Nathaniel L. Rosi

Systematic Adjustment of Pitch and Particle Dimensions within a Family of Chiral Plasmonic Gold Nanoparticle Single Helices

Co-reporter:Soumitra Mokashi-Punekar, Andrea D. Merg, and Nathaniel L. Rosi

Journal of the American Chemical Society October 25, 2017 Volume 139(Issue 42) pp:15043-15043

Publication Date(Web):September 6, 2017

DOI:10.1021/jacs.7b07143

Systematically controlling the assembly architecture within a class of chiral nanoparticle superstructures is important for fine-tuning their chiroptical properties. Here, we report a family of chiral gold nanoparticle single helices, varying in helical pitch and nanoparticle dimensions, that is assembled using a series of peptide conjugate molecules Cx-(PEPAuM-ox)2 (PEPAuM-ox = AYSSGAPPMoxPPF; x = 16–22). We demonstrate that the aliphatic tail length (i) can be used as a handle to systematically tune the helical pitch from 80 to 130 nm; and (ii) influences the size, shape, and aspect ratio of the component nanoparticles. Certain members of this family of materials exhibit intense plasmonic chiroptical activity. These studies highlight the multiple levels of structural control that can be achieved within a class of chiral nanoparticle superstructures via careful design and selection of peptide conjugate precursor.

Triblock peptide–oligonucleotide chimeras (POCs): programmable biomolecules for the assembly of morphologically tunable and responsive hybrid materials

Co-reporter:Andrea D. Merg;Ryan V. Thaner;Soumitra Mokashi-Punekar;SonBinh T. Nguyen

Chemical Communications 2017 vol. 53(Issue 90) pp:12221-12224

Publication Date(Web):2017/11/09

DOI:10.1039/C7CC07708D

Triblock peptide–oligonucleotide chimeras (POCs) consisting of peptides and oligonucleotides interlinked by an organic core are presented and their assembly behaviour is investigated. Several factors influence POC assembly, resulting in the formation of either vesicles or fibres. Design rules are introduced and used to predict and alter POC assembly morphology.

Effect of countercation on the water stability of an anionic metal–organic framework

Co-reporter:A. B. Spore;N. L. Rosi

CrystEngComm (1999-Present) 2017 vol. 19(Issue 36) pp:5417-5421

Publication Date(Web):2017/09/18

DOI:10.1039/C7CE01228D

Methods for adjusting and potentially improving the water stability of metal–organic frameworks (MOFs) are important for many potential applications. Herein, we investigate how the identity of uncoordinated countercations housed within the channels of an anionic MOF affect its structure and porosity after exposure to liquid water and water vapour. bMOF-1, Zn8(ad)4(BPDC)6O·2 cations (ad = adeninate; BPDC = biphenyldicarboxylate), was used for this study and different alkylammonium countercations were incorporated into the framework via cation exchange. In general, it was determined that cations having larger alkyl chains resulted in a more water stable bMOF-1 material; conversely, more hydrophilic cations detrimentally affected bMOF-1 stability to water. Finally, bMOF-1 was loaded with mixtures of both hydrophilic and hydrophobic cations. It was found that these bMOF-1 samples, despite the presence of the hydrophilic cations, still maintained their structure and porosity after exposure to water vapour.

Ternary gradient metal–organic frameworks

Co-reporter:Chong Liu

Faraday Discussions 2017 (Volume 201) pp:163-174

Publication Date(Web):2017/09/06

DOI:10.1039/C7FD00045F

Gradient MOFs contain directional gradients of either structure or functionality. We have successfully prepared two ternary gradient MOFs based on bMOF-100 analogues, namely bMOF-100/102/106 and bMOF-110/100/102, via cascade ligand exchange reactions. The cubic unit cell parameter discrepancy within an individual ternary gradient MOF crystal is as large as ∼1 nm, demonstrating the impressive compatibility and flexibility of the component MOF materials. Because of the presence of a continuum of unit cells, the pore diameters within individual crystals also change in a gradient fashion from ∼2.5 nm to ∼3.0 nm for bMOF-100/102/106, and from ∼2.2 nm to ∼2.7 nm for bMOF-110/100/102, indicating significant porosity gradients. Like previously reported binary gradient MOFs, the composition of the ternary gradient MOFs can be easily controlled by adjusting the reaction conditions. Finally, X-ray diffraction and microspectrophotometry were used to analyse fractured gradient MOF crystals by comparing unit cell parameters and absorbance spectra at different locations, thus revealing the profile of heterogeneity (i.e. gradient distribution of properties) and further confirming the formation of ternary gradient MOFs.

