 23( Issue 25) pp:2839-2842
Publication Date(Web):
DOI:10.1002/adma.201004409
Co-reporter:Vikas Nandwana, Chandramouleeswaran Subramani, Yi-Cheun Yeh, Boqian Yang, Stefan Dickert, Michael D. Barnes, Mark T. Tuominen and Vincent M. Rotello
Journal of Materials Chemistry A 2011 vol. 21(Issue 42) pp:16859-16862
Publication Date(Web):25 Jul 2011
DOI:10.1039/C1JM11782C
Patterned quantum dot (QD) nanostructures were prepared by direct electron beam lithography on QD films. Time resolved photoluminescence measurements show that the optical properties of these QDs were retained after cross-linking.
Co-reporter:Chandramouleeswaran Subramani, Xi Yu, Sarit. S. Agasti, Bradley Duncan, Serkan Eymur, Murat Tonga and Vincent M. Rotello
Journal of Materials Chemistry A 2011 vol. 21(Issue 37) pp:14156-14158
Publication Date(Web):18 May 2011
DOI:10.1039/C1JM11035G
Photoactivatable gold NPs were patterned viaphotolithography. In this approach, charge reversal of the ligands on NPs upon UV irradiation induces crosslinking to generate stable NP patterns.
Co-reporter:Youngdo Jeong, Bradley Duncan, Myoung-Hwan Park, Chaekyu Kim and Vincent M. Rotello
Chemical Communications 2011 vol. 47(Issue 44) pp:12077-12079
Publication Date(Web):14 Oct 2011
DOI:10.1039/C1CC14448K
Emulsions stabilized by enzyme-nanoparticle (NP) complexes were used to fabricate robust biocatalytic scaffolds after core solidification via crosslinking. These biocatalysts feature ease of formation, high retention of enzymatic activity and reusability.
Co-reporter:Yi-Cheun Yeh, Debabrata Patra, Bo Yan, Krishnendu Saha, Oscar R. Miranda, Chae Kyu Kim and Vincent M. Rotello
Chemical Communications 2011 vol. 47(Issue 11) pp:3069-3071
Publication Date(Web):08 Feb 2011
DOI:10.1039/C0CC04975A
A new class of quaternary ammonium derivatives has been used to synthesize cationic CdSe/ZnS quantum dots with exceptional stability in water as well as in biological media.
Co-reporter:Niall A. McDonald, Chandramouleeswaran Subramani, Stuart T. Caldwell, Nada Y. Zainalabdeen, Graeme Cooke, Vincent M. Rotello
Tetrahedron Letters 2011 Volume 52(Issue 17) pp:2107-2110
Publication Date(Web):27 April 2011
DOI:10.1016/j.tetlet.2010.11.004
In this Letter, we describe the formation of complexes between flavin and diamidopyridine functionalized porphyrin systems via hydrogen bonding and π-stacking interactions.
Co-reporter:Daniel F. Moyano and Vincent M. Rotello
Langmuir 2011 Volume 27(Issue 17) pp:10376-10385
Publication Date(Web):April 8, 2011
DOI:10.1021/la2004535
Understanding the interactions of nanomaterials with biosystems is a critical goal in both biomedicine and environmental science. Engineered nanoparticles provide excellent tools for probing this interface. In this feature article, we will summarize one of the themes presented in our recent Langmuir lecture discussing the use of monolayer design to understand and control the interactions of nanoparticles with biomolecules and cells.
Co-reporter:Dr. Xiao-Chao Yang;Dr. Bappaditya Samanta;Sarit S. Agasti;Youngdo Jeong;Zheng-Jiang Zhu;Subinoy Rana;Oscar R. Mira; Vincent M. Rotello
Angewandte Chemie International Edition 2011 Volume 50( Issue 2) pp:477-481
Publication Date(Web):
DOI:10.1002/anie.201005662
Co-reporter:Chandramouleeswaran Subramani, Stefan Dickert, Yi-Cheun Yeh, Mark T. Tuominen, and Vincent M. Rotello
Langmuir 2011 Volume 27(Issue 4) pp:1543-1545
Publication Date(Web):November 29, 2010
DOI:10.1021/la1039514
Electron-beam lithography was used to pattern poly(styrene-co-(methyldiaminotriazine) styrene) (PS-Triaz). These polymer nanopatterns were utilized as molecular scaffolds for assembling complementary thymine-functionalized CdSe-ZnS quantum dots (Thy-QDs) via three-point hydrogen-bonding molecular recognition. This interaction was very specific, with N-methyl thymine-functionalized QDs (MeThy-QDs) not depositing on the surfaces. The “lock and key” specificity of the assembly is mirrored in the disassembly process, where complete removal of the QD was observed using a competing thymine guest.
Co-reporter:Dr. Xiao-Chao Yang;Dr. Bappaditya Samanta;Sarit S. Agasti;Youngdo Jeong;Zheng-Jiang Zhu;Subinoy Rana;Oscar R. Mira; Vincent M. Rotello
Angewandte Chemie 2011 Volume 123( Issue 2) pp:497-501
Publication Date(Web):
DOI:10.1002/ange.201005662
Co-reporter:Chramouleeswaran Subramani;Avinash Bajaj;Oscar R. Mira
Advanced Materials 2010 Volume 22( Issue 47) pp:5420-5423
Publication Date(Web):
DOI:10.1002/adma.201002851
Co-reporter:Yuval Ofir;Isaac W. Moran;Chramouleeswaran Subramani;Kenneth R. Carter
Advanced Materials 2010 Volume 22( Issue 32) pp:3608-3614
Publication Date(Web):
DOI:10.1002/adma.200904396
Abstract
Nanoimprint lithography (NIL) is viewed as an alternative nanopatterning technique to traditional photolithography, allowing micrometer-scale and sub-hundred-nanometer resolution as well as three-dimensional structure fabrication. In this Research News article we highlight current activities towards the use of NIL in patterning active or functional materials, and the application of NIL in patterning materials that present both chemistry and structure/topography in the patterned structures, which provide scaffolds for subsequent manipulation. We discuss and give examples of the various materials and chemistries that have been used to create functional patterns and their implication in various fields as electronic and magnetic devices, optically relevant structures, biologically important surfaces, and 3D particles.
Co-reporter:Partha Ghosh ; Xiaochao Yang ; Rochelle Arvizo ; Zheng-Jiang Zhu ; Sarit S. Agasti ; Zhihong Mo
Journal of the American Chemical Society 2010 Volume 132(Issue 8) pp:2642-2645
Publication Date(Web):February 4, 2010
DOI:10.1021/ja907887z
Gold nanoparticles were coated with a short peptide to promote intracellular delivery of membrane-impermeable proteins. Through microscopy and enzyme assays, we demonstrated the particles were able to transport functional enzymes into a variety of cell lines. Significantly, the transported proteins were able to escape from endosomes. Moreover, these particles showed no apparent cytotoxicity.
Co-reporter:Oscar R. Miranda ; Hung-Ting Chen ; Chang-Cheng You ; David E. Mortenson ; Xiao-Chao Yang ; Uwe H. F. Bunz
Journal of the American Chemical Society 2010 Volume 132(Issue 14) pp:5285-5289
Publication Date(Web):March 23, 2010
DOI:10.1021/ja1006756
We have developed an enzyme−nanoparticle sensor array where the sensitivity is amplified through enzymatic catalysis. In this approach cationic gold nanoparticles are electrostatically bound to an enzyme (β-galactosidase, β-Gal), inhibiting enzyme activity. Analyte proteins release the β-Gal, restoring activity and providing an amplified readout of the binding event. Using this strategy we have been able to identify proteins in buffer at a concentration of 1 nM, substantially lower than current strategies for array-based protein sensing. Moreover, we have obtained identical sensitivity in studies where the proteins are spiked into the complex protein matrix provided by desalted human urine (∼1.5 μM total protein; spiked protein concentrations were 0.067% of the overall protein concentration), demonstrating the potential of the method for diagnostic applications.
Co-reporter:Avinash Bajaj, Subinoy Rana, Oscar R. Miranda, Joseph C. Yawe, D. Joseph Jerry, Uwe H. F. Bunz and Vincent M. Rotello
Chemical Science 2010 vol. 1(Issue 1) pp:134-138
Publication Date(Web):24 May 2010
DOI:10.1039/C0SC00165A
Gold nanoparticle-green fluorescent protein (NP-GFP) based arrays have been created for rapid identification of mammalian cells on the basis of cell surface properties. Highly reproducible characteristic patterns were obtained from different cell types enabling the identification of cell types and cancer states. Using these arrays we could differentiate between isogenic normal, cancer and metastatic cell types using only ∼5000 cells.
Co-reporter:Dawn Ernenwein, Partha Ghosh, Vincent Rotello and Jean Chmielewski
Journal of Materials Chemistry A 2010 vol. 20(Issue 27) pp:5608-5611
Publication Date(Web):08 Jun 2010
DOI:10.1039/C0JM01108H
Non-covalent interactions between cationic gold nanoparticles and an anionic coiled-coil peptide were harnessed for coiled-coil mediated self-assembly of gold nanoparticles (GNPs).
Co-reporter:Bradley Duncan, Chaekyu Kim, Vincent M. Rotello
Journal of Controlled Release 2010 Volume 148(Issue 1) pp:122-127
Publication Date(Web):20 November 2010
DOI:10.1016/j.jconrel.2010.06.004
Gold nanoparticles (AuNPs) are a suitable platform for development of efficient delivery systems. AuNPs can be easily synthesized, functionalized, and are biocompatible. The tunability of the AuNP monolayer allows for complete control of surface properties for targeting and stability/release using these nanocarriers. This review will discuss several delivery strategies utilizing AuNPs.Gold nanoparticles provide effective platforms for drug delivery via multiple controlled release strategies due to their stability, tunable monolayers, functional flexibility, and low toxicity.
Co-reporter:Chandramouleeswaran Subramani, Gulen Yesilbag, Brian J. Jordan, Xiaoning Li, Abraham Khorasani, Graeme Cooke, Amitav Sanyal and Vincent M. Rotello
Chemical Communications 2010 vol. 46(Issue 12) pp:2067-2069
Publication Date(Web):17 Feb 2010
DOI:10.1039/B926746H
Diaminopyridine dendritic scaffolds encapsulate polymeric flavin via non-covalent interactions and demonstrate isolation of the redox moiety.
