Alon A. Gorodetsky

Protochromic Devices from a Cephalopod Structural Protein

Co-reporter:David D. Ordinario;Erica M. Leung;Long Phan;Rylan Kautz;Woo Kyung Lee;Mahan Naeim;Justin P. Kerr;Mercedeez J. Aquino;Paul E. Sheehan

Advanced Optical Materials 2017 Volume 5(Issue 20) pp:

Publication Date(Web):2017/10/01

DOI:10.1002/adom.201600751

AbstractCephalopods possess remarkable camouflage capabilities, which are enabled by their complex innervated skin architectures and advanced nervous systems. As such, cephalopod skin constitutes an exciting model for biomimetic camouflage technologies. This study draws inspiration from the constituent components of optically active ultrastructures found in squid skin cells to help design color-changing bioelectronic devices, which consist of a proton-transporting active layer contacted by a proton-conducting actuating electrode. The devices exhibit distinct shifts in their reflectance and coloration, which are attributed to active layer thickness changes induced by the direct electrical injection/extraction of protons. The reported findings may hold relevance for developing novel color-changing technologies, understanding ion-transporting biological systems, and engineering improved bioelectronic platforms.

Unexpected length dependence of excited-state charge transfer dynamics for surface-confined perylenediimide ensembles

Co-reporter:Amir Mazaheripour;Gregor Kladnik;Jonah-Micah Jocson;Austin G. Wardrip;Cade B. Markegard;Nathan Frey;Albano Cossaro;Luca Floreano;Alberto Verdini;Andrew Bartlett;Anthony M. Burke;Nina Hüsken;Kelsey Miller;Katarina Van Wonterghem;Robert Lopez;Michelle Lu;Amrita Masurkar;Mary N. Dickson;Sahar Sharifzadeh;Hung D. Nguyen;Ioannis Kymissis;Dean Cvetko;Alberto Morgante

Materials Horizons (2014-Present) 2017 vol. 4(Issue 3) pp:437-441

Publication Date(Web):2017/05/09

DOI:10.1039/C6MH00465B

The performance of devices from organic semiconductors is often governed by charge transfer phenomena at structurally and electronically complex interfaces, which remain challenging to access and study with excellent chemical and temporal resolution. Herein, we report the preparation and X-ray spectroscopic characterization of well-defined model organic–inorganic interfaces. We discover an unexpected trend for our systems' associated charge transfer times, and we rationalize this trend with density functional theory calculations. Our findings hold relevance for understanding interfacial charge transfer phenomena in a variety of organic, biological, and bioinspired systems.

Dynamic Materials Inspired by Cephalopods

Co-reporter:Long Phan, Rylan Kautz, Erica M. Leung, Kyle L. Naughton, Yegor Van Dyke, and Alon A. Gorodetsky

Chemistry of Materials 2016 Volume 28(Issue 19) pp:6804

Publication Date(Web):September 21, 2016

DOI:10.1021/acs.chemmater.6b01532

The related concepts of disguising an object or physically changing it to resemble something entirely different have long captivated the human imagination. Although such notions are seemingly derived from fables and science fiction, cephalopods have perfected analogous capabilities over millions of years of natural evolution. Consequently, these invertebrates have emerged as exciting sources of inspiration for futuristic adaptive camouflage and shapeshifter-like technologies. Herein, we provide an overview of selected literature examples that have used cephalopods as models for the development of novel adaptive materials, devices, and systems. We in turn highlight some significant remaining challenges and potential future directions for such studies. Through this perspective, we hope to stimulate additional dialogue and continued scientific exploration within the area of cephalopod-inspired dynamic materials.

Photochemical Doping of Protonic Transistors from a Cephalopod Protein

Co-reporter:David D. Ordinario, Long Phan, Yegor Van Dyke, Tam Nguyen, Amanda G. Smith, Michael Nguyen, Nikka M. Mofid, MyAnh Kaylee Dao, and Alon A. Gorodetsky

Chemistry of Materials 2016 Volume 28(Issue 11) pp:3703

Publication Date(Web):May 23, 2016

DOI:10.1021/acs.chemmater.6b00336

The field of bioelectronics has the potential to revolutionize both fundamental biology and personalized medicine. As such, much research effort has been devoted to the development of devices and materials that are intrinsically compatible with biological systems. Within this context, several recent studies have focused on protonic transistors from naturally occurring materials, such as squid-derived polysaccharides and proteins. Herein, we report the rational design, fabrication, and characterization of two- and three-terminal protonic devices, for which the active material consists of a protein-based proton conductor doped with a small molecular photoacid. We electrically interrogate these devices both in the absence and presence of illumination, demonstrating that an exogenous photophysical stimulus selectively enhances their electrical properties. Our findings hold significance for understanding and controlling proton transport not only in bioelectronic platforms but also across a wide range of voltage-regulated proton-conducting materials and device platforms.