Peptide-Directed Assembly of Single-Helical Gold Nanoparticle Superstructures Exhibiting Intense Chiroptical Activity

Co-reporter:Andrea D. Merg, Jennifer C. Boatz, Abhishek Mandal, Gongpu Zhao, Soumitra Mokashi-Punekar, Chong Liu, Xianting Wang, Peijun Zhang, Patrick C. A. van der Wel, and Nathaniel L. Rosi

Journal of the American Chemical Society 2016 Volume 138(Issue 41) pp:13655-13663

Publication Date(Web):September 26, 2016

DOI:10.1021/jacs.6b07322

Chiral nanoparticle assemblies are an interesting class of materials whose chiroptical properties make them attractive for a variety of applications. Here, C18-(PEPAuM-ox)2 (PEPAuM-ox = AYSSGAPPMoxPPF) is shown to direct the assembly of single-helical gold nanoparticle superstructures that exhibit exceptionally strong chiroptical activity at the plasmon frequency with absolute g-factor values up to 0.04. Transmission electron microscopy (TEM) and cryogenic electron tomography (cryo-ET) results indicate that the single helices have a periodic pitch of approximately 100 nm and consist of oblong gold nanoparticles. The morphology and assembled structure of C18-(PEPAuM-ox)2 are studied using TEM, atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, circular dichroism (CD) spectroscopy, X-ray diffraction (XRD), and solid-state nuclear magnetic resonance (ssNMR) spectroscopy. TEM and AFM reveal that C18-(PEPAuM-ox)2 assembles into linear amyloid-like 1D helical ribbons having structural parameters that correlate to those of the single-helical gold nanoparticle superstructures. FTIR, CD, XRD, and ssNMR indicate the presence of cross-β and polyproline II secondary structures. A molecular assembly model is presented that takes into account all experimental observations and that supports the single-helical nanoparticle assembly architecture. This model provides the basis for the design of future nanoparticle assemblies having programmable structures and properties.

Establishing Porosity Gradients within Metal–Organic Frameworks Using Partial Postsynthetic Ligand Exchange

Co-reporter:Chong Liu, Chenjie Zeng, Tian-Yi Luo, Andrea D. Merg, Rongchao Jin, and Nathaniel L. Rosi

Journal of the American Chemical Society 2016 Volume 138(Issue 37) pp:12045-12048

Publication Date(Web):September 3, 2016

DOI:10.1021/jacs.6b07445

Crystalline 3-D materials bearing interlinked domains of differential porosity and functionality offer the potential for organizing and shuttling molecular and nanoscale matter to specific locations within 3-D space. Here, we present methods for creating prototype MOF materials that have such structural features. Specifically, the process of pore expansion via ligand exchange was studied for an isoreticular series of mesoporous MOFs based on bMOF-100. It was found that pore expansion occurs incrementally in small steps and that it proceeds gradually in an “outside→in” fashion within individual crystals. The ligand exchange reaction can be terminated prior to complete crystal conversion to yield intermediate product MOFs, denoted bMOF-100/102 and bMOF-102/106, which bear descending porosity gradients from the crystal periphery to the crystal core. As a proof of concept, size-sensitive incorporation of a gold–thiolate nanocluster, Au133(SR)52, selectively in the bMOF-102/106 crystal periphery region was accomplished via cation exchange. These new methods open up the possibility of controlling molecular organization and transport within porous MOF materials.

Fabrication of MMMs with improved gas separation properties using externally-functionalized MOF particles

Co-reporter:Surendar R. Venna, Michael Lartey, Tao Li, Alex Spore, Santosh Kumar, Hunaid B. Nulwala, David R. Luebke, Nathaniel L. Rosi and Erik Albenze

Journal of Materials Chemistry A 2015 vol. 3(Issue 9) pp:5014-5022

Publication Date(Web):27 Jan 2015

DOI:10.1039/C4TA05225K

Mixed matrix membranes (MMM) have the potential to overcome the limitations of traditional polymeric membranes for gas separation by improving both the permeability and selectivity. The most difficult challenge is accessing defect free and optimized MMM membranes. Defects are generally due to incompatible interfaces between the polymer and the filler particle. Herein, we present a new approach to modify and optimize the surface of UiO-66-NH2 based MOF particles to improve its interaction with Matrimid® polymer. A series of surface modified UiO-66-NH2 particles were synthesized and characterized using 1H NMR spectroscopy, mass spectrometry, XPS, and powder X-ray diffraction. MMMs containing surface optimized MOF particles exhibit improved thermal and mechanical properties. Most importantly, the MMMs show significantly enhanced gas separation properties; CO2 permeability was increased by ∼200% and CO2/N2 ideal selectivity was increased by ∼25%. These results confirm the success of the proposed technique to mitigate defective MOF/Matrimid® interfaces.

Loading and triggered release of cargo from hollow spherical gold nanoparticle superstructures

Co-reporter:Chen Zhang, Thomas Brinzer, Chong Liu, Sean Garrett-Roe and Nathaniel L. Rosi

RSC Advances 2015 vol. 5(Issue 93) pp:76291-76295

Publication Date(Web):01 Sep 2015

DOI:10.1039/C5RA15492H

Hollow spherical gold nanoparticle superstructures having different average diameters (∼75 nm and ∼150 nm) and near-infrared (NIR) extinction were prepared and loaded with an anti-cancer drug, doxorubicin (DOX). The stability of these structures and drug release was monitored in the presence of proteinase and upon irradiation with NIR light. Proteinase K promotes DOX release from the ∼150 nm superstructures and NIR light promotes DOX release from both the ∼75 nm and ∼150 nm superstructures.