Co-reporter:Myoung-Hwan Park, Xuexin Duan, Yuval Ofir, Brian Creran, Debabrata Patra, Xing Yi Ling, Jurriaan Huskens and Vincent M. Rotello
ACS Applied Materials & Interfaces 2010 Volume 2(Issue 3) pp:795
Publication Date(Web):February 16, 2010
DOI:10.1021/am9009007
Dithiocarbamate-mediated bond formation combined with soft lithography was used for the selective immobilization of amine-functionalized silica nanoparticles on gold substrates. The available amine groups on the upper surface of the immobilized silica nanoparticles were further utilized for postdeposition of additional materials including particles, dyes, and biomolecules. The robustness of dithiocarbamate-mediated immobilization enables orthogonal assembly on surfaces via selective removal of the masking thiol ligands using iodine vapor etching followed by further functionalization.Keywords: dithiocarbamate; immobilization; iodine etching; nanoparticles; orthogonal assembly
Co-reporter:Xi Yu;Chramouleeswaran Subramani;Xiaochao Yang;Chae Kyu Kim
Macromolecular Rapid Communications 2010 Volume 31( Issue 9-10) pp:910-914
Publication Date(Web):
DOI:10.1002/marc.200900925
Co-reporter:Oktay Uzun;Amitav Sanyal;Youngdo Jeong
Macromolecular Bioscience 2010 Volume 10( Issue 5) pp:481-487
Publication Date(Web):
DOI:10.1002/mabi.200900455
Co-reporter:Xuexin Duan, Myoung-Hwan Park, Yiping Zhao, Erwin Berenschot, Zheyao Wang, David N. Reinhoudt, Vincent M. Rotello, and Jurriaan Huskens
ACS Nano 2010 Volume 4(Issue 12) pp:7660
Publication Date(Web):November 17, 2010
DOI:10.1021/nn102463r
We report here the use of nanomolding in capillaries (NAMIC) coupled with dithiocarbamate (DTC) chemistry to fabricate sub-50 nm quasi-1D arrays of 3.5 nm core gold nanoparticles (Au NPs) over large areas. Owing to chemical immobilization via the DTC bond, the patterned NP systems are stable in water and organic solvents, thus allowing the surface modification of the patterned Au NP arrays through thiol chemistry and further orthogonal binding of proteins. The electrical properties of these patterned Au NP wires have also been studied. Our results show that NAMIC combined with surface chemistry is a simple but powerful tool to create metal NP arrays that can potentially be applied to fabricate nanoelectronic or biosensing devices.Keywords: conductance; nanomolding in capillaries; nanoparticle wires; nanoparticles; soft lithography
Co-reporter:Debabrata Patra; Amitav Sanyal; Vincent M. Rotello
Chemistry – An Asian Journal 2010 Volume 5( Issue 12) pp:2442-2453
Publication Date(Web):
DOI:10.1002/asia.201000301
Abstract
Colloidal microcapsules (MCs) are highly modular, inherently multiscale constructs of capsules stabilized by nano-/microparticle shells, with applications in many areas of materials and biological sciences, such as drug delivery, encapsulation, and microreactors. Until recently, fabrication of colloidal MCs focused on the use of submicron-sized particles because the smaller nanoparticles (NPs) are inherently unstable at the interface owing to thermal disorder. However, stable microcapsules can now be obtained by tuning the interactions between the nanometer-sized building blocks at the liquid–liquid interface. This Review highlights recent developments in the fabrication of colloidal MCs using NPs.
Co-reporter:UweH.F. Bunz ;VincentM. Rotello
Angewandte Chemie International Edition 2010 Volume 49( Issue 19) pp:3268-3279
Publication Date(Web):
DOI:10.1002/anie.200906928
Abstract
Gold nanoparticles (NPs) efficiently quench adsorbed fluorophores. Upon disruption of such complexes by an analyte, fluorescence turn-on is observed. By judicious choice of the functionalized NP and the fluorophore, these complexes display different responses to analytes, thus leading to versatile yet simple array-based sensor platforms. Using this strategy, we can identify proteins in buffer and serum, distinguish between both different species and different strains of bacteria, and differentiate between healthy, cancerous, and metastatic human and murine cells.
Co-reporter:Bo Yan;Zheng-Jiang Zhu;Oscar R. Miranda
Analytical and Bioanalytical Chemistry 2010 Volume 396( Issue 3) pp:1025-1035
Publication Date(Web):2010 February
DOI:10.1007/s00216-009-3250-6
Monolayer-protected gold nanoparticles (AuNPs) feature unique surface properties that enable numerous applications. Thus, there is a need for simple, rapid, and accurate methods to confirm the surface structures of these materials. Here, we describe how laser desorption/ionization mass spectrometry (LDI-MS) can be used to characterize AuNPs with neutral, positively, and negatively charged surface functional groups. LDI readily desorbs and ionizes the gold-bound ligands to produce both free thiols and disulfide ions in pure and complex samples. We also find that LDI-MS can provide a semi-quantitative measure of the ligand composition of mixed-monolayer AuNPs by monitoring mixed disulfide ions that are formed. Overall, the LDI-MS approach requires very little sample, provides an accurate measure of the surface ligands, and can be used to monitor AuNPs in complex mixtures.
Co-reporter:Myoung-Hwan Park;Yuval Ofir;Bappaditya Samanta
Advanced Materials 2009 Volume 21( Issue 22) pp:2323-2327
Publication Date(Web):
DOI:10.1002/adma.200803368
Co-reporter:Avinash Bajaj ; Oscar R. Miranda ; Ronnie Phillips ; Ik-Bum Kim ; D. Joseph Jerry ; Uwe H. F. Bunz
Journal of the American Chemical Society 2009 Volume 132(Issue 3) pp:1018-1022
Publication Date(Web):December 29, 2009
DOI:10.1021/ja9061272
A family of conjugated fluorescent polymers was used to create an array for cell sensing. Fluorescent conjugated polymers with pendant charged residues provided multivalent interactions with cell membranes, allowing the detection of subtle differences between different cell types on the basis of cell surface features. Highly reproducible characteristic patterns were obtained from different cell types as well as from isogenic cell lines, enabling the identification of the cell type as well differentiating between normal, cancerous, and metastatic isogenic cell types with high accuracy.
Co-reporter:Chramouleeswaran Subramani;Yuval Ofir;Debabrata Patra;Brian J. Jordan;Isaac W. Moran;Myoung-Hwan Park;Kenneth R. Carter
Advanced Functional Materials 2009 Volume 19( Issue 18) pp:2937-2942
Publication Date(Web):
DOI:10.1002/adfm.200900805
Abstract
Polyethyleneimine (PEI) is used as a scaffold for integrated top-down/bottom-up fabrication. In this synergistic strategy, patterned PEI surfaces are created using thermal nanoimprint lithography (NIL) using a sacrificial polystyrene (PS) overlayer. These imprinted surfaces act as versatile templates for assembling nanoparticles and dyes, with the amine groups of the PEI enabling electrostatic assembly, carbodiimide coupling, and dithiocarbamate attachment to the nanoimprinted features. The efficient assembly of particles and dyes is confirmed through fluorescence and atomic force microscopy. In these studies the PS overlayer serves two roles. First, the PS layer protects the PEI surface during the plasma-etch removal of the residual layer of the NIL process. Second, the PS overlayer serves as a mask, enabling sequential functionalization of the sides and the tops of the PEI features.
Co-reporter:Avinash Bajaj, Bappaditya Samanta, Haoheng Yan, D. Joseph Jerry and Vincent M. Rotello
Journal of Materials Chemistry A 2009 vol. 19(Issue 35) pp:6328-6331
Publication Date(Web):08 Apr 2009
DOI:10.1039/B901616C
We have explored the mechanism and differential uptake of BSA coated Fe3O4nanoparticles (NPs) by different cancerous and isogenic cell types.
Co-reporter:Hung-Ting Chen, Todd A. Crosby, Myoung-Hwan Park, Sivakumar Nagarajan, Vincent M. Rotello and James J. Watkins
Journal of Materials Chemistry A 2009 vol. 19(Issue 1) pp:70-74
Publication Date(Web):12 Nov 2008
DOI:10.1039/B815055A
Mesoporous silica films with well ordered nanochannels (approximately 7 nm in diameter) oriented parallel to the substrate were synthesized using supercritical carbon dioxide mediated silica deposition within templates comprised of triblock copolymers blended with strongly associating homopolymers. The films were patterned at the device level by conventional lithography and etched to yield periodic circular features approximately 20 µm in diameter. The nanoscale channels remained accessible to penetrant diffusion as shown by dye uptake experiments. The nanochannel arrays were used as miniature size exclusion columns to mediate nanoparticle diffusion.
Co-reporter:Debabrata Patra, Chiara Pagliuca, Chandramouleeswaran Subramani, Bappaditya Samanta, Sarit S. Agasti, Nada Zainalabdeen, Stuart T. Caldwell, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2009 (Issue 28) pp:4248-4250
Publication Date(Web):09 Jun 2009
DOI:10.1039/B906458C
Dithiocarbamate chemistry is used as a crosslinking tool to fabricate FePt colloidal microcapsules which provide a versatile scaffold for “host–guest” recognition at the liquid–liquid interface.
Co-reporter:Mrinmoy De, Oscar R. Miranda, Subinoy Rana and Vincent M. Rotello
Chemical Communications 2009 (Issue 16) pp:2157-2159
Publication Date(Web):18 Mar 2009
DOI:10.1039/B900552H
Fundamentally different assembly motifs are observed when proteins of different sizes are complexed with monolayer-protected nanoparticles.
Co-reporter:Mrinmoy De;Subinoy Rana
Macromolecular Bioscience 2009 Volume 9( Issue 2) pp:174-178
Publication Date(Web):
DOI:10.1002/mabi.200800289
Co-reporter:Bappaditya Samanta, Yuval Ofir, Debabrata Patra and Vincent M. Rotello
Soft Matter 2009 vol. 5(Issue 6) pp:1247-1250
Publication Date(Web):29 Jul 2008
DOI:10.1039/B808494G
Controlled self-assembly of fluorinated FePt nanoparticles from different solvent mixtures has been used to create superhydrophobic surfaces with varying topology and stickiness towards water. The ability to tune surface stickiness provides a means for fluid handling, as demonstrated by surface-to-surface transfer of water droplets.
Co-reporter:Zheng-Jiang Zhu, Vincent M. Rotello and Richard W. Vachet
Analyst 2009 vol. 134(Issue 11) pp:2183-2188
Publication Date(Web):21 Sep 2009
DOI:10.1039/B910428C
Engineering of nanoparticle surface functionality provides controlled interactions with biomolecules such as cell membrane lipids, proteins and nucleic acids. Concurrently, this surface chemistry control also opens up new avenues for improving mass spectral analyses. In this Minireview, we highlight some of the emerging work that integrates surface-engineered nanoparticles with mass spectrometry to improve the analysis of a wide variety of chemical and biological systems.
