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Full-Text Articles in Chemistry

Evolution From The Plasmon To Exciton State In Ligand-Protected Atomically Precise Gold Nanoparticles, Meng Zhou, Chenjie Zeng, Yuxiang Chen, Shuo Zhao, Matthew Y. Sfeir, Manzhou Zhu, Rongchao Jin Oct 2016

Evolution From The Plasmon To Exciton State In Ligand-Protected Atomically Precise Gold Nanoparticles, Meng Zhou, Chenjie Zeng, Yuxiang Chen, Shuo Zhao, Matthew Y. Sfeir, Manzhou Zhu, Rongchao Jin

Publications and Research

The evolution from the metallic (or plasmonic) to molecular state in metal nanoparticles constitutes a central question in nanoscience research because of its importance in revealing the origin of metallic bonding and offering fundamental insights into the birth of surface plasmon resonance. Previous research has not been able to probe the transition due to the unavailability of atomically precise nanoparticles in the 1-3 nm size regime. Herein, we investigate the transition by performing ultrafast spectroscopic studies on atomically precise thiolate-protected Au25, Au38, Au144, Au333, Au∼520 and Au∼940 nanoparticles. Our results …


Free Energy-Based Virtual Screening And Optimization Of Rnase H Inhibitors Of Hiv‑1 Reverse Transcriptase, Baofeng Zhang, Michael P. D'Erasmo, Ryan P. Murelli, Emilio Gallicchio Sep 2016

Free Energy-Based Virtual Screening And Optimization Of Rnase H Inhibitors Of Hiv‑1 Reverse Transcriptase, Baofeng Zhang, Michael P. D'Erasmo, Ryan P. Murelli, Emilio Gallicchio

Publications and Research

We report the results of a binding free energy-based virtual screening campaign of a library of 77 α-hydroxytropolone derivatives against the challenging RNase H active site of the reverse transcriptase (RT) enzyme of human immunodeficiency virus-1. Multiple protonation states, rotamer states, and binding modalities of each compound were individually evaluated. The work involved more than 300 individual absolute alchemical binding free energy parallel molecular dynamics calculations and over 1 million CPU hours on national computing clusters and a local campus computational grid. The thermodynamic and structural measures obtained in this work rationalize a series of characteristics of this system useful …


Electrochemical Properties Of Melting Gel Coatings, Lisa C. Klein, Ahmad Dengah, Kutaiba Al-Marzoki, Gabriela Rodriguez, Andrei Jitianu, Jadra Mosa, Mario Amapricio Sep 2016

Electrochemical Properties Of Melting Gel Coatings, Lisa C. Klein, Ahmad Dengah, Kutaiba Al-Marzoki, Gabriela Rodriguez, Andrei Jitianu, Jadra Mosa, Mario Amapricio

Publications and Research

Organic-inorganic melting gel coatings were applied to titanium alloy substrates to decrease their corrosion and extend their lifetime in an electrochemical application. Melting gels containing phenyl substitutions were coated onto the substrates. The ratio of diphenyl dimethoxysilane (DPhDMS) to methanol was varied to change the thickness of the coatings. The coatings were inspected visually to see that there is good adhesion between the coating and the substrate. Nanoindenter tests were performed to determine hardness


Ionophoric Polyphenols Selectively Bind Cu2+, Display Potent Antioxidant And Anti-Amyloidogenic Properties, And Are Non-Toxic Toward Tetrahymena Thermophila, Alberto Martinez, Ralph Alcendor, Tanzeen Rahman, Magdalena Podgorny, Ismaila Sanogo, Rebecca Mccurdy Aug 2016

Ionophoric Polyphenols Selectively Bind Cu2+, Display Potent Antioxidant And Anti-Amyloidogenic Properties, And Are Non-Toxic Toward Tetrahymena Thermophila, Alberto Martinez, Ralph Alcendor, Tanzeen Rahman, Magdalena Podgorny, Ismaila Sanogo, Rebecca Mccurdy

Publications and Research

Alzheimer’s disease (AD) is the most common form of dementia affecting more than 28 million people in the world. Only symptomatic treatments are currently available. Anticipated tri-fold increase of AD incidence in the next 50 years has established the need to explore new possible treatments. Accumulation of extracellular amyloid-b (Ab) plaques, intracellular tangles in the brain, and formation of reactive oxygen species (ROS) are the major hallmarks of the disease. The active role of some metal ions, especially Cu2+, in promoting both Ab aggregation and reactive oxygen species formation has rendered ionophoric drugs as a promising treatment strategy. …


Atomistic Corrective Scheme For Supercell Density Functional Theory Calculations Of Charged Defects, Tengfei Cao, Angelo Bongiorno Jun 2016

Atomistic Corrective Scheme For Supercell Density Functional Theory Calculations Of Charged Defects, Tengfei Cao, Angelo Bongiorno

Publications and Research

A new method to correct formation energies of charged defects obtained by supercell densityfunctional calculations is presented and applied to bulk, surface, and low-dimensional systems. The method relies on atomistic models and a polarizable force field to describe a material system and its dielectric properties. The polarizable force field is based on a minimal set of fitting parameters, it accounts for the dielectric screening arising from ions and electrons separately, and it can be easily implemented in any software for atomistic molecular dynamics simulations. This work illustrates both technical aspects and applications of the new corrective scheme. The method is …