Adjusting the Metrics of 1-D Helical Gold Nanoparticle Superstructures Using Multivalent Peptide Conjugates

Co-reporter:Andrea D. Merg, Joseph Slocik, Martin G. Blaber, George C. Schatz, Rajesh Naik, and Nathaniel L. Rosi

Langmuir 2015 Volume 31(Issue 34) pp:9492-9501

Publication Date(Web):August 11, 2015

DOI:10.1021/acs.langmuir.5b02208

The properties of nanoparticle superstructures depend on many factors, including the structural metrics of the nanoparticle superstructure (particle diameter, interparticle distances, etc.). Here, we introduce a family of gold-binding peptide conjugate molecules that can direct nanoparticle assembly, and we describe how these molecules can be systematically modified to adjust the structural metrics of linear double-helical nanoparticle superstructures. Twelve new peptide conjugates are prepared via linking a gold-binding peptide, AYSSGAPPMPPF (PEPAu), to a hydrophobic aliphatic tail. The peptide conjugates have 1, 2, or 3 PEPAu headgroups and a C12, C14, C16, or C18 aliphatic tail. The soft assembly of these peptide conjugates was studied using transmission electron microscopy (TEM), atomic force microscopy (AFM), and infrared (IR) spectroscopy. Several peptide conjugates assemble into 1-D twisted fibers having measurable structural parameters such as fiber width, thickness, and pitch that can be systematically varied by adjusting the aliphatic tail length and number of peptide headgroups. The linear soft assemblies serve as structural scaffolds for arranging gold nanoparticles into double-helical superstructures, which are examined via TEM. The pitch and interparticle distances of the gold nanoparticle double helices correspond to the underlying metrics of the peptide conjugate soft assemblies, illustrating that designed peptide conjugate molecules can be used to not only direct the assembly of gold nanoparticles but also control the metrics of the assembled structure.

Hollow spherical gold nanoparticle superstructures with tunable diameters and visible to near-infrared extinction

Co-reporter:Chen Zhang, Yong Zhou, Andrea Merg, Chengyi Song, George C. Schatz and Nathaniel L. Rosi

Nanoscale 2014 vol. 6(Issue 21) pp:12328-12332

Publication Date(Web):22 Aug 2014

DOI:10.1039/C4NR04289A

Hollow spherical gold nanoparticle superstructures with tunable diameters (∼40 nm, ∼70 nm and ∼150 nm) and visible to near-infrared surface plasmon resonances (545 nm, 670 nm, and 740 nm) are prepared using a single peptide conjugate, C6-AA-PEPAu, as the structure-directing agent. Computational models are developed to understand their optical properties.

Alumina-supported cobalt–adeninate MOF membranes for CO2/CH4 separation

Co-reporter:Zhenzhen Xie, Tao Li, Nathaniel L. Rosi and Moises A. Carreon

Journal of Materials Chemistry A 2014 vol. 2(Issue 5) pp:1239-1241

Publication Date(Web):25 Nov 2013

DOI:10.1039/C3TA14058J

The synthesis of continuous cobalt–adeninate MOF (bio-MOF-13 (I) and bio-MOF-14 (II)) membranes supported on porous alumina tubes is demonstrated. The membranes showed high CO2 permeabilities and low to moderate CO2 separation selectivities for CO2/CH4 gas mixtures. The observed CO2/CH4 selectivities are attributed to preferential CO2 adsorption within the framework.

Peptide Conjugates for Directing the Morphology and Assembly of 1D Nanoparticle Superstructures

Co-reporter:Chen Zhang;Dr. Chengyi Song;Dr. H. Christopher Fry; Nathaniel L. Rosi

Chemistry - A European Journal 2014 Volume 20( Issue 4) pp:941-945

Publication Date(Web):

DOI:10.1002/chem.201304074

Abstract

Designed peptide conjugates molecules are used to direct the synthesis and assembly of gold nanoparticles into complex 1D nanoparticle superstructures with various morphologies. Four peptide conjugates, each based on the gold-binding peptide (AYSSGAPPMPPF; PEP_Au), are prepared: C₁₂H₂₃O-AYSSGAPPMPP (1), C₁₂H₂₃O-AYSSGAPPMPPF (2), C₁₂H₂₃O-AYSSGAPPMPPFF (3), and C₁₂H₂₃O-AYSSGAPPMPPFFF (4). The affect that C-terminal hydrophobic F residues have on both the soft-assembly of the peptide conjugates and the resulting assembly of gold nanoparticle superstructures is examined. It is shown that the addition of two C-terminal F residues (3) leads to thick, branched 1D gold nanoparticle superstructures, whereas the addition of three C-terminal F residues (4) leads to bundling of thin 1D nanoparticle superstructures.

Tailorable Plasmonic Circular Dichroism Properties of Helical Nanoparticle Superstructures

Co-reporter:Chengyi Song, Martin G. Blaber, Gongpu Zhao, Peijun Zhang, H. Christopher Fry, George C. Schatz, and Nathaniel L. Rosi

Nano Letters 2013 Volume 13(Issue 7) pp:3256-3261

Publication Date(Web):June 18, 2013

DOI:10.1021/nl4013776

We utilize a peptide-based methodology to prepare a diverse collection of double-helical gold nanoparticle superstructures having controllable handedness and structural metrics. These materials exhibit well-defined circular dichroism signatures at visible wavelengths owing to the collective dipole–dipole interactions between the nanoparticles. We couple theory and experiment to show how tuning the metrics and structure of the helices results in predictable and tailorable chirooptical properties. Finally, we experimentally and theoretically demonstrate that the intensity, position, and nature of the chirooptical activity can be carefully adjusted via silver overgrowth. These studies illustrate the utility of peptide-based nanoparticle assembly platforms for designing and preparing complex plasmonic materials with tailorable optical properties.