Co-reporter:Bappaditya Samanta;Xiao-Chao Yang;Yuval Ofir Dr.;Myoung-Hawn Park;Debabrata Patra;SaritS. Agasti;OscarR. Mira;Zhi-Hong Mo ;VincentM. Rotello
Angewandte Chemie 2009 Volume 121( Issue 29) pp:5445-5448
Publication Date(Web):
DOI:10.1002/ange.200901590
Co-reporter:Bappaditya Samanta;Xiao-Chao Yang;Yuval Ofir Dr.;Myoung-Hawn Park;Debabrata Patra;SaritS. Agasti;OscarR. Mira;Zhi-Hong Mo ;VincentM. Rotello
Angewandte Chemie International Edition 2009 Volume 48( Issue 29) pp:5341-5344
Publication Date(Web):
DOI:10.1002/anie.200901590
Co-reporter:Debabrata Patra, Firat Ozdemir, Oscar R. Miranda, Bappaditya Samanta, Amitav Sanyal and Vincent M. Rotello
Langmuir 2009 Volume 25(Issue 24) pp:13852-13854
Publication Date(Web):June 18, 2009
DOI:10.1021/la9015756
Stimuli-responsive colloidal microcapsules have been fabricated at the oil−water interface using molecular recognition between functionalized gold nanoparticles. Water-soluble β-cyclodextrin-capped gold nanoparticles and organo-soluble adamantyl-functionalized gold nanoparticles are self-assembled at the water−toluene interface via specific host−guest molecular interactions to provide robust microcapsules. Multivalent interactions of complementary ligands on the nanoparticle surface provide stability to these capsules. Unlike covalently cross-linked microcapsules, the reversible nature of these bridging interactions can be used to manipulate the size of these capsules via introduction of competing adamantane containing amphiphilic guest molecules. Partial disruption of interfacial cross-linking allows microcapsules to coalesce with each other to form larger capsules.
Co-reporter:Avinash Bajaj;Oscar R. Miranda;Ik-Bum Kim;Ronnie L. Phillips;D. Joseph Jerry;Uwe H. F. Bunz;
Proceedings of the National Academy of Sciences 2009 106(27) pp:10912-10916
Publication Date(Web):June 23, 2009
DOI:10.1073/pnas.0900975106
Rapid and effective differentiation between normal and cancer cells is an important challenge for the diagnosis and treatment
of tumors. Here, we describe an array-based system for identification of normal and cancer cells based on a “chemical nose/tongue”
approach that exploits subtle changes in the physicochemical nature of different cell surfaces. Their differential interactions
with functionalized nanoparticles are transduced through displacement of a multivalent polymer fluorophore that is quenched
when bound to the particle and fluorescent after release. Using this sensing strategy we can rapidly (minutes/seconds) and
effectively distinguish (i) different cell types; (ii) normal, cancerous and metastatic human breast cells; and (iii) isogenic normal, cancerous and metastatic murine epithelial cell lines.
Co-reporter:Yuval Ofir, Bappaditya Samanta and Vincent M. Rotello
Chemical Society Reviews 2008 vol. 37(Issue 9) pp:1814-1825
Publication Date(Web):23 Jul 2008
DOI:10.1039/B712689C
Gold nanoparticle–polymer composites are versatile and diverse functional materials, with applications in optical, electronic and sensing devices. This tutorial review focuses on the use of polymers to control the assembly of gold nanoparticles. Examples of synthetic polymers and biopolymers are provided, as well as applications of the composite materials in sensing and memory devices.
Co-reporter:Mrinmoy De;Partha S. Ghosh
Advanced Materials 2008 Volume 20( Issue 22) pp:4225-4241
Publication Date(Web):
DOI:10.1002/adma.200703183
Co-reporter:Yuval Ofir;Bappaditya Samanta;Qijun Xiao;Brian J. Jordan;Hao Xu;Palaniappan Arumugam;Rochelle Arvizo;Mark T. Tuominen
Advanced Materials 2008 Volume 20( Issue 13) pp:
Publication Date(Web):
DOI:10.1002/adma.200890051
Co-reporter:Yuval Ofir;Bappaditya Samanta;Qijun Xiao;Brian J. Jordan;Hao Xu;Palaniappan Arumugam;Rochelle Arvizo;Mark T. Tuominen
Advanced Materials 2008 Volume 20( Issue 13) pp:2561-2566
Publication Date(Web):
DOI:10.1002/adma.200703095
Co-reporter:Myoung-Hwan Park;Yuval Ofir;Bappaditya Samanta;Palaniappan Arumugam;Oscar R. Mira
Advanced Materials 2008 Volume 20( Issue 21) pp:4185-4188
Publication Date(Web):
DOI:10.1002/adma.200801155
Co-reporter:Bappaditya Samanta, Haoheng Yan, Nicholas O. Fischer, Jing Shi, D. Joseph Jerry and Vincent M. Rotello
Journal of Materials Chemistry A 2008 vol. 18(Issue 11) pp:1204-1208
Publication Date(Web):19 Feb 2008
DOI:10.1039/B718745A
Thermotherapy is a promising technique for the minimally invasive elimination of solid tumors. Here we report the fabrication of protein-coated iron oxide NPs (12 nm core) for use as thermal therapeutic agents. These albumin-passivated NPs are stable under physiological conditions, with rapid heating and cell killing capacity upon alternating magnetic field (AMF) exposure. The mode of action is specific: no measurable cytotoxicity was observed for the particle without AMF or for AMF exposure without the particle.
Co-reporter:Sarit S. Agasti, Chang-Cheng You, Palaniappan Arumugam and Vincent M. Rotello
Journal of Materials Chemistry A 2008 vol. 18(Issue 1) pp:70-73
Publication Date(Web):15 Oct 2007
DOI:10.1039/B711434F
The thermodynamic and kinetic stability of three structurally related monolayer-protected gold clusters have been systematically investigated, revealing that the nanoparticles display significantly different stability against thermo- and cyanide-induced decomposition and external thiol agents.
Co-reporter:Mrinmoy De and Vincent M. Rotello
Chemical Communications 2008 (Issue 30) pp:3504-3506
Publication Date(Web):23 May 2008
DOI:10.1039/B805242E
Thermally denatured chymotrypsin, lysozyme and papain are substantially refolded towards their native conformation by gold nanoparticle bearing dicarboxylate sidechains.
Co-reporter:Brian J. Jordan, Michael A. Pollier, Yuval Ofir, Steven Joubanian, Jonathan G. Mehtala, Carsten Sinkel, Stuart T. Caldwell, Andrew Kennedy, Gouher Rabani, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2008 (Issue 14) pp:1653-1655
Publication Date(Web):01 Feb 2008
DOI:10.1039/B718015B
We report the modulation of the absorbance of a flavin push–pull derivative through specific recognition by a complementary diamidopyridine (DAP), shifting the flavin intramolecular charge transfer band by ∼30 nm.
Co-reporter:Apiwat Chompoosor, Gang Han and Vincent M. Rotello
Bioconjugate Chemistry 2008 Volume 19(Issue 7) pp:1342
Publication Date(Web):June 14, 2008
DOI:10.1021/bc8000694
The effect of surface charge on the stability of gold nanoparticles (AuNPs) to the biogenic thiols glutathione (GSH), dihydrolipoic acid (DHLA), and cysteine was quantified. It was observed that the rate of release of fluorescein-tagged ligand was determined by the surface charge of the AuNPs, with cationic particles much more labile than anionic analogues. This ability to tune stability is significant for the design of both delivery vehicles and intracellular probes.
Co-reporter:Halil Bayraktar, Sudhanshu Srivastava, Chang-Cheng You, Vincent M. Rotello and Michael J. Knapp
Soft Matter 2008 vol. 4(Issue 4) pp:751-756
Publication Date(Web):24 Jan 2008
DOI:10.1039/B716386J
Selective surface recognition by proteins provides programmed bottom-up assembly of synthetic nanomaterials. We have investigated the controlled self-assembly of functionalized gold nanoparticles (Au-TAsp) with cytochrome c (Cyt c) and apoCyt c through complementary electrostatic interactions. Au-TAsp formed discrete, water-soluble adducts with native Cyt c, whereas unfolded apoCyt c induced nanocomposite formation at high Cyt c : Au-TAsp ratios. The binding of random-coil apoCyt c to Au-TAsp at low ratios induced α-helix formation in soluble nanocomposites, but at elevated ratios insoluble micron-scale aggregates were formed. The local structure of the assemblies was critically dependent on the Cyt c : Au-TAsp ratio. The dispersibility of apoCyt c–Au-TAsp was pH dependent, providing rapid and reversible control over nanocomposite assembly. The apoCyt c–Au-TAsp aggregates could likewise be disassembled through proteolytic cleavage of apoCyt c, demonstrating the ability to selectively remodel these hybrid materials.
Co-reporter:Vincent M. Rotello
Chemical Biology & Drug Design 2008 Volume 72( Issue 1) pp:1-2
Publication Date(Web):
DOI:10.1111/j.1747-0285.2008.00674.x
No abstract is available for this article.
Co-reporter:Vincent M. Rotello
ACS Nano 2008 Volume 2(Issue 1) pp:4
Publication Date(Web):January 8, 2008
DOI:10.1021/nn700434c
The exquisite structures produced by biological systems provide inspiration for the fabrication of nanomaterials. We sometimes forget, however, that Nature can provide muscle while serving as a Muse—a wide array of nanosystems are produced biologically that can be used for the design of functional materials. At the 2007 Materials Research Society Fall Meeting in Boston, Symposium MM (Biomolecular and Biologically Inspired Interfaces and Assemblies) highlighted the synergy between researchers using biomaterials and those using nature as a model for synthetic and quasi-synthetic systems. The symposium was organized by Vincent Rotello, Paula Hammond, Molly Stevens, Jeffrey Tok, and Darrin Pochan, with support provided by the U.S. Army Research Office and the RSC journal Soft Matter, and featured over 70 talks and 75 posters.
Co-reporter:Partha S. Ghosh, Chae-Kyu Kim, Gang Han, Neil S. Forbes and Vincent M. Rotello
ACS Nano 2008 Volume 2(Issue 11) pp:2213
Publication Date(Web):October 24, 2008
DOI:10.1021/nn800507t
Gold colloids functionalized with amino acids provide a scaffold for effective DNA binding with subsequent condensation. Particles with lysine and lysine dendron functionality formed particularly compact complexes and provided highly efficient gene delivery without any observed cytotoxicity. Nanoparticles functionalized with first generation lysine dendrons (NP−LysG1) were ∼28-fold superior to polylysine in reporter gene expression. These amino acid-based nanoparticles were responsive to intracellular glutathione levels, providing a tool for controlled release and concomitant expression of DNA.Keywords: delivery; DNA; glutathione; gold nanoparticles; transfection
Co-reporter:RonnieL. Phillips;OscarR. Mira;Chang-Cheng You Dr.;VincentM. Rotello Dr.;UweH.F. Bunz Dr.
Angewandte Chemie International Edition 2008 Volume 47( Issue 14) pp:2590-2594
Publication Date(Web):
DOI:10.1002/anie.200703369
Co-reporter:RonnieL. Phillips;OscarR. Mira;Chang-Cheng You Dr.;VincentM. Rotello Dr.;UweH.F. Bunz Dr.