Synthesis of polyquinolines via an AA/BB-type aza-Diels–Alder polymerization reaction

Co-reporter:Mehran J. Umerani, David J. Dibble, Austin G. Wardrip, Amir Mazaheripour, Eriberto Vargas, Joseph W. Ziller and Alon A. Gorodetsky

Journal of Materials Chemistry A 2016 vol. 4(Issue 18) pp:4060-4066

Publication Date(Web):08 Apr 2016

DOI:10.1039/C5TC03974F

Polyquinolines have attracted attention as functional materials due to their excellent combination of optical, electrical, chemical, thermal, and mechanical properties. However, only a handful of synthetic routes for the preparation of these polymers have been established to date. Here, we demonstrate the preparation of polyquinolines via an AA/BB-type aza-Diels–Alder polymerization reaction. This approach requires only commercial starting materials and two straightforward synthetic steps to furnish the desired products in high yield. Overall, our modular and general route may afford new opportunities for the rational design and preparation of quinoline-based materials.

Reflectin as a Material for Neural Stem Cell Growth

Co-reporter:Long Phan, Rylan Kautz, Janahan Arulmoli, Iris H. Kim, Dai Trang T. Le, Michael A. Shenk, Medha M. Pathak, Lisa A. Flanagan, Francesco Tombola, and Alon A. Gorodetsky

ACS Applied Materials & Interfaces 2016 Volume 8(Issue 1) pp:278

Publication Date(Web):December 24, 2015

DOI:10.1021/acsami.5b08717

Cephalopods possess remarkable camouflage capabilities, which are enabled by their complex skin structure and sophisticated nervous system. Such unique characteristics have in turn inspired the design of novel functional materials and devices. Within this context, recent studies have focused on investigating the self-assembly, optical, and electrical properties of reflectin, a protein that plays a key role in cephalopod structural coloration. Herein, we report the discovery that reflectin constitutes an effective material for the growth of human neural stem/progenitor cells. Our findings may hold relevance both for understanding cephalopod embryogenesis and for developing improved protein-based bioelectronic devices.Keywords: bioelectronics; biointerfaces; cephalopods; reflectin; stem cells

An Aza-Diels–Alder Approach to Crowded Benzoquinolines

Co-reporter:Amir Mazaheripour; David J. Dibble; Mehran J. Umerani; Young S. Park; Robert Lopez; Dylan Laidlaw; Eriberto Vargas; Joseph W. Ziller

Organic Letters 2016 Volume 18(Issue 2) pp:156-159

Publication Date(Web):December 24, 2015

DOI:10.1021/acs.orglett.5b02939

Graphene nanoribbons (GNRs) are promising candidate materials for the next generation of nanoscale electronics. Described herein is the synthesis of 2,4,6-substituted benzoquinolines, which constitute building blocks for nitrogen-doped GNRs. The presented facile and modular aza-Diels–Alder chemistry accommodates the installation of diverse functionalities at the crowded benzoquinolines’ 2 positions. Given the general utility of the benzoquinoline motif, these findings hold relevance not only for carbon-based electronics but also for a range of chemical disciplines.

Production and electrical characterization of the reflectin A2 isoform from Doryteuthis (Loligo) pealeii

Co-reporter:David D. Ordinario, Long Phan, Ward G. Walkup IV, Yegor Van Dyke, Erica M. Leung, Michael Nguyen, Amanda G. Smith, Justin Kerr, Mahan Naeim, Ioannis Kymissis and Alon A. Gorodetsky

RSC Advances 2016 vol. 6(Issue 62) pp:57103-57107

Publication Date(Web):15 Jun 2016

DOI:10.1039/C6RA05405F

Cephalopods have recently emerged as a source of inspiration for the development of novel functional materials. Within this context, a number of studies have explored structural proteins known as reflectins, which play a key role in cephalopod adaptive coloration in vivo and exhibit interesting properties in vitro. Herein, we report an improved high-yield strategy for the preparation and isolation of reflectins in quantities sufficient for materials applications. We first select the Doryteuthis (Loligo) pealeii reflectin A2 (RfA2) isoform as a “model” system and validate our approach for the expression and purification of this protein. We in turn fabricate RfA2-based two-terminal devices and employ both direct and alternating current measurements to demonstrate that RfA2 films conduct protons. Our findings underscore the potential of reflectins as functional materials and may allow a wider range of researchers to investigate their properties.