Design and Preparation of a Core–Shell Metal–Organic Framework for Selective CO2 Capture

Co-reporter:Tao Li ; Jeanne E. Sullivan

Journal of the American Chemical Society 2013 Volume 135(Issue 27) pp:9984-9987

Publication Date(Web):June 24, 2013

DOI:10.1021/ja403008j

The design of a core–shell metal–organic framework comprising a porous bio-MOF-11/14 mixed core and a less porous bio-MOF-14 shell is reported. The growth of the MOF shell was directly observed and supported by SEM and PXRD. The resulting core–shell material exhibits 30% higher CO2 uptake than bio-MOF-14 and low N2 uptake in comparison to the core. When the core–shell architecture is destroyed by fracturing the crystallites via grinding, the amount of N2 adsorbed doubles but the CO2 adsorption capacity remains the same. Finally, the more water stable bio-MOF-14 shell serves to prevent degradation of the water-sensitive core in aqueous environments, as evidenced by SEM and PXRD.

Stepwise Ligand Exchange for the Preparation of a Family of Mesoporous MOFs

Co-reporter:Tao Li ; Mark T. Kozlowski ; Evan A. Doud ; Maike N. Blakely

Journal of the American Chemical Society 2013 Volume 135(Issue 32) pp:11688-11691

Publication Date(Web):May 20, 2013

DOI:10.1021/ja403810k

A stepwise ligand exchange strategy is utilized to prepare a series of isoreticular bio-MOF-100 analogues. Specifically, in situ ligand exchange with progressively longer dicarboxylate linkers is performed on single crystalline starting materials to synthesize products with progressively larger mesoporous cavities. The new members of this series of materials, bio-MOFs 101–103, each exhibit permanent mesoporosity and pore sizes ranging from ∼2.1–2.9 nm and surface areas ranging from 2704 to 4410 m2/g. The pore volume for bio-MOF 101 is 2.83 cc/g. Bio-MOF-102 and 103 have pore volumes of 4.36 and 4.13 cc/g, respectively. Collectively, these data establish this unique family of MOFs as one of the most porous reported to date.

Systematic modulation and enhancement of CO2:N2 selectivity and water stability in an isoreticular series of bio-MOF-11 analogues

Co-reporter:Tao Li, De-Li Chen, Jeanne E. Sullivan, Mark T. Kozlowski, J. Karl Johnson and Nathaniel L. Rosi

Chemical Science 2013 vol. 4(Issue 4) pp:1746-1755

Publication Date(Web):01 Feb 2013

DOI:10.1039/C3SC22207A

An isoreticular series of cobalt-adeninate bio-MOFs (bio-MOFs-11–14) is reported. The pores of bio-MOFs-11–14 are decorated with acetate, propionate, butyrate, and valerate, respectively. The nitrogen (N2) and carbon dioxide (CO2) adsorption properties of these materials are studied and compared. The isosteric heats of adsorption for CO2 are calculated, and the CO2:N2 selectivities for each material are determined. As the lengths of the aliphatic chains decorating the pores in bio-MOFs-11–14 increase, the BET surface areas decrease from 1148 m2 g−1 to 17 m2 g−1 while the CO2:N2 selectivities predicted from ideal adsorbed solution theory at 1 bar and 273 K for a 10:90 CO2:N2 mixture range from 73:1 for bio-MOF-11 to 123:1 for bio-MOF-12 and finally to 107:1 for bio-MOF-13. At 298 K, the selectivities are 43:1 for bio-MOF-11, 52:1 for bio-MOF-12, and 40:1 for bio-MOF-13. Additionally, it is shown that bio-MOF-14 exhibits a unique molecular sieving property that allows it to adsorb CO2 but not N2 at 273 and 298 K. Finally, the water stability of bio-MOFs-11–14 increases with increasing aliphatic chain length. Bio-MOF-14 exhibits no loss of crystallinity or porosity after soaking in water for one month.

Screening and evaluating aminated cationic functional moieties for potential CO2 capture applications using an anionic MOF scaffold

Co-reporter:Tao Li and Nathaniel L. Rosi

Chemical Communications 2013 vol. 49(Issue 97) pp:11385-11387

Publication Date(Web):28 Oct 2013

DOI:10.1039/C3CC47031H

Three cations with different amine density, guanidinium, aminoguanidinium, and diaminoguanidinium, were loaded into anionic bio-MOF-1via cation-exchange. The structures and compositions of the cation-exchange products were characterized, and their N2 and CO2 adsorption properties were studied and compared.