Angewandte Chemie 2008 Volume 120( Issue 14) pp:2628-2632
Publication Date(Web):
DOI:10.1002/ange.200703369
Co-reporter:H. Xu;R. Hong;X. Wang;R. Arvizo;C. You;B. Samanta;D. Patra;M. T. Tuominen;V. M. Rotello
Advanced Materials 2007 Volume 19(Issue 10) pp:
Publication Date(Web):20 APR 2007
DOI:10.1002/adma.200700124
A positively charged polyvinyl N-methylpyridine (PVMP) polymer is patterned on a solid substrate via photochemical crosslinking, with the resultant cationic surface directing the adsorption of water-soluble Au nanoparticles, producing patterned nanostructured conductive films (see figure). These surfaces could be further modified with thiol ligands allowing fine-tuning of surface wettability and biocompatibility.
Co-reporter:Sudhanshu Srivastava, Bappaditya Samanta, Palaniappan Arumugam, Gang Han and Vincent M. Rotello
Journal of Materials Chemistry A 2007 vol. 17(Issue 1) pp:52-55
Publication Date(Web):30 Oct 2006
DOI:10.1039/B613887J
Nanocomposite materials consisting of FePt nanoparticles and DNA were constructed via DNA-mediated “bricks and mortar” self-assembly. Electrostatic interaction between the cationic nanoparticles and the DNA through surface recognition led to the formation of extended composite aggregates. These DNA-assembled aggregates feature increased interparticle spacing arising from the DNA “mortar”. The enhanced structure and increased spacing in the bio-nanocomposite assembly was found to alter the magnetic properties of the assemblies, as demonstrated by a 54 K change in blocking temperature (TB).
Co-reporter:Partha S. Ghosh, Ayush Verma and Vincent M. Rotello
Chemical Communications 2007 (Issue 27) pp:2796-2798
Publication Date(Web):07 Jun 2007
DOI:10.1039/B705554D
Nanoparticles featuring highly flexible sidechains template to peptides, demonstrating substantial pre-organization of the particle monolayer.
Co-reporter:Palaniappan Arumugam;Hao Xu;Sudhanshu Srivastava;Vincent M Rotello
Polymer International 2007 Volume 56(Issue 4) pp:
Publication Date(Web):6 FEB 2007
DOI:10.1002/pi.2210
Developments in self-assembly methods allow access to hierarchical materials featuring a wide range of functionality and applications. Polymer-based self-assembly of nanoparticles opens up new avenues for the fabrication of highly structured nanocomposites that can serve as bridges between ‘bottom-up’ and ‘top-down’ methods. Of various interactions leading to self-assembly of nanocomposites, hydrogen bonding and electrostatic interactions are commonly utilized. In this review, we illustrate the design and subsequent property tuning of various self-assembled nanocomposite materials that were developed based on these interactions. Copyright © 2007 Society of Chemical Industry
Co-reporter:Chang-Cheng You Dr.;SaritS. Agasti ;VincentM. Rotello Dr.
Chemistry - A European Journal 2007 Volume 14( Issue 1) pp:143-150
Publication Date(Web):
DOI:10.1002/chem.200701234
Abstract
Amino acid and dipeptide-functionalized gold nanoparticles (NPs) possessing L/D-leucine and/or L/D-phenylalanine residues have been constructed in order to target the surfaces of α-chymotrypsin (ChT) and cytochrome c (CytC). Isothermal titration calorimetry (ITC) was conducted to evaluate the binding thermodynamics and selectivity of these NP–protein interactions. The chirality of the NP end-groups substantially affects the resultant complex stability, with up to 20-fold differences seen between particles of identical hydrophobicity, demonstrating that structural information from the ligands can be used to control protein recognition.
Co-reporter:Chang-Cheng You, Apiwat Chompoosor, Vincent M. Rotello
Nano Today 2007 Volume 2(Issue 3) pp:34-43
Publication Date(Web):June 2007
DOI:10.1016/S1748-0132(07)70085-3
The wide variety of core materials, coupled with the ability to engineer their surface properties, make monolayer-protected nanoparticles (NPs) excellent scaffolds for targeting biomacromolecules. In this review, we focus on recent advances in NP-biomacromolecule interactions, highlighting the control of biomacromolecule structure and function through engineered interactions with NP surfaces.
Co-reporter:R. Hong;V. M. Rotello;R. J. Thibault;O. Uzun
Advanced Materials 2006 Volume 18(Issue 16) pp:2179-2183
Publication Date(Web):25 JUL 2006
DOI:10.1002/adma.200600357
Photocrosslinking of recognition-induced polymersomes provides robust hollow spheres with tunable sizes from 3 to 15 μm (see figure). These capsules selectively integrate complementary nanoparticles into their walls, providing direct access to assemblies.
Co-reporter:Chang-Cheng You, Rochelle R. Arvizo and Vincent M. Rotello
Chemical Communications 2006 (Issue 27) pp:2905-2907
Publication Date(Web):02 Jun 2006
DOI:10.1039/B605508G
A gold nanoparticle functionalized with substrates for α-chymotrypsin was fabricated to afford an enzyme modulator that exhibited enzyme-specific activation coupled with general inhibition of other proteases.
Co-reporter:Ali Bayir, Brian J. Jordan, Ayush Verma, Michael A. Pollier, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2006 (Issue 38) pp:4033-4035
Publication Date(Web):21 Aug 2006
DOI:10.1039/B608928C
We have used mixed monolayer protected gold clusters (MMPCs) to provide flavoenzyme model systems with a high affinity and ability to modulate cofactor reduction potential.
Co-reporter:Rui Hong, Joseph M. Fernández, Hiroshi Nakade, Rochelle Arvizo, Todd Emrick and Vincent M. Rotello
Chemical Communications 2006 (Issue 22) pp:2347-2349
Publication Date(Web):12 May 2006
DOI:10.1039/B603988J
Place exchange reactions were studied using dye displacement: subtle changes in ligand structure greatly affected both the rate of displacement and the stability of the monolayer.
Co-reporter:Halil Bayraktar, Partha S. Ghosh, Vincent M. Rotello and Michael J. Knapp
Chemical Communications 2006 (Issue 13) pp:1390-1392
Publication Date(Web):21 Feb 2006
DOI:10.1039/B516096K
Functionalized gold nanoparticles bind selectively to cytochrome c or cytochrome c peroxidase and inhibit enzyme turnover.
Co-reporter:Chang-Cheng You, Ayush Verma and Vincent M. Rotello
Soft Matter 2006 vol. 2(Issue 3) pp:190-204
Publication Date(Web):24 Jan 2006
DOI:10.1039/B517354J
Monolayer-protected nanoparticles feature tunable size, surface functionality and core material, providing scaffolds for targeting biomacromolecules. This review highlights recent advances in nanoparticle-biomacromolecule interactions, focusing on two key areas: (1) The modulation of structure and function of biomacromolecules through engineered interactions with nanoparticle surfaces; (2) The use of biomacromolecules as building blocks for nanostructured materials.
Co-reporter:Brian J. Jordan, Rui Hong, Basar Gider, Jason Hill, Todd Emrick and Vincent M. Rotello
Soft Matter 2006 vol. 2(Issue 7) pp:558-560
Publication Date(Web):18 May 2006
DOI:10.1039/B603980D
Gold nanoparticles stabilize chymotrypsin (ChT) against denaturation at the air–water interface through catenation and preferential localization of the nanoparticles at the air–water interface with concomitant decrease in interfacial energy.
Co-reporter:Catherine M. Goodman;Nini S. Chari;Gang Han;Rui Hong;Partha Ghosh
Chemical Biology & Drug Design 2006 Volume 67(Issue 4) pp:
Publication Date(Web):18 APR 2006
DOI:10.1111/j.1747-0285.2006.00372.x
A family of nanoparticles featuring surfaces of varying hydrophobicity was synthesized. The efficiency of DNA-binding was determined, demonstrating in a fivefold modulation in binding a 37-mer DNA strand. Nanoparticle-binding causes a reversible conformational change in the DNA structure, as demonstrated by circular dichroism and fluorescence experiments. Furthermore, the affinity of the nanoparticle for the DNA can be regulated by external agents, though stability of the complex is observed at relatively high ionic strengths.
Co-reporter:Gang Han;Craig T. Martin
Chemical Biology & Drug Design 2006 Volume 67(Issue 1) pp:
Publication Date(Web):21 DEC 2005
DOI:10.1111/j.1747-0285.2005.00324.x
Positively charged trimethylammonium-modified mixed monolayer protected clusters (MMPCs) interact with DNA by complementary electrostatic binding, serving as efficient DNA delivery systems. The stability of gold nanoparticle-bound DNA toward biological, physical, and chemical agents is investigated. The MMPC-bound DNA is efficiently protected from DNAse I digestion and experiences nicking/cleavage-induced morphology changes with higher concentrations of DNAse I. Significant protection of MMPC-bound DNA was also observed in a physical sonication assay. However, the MMPC-bound DNA was found to show enhanced cleavage upon exposure to chemically induced radicals. The latter may indicate that bound DNA is bent and wrapped on the surface of the cationic MMPC.
Co-reporter:Gang Han;Chang-Cheng You Dr.;Byoung-jin Kim;Rosemary S. Turingan;Neil S. Forbes Dr.;Craig T. Martin Dr. Dr.
Angewandte Chemie 2006 Volume 118(Issue 19) pp:
Publication Date(Web):30 MAR 2006
DOI:10.1002/ange.200600214
Licht und Leben: Ein photolabiles Goldnanopartikel, das als DNA-Transporter dient, wurde konstruiert. UV-Bestrahlung bewirkt die Umkehrung der Nanopartikel-Oberflächenladung, was in vitro zu einer effektiven Freisetzung von DNA und einer Reaktivierung unterdrückter DNA-Transkription führt. Dieser Effekt wurde auch in lebenden Zellen beobachtet, in denen die DNA zudem effizient vom Zellkern aufgenommen wird.
Co-reporter:Gang Han, Chang-Cheng You, Byoung-jin Kim, Rosemary S. Turingan, Neil S. Forbes, Craig T. Martin,Vincent M. Rotello
Angewandte Chemie International Edition 2006 45(19) pp:3165-3169
Publication Date(Web):
DOI:10.1002/anie.200600214
Co-reporter:S. Srivastava;A. Verma;B. L. Frankamp;V. M. Rotello
Advanced Materials 2005 Volume 17(Issue 5) pp:
Publication Date(Web):3 MAR 2005
DOI:10.1002/adma.200400776
Controlled assembly of protein–nanoparticle composites through complementary protein surface recognition is demonstrated. Interaction of an unstable protein (chymotrypsin) with a gold nanoparticle results in close interparticle spacing, while a stable protein (cytochrome C) that retains its structure upon binding produces a hybrid material with a larger interparticle distance (see Figure).