Light-Activated Photocurrent Degradation And Self-Healing In Perovskite Solar Cells, Wanyi Nie, Jean-Christophe Blancon, Amanda J. Neukirch, Kannatassen Appavoo, Hsinhan Tsai, Manish Chhowalla, Muhammad A. Alam, Matthew Y. Sfeir, Claudine Katan, Jacky Even, Sergei Tretiak, Jared J. Crochet, Gautam Gupta, Aditya D. Mohite May 2016

Light-Activated Photocurrent Degradation And Self-Healing In Perovskite Solar Cells, Wanyi Nie, Jean-Christophe Blancon, Amanda J. Neukirch, Kannatassen Appavoo, Hsinhan Tsai, Manish Chhowalla, Muhammad A. Alam, Matthew Y. Sfeir, Claudine Katan, Jacky Even, Sergei Tretiak, Jared J. Crochet, Gautam Gupta, Aditya D. Mohite

Publications and Research

Solution-processed organometallic perovskite solar cells have emerged as one of the most promising thin-film photovoltaic technology. However, a key challenge is their lack of stability over prolonged solar irradiation. Few studies have investigated the effect of light soaking on hybrid perovskites and have attributed the degradation in the optoelectronic properties to photochemical or field-assisted ion migration. Here we show that the slow photocurrent degradation in thin-film photovoltaic devices is due to the formation of light-activated meta-stable deep-level trap states. However, the devices can self-heal completely by resting them in the dark for <1 min or the degradation can be completely prevented by operating the devices at 0°C. We investigate several physical mechanisms to explain the microscopic origin for the formation of these trap states, among which the creation of small polaronic states involving localized cooperative lattice strain and molecular orientations emerges as a credible microscopic mechanism requiring further detailed studies.


A Direct Mechanism Of Ultrafast Intramolecular Singlet Fission In Pentacene Dimers, Eric G. Fuemmeler, Samuel N. Sanders, Andrew B. Pun, Elango Kumarasamy, Tao Zeng, Kiyoshi Miyata, Michael L. Steigerwald, X.-Y. Zhu, Matthew Y. Sfeir, Luis M. Campos, Nandini Ananth May 2016

A Direct Mechanism Of Ultrafast Intramolecular Singlet Fission In Pentacene Dimers, Eric G. Fuemmeler, Samuel N. Sanders, Andrew B. Pun, Elango Kumarasamy, Tao Zeng, Kiyoshi Miyata, Michael L. Steigerwald, X.-Y. Zhu, Matthew Y. Sfeir, Luis M. Campos, Nandini Ananth

Publications and Research

Interest in materials that undergo singlet fission (SF) has been catalyzed by the potential to exceed the Shockley–Queisser limit of solar power conversion efficiency. In conventional materials, the mechanism of SF is an intermolecular process (xSF), which is mediated by charge transfer (CT) states and depends sensitively on crystal packing or molecular collisions. In contrast, recently reported covalently coupled pentacenes yield ∼2 triplets per photon absorbed in individual molecules: the hallmark of intramolecular singlet fission (iSF). However, the mechanism of iSF is unclear. Here, using multireference electronic structure calculations and transient absorption spectroscopy, we establish that iSF can occur via …


The Synthesis Of Angucyclines Using An Intramolecular Bradsher Cycloaddition, Abdullah Allaoa, Tony E. Nicolas May 2016

The Synthesis Of Angucyclines Using An Intramolecular Bradsher Cycloaddition, Abdullah Allaoa, Tony E. Nicolas

Publications and Research

The Angucyclines are natural products which possess a broad spectrum of biological properties. Of particular interest are the natural products which contain the cis-hydroxyl motif at the AB ring junction. Their synthesis is particularly challenging. Our model study has resulted in the synthesis of a model of the angucyclines with the required cis-hydroxyl features. The present work will apply the previously developed chemistry to an intramolecular version which will lead to the synthesis of the ABC ring system


From Mollusks To Medicine: A Venomics Approach For The Discovery And Characterization Of Therapeutics From Terebridae Peptide Toxins, Aida Verdes, Prachi Anand, Juliette Gorson, Stephen Jannetti, Patrick Kelly, Abba Leffler, Danny Simpson, Girish Ramrattan, Mandë Holford Apr 2016

From Mollusks To Medicine: A Venomics Approach For The Discovery And Characterization Of Therapeutics From Terebridae Peptide Toxins, Aida Verdes, Prachi Anand, Juliette Gorson, Stephen Jannetti, Patrick Kelly, Abba Leffler, Danny Simpson, Girish Ramrattan, Mandë Holford

Publications and Research

Animal venoms comprise a diversity of peptide toxins that manipulate molecular targets such as ion channels and receptors, making venom peptides attractive candidates for the development of therapeutics to benefit human health. However, identifying bioactive venom peptides remains a significant challenge. In this review we describe our particular venomics strategy for the discovery, characterization, and optimization of Terebridae venom peptides, teretoxins. Our strategy reflects the scientific path from mollusks to medicine in an integrative sequential approach with the following steps: (1) delimitation of venomous Terebridae lineages through taxonomic and phylogenetic analyses; (2) identification and classification of putative teretoxins through omics …


Titanocene−Gold Complexes Containing N‑Heterocyclic Carbene Ligands Inhibit Growth Of Prostate, Renal, And Colon Cancers In Vitro, Yiu Fung Mui, Jacob FernáNdez-Gallardo, Benelita T. Elie, Ahmed Gubran, Irene Maluenda, Mercedes Sanau, Marıá Contel Apr 2016

Titanocene−Gold Complexes Containing N‑Heterocyclic Carbene Ligands Inhibit Growth Of Prostate, Renal, And Colon Cancers In Vitro, Yiu