Synthesis of Nitrogen-Containing Rubicene and Tetrabenzopentacene Derivatives

Co-reporter:Dr. Young S. Park;Dr. David J. Dibble;Dr. Juhwan Kim;Robert C. Lopez;Eriberto Vargas; Alon A. Gorodetsky

Angewandte Chemie International Edition 2016 Volume 55( Issue 10) pp:3352-3355

Publication Date(Web):

DOI:10.1002/anie.201510320

Abstract

Carbon-based materials, such as acenes, fullerenes, and graphene nanoribbons, are viewed as the potential successors to silicon in the next generation of electronics. Although a number of methodologies provide access to these materials’ all-carbon variants, relatively fewer strategies readily furnish their nitrogen-doped analogues. Herein, we report the rational design, preparation, and characterization of nitrogen-containing rubicenes and tetrabenzopentacenes, which can be viewed either as acene derivatives or as molecular fragments of fullerenes and graphene nanoribbons. The reported findings may prove valuable for the development of electron transporting organic semiconductors and for the eventual construction of larger carbonaceous systems.

Synthesis of Nitrogen-Containing Rubicene and Tetrabenzopentacene Derivatives

Co-reporter:Dr. Young S. Park;Dr. David J. Dibble;Dr. Juhwan Kim;Robert C. Lopez;Eriberto Vargas; Alon A. Gorodetsky

Angewandte Chemie 2016 Volume 128( Issue 10) pp:3413-3416

Publication Date(Web):

DOI:10.1002/ange.201510320

Abstract

Carbon-based materials, such as acenes, fullerenes, and graphene nanoribbons, are viewed as the potential successors to silicon in the next generation of electronics. Although a number of methodologies provide access to these materials’ all-carbon variants, relatively fewer strategies readily furnish their nitrogen-doped analogues. Herein, we report the rational design, preparation, and characterization of nitrogen-containing rubicenes and tetrabenzopentacenes, which can be viewed either as acene derivatives or as molecular fragments of fullerenes and graphene nanoribbons. The reported findings may prove valuable for the development of electron transporting organic semiconductors and for the eventual construction of larger carbonaceous systems.

Infrared invisibility stickers inspired by cephalopods

Co-reporter:Long Phan, David D. Ordinario, Emil Karshalev, Ward G. Walkup IV, Michael A. Shenk and Alon A. Gorodetsky

Journal of Materials Chemistry A 2015 vol. 3(Issue 25) pp:6493-6498

Publication Date(Web):19 Feb 2015

DOI:10.1039/C5TC00125K

The skin morphology of cephalopods endows them with remarkable dynamic camouflage capabilities. Cephalopod skin has therefore served as an inspiration for the design of camouflage devices that function in the visible region of the electromagnetic spectrum. In contrast, despite the importance of infrared signaling and detection for numerous industrial and military applications, there have been fewer attempts to translate the principles underlying cephalopod adaptive coloration to infrared camouflage systems. Herein, we draw inspiration from the structures and proteins found in cephalopod skin to fabricate biomimetic camouflage coatings on transparent and flexible adhesive substrates. The substrates can be deployed on arbitrary surfaces, and we can reversibly modulate their reflectance from the visible to the near infrared regions of the electromagnetic spectrum with a mechanical stimulus. These stickers make it possible to disguise common objects with varied roughnesses and geometries from infrared visualization. Our findings represent a key step towards the development of wearable biomimetic color- and shape-shifting technologies for stealth applications.

Molecular Dynamics Simulations of Perylenediimide DNA Base Surrogates

Co-reporter:Cade B. Markegard, Amir Mazaheripour, Jonah-Micah Jocson, Anthony M. Burke, Mary N. Dickson, Alon A. Gorodetsky, and Hung D. Nguyen

The Journal of Physical Chemistry B 2015 Volume 119(Issue 35) pp:11459-11465

Publication Date(Web):August 21, 2015

DOI:10.1021/acs.jpcb.5b03874

Perylene-3,4,9,10-tetracarboxylic diimides (PTCDIs) are a well-known class of organic materials. Recently, these molecules have been incorporated within DNA as base surrogates, finding ready applications as probes of DNA structure and function. However, the assembly dynamics and kinetics of PTCDI DNA base surrogates have received little attention to date. Herein, we employ constant temperature molecular dynamics simulations to gain an improved understanding of the assembly of PTCDI dimers and trimers. We also use replica-exchange molecular dynamics simulations to elucidate the energetic landscape dictating the formation of stacked PTCDI structures. Our studies provide insight into the equilibrium configurations of multimeric PTCDIs and hold implications for the construction of DNA-inspired systems from perylene-derived organic semiconductor building blocks.