Co-reporter:R. Shenhar;E. Jeoung;S. Srivastava;T. B. Norsten;V. M. Rotello
Advanced Materials 2005 Volume 17(Issue 18) pp:
Publication Date(Web):6 SEP 2005
DOI:10.1002/adma.200590094
The construction and fixation of ordered nanoparticle arrays allow not only the exploitation of the array's collective physical properties but also the possibility of manipulating discrete aggregates within a larger-scale assembly scheme. A simple approach utilizing block copolymer thin films as templates and coordination chemistry as a mild crosslinking mechanism is reported by Shenhar, Rotello, and co-workers on p. 2206. The cover image (by Nicholas Fischer) shows terpyridine-functionalized gold nanoparticles organized in stripes on top of a microphase-separated thin film of polystyrene-block-poly(methyl methacrylate) and crosslinked thorough the formation of iron–bisterpyridine complexes.
Co-reporter:R. Shenhar;E. Jeoung;S. Srivastava;T. B. Norsten;V. M. Rotello
Advanced Materials 2005 Volume 17(Issue 18) pp:
Publication Date(Web):29 JUL 2005
DOI:10.1002/adma.200500624
Robust arrays of ordered nanoparticles (see Figure and cover) have been created by combining two self-assembly strategies: microphase separation of block copolymers and coordination chemistry. Thin films of a microphase-separated block copolymer serve as templates for patterning of terpyridine-functionalized gold nanoparticles. Subsequent treatment with iron salts crosslinks the patterned nanoparticles via the formation of iron–terpyridine complexes.
Co-reporter:R. Shenhar;T. B. Norsten;V. M. Rotello
Advanced Materials 2005 Volume 17(Issue 6) pp:
Publication Date(Web):11 MAR 2005
DOI:10.1002/adma.200401291
Nanoparticle–polymer composites are diverse and versatile functional materials, with applications ranging from electronic device fabrication to catalysis. This review focuses on the use of chemical design to control the structural attributes of polymer-mediated assembly of nanoparticles. We will illustrate the use of designed particles and polymers to create nanocomposites featuring interesting and pragmatic structures and properties. We will also describe applications of these engineered materials.
Co-reporter:Ayush Verma and Vincent M. Rotello
Chemical Communications 2005 (Issue 3) pp:303-312
Publication Date(Web):08 Dec 2004
DOI:10.1039/B410889B
Nanoparticles present a versatile scaffold to target biomacromolecule surfaces via complementary interactions. This review highlights some unique features of nanoparticles that make them particularly attractive resources for biomacromolecular recognition, and displays their use in modulation of structure and function of biomacromolecules.
Co-reporter:Hao Xu, Tyler B. Norsten, Oktay Uzun, Eunhee Jeoung and Vincent M. Rotello
Chemical Communications 2005 (Issue 41) pp:5157-5159
Publication Date(Web):20 Sep 2005
DOI:10.1039/B509572G
Specific three-point hydrogen bonding between diamidopyridine (DAP) and thymine (Thy) was employed to reversibly anchor “brush-like” Tri-DAP end-functionalized polystyrene onto Thy-modified silica surfaces.
Co-reporter:Catherine McCusker, Joseph B. Carroll and Vincent M. Rotello
Chemical Communications 2005 (Issue 8) pp:996-998
Publication Date(Web):10 Jan 2005
DOI:10.1039/B416266H
Quaternary ammonium functionalized polyhedral oligomeric silsesquioxane (OctaAmmonium–POSS®) units, widely employed as additives in ceramic and polymeric systems, possess many attributes which make them attractive as biocompatible drug carriers: nanoscale size, three-dimensional functionality, efficient cellular uptake, low toxicity, and high solubility.
Co-reporter:Oktay Uzun;Hao Xu;Eunhee Jeoung Dr.;Raymond J. Thibault
Chemistry - A European Journal 2005 Volume 11(Issue 23) pp:
Publication Date(Web):27 SEP 2005
DOI:10.1002/chem.200500809
Random polystyrene copolymers grafted with complementary recognition elements were combined in chloroform producing vesicular aggregates, that is, recognition-induced polymersomes (RIPs). Reflection interference contrast microscopy (RICM) in solution, coupled with optical microscopy (OM) and atomic force microscopy (AFM) on solid substrates, were used to determine the wall thickness of the RIPs. Rather than a conventional mono- or bilayer structure (∼10 or ∼20 nm, respectively) the RIP membrane was 43±7 nm thick. Structural arrangement of the polymer chains on the RIP wall were characterized by using angle-resolved X-ray photoelectron spectroscopy (AR-XPS). The interior portion of the vesicle membrane was found to be more polar, containing more recognition units, than the exterior part. This gradient suggests that a rapid self-sorting of polymers takes place during the formation of RIPs, providing the likely mechanism for vesicle self-assembly.
Co-reporter:U. Drechsler;N. O. Fischer;B. L. Frankamp;V. M. Rotello
Advanced Materials 2004 Volume 16(Issue 3) pp:
Publication Date(Web):11 FEB 2004
DOI:10.1002/adma.200306022
Co-reporter:Joseph B. Carroll, Benjamin L. Frankamp, Sudhanshu Srivastava and Vincent M. Rotello
Journal of Materials Chemistry A 2004 vol. 14(Issue 4) pp:690-694
Publication Date(Web):05 Jan 2004
DOI:10.1039/B311423F
Hybrid inorganic/organic composite materials composed of gold nanoparticles of varying size (1.5 and 6.8 nm) and polyhedral oligomeric silsesquioxane (POSS) units were created using electrostatic self-assembly. Carboxylic acid-functionalized mixed monolayer protected gold clusters (MMPCs) were mixed with trimethyl quaternary ammonium-functionalized POSS units, providing well-ordered aggregates. The aggregates were characterized with transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS), revealing an increase in average interparticle spacing upon assembly with POSS. This increase in spacing was shown to influence the surface plasmon resonance band of the larger 6.8 nm Au nanoparticles as characterized by UV/Vis spectroscopy.
Co-reporter:Nicholas O. Fischer, Ralph Paulini, Ulf Drechsler and Vincent M. Rotello
Chemical Communications 2004 (Issue 24) pp:2866-2867
Publication Date(Web):25 Oct 2004
DOI:10.1039/B408972C
Positively charged gold nanoparticles featuring photocleavable units within their surrounding monolayer are switched from non-interacting species to inhibitors of chymotrypsin through UV irradiation.
Co-reporter:Joseph B. Carroll, Mark Gray, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2004 (Issue 4) pp:442-443
Publication Date(Web):23 Jan 2004
DOI:10.1039/B312349A
Phenanthrenequinone undergoes highly efficient proton transfer processes in the presence of a thiourea-funtionalised polystyrene copolymer whereas interactions with a similar benzyl-thiourea monomer show strong redox modulation of the quinone without proton transfer.
Co-reporter:Ulf Drechsler Dr.;Belma Erdogan Dr.
Chemistry - A European Journal 2004 Volume 10(Issue 22) pp:
Publication Date(Web):2 SEP 2004
DOI:10.1002/chem.200306076
Monolayer and mixed-monolayer protected clusters (MPCs and MMPCs) have great potential to combine molecular functionality with the intrinsic properties of nanometer-sized scaffolds. This synergy can be used to create complex functional devices, including redox-active, electronic, or magnetic storage devices, solution-based sensors, and highly efficient catalysts. This review outlines some of the recent developments in nanoscale receptors based on synthetic and nonbiological recognition elements. In these nanoparticle systems, molecular recognition is achieved by covalent attachment of receptors on the nanoparticles coupled with noncovalent interactions to target substrates. Synthetic host–guest systems, hydrogen bonding, change in redox states, π–π stacking, rotaxane formation, and ion recognition are the main topics covered in this review.
Co-reporter:Cheryl Briggs, Tyler B. Norsten and Vincent M. Rotello
Chemical Communications 2002 (Issue 17) pp:1890-1891
Publication Date(Web):24 Jul 2002
DOI:10.1039/B203878A
Hydrogen/deuterium exchange rates in amide-functionalized monolayer protected gold clusters (MPCs) are controlled by the radial nature of the surface, with inhibition and catalysis observed at different chain lengths.
Co-reporter:Trent H. Galow, Ulf Drechsler, Jarrod A. Hanson and Vincent M. Rotello
Chemical Communications 2002 (Issue 10) pp:1076-1077
Publication Date(Web):16 Apr 2002
DOI:10.1039/B200334A
Polymer-mediated self-assembly of functionalized Pd and SiO2 nanoparticles provides highly active hydrogenation and Heck coupling catalysts.
Co-reporter:Eunhee Jeoung, Joseph B. Carroll and Vincent M. Rotello
Chemical Communications 2002 (Issue 14) pp:1510-1511
Publication Date(Web):19 Jun 2002
DOI:10.1039/B201995G
Diaminopyridine (DAP) functionalized POSS derivatives self-assemble on thymine functionalized monolayers on gold surfaces affording hybrid inorganic/organic surfaces.
Co-reporter:Eunhee Jeoung, Vincent M. Rotello
Journal of Supramolecular Chemistry 2002 Volume 2(1–3) pp:53-55
Publication Date(Web):January–June 2002
DOI:10.1016/S1472-7862(02)00078-3
The photochemical control of interfacial recognition process between diaminopyridine (DAP)-functionalized colloids and naphthalimide has been explored through the incorporation of azobenzene moieties into nanoparticle monolayers.Interfacial control of host–guest interactions at nanoparticle-solution interfaces has been photochemically controlled using azobenzene sidechains
Co-reporter:Catherine M. McIntosh;Nicholas O. Fischer;Joseph M. Simard
PNAS 2002 Volume 99 (Issue 8 ) pp:5018-5023
Publication Date(Web):2002-04-16
DOI:10.1073/pnas.082644099
Efficient binding of biomacromolecular surfaces by synthetic systems requires the effective presentation of complementary
elements over large surface areas. We demonstrate here the use of mixed monolayer protected gold clusters (MMPCs) as scaffolds
for the binding and inhibition of chymotrypsin. In these studies anionically functionalized amphiphilic MMPCs were shown to
inhibit chymotrypsin through a two-stage mechanism featuring fast reversible inhibition followed by a slower irreversible
process. This interaction is very efficient, with a K = 10.4 ± 1.3 nM. The MMPC–protein complex was characterized by CD, demonstrating an almost complete denaturation of the enzyme
over time. Dynamic light scattering studies confirm that inhibition proceeds without substantial MMPC aggregation. The electrostatic
nature of the engineered interactions provides a level of selectivity: little or no inhibition of function was observed with
elastase, β-galactosidase, or cellular retinoic acid binding protein.
Co-reporter:A. K. Boal;T. H. Galow;F. Ilhan;V. M. Rotello
Advanced Functional Materials 2001 Volume 11(Issue 6) pp:
Publication Date(Web):6 DEC 2001
DOI:10.1002/1616-3028(200112)11:6<461::AID-ADFM461>3.0.CO;2-0
An amine-functionalized polymer has been used to simultaneously assemble carboxylic acid functionalized gold and silica nanoparticles into extended aggregates. This three component assembly process is highly versatile, with aggregate morphology controlled through stoichiometry, and nanoparticle segregation within the aggregate regulated through order of component addition.