Lanthanide near infrared imaging in living cells with Yb3+ nano metal organic frameworks

Co-reporter:Kristy A. Gogick;Alexandra Foucault-Collet;Sandrine Villette;Kiley A. White;Agnès Pallier;Steven J. Geib;Claudine Kieda;Guillaume Collet;Tao Li;Stéphane Petoud

PNAS 2013 Volume 110 (Issue 43 ) pp:17199-17204

Publication Date(Web):2013-10-22

DOI:10.1073/pnas.1305910110

We have created unique near-infrared (NIR)–emitting nanoscale metal-organic frameworks (nano-MOFs) incorporating a high density of Yb3+ lanthanide cations and sensitizers derived from phenylene. We establish here that these nano-MOFs can be incorporated into living cells for NIR imaging. Specifically, we introduce bulk and nano-Yb-phenylenevinylenedicarboxylate-3 (nano-Yb-PVDC-3), a unique MOF based on a PVDC sensitizer-ligand and Yb3+ NIR-emitting lanthanide cations. This material has been structurally characterized, its stability in various media has been assessed, and its luminescent properties have been studied. We demonstrate that it is stable in certain specific biological media, does not photobleach, and has an IC50 of 100 μg/mL, which is sufficient to allow live cell imaging. Confocal microscopy and inductively coupled plasma measurements reveal that nano-Yb-PVDC-3 can be internalized by cells with a cytoplasmic localization. Despite its relatively low quantum yield, nano-Yb-PVDC-3 emits a sufficient number of photons per unit volume to serve as a NIR-emitting reporter for imaging living HeLa and NIH 3T3 cells. NIR microscopy allows for highly efficient discrimination between the nano-MOF emission signal and the cellular autofluorescence arising from biological material. This work represents a demonstration of the possibility of using NIR lanthanide emission for biological imaging applications in living cells with single-photon excitation.

Peptide-Directed Synthesis and Assembly of Hollow Spherical CoPt Nanoparticle Superstructures

Co-reporter:Chengyi Song;Yang Wang ; Nathaniel L. Rosi

Angewandte Chemie International Edition 2013 Volume 52( Issue 14) pp:3993-3995

Publication Date(Web):

DOI:10.1002/anie.201209910

Peptide-Directed Synthesis and Assembly of Hollow Spherical CoPt Nanoparticle Superstructures

Co-reporter:Chengyi Song;Yang Wang ; Nathaniel L. Rosi

Angewandte Chemie 2013 Volume 125( Issue 14) pp:4085-4087

Publication Date(Web):

DOI:10.1002/ange.201209910

Strain-Promoted “Click” Modification of a Mesoporous Metal–Organic Framework

Co-reporter:Chong Liu ; Tao Li

Journal of the American Chemical Society 2012 Volume 134(Issue 46) pp:18886-18888

Publication Date(Web):October 31, 2012

DOI:10.1021/ja307713q

Strain-promoted “click” chemistry is used to post-synthetically modify the pore walls of azide-functionalized mesoporous bio-MOF-100 (N3-bio-MOF-100). The reactions proceed in high yield and produce no byproduct. This new method was used to introduce various functional groups into the MOF mesopores, including succinimidyl ester bioconjugation moieties that allow for straightforward coupling of biomolecules to the pore walls.

Zinc-Adeninate Metal−Organic Framework for Aqueous Encapsulation and Sensitization of Near-infrared and Visible Emitting Lanthanide Cations

Co-reporter:Jihyun An ; Chad M. Shade ; Demetra A. Chengelis-Czegan ; Stéphane Petoud

Journal of the American Chemical Society 2011 Volume 133(Issue 5) pp:1220-1223

Publication Date(Web):January 4, 2011

DOI:10.1021/ja109103t

Luminescent metal−organic frameworks (MOFs), Ln3+@bio-MOF-1, were synthesized via postsynthetic cation exchange of bio-MOF-1 with Tb3+, Sm3+, Eu3+, or Yb3+, and their photophysical properties were studied. We demonstrate that bio-MOF-1 encapsulates and sensitizes visible and near-infrared emitting lanthanide cations in aqueous solution.

Metal–biomolecule frameworks (MBioFs)

Co-reporter:Inhar Imaz, Marta Rubio-Martínez, Jihyun An, Isabel Solé-Font, Nathaniel L. Rosi and Daniel Maspoch

Chemical Communications 2011 vol. 47(Issue 26) pp:7287-7302

Publication Date(Web):18 Apr 2011

DOI:10.1039/C1CC11202C

Biomolecules are the building blocks of life. Nature has evolved countless biomolecules that show promise for bridging metal ions. These molecules have emerged as an excellent source of biocompatible building blocks that can be used to design Metal–Biomolecule Frameworks (MBioFs). This feature article highlights the advances in the synthesis of this class of MOFs. Special emphasis is provided on the crystal structures of these materials, their miniaturization to the submicron length scale, and their new potential storage, catalytic, and biomedical applications.

Preparation of 1-D nanoparticle superstructures with tailorable thicknesses using gold-binding peptide conjugates

Co-reporter:Leekyoung Hwang, Chun-Long Chen and Nathaniel L. Rosi

Chemical Communications 2011 vol. 47(Issue 1) pp:185-187

Publication Date(Web):23 Aug 2010

DOI:10.1039/C0CC02257H

We describe the preparation of new 1-D gold nanoparticle superstructures with tailorable thicknesses formed using a self-assembled gold-binding peptide conjugate template and examine how the synthesis and assembly mechanism impacts the organization of the superstructures.