An Aza-Diels–Alder Route to Polyquinolines

Co-reporter:David J. Dibble, Mehran J. Umerani, Amir Mazaheripour, Young S. Park, Joseph W. Ziller, and Alon A. Gorodetsky

Macromolecules 2015 Volume 48(Issue 3) pp:557-561

Publication Date(Web):January 16, 2015

DOI:10.1021/ma5020726

Polyquinolines have been studied since the early 1970s due to their favorable chemical, optical, electrical, and mechanical properties. However, surprisingly few synthetic strategies have been developed for the preparation of these polymers. Herein, we demonstrate the application of the aza-Diels–Alder (Povarov) reaction for the synthesis of soluble polyquinolines from a bifunctional monomer. Our approach furnishes polyquinolines with a unique architecture and connectivity in only two synthetic steps from inexpensive, commercially available reagents. The reported strategy may therefore represent a welcome addition to the polymer chemist’s toolkit by providing ready access to a diverse library of polyquinoline-type materials.

Synthesis of Polybenzoquinolines as Precursors for Nitrogen-Doped Graphene Nanoribbons

Co-reporter:Dr. David J. Dibble;Dr. Young S. Park;Amir Mazaheripour;Mehran J. Umerani;Dr. Joseph W. Ziller; Alon A. Gorodetsky

Angewandte Chemie 2015 Volume 127( Issue 20) pp:5981-5985

Publication Date(Web):

DOI:10.1002/ange.201411740

Abstract

Graphene nanoribbons (GNRs) represent promising materials for the next generation of nanoscale electronics. However, despite substantial progress towards the bottom-up synthesis of chemically and structurally well-defined all-carbon GNRs, strategies for the preparation of their nitrogen-doped analogs remain at a nascent stage. This scarce literature precedent is surprising given the established use of substitutional doping for tuning the properties of electronic materials. Herein, we report the synthesis of a previously unknown class of polybenzoquinoline-based materials, which have potential as GNR precursors. Our scalable and facile approach employs few synthetic steps, inexpensive commercial starting materials, and straightforward reaction conditions. Moreover, due to the importance of quinoline derivatives for a variety of applications, the reported findings may hold implications across a diverse range of chemical and physical disciplines.

Synthesis of Polybenzoquinolines as Precursors for Nitrogen-Doped Graphene Nanoribbons

Co-reporter:Dr. David J. Dibble;Dr. Young S. Park;Amir Mazaheripour;Mehran J. Umerani;Dr. Joseph W. Ziller; Alon A. Gorodetsky

Angewandte Chemie International Edition 2015 Volume 54( Issue 20) pp:5883-5887

Publication Date(Web):

DOI:10.1002/anie.201411740

Abstract

Graphene nanoribbons (GNRs) represent promising materials for the next generation of nanoscale electronics. However, despite substantial progress towards the bottom-up synthesis of chemically and structurally well-defined all-carbon GNRs, strategies for the preparation of their nitrogen-doped analogs remain at a nascent stage. This scarce literature precedent is surprising given the established use of substitutional doping for tuning the properties of electronic materials. Herein, we report the synthesis of a previously unknown class of polybenzoquinoline-based materials, which have potential as GNR precursors. Our scalable and facile approach employs few synthetic steps, inexpensive commercial starting materials, and straightforward reaction conditions. Moreover, due to the importance of quinoline derivatives for a variety of applications, the reported findings may hold implications across a diverse range of chemical and physical disciplines.

Sequence Specific Detection of Restriction Enzymes at DNA-Modified Carbon Nanotube Field Effect Transistors

Co-reporter:David D. Ordinario, Anthony M. Burke, Long Phan, Jonah-Micah Jocson, Hanfei Wang, Mary N. Dickson, and Alon A. Gorodetsky

Analytical Chemistry 2014 Volume 86(Issue 17) pp:8628

Publication Date(Web):August 19, 2014

DOI:10.1021/ac501441d

Protein–DNA interactions play a central role in many cellular processes, and their misregulation has been implicated in a number of human diseases. Thus, there is a pressing need for the development of analytical strategies for interrogating the binding of proteins to DNA. Herein, we report the electrical monitoring of a prototypical DNA-binding protein, the PvuII restriction enzyme, at microfluidic-encapsulated, DNA-modified carbon nanotube field effect transistors. Our integrated platform enables the sensitive, sequence specific detection of PvuII at concentrations as low as 0.5 pM in a volume of 0.025 μL (corresponding to ∼7500 proteins). These figures of merit compare favorably to state of the art values reported for alternative fluorescent and electrical assays. The overall detection strategy represents a step toward the massively parallel electrical monitoring, identification, and quantification of protein–DNA interactions at arrayed nanoscale devices.