Co-reporter:Hugues Augier de Cremiers, Gilles Clavier, Faysal Ilhan, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2001 (Issue 21) pp:2232-2233
Publication Date(Web):15 Oct 2001
DOI:10.1039/B106588M
Polymer 4 and its monomeric counterpart 3 exhibit electrochemically tuneable interactions with anthracene polymer 2 and a structurally similar monomer 1 as seen by the variation of the oxidation waves of TTF groups and the fluorescence of the anthracene.
Co-reporter:Faysal Ilhan, Laura Diamondis, Leigh Gautreau and Vincent M. Rotello
Chemical Communications 2000 (Issue 6) pp:447-448
Publication Date(Web):29 Feb 2000
DOI:10.1039/A909454G
Diaminotriazine–flavin host–guest complexes are
kinetically trapped in spin-cast polystyrene films.
Co-reporter:Joseph Simard, Cheryl Briggs, Andrew K. Boal and Vincent M. Rotello
Chemical Communications 2000 (Issue 19) pp:1943-1944
Publication Date(Web):20 Sep 2000
DOI:10.1039/B004162I
Alkanethiolate-protected gold nanoclusters are solublized
through place exchange reaction with ω-thiocarboxylic acids.
Co-reporter:Andrew K. Boal;Faysal Ilhan;Jason E. DeRouchey;Thomas Thurn-Albrecht;Thomas P. Russell
Nature 2000 404(6779) pp:746-748
Publication Date(Web):2000-04-13
DOI:10.1038/35008037
Multi-scale ordering of materials is central for the application of molecular
systems1, 2, 3 in macroscopic devices4, 5. Self-assembly
based on selective control of non-covalent interactions6, 7, 8
provides a powerful tool for the creation of structured systems at a molecular
level, and application of this methodology to macromolecular systems provides
a means for extending such structures to macroscopic length scale9, 10, 11.
Monolayer-functionalized nanoparticles can be made with a wide variety of
metallic and non-metallic cores, providing a versatile building block for
such approaches. Here we present a polymer-mediated ‘bricks and mortar’
strategy for the ordering of nanoparticles into structured assemblies. This
methodology allows monolayer-protected gold particles to self-assemble into
structured aggregates while thermally controlling their size and morphology.
Using 2-nm gold particles as building blocks, we show that spherical aggregates
of size 97 ± 17 nm can be produced at 23 °C, and
that 0.5–1 µm spherical assemblies with (5–40) ×
105 individual subunits form at -20 °C. Intriguingly,
extended networks of ~50-nm subunits are formed at 10 °C, illustrating
the potential of our approach for the formation of diverse structural motifs
such as wires and rods. These findings demonstrate that the assembly process
provides control over the resulting aggregates, while the modularity of the
‘bricks and mortar’ approach allows combinatorial control over
the constituents, providing a versatile route to new materials systems.
Co-reporter:Tatsuyuki Yoshii, Yingying Geng, Shelly Peyton, Arthur M. Mercurio, Vincent M. Rotello
Drug Discovery Today (September 2016) Volume 21(Issue 9) pp:1489-1494
Publication Date(Web):1 September 2016
DOI:10.1016/j.drudis.2016.05.011
•Biomolecules including integrins are key factors in cancer progression.•Nanomaterials provide tools for regulating the chemical environment of cells.•Mechanobiology is an emerging determinant in designing cancer therapies.Metastasis, drug resistance and recurrence in cancer are regulated by the tumor microenvironment. This review describes recent advances in understanding how cancer cells respond to extracellular environmental cues via integrins, how to build engineered microenvironments to study these interactions in vitro and how nanomaterials can be used to detect and target tumor microenvironments.
Co-reporter:Hedi Mattoussi, Vincent M. Rotello
Advanced Drug Delivery Reviews (May 2013) Volume 65(Issue 5) pp:605-606
Publication Date(Web):1 May 2013
DOI:10.1016/j.addr.2013.04.012
Co-reporter:Ya Ding, Ziwen Jiang, Krishnendu Saha, Chang Soo Kim, ... Vincent M Rotello
Molecular Therapy (June 2014) Volume 22(Issue 6) pp:1075-1083
Publication Date(Web):1 June 2014
DOI:10.1038/mt.2014.30
Gold nanoparticles provide an attractive and applicable scaffold for delivery of nucleic acids. In this review, we focus on the use of covalent and noncovalent gold nanoparticle conjugates for applications in gene delivery and RNA-interference technologies. We also discuss challenges in nucleic acid delivery, including endosomal entrapment/escape and active delivery/presentation of nucleic acids in the cell.
Co-reporter:Chang Soo Kim, Gülen Yesilbag Tonga, David Solfiell, Vincent M. Rotello
Advanced Drug Delivery Reviews (January 2013) Volume 65(Issue 1) pp:93-99
Publication Date(Web):1 January 2013
DOI:10.1016/j.addr.2012.08.011
Inorganic nanomaterials have an array of structural and physical properties that can be used in therapeutic delivery systems. The sizes, shapes, and surfaces of inorganic nanomaterials can be tailored to produce distinct interactions with biological systems both in vitro and in vivo. Nanoparticle cores can likewise be engineered to possess unique opticophysical properties, including upconversion, size-dependent absorbance/emission as well as magnetic properties such as superparamagnetism. These properties make inorganic nanomaterials as useful imaging agents for noninvasive diagnostics and remotely activated theragnostics. Taken together, these unique properties of inorganic nanomaterials make them promising delivery systems.Download high-res image (238KB)Download full-size image
Co-reporter:Subinoy Rana, Avinash Bajaj, Rubul Mout, Vincent M. Rotello
Advanced Drug Delivery Reviews (February 2012) Volume 64(Issue 2) pp:200-216
Publication Date(Web):1 February 2012
DOI:10.1016/j.addr.2011.08.006
Gold nanoparticles (AuNPs) provide attractive vehicles for delivery of drugs, genetic materials, proteins, and small molecules. AuNPs feature low core toxicity coupled with the ability to parametrically control particle size and surface properties. In this review, we focus on engineering of the AuNP surface monolayer, highlighting recent advances in tuning monolayer structures for efficient delivery of drugs and biomolecules. This review covers two broad categories of particle functionalization, organic monolayers and biomolecule coatings, and discusses their applications in drug, DNA/RNA, protein and small molecule delivery.Download high-res image (195KB)Download full-size image
Co-reporter:Sarit S. Agasti, Subinoy Rana, Myoung-Hwan Park, Chae Kyu Kim, ... Vincent M. Rotello
Advanced Drug Delivery Reviews (8 March 2010) Volume 62(Issue 3) pp:316-328
Publication Date(Web):8 March 2010
DOI:10.1016/j.addr.2009.11.004
Nanoparticle based platforms for identification of chemical and biological agents offer substantial benefits to biomedical and environmental science. These platforms benefit from the availability of a wide variety of core materials as well as the unique physical and chemical properties of these nanoscale materials. This review surveys some of the emerging approaches in the field of nanoparticle based detection systems, highlighting the nanoparticle based screening methods for metal ions, proteins, nucleic acids, and biologically relevant small molecules.
Co-reporter:Chang Soo Kim, Xiaoning Li, Ying Jiang, Bo Yan, Gulen Y. Tonga, Moumita Ray, David J. Solfiell, Vincent M. Rotello
MethodsX (2015) Volume 2() pp:306-315
Publication Date(Web):1 January 2015
DOI:10.1016/j.mex.2015.06.001
Small gold nanoparticles (sAuNPs, <10 nm in a core diameter) have been used for drug delivery and cancer therapy due to their high payload to carrier ratio. Information about the amount and location of sAuNPs in cells and tissues is critical to many applications. However, the current detection method (i.e., transmission electron microscopy) for such sAuNPs is limited due to the extensive sample preparation and the limited field of view. Here we use confocal laser scanning microscopy to provide endosome-entrapped sAuNP distributions and to quantify particle uptake into cells. The quantitative capabilities of the system were confirmed by inductively coupled plasma-mass spectrometry, with an observed linear relation between scattering intensity and the initial cellular uptake of sAuNPs using 4 nm and 6 nm core particles.The summary of the method is:•This non-invasive imaging strategy provides a tool for label-free real-time tracking and quantification of sAuNPs using a commercially available confocal laser scanning microscope.•Scattering intensity depends on particle size.•The linear relation established between scattering intensity and uptaken gold amount enables simultaneous quantitative assessment through simple image analysis.Download full-size image
Co-reporter:Federica Scaletti, Chang Soo Kim, Luigi Messori, Vincent M. Rotello
MethodsX (2014) Volume 1() pp:118-123
Publication Date(Web):1 January 2014
DOI:10.1016/j.mex.2014.07.007
Small gold nanorods (GNRs) with longitudinal plasmon absorption in the near-infrared window (700–900 nm) are of great interest for in vivo optical applications (e.g., photothermal therapy) and for their high-payload-to-carrier ratio for drug delivery. Common synthetic strategies for GNR production afford spherical and cubical nanoparticles in addition to the desired GNRs. Thus, several methods have been proposed for the selective separation of GNRs from the reaction by-products. For example, centrifugation has been used to separate the high aspect ratio (AR) GNRs (AR > 4). However, it is difficult to separate small sized GNRs with low AR (AR ≤ 4) that are particularly promising for biomedical applications. Here, we describe a simple and fast procedure for the separation of small GNRs with AR of 4, and length of 28 nm from reaction by-products.The shape separation is achieved through centrifugation according to the following steps:•Isolation of all gold products of the reaction from the excess of cetyltrimethylammonium bromide through a first cycle of centrifugation.•Optimization of the speed and the time of centrifugation for the separation of GNRs from the reaction by-products.•Shape separation of GNRs through a second cycle of centrifugation.The effectiveness of this procedure is documented.Download full-size image
Co-reporter:V.M. Rotello
Advanced Drug Delivery Reviews (17 August 2008) Volume 60(Issue 11) pp:1225
Publication Date(Web):17 August 2008
DOI:10.1016/j.addr.2008.04.003
Co-reporter:Partha Ghosh, Gang Han, Mrinmoy De, Chae Kyu Kim, Vincent M. Rotello
Advanced Drug Delivery Reviews (17 August 2008) Volume 60(Issue 11) pp:1307-1315
Publication Date(Web):17 August 2008
DOI:10.1016/j.addr.2008.03.016
Gold nanoparticles (AuNPs) provide non-toxic carriers for drug and gene delivery applications. With these systems, the gold core imparts stability to the assembly, while the monolayer allows tuning of surface properties such as charge and hydrophobicity. An additional attractive feature of AuNPs is their interaction with thiols, providing an effective and selective means of controlled intracellular release.