Tuning MOF CO2 Adsorption Properties via Cation Exchange

Co-reporter:Jihyun An

Journal of the American Chemical Society 2010 Volume 132(Issue 16) pp:5578-5579

Publication Date(Web):April 7, 2010

DOI:10.1021/ja1012992

The pore volume and BET surface area of bio-MOF-1 (a), Zn8(ad)4(BPDC)6O •2Me2NH2, is systematically modified via postsynthetic cation exchange with either tetramethylammonium, tetraethylammonium, or tetrabutylammonium cations to yield Zn8(ad)4(BPDC)6O•2Me4N (b), Zn8(ad)4(BPDC)6O•2Et4N (c), and Zn8(ad)4(BPDC)6O•2Bu4N (d), respectively. The impact that pore volume and BET surface area have on CO2 capacity is evaluated, and it is found that materials with intermediate porosity (b and c) have the largest CO2 capacities under the conditions studied.

Preparation of Unique 1-D Nanoparticle Superstructures and Tailoring their Structural Features

Co-reporter:Chun-Long Chen

Journal of the American Chemical Society 2010 Volume 132(Issue 20) pp:6902-6903

Publication Date(Web):April 29, 2010

DOI:10.1021/ja102000g

Designed peptide conjugate molecules are used to simultaneously direct both the synthesis and assembly of gold nanoparticles into various complex 1-D nanoparticle superstructures. We show how synthetic conditions, including reaction time and temperature, can be varied to carefully control the structure of the gold nanoparticle assembly and also the size and density of the nanoparticles within the assembly. We also demonstrate that particle capping agents such as citrate and adenosine triphosphate can be used to adjust the metrics of double-helical gold nanoparticle assemblies, in particular interhelical distances and particle size.

Peptidbasierte Verfahren zur Herstellung nanostrukturierter anorganischer Materialien

Co-reporter:Chun-Long Chen Dr. ;NathanielL. Rosi

Angewandte Chemie 2010 Volume 122( Issue 11) pp:1968-1986

Publication Date(Web):

DOI:10.1002/ange.200903572

Abstract

Mit ihrer einzigartigen sequenzspezifischen Selbstorganisation und der Fähigkeit zur Substraterkennung spielen Peptide in natürlichen Systemen eine entscheidende Rolle bei der Steuerung der Biomineralisation anorganischer Nanostrukturen und der Entstehung von Weichgewebe. Daher sind Peptide auch besonders wertvoll für die Herstellung neuer Materialien, und Forscher vieler Disziplinen bedienen sich heute dieser Moleküle, um die Synthese anorganischer Nanostrukturen und den Aufbau weicher Biomaterialien zu steuern. In diesem Aufsatz schildern wir die Entwicklungen auf diesem Gebiet, wobei unser spezielles Augenmerk der Fähigkeit von Peptiden gilt, die Zusammensetzung und Struktur neuer anorganischer Materialien zu steuern.

Peptide-Based Methods for the Preparation of Nanostructured Inorganic Materials

Co-reporter:Chun-Long Chen Dr. ;NathanielL. Rosi

Angewandte Chemie International Edition 2010 Volume 49( Issue 11) pp:1924-1942

Publication Date(Web):

DOI:10.1002/anie.200903572

Abstract

With their unique sequence-specific self-assembly and their substrate recognition properties, peptides play critical roles in controlling the biomineralization of inorganic nanostructures in natural systems and in directing the assembly of important soft matter. These attributes render them particularly useful molecules for the fabrication of new materials. Researchers from many scientific disciplines now use peptides to direct the synthesis of new inorganic nanostructures and the assembly of soft biomaterials. In this Review we describe the developments in this field and focus on the versatility of peptides and their ability to direct the composition and structure of new inorganic materials.

Near-Infrared Luminescent Lanthanide MOF Barcodes

Co-reporter:Kiley A. White ; Demetra A. Chengelis ; Kristy A. Gogick ; Jack Stehman ; Nathaniel L. Rosi ;Stéphane Petoud

Journal of the American Chemical Society 2009 Volume 131(Issue 50) pp:18069-18071

Publication Date(Web):November 25, 2009

DOI:10.1021/ja907885m

We demonstrate the conceptual advantage of using metal−organic frameworks (MOFs) for the creation of a polymetallic material that contains several different near-IR-emitting lanthanide cations and operates as a barcode material with unique luminescence properties. By choosing the ratio of lanthanide salts used during the synthesis, we can control the ratio of lanthanide cations present in the resulting material. We have demonstrated that the emission intensity of each of the different lanthanide cations is proportional to its amount in the MOF crystal, resulting in unique spectroscopic barcodes that depend on the lanthanide cation ratios and compositions.

Synthesis, Structure, Assembly, and Modulation of the CO2 Adsorption Properties of a Zinc-Adeninate Macrocycle

Co-reporter:Jihyun An ; Richard P. Fiorella ; Steven J. Geib

Journal of the American Chemical Society 2009 Volume 131(Issue 24) pp:8401-8403

Publication Date(Web):June 2, 2009

DOI:10.1021/ja901869m

The preparation and self-assembly of zinc adeninate macrocycles [Zn6(adeninate)6(pyridine)6(dimethylcarbamate)6] is described. The macrocycles self-assemble through adenine−adenine hydrogen bonding interactions into a 3-D porous crystalline material that maintains its structural integrity after removal of guest molecules and coordinated pyridine molecules. By adjusting the activation temperature prior to gas adsorption measurements, the size of the pore aperture can be modulated to afford unique gas sorption properties including selective gas adsorption and CO2 sequestration.