Electrochemistry of DNA Monolayers Modified With a Perylenediimide Base Surrogate

Co-reporter:Chris H. Wohlgamuth ; Marc A. McWilliams ; Amir Mazaheripour ; Anthony M. Burke ; Kuo-Yao Lin ; Linh Doan ; Jason D. Slinker

The Journal of Physical Chemistry C 2014 Volume 118(Issue 50) pp:29084-29090

Publication Date(Web):August 12, 2014

DOI:10.1021/jp5041508

Electrochemistry of self-assembled DNA monolayers represents an attractive strategy for understanding the intrinsic properties of DNA and for developing DNA-based sensors. Thus, there is much interest in the discovery and characterization of new redox-active probes for application in DNA-based technologies. Herein, we report a detailed study of the electrochemical properties of a perylene-3,4,9,10-tetracarboxylic diimide base surrogate, when incorporated at various positions within a DNA monolayer. We demonstrate that the redox chemistry of this perylenediimide probe is mediated by the DNA base pair stack, dependent on its location within the DNA monolayer, and activated thermally. The electrochemical features and general synthetic flexibility of the perylenediimide base surrogate appear favorable for assays that leverage DNA-mediated charge transport.

Reconfigurable Infrared Camouflage Coatings from a Cephalopod Protein

Co-reporter:Long Phan;Ward G. Walkup IV;David D. Ordinario;Emil Karshalev;Jonah-Micah Jocson;Anthony M. Burke

Advanced Materials 2013 Volume 25( Issue 39) pp:5621-5625

Publication Date(Web):

DOI:10.1002/adma.201301472

Infrared invisibility stickers inspired by cephalopods

Co-reporter:Long Phan, David D. Ordinario, Emil Karshalev, Ward G. Walkup IV, Michael A. Shenk and Alon A. Gorodetsky

Journal of Materials Chemistry A 2015 - vol. 3(Issue 25) pp:NaN6498-6498

Publication Date(Web):2015/02/19

DOI:10.1039/C5TC00125K

The skin morphology of cephalopods endows them with remarkable dynamic camouflage capabilities. Cephalopod skin has therefore served as an inspiration for the design of camouflage devices that function in the visible region of the electromagnetic spectrum. In contrast, despite the importance of infrared signaling and detection for numerous industrial and military applications, there have been fewer attempts to translate the principles underlying cephalopod adaptive coloration to infrared camouflage systems. Herein, we draw inspiration from the structures and proteins found in cephalopod skin to fabricate biomimetic camouflage coatings on transparent and flexible adhesive substrates. The substrates can be deployed on arbitrary surfaces, and we can reversibly modulate their reflectance from the visible to the near infrared regions of the electromagnetic spectrum with a mechanical stimulus. These stickers make it possible to disguise common objects with varied roughnesses and geometries from infrared visualization. Our findings represent a key step towards the development of wearable biomimetic color- and shape-shifting technologies for stealth applications.

Synthesis of polyquinolines via an AA/BB-type aza-Diels–Alder polymerization reaction

Co-reporter:Mehran J. Umerani, David J. Dibble, Austin G. Wardrip, Amir Mazaheripour, Eriberto Vargas, Joseph W. Ziller and Alon A. Gorodetsky

Journal of Materials Chemistry A 2016 - vol. 4(Issue 18) pp:NaN4066-4066

Publication Date(Web):2016/04/08

DOI:10.1039/C5TC03974F

Polyquinolines have attracted attention as functional materials due to their excellent combination of optical, electrical, chemical, thermal, and mechanical properties. However, only a handful of synthetic routes for the preparation of these polymers have been established to date. Here, we demonstrate the preparation of polyquinolines via an AA/BB-type aza-Diels–Alder polymerization reaction. This approach requires only commercial starting materials and two straightforward synthetic steps to furnish the desired products in high yield. Overall, our modular and general route may afford new opportunities for the rational design and preparation of quinoline-based materials.