Co-reporter:Qian Liu, Yi-Cheun Yeh, Subinoy Rana, Ying Jiang, Lin Guo, Vincent M. Rotello
Cancer Letters (1 July 2013) Volume 334(Issue 2) pp:196-201
Publication Date(Web):1 July 2013
DOI:10.1016/j.canlet.2012.09.013
We demonstrate rapid and efficient sensing of mammalian cell types and states using nanoparticle-based sensor arrays. These arrays are comprised of cationic quantum dots (QDs) and gold nanoparticles (AuNPs) that interact with cell surfaces to generate distinguishable fluorescence responses based on cell surface signatures. The use of QDs as the recognition elements as well as the signal transducers presents the potential for direct visualization of selective cell surface interactions. Notably, this sensor is unbiased, precluding the requirement of pre-knowledge of cell state biomarkers and thus providing a general approach for phenotypic profiling of cell states, with additional potential for imaging applications.Highlights► A rapid and efficient sensor for mammalian cell types and states using nanoparticle-based sensor arrays is presented. ► The sensing approach relies on selective interactions between nanoparticles and cell surfaces. ► This unbiased array-based sensor possesses the potential of cancer detectionanddiagnostic imaging.
Co-reporter:Oscar R. Miranda ; Xiaoning Li ; Limary Garcia-Gonzalez ; Zheng-Jiang Zhu ; Bo Yan ; Uwe H. F. Bunz
Journal of the American Chemical Society () pp:
Publication Date(Web):May 31, 2011
DOI:10.1021/ja2021729
Rapid and sensitive detection of pathogens is a key requirement for both environmental and clinical settings. We report here a colorimetric enzyme–nanoparticle conjugate system for detection of microbial contamination. In this approach, cationic gold nanoparticles (NPs) featuring quaternary amine headgroups are electrostatically bound to an enzyme [β-galactosidase (β-Gal)], inhibiting enzyme activity. Analyte bacteria bind to the NP, which releases the β-Gal and restores its activity, providing an enzyme-amplified colorimetric readout of the binding event. Using this strategy, we have been able to quantify bacteria at concentrations of 1 × 102 bacteria/mL in solution and 1 × 104 bacteria/mL in a field-friendly test strip format.
Co-reporter:Chaekyu Kim, Gulen Yesilbag Tonga, Bo Yan, Chang Soo Kim, Sung Tae Kim, Myoung-Hwan Park, Zhengjiang Zhu, Bradley Duncan, Brian Creran and Vincent M. Rotello
Organic & Biomolecular Chemistry 2015 - vol. 13(Issue 8) pp:NaN2479-2479
Publication Date(Web):2014/12/23
DOI:10.1039/C4OB02433H
Prolonged retention of internalized nanoparticulate systems inside cells improves their efficacy in imaging, drug delivery, and theranostic applications. Especially, regulating exocytosis of the nanoparticles is a key factor in the fabrication of effective nanocarriers for chemotherapeutic treatments but orthogonal control of exocytosis in the cellular environment is a major challenge. Herein, we present the first example of regulating exocytosis of gold nanoparticles (AuNPs), a model drug carrier, by using a simple host–guest supramolecular system. AuNPs featuring quaternary amine head groups were internalized into the cells through endocytosis. Subsequent in situ treatment of a complementary cucurbit[7]uril (CB[7]) to the amine head groups resulted in the AuNP-CB[7] complexation inside cells, rendering particle assembly. This complexation induced larger particle assemblies that remained sequestered in the endosomes, inhibiting exocytosis of the particles without any observed cytotoxicity.
Co-reporter:Ryan F. Landis, Mahdieh Yazdani, Brian Creran, Xi Yu, Vikas Nandwana, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2014 - vol. 50(Issue 35) pp:NaN4581-4581
Publication Date(Web):2014/03/17
DOI:10.1039/C4CC00805G
Hydrogen bonding heavily influences conformations, rate of reactions, and chemical equilibria. The development of a method to monitor hydrogen bonding interactions independent of polarity is challenging as both are linked. We have developed two solvatochromic dyes that detect hydrogen-bond-donating solvents. The unique solvatochromism of the triazine architecture has allowed the development of probes that monitor hydrogen-bond-donating species including water.
Co-reporter:Mrinmoy De, Oscar R. Miranda, Subinoy Rana and Vincent M. Rotello
Chemical Communications 2009(Issue 16) pp:NaN2159-2159
Publication Date(Web):2009/03/18
DOI:10.1039/B900552H
Fundamentally different assembly motifs are observed when proteins of different sizes are complexed with monolayer-protected nanoparticles.
Co-reporter:Partha S. Ghosh, Ayush Verma and Vincent M. Rotello
Chemical Communications 2007(Issue 27) pp:NaN2798-2798
Publication Date(Web):2007/06/07
DOI:10.1039/B705554D
Nanoparticles featuring highly flexible sidechains template to peptides, demonstrating substantial pre-organization of the particle monolayer.
Co-reporter:Ziwen Jiang, Ngoc D. B. Le, Akash Gupta and Vincent M. Rotello
Chemical Society Reviews 2015 - vol. 44(Issue 13) pp:NaN4274-4274
Publication Date(Web):2015/04/08
DOI:10.1039/C4CS00387J
Metallic nanoparticles provide versatile scaffolds for biosensing applications. In this review, we focus on the use of metallic nanoparticles for cell surface sensings. Examples of the use of both specific recognition and array-based “chemical nose” approaches to cell surface sensing will be discussed.
Co-reporter:Yuval Ofir, Bappaditya Samanta and Vincent M. Rotello
Chemical Society Reviews 2008 - vol. 37(Issue 9) pp:NaN1825-1825
Publication Date(Web):2008/07/23
DOI:10.1039/B712689C
Gold nanoparticle–polymer composites are versatile and diverse functional materials, with applications in optical, electronic and sensing devices. This tutorial review focuses on the use of polymers to control the assembly of gold nanoparticles. Examples of synthetic polymers and biopolymers are provided, as well as applications of the composite materials in sensing and memory devices.
Co-reporter:Yi-Cheun Yeh, Sung Tae Kim, Rui Tang, Bo Yan and Vincent M. Rotello
Journal of Materials Chemistry A 2014 - vol. 2(Issue 29) pp:NaN4614-4614
Publication Date(Web):2014/05/21
DOI:10.1039/C4TB00608A
Effective regulation of nanoparticle (NP) uptake facilitates the NP-based therapeutics and diagnostics. Here, we report the use of insulin and 2-deoxyglucose (2-DG) to modulate the cellular uptake of glucose-functionalized quantum dots (Glc-QDs) in C2C12 muscle cells. The cellular uptake of Glc-QDs can be modulated up to almost two-fold under insulin stimulation while be down-regulated in the presence of 2-DG. These results demonstrate the use of secondary regulators to control the cellular uptake of NPs through membrane protein recognition in a specific and fine-tunable fashion.
Co-reporter:Dawn Ernenwein, Partha Ghosh, Vincent Rotello and Jean Chmielewski
Journal of Materials Chemistry A 2010 - vol. 20(Issue 27) pp:NaN5611-5611
Publication Date(Web):2010/06/08
DOI:10.1039/C0JM01108H
Non-covalent interactions between cationic gold nanoparticles and an anionic coiled-coil peptide were harnessed for coiled-coil mediated self-assembly of gold nanoparticles (GNPs).
Co-reporter:Juhong Chen, Stephanie M. Andler, Julie M. Goddard, Sam R. Nugen and Vincent M. Rotello
Chemical Society Reviews 2017 - vol. 46(Issue 5) pp:NaN1283-1283
Publication Date(Web):2016/12/12
DOI:10.1039/C6CS00313C
Pathogenic bacterial contamination is a major threat to human health and safety. In this review, we summarize recent strategies for the integration of recognition elements with nanomaterials for the detection and sensing of pathogenic bacteria. Nanoprobes can provide sensitive and specific detection of bacterial cells, which can be applied across multiple applications and industries.
Co-reporter:Ngoc D. B. Le, Xian Wang, Yingying Geng, Rui Tang, Gulen Yesilbag Tonga, Ziwen Jiang and Vincent M. Rotello
Chemical Communications 2017 - vol. 53(Issue 62) pp:NaN8797-8797
Publication Date(Web):2017/07/13
DOI:10.1039/C7CC04561A
Endocrine disrupting chemicals (EDCs) interact with estrogen receptors (ERs), causing a broad range of adverse health effects. Current assays for EDC activity are slow and often lack sensitivity. We report here an ultra-sensitive nanosensor that can detect estrogenic cellular changes in ER(+) MCF-7 cells rapidly (minutes) at several orders of magnitude lower than the generally used assays. Notably, the sensor responses at these ultra-low EDC levels correlated with an increased synthesis phase (S-phase) cell population of EDC-treated cells. The nanosensor was also able to detect binary EDC mixture effects, with synergism observed for bisphenol A (BPA) – 17β-estradiol (E2), and antagonism for dicyclohexylphthalate (DCHP) – E2 and benzo(a)pyrene (BaP) – E2.
Co-reporter:Avinash Bajaj, Bappaditya Samanta, Haoheng Yan, D. Joseph Jerry and Vincent M. Rotello
Journal of Materials Chemistry A 2009 - vol. 19(Issue 35) pp:NaN6331-6331
Publication Date(Web):2009/04/08
DOI:10.1039/B901616C
We have explored the mechanism and differential uptake of BSA coated Fe3O4nanoparticles (NPs) by different cancerous and isogenic cell types.
Co-reporter:Hung-Ting Chen, Todd A. Crosby, Myoung-Hwan Park, Sivakumar Nagarajan, Vincent M. Rotello and James J. Watkins
Journal of Materials Chemistry A 2009 - vol. 19(Issue 1) pp:NaN74-74
Publication Date(Web):2008/11/12
DOI:10.1039/B815055A
Mesoporous silica films with well ordered nanochannels (approximately 7 nm in diameter) oriented parallel to the substrate were synthesized using supercritical carbon dioxide mediated silica deposition within templates comprised of triblock copolymers blended with strongly associating homopolymers. The films were patterned at the device level by conventional lithography and etched to yield periodic circular features approximately 20 µm in diameter. The nanoscale channels remained accessible to penetrant diffusion as shown by dye uptake experiments. The nanochannel arrays were used as miniature size exclusion columns to mediate nanoparticle diffusion.
Co-reporter:Bappaditya Samanta, Haoheng Yan, Nicholas O. Fischer, Jing Shi, D. Joseph Jerry and Vincent M. Rotello
Journal of Materials Chemistry A 2008 - vol. 18(Issue 11) pp:NaN1208-1208
Publication Date(Web):2008/02/19
DOI:10.1039/B718745A
Thermotherapy is a promising technique for the minimally invasive elimination of solid tumors. Here we report the fabrication of protein-coated iron oxide NPs (12 nm core) for use as thermal therapeutic agents. These albumin-passivated NPs are stable under physiological conditions, with rapid heating and cell killing capacity upon alternating magnetic field (AMF) exposure. The mode of action is specific: no measurable cytotoxicity was observed for the particle without AMF or for AMF exposure without the particle.