Cation-Triggered Drug Release from a Porous Zinc−Adeninate Metal−Organic Framework

Co-reporter:Jihyun An ; Steven J. Geib

Journal of the American Chemical Society 2009 Volume 131(Issue 24) pp:8376-8377

Publication Date(Web):June 2, 2009

DOI:10.1021/ja902972w

A porous anionic metal-organic framework, bio-MOF-1, constructed using adenine as a biomolecular building block is described. The porosity of this material is evaluated, its stability in biological buffers is studied, and its potential as a material for controlled drug release is investigated. Specifically, procainamide HCl is loaded into the pores of bio-MOF-1 using a simple cation exchange process. Exogenous cations from biological buffers are shown to affect the release of the adsorbed drug molecules.

High and Selective CO2 Uptake in a Cobalt Adeninate Metal−Organic Framework Exhibiting Pyrimidine- and Amino-Decorated Pores

Co-reporter:Jihyun An ; Steven J. Geib

Journal of the American Chemical Society 2009 Volume 132(Issue 1) pp:38-39

Publication Date(Web):December 14, 2009

DOI:10.1021/ja909169x

The synthesis and structure of Co2(ad)2(CO2CH3)2·2DMF·0.5H2O (bio-MOF-11) is described. Pyrimidine and amino groups of adeninate (ad) decorate the pores of the framework. The porosity of this material was studied, and its CO2 and H2 adsorption properties were evaluated. bio-MOF-11 exhibits a high heat of adsorption for CO2 (∼45 kJ/mol), a high CO2 capacity (∼6 mmol/g, 273 K), and exceptional selectivity for CO2 over N2 at 273 K (81:1) and 298 K (75:1).

Near-infrared emitting ytterbium metal–organic frameworks with tunable excitation properties

Co-reporter:Kiley A. White, Demetra A. Chengelis, Matthias Zeller, Steven J. Geib, Jessica Szakos, Stéphane Petoud and Nathaniel L. Rosi

Chemical Communications 2009 (Issue 30) pp:4506-4508

Publication Date(Web):06 Jul 2009

DOI:10.1039/B909658B

The design of metal–organic frameworks (MOFs) incorporating near-infrared emitting ytterbium cations and organic sensitizers allows for the preparation of new materials with tunable and enhanced photophysical properties.

Orthogonal Ternary Functionalization of a Mesoporous Metal–Organic Framework via Sequential Postsynthetic Ligand Exchange

Co-reporter:Chong Liu; Tian-Yi Luo; Evan S. Feura; Chen Zhang

Journal of the American Chemical Society () pp:

Publication Date(Web):August 10, 2015

DOI:10.1021/jacs.5b06780

A sequential postsynthetic ligand exchange process was used to prepare a series of mono-, di-, and trifunctionalized mesoporous metal–organic frameworks (MOFs). Using this process, orthogonal functional groups were installed and thereafter postsynthetically modified with dye and quencher molecules. Microspectrophotometry studies were used to determine the distribution of the two orthogonal functional groups within the MOF crystals.

Expeditious Synthesis and Assembly of Sub-100 nm Hollow Spherical Gold Nanoparticle Superstructures

Co-reporter:Chengyi Song ; Gongpu Zhao ; Peijun Zhang

Journal of the American Chemical Society () pp:

Publication Date(Web):

DOI:10.1021/ja106833g

Sub-100 nm hollow gold nanoparticle superstructures were prepared in a direct one-pot reaction. A gold-binding peptide conjugate, C6-AA-PEPAu (PEPAu = AYSSGAPPMPPF), was constructed and used to direct the simultaneous synthesis and assembly of gold nanoparticles. Transmission electron microscopy and electron tomography revealed that the superstructures are uniform and consist of monodisperse gold nanoparticles arranged into a spherical monolayer shell.

Screening and evaluating aminated cationic functional moieties for potential CO2 capture applications using an anionic MOF scaffold

Co-reporter:Tao Li and Nathaniel L. Rosi

Chemical Communications 2013 - vol. 49(Issue 97) pp:NaN11387-11387

Publication Date(Web):2013/10/28

DOI:10.1039/C3CC47031H

Three cations with different amine density, guanidinium, aminoguanidinium, and diaminoguanidinium, were loaded into anionic bio-MOF-1via cation-exchange. The structures and compositions of the cation-exchange products were characterized, and their N2 and CO2 adsorption properties were studied and compared.

Preparation of 1-D nanoparticle superstructures with tailorable thicknesses using gold-binding peptide conjugates

Co-reporter:Leekyoung Hwang, Chun-Long Chen and Nathaniel L. Rosi

Chemical Communications 2011 - vol. 47(Issue 1) pp:NaN187-187

Publication Date(Web):2010/08/23

DOI:10.1039/C0CC02257H

We describe the preparation of new 1-D gold nanoparticle superstructures with tailorable thicknesses formed using a self-assembled gold-binding peptide conjugate template and examine how the synthesis and assembly mechanism impacts the organization of the superstructures.