Co-reporter:Sarit S. Agasti, Chang-Cheng You, Palaniappan Arumugam and Vincent M. Rotello
Journal of Materials Chemistry A 2008 - vol. 18(Issue 1) pp:NaN73-73
Publication Date(Web):2007/10/15
DOI:10.1039/B711434F
The thermodynamic and kinetic stability of three structurally related monolayer-protected gold clusters have been systematically investigated, revealing that the nanoparticles display significantly different stability against thermo- and cyanide-induced decomposition and external thiol agents.
Co-reporter:Chandramouleeswaran Subramani, Xi Yu, Sarit. S. Agasti, Bradley Duncan, Serkan Eymur, Murat Tonga and Vincent M. Rotello
Journal of Materials Chemistry A 2011 - vol. 21(Issue 37) pp:NaN14158-14158
Publication Date(Web):2011/05/18
DOI:10.1039/C1JM11035G
Photoactivatable gold NPs were patterned viaphotolithography. In this approach, charge reversal of the ligands on NPs upon UV irradiation induces crosslinking to generate stable NP patterns.
Co-reporter:Vikas Nandwana, Chandramouleeswaran Subramani, Yi-Cheun Yeh, Boqian Yang, Stefan Dickert, Michael D. Barnes, Mark T. Tuominen and Vincent M. Rotello
Journal of Materials Chemistry A 2011 - vol. 21(Issue 42) pp:NaN16862-16862
Publication Date(Web):2011/07/25
DOI:10.1039/C1JM11782C
Patterned quantum dot (QD) nanostructures were prepared by direct electron beam lithography on QD films. Time resolved photoluminescence measurements show that the optical properties of these QDs were retained after cross-linking.
Co-reporter:Yisheng Xu, Yoni Engel, Yunfeng Yan, Kaimin Chen, Daniel F. Moyano, Paul L. Dubin and Vincent M. Rotello
Journal of Materials Chemistry A 2013 - vol. 1(Issue 39) pp:NaN5234-5234
Publication Date(Web):2013/04/30
DOI:10.1039/C3TB20377H
Two β-lactoglobulin (BLG) isoforms, BLGA and BLGB, were used as a test bed for the differentiation of proteins using electrostatics. In these studies, the BLGA and BLGB binding to a highly charged, cationic gold nanoparticle (GNP) modified surface was investigated by atomic force microscopy (AFM) and surface plasmon resonance (SPR) spectroscopy. The binding affinity, and more importantly, the selectivity of this surface towards these two almost identical protein isoforms were both significantly increased on the cationic GNP surface array relative to the values measured with the same free cationic GNP in solution. While protein recognition is traditionally achieved almost exclusively via orientation dependent short-range interactions such as hydrogen bonds and hydrophobic interactions, our results show the potential of protein recognition platforms based on enhanced electrostatic interactions.
Co-reporter:Avinash Bajaj, Subinoy Rana, Oscar R. Miranda, Joseph C. Yawe, D. Joseph Jerry, Uwe H. F. Bunz and Vincent M. Rotello
Chemical Science (2010-Present) 2010 - vol. 1(Issue 1) pp:NaN138-138
Publication Date(Web):2010/05/24
DOI:10.1039/C0SC00165A
Gold nanoparticle-green fluorescent protein (NP-GFP) based arrays have been created for rapid identification of mammalian cells on the basis of cell surface properties. Highly reproducible characteristic patterns were obtained from different cell types enabling the identification of cell types and cancer states. Using these arrays we could differentiate between isogenic normal, cancer and metastatic cell types using only ∼5000 cells.
Co-reporter:S. Gokhan Elci, Daniel F. Moyano, Subinoy Rana, Gulen Yesilbag Tonga, Ronnie L. Phillips, Uwe H. F. Bunz and Vincent M. Rotello
Chemical Science (2010-Present) 2013 - vol. 4(Issue 5) pp:NaN2080-2080
Publication Date(Web):2013/03/01
DOI:10.1039/C3SC22279A
A sensor array composed of eight functionalized gold nanoparticles and a fluorescent polymer was utilized to identify 11 glycosaminoglycans (GAGs) by their chemical signatures. Particle ligand structure was key in differentiating analytes, with aromatic and specific sugar functionalities recognizing GAG structural parameters including sulfonation, acetylation, epimeric structure, size, and charge.
Co-reporter:Mrinmoy De and Vincent M. Rotello
Chemical Communications 2008(Issue 30) pp:
Publication Date(Web):
DOI:10.1039/B805242E
Co-reporter:Debabrata Patra, Chiara Pagliuca, Chandramouleeswaran Subramani, Bappaditya Samanta, Sarit S. Agasti, Nada Zainalabdeen, Stuart T. Caldwell, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2009(Issue 28) pp:NaN4250-4250
Publication Date(Web):2009/06/09
DOI:10.1039/B906458C
Dithiocarbamate chemistry is used as a crosslinking tool to fabricate FePt colloidal microcapsules which provide a versatile scaffold for “host–guest” recognition at the liquid–liquid interface.
Co-reporter:Youngdo Jeong, Bradley Duncan, Myoung-Hwan Park, Chaekyu Kim and Vincent M. Rotello
Chemical Communications 2011 - vol. 47(Issue 44) pp:NaN12079-12079
Publication Date(Web):2011/10/14
DOI:10.1039/C1CC14448K
Emulsions stabilized by enzyme-nanoparticle (NP) complexes were used to fabricate robust biocatalytic scaffolds after core solidification via crosslinking. These biocatalysts feature ease of formation, high retention of enzymatic activity and reusability.
Co-reporter:Brian J. Jordan, Michael A. Pollier, Yuval Ofir, Steven Joubanian, Jonathan G. Mehtala, Carsten Sinkel, Stuart T. Caldwell, Andrew Kennedy, Gouher Rabani, Graeme Cooke and Vincent M. Rotello
Chemical Communications 2008(Issue 14) pp:NaN1655-1655
Publication Date(Web):2008/02/01
DOI:10.1039/B718015B
We report the modulation of the absorbance of a flavin push–pull derivative through specific recognition by a complementary diamidopyridine (DAP), shifting the flavin intramolecular charge transfer band by ∼30 nm.
Co-reporter:Yi-Cheun Yeh, Debabrata Patra, Bo Yan, Krishnendu Saha, Oscar R. Miranda, Chae Kyu Kim and Vincent M. Rotello
Chemical Communications 2011 - vol. 47(Issue 11) pp:NaN3071-3071
Publication Date(Web):2011/02/08
DOI:10.1039/C0CC04975A
A new class of quaternary ammonium derivatives has been used to synthesize cationic CdSe/ZnS quantum dots with exceptional stability in water as well as in biological media.
Co-reporter:Brian Creran, Bo Yan, Daniel F. Moyano, Michael M. Gilbert, Richard W. Vachet and Vincent M. Rotello
Chemical Communications 2012 - vol. 48(Issue 38) pp:NaN4545-4545
Publication Date(Web):2012/03/01
DOI:10.1039/C2CC30499F
Patterns created by the inkjet printing of functionalized gold nanoparticles (NPs) can be selectively detected by laser desorption/ionization imaging mass spectrometry (LDI-IMS). These patterns can only be visualized by mass, providing a robust yet tunable system for potential anti-counterfeiting applications.
Co-reporter:Chandramouleeswaran Subramani, Gulen Yesilbag, Brian J. Jordan, Xiaoning Li, Abraham Khorasani, Graeme Cooke, Amitav Sanyal and Vincent M. Rotello
Chemical Communications 2010 - vol. 46(Issue 12) pp:NaN2069-2069
Publication Date(Web):2010/02/17
DOI:10.1039/B926746H
Diaminopyridine dendritic scaffolds encapsulate polymeric flavin via non-covalent interactions and demonstrate isolation of the redox moiety.
Co-reporter:Yi-Cheun Yeh, Subinoy Rana, Rubul Mout, Bo Yan, Felix S. Alfonso and Vincent M. Rotello
Chemical Communications 2014 - vol. 50(Issue 42) pp:NaN5568-5568
Publication Date(Web):2014/04/14
DOI:10.1039/C4CC01257G
Supramolecular modification of nanoparticle surfaces through threading of cucurbit[7]uril (CB[7]) onto surface ligands is used to regulate protein–nanoparticle interactions.
Co-reporter:Xiaoning Li, Yi-Cheun Yeh, Karuna Giri, Rubul Mout, Ryan F. Landis, Y. S. Prakash and Vincent M. Rotello
Chemical Communications 2015 - vol. 51(Issue 2) pp:NaN285-285
Publication Date(Web):2014/11/10
DOI:10.1039/C4CC07737G
Quantum dots were used as fluorescent probes to investigate nanoparticle penetration into biofilms. The particle penetration behavior was found to be controlled by surface chemical properties.
Co-reporter:Xi Yu, Serkan Eymur, Vijay Singh, Boqian Yang, Murat Tonga, Amarnath Bheemaraju, Graeme Cooke, Chandramouleeswaran Subramani, Dhandapani Venkataraman, Robert J. Stanley and Vincent M. Rotello
Physical Chemistry Chemical Physics 2012 - vol. 14(Issue 19) pp:NaN6754-6754
Publication Date(Web):2012/03/20
DOI:10.1039/C2CP40073A
A donor–acceptor dyad model system using a flavin moiety as a photo-active acceptor has been synthesized for an energy and photo-induced electron transfer study. The photophysical investigations of the dyad revealed a multi-path energy and electron transfer process with a very high transfer efficiency. The photo-activity of flavin was believed to play an important role in the process, implying the potential application of flavin as a novel acceptor molecule for photovoltaics.
Co-reporter:Sudhanshu Srivastava, Bappaditya Samanta, Palaniappan Arumugam, Gang Han and Vincent M. Rotello
Journal of Materials Chemistry A 2007 - vol. 17(Issue 1) pp:NaN55-55
Publication Date(Web):2006/10/30
DOI:10.1039/B613887J
Nanocomposite materials consisting of FePt nanoparticles and DNA were constructed via DNA-mediated “bricks and mortar” self-assembly. Electrostatic interaction between the cationic nanoparticles and the DNA through surface recognition led to the formation of extended composite aggregates. These DNA-assembled aggregates feature increased interparticle spacing arising from the DNA “mortar”. The enhanced structure and increased spacing in the bio-nanocomposite assembly was found to alter the magnetic properties of the assemblies, as demonstrated by a 54 K change in blocking temperature (TB).
Co-reporter:Rubul Mout, Daniel F. Moyano, Subinoy Rana and Vincent M. Rotello
Chemical Society Reviews 2012 - vol. 41(Issue 7) pp:NaN2544-2544
Publication Date(Web):2012/02/06
DOI:10.1039/C2CS15294K
Control of interactions between nanoparticles and biosystems is essential for the effective utilization of these materials in biomedicine. A wide variety of nanoparticle surface structures have been developed for imaging, sensing, and delivery applications. In this research Highlight, we will emphasize advances in tailoring nanoparticle interfaces for implementation in nanomedicine.