Near-infrared emitting ytterbium metal–organic frameworks with tunable excitation properties

Co-reporter:Kiley A. White, Demetra A. Chengelis, Matthias Zeller, Steven J. Geib, Jessica Szakos, Stéphane Petoud and Nathaniel L. Rosi

Chemical Communications 2009(Issue 30) pp:

Publication Date(Web):

DOI:10.1039/B909658B

Alumina-supported cobalt–adeninate MOF membranes for CO2/CH4 separation

Co-reporter:Zhenzhen Xie, Tao Li, Nathaniel L. Rosi and Moises A. Carreon

Journal of Materials Chemistry A 2014 - vol. 2(Issue 5) pp:NaN1241-1241

Publication Date(Web):2013/11/25

DOI:10.1039/C3TA14058J

The synthesis of continuous cobalt–adeninate MOF (bio-MOF-13 (I) and bio-MOF-14 (II)) membranes supported on porous alumina tubes is demonstrated. The membranes showed high CO2 permeabilities and low to moderate CO2 separation selectivities for CO2/CH4 gas mixtures. The observed CO2/CH4 selectivities are attributed to preferential CO2 adsorption within the framework.

Systematic modulation and enhancement of CO2:N2 selectivity and water stability in an isoreticular series of bio-MOF-11 analogues

Co-reporter:Tao Li, De-Li Chen, Jeanne E. Sullivan, Mark T. Kozlowski, J. Karl Johnson and Nathaniel L. Rosi

Chemical Science (2010-Present) 2013 - vol. 4(Issue 4) pp:NaN1755-1755

Publication Date(Web):2013/02/01

DOI:10.1039/C3SC22207A

An isoreticular series of cobalt-adeninate bio-MOFs (bio-MOFs-11–14) is reported. The pores of bio-MOFs-11–14 are decorated with acetate, propionate, butyrate, and valerate, respectively. The nitrogen (N2) and carbon dioxide (CO2) adsorption properties of these materials are studied and compared. The isosteric heats of adsorption for CO2 are calculated, and the CO2:N2 selectivities for each material are determined. As the lengths of the aliphatic chains decorating the pores in bio-MOFs-11–14 increase, the BET surface areas decrease from 1148 m2 g−1 to 17 m2 g−1 while the CO2:N2 selectivities predicted from ideal adsorbed solution theory at 1 bar and 273 K for a 10:90 CO2:N2 mixture range from 73:1 for bio-MOF-11 to 123:1 for bio-MOF-12 and finally to 107:1 for bio-MOF-13. At 298 K, the selectivities are 43:1 for bio-MOF-11, 52:1 for bio-MOF-12, and 40:1 for bio-MOF-13. Additionally, it is shown that bio-MOF-14 exhibits a unique molecular sieving property that allows it to adsorb CO2 but not N2 at 273 and 298 K. Finally, the water stability of bio-MOFs-11–14 increases with increasing aliphatic chain length. Bio-MOF-14 exhibits no loss of crystallinity or porosity after soaking in water for one month.

Metal–biomolecule frameworks (MBioFs)

Co-reporter:Inhar Imaz, Marta Rubio-Martínez, Jihyun An, Isabel Solé-Font, Nathaniel L. Rosi and Daniel Maspoch

Chemical Communications 2011 - vol. 47(Issue 26) pp:NaN7302-7302

Publication Date(Web):2011/04/18

DOI:10.1039/C1CC11202C

Biomolecules are the building blocks of life. Nature has evolved countless biomolecules that show promise for bridging metal ions. These molecules have emerged as an excellent source of biocompatible building blocks that can be used to design Metal–Biomolecule Frameworks (MBioFs). This feature article highlights the advances in the synthesis of this class of MOFs. Special emphasis is provided on the crystal structures of these materials, their miniaturization to the submicron length scale, and their new potential storage, catalytic, and biomedical applications.

Fabrication of MMMs with improved gas separation properties using externally-functionalized MOF particles

Co-reporter:Surendar R. Venna, Michael Lartey, Tao Li, Alex Spore, Santosh Kumar, Hunaid B. Nulwala, David R. Luebke, Nathaniel L. Rosi and Erik Albenze

Journal of Materials Chemistry A 2015 - vol. 3(Issue 9) pp:NaN5022-5022

Publication Date(Web):2015/01/27

DOI:10.1039/C4TA05225K

Mixed matrix membranes (MMM) have the potential to overcome the limitations of traditional polymeric membranes for gas separation by improving both the permeability and selectivity. The most difficult challenge is accessing defect free and optimized MMM membranes. Defects are generally due to incompatible interfaces between the polymer and the filler particle. Herein, we present a new approach to modify and optimize the surface of UiO-66-NH2 based MOF particles to improve its interaction with Matrimid® polymer. A series of surface modified UiO-66-NH2 particles were synthesized and characterized using 1H NMR spectroscopy, mass spectrometry, XPS, and powder X-ray diffraction. MMMs containing surface optimized MOF particles exhibit improved thermal and mechanical properties. Most importantly, the MMMs show significantly enhanced gas separation properties; CO2 permeability was increased by ∼200% and CO2/N2 ideal selectivity was increased by ∼25%. These results confirm the success of the proposed technique to mitigate defective MOF/Matrimid® interfaces.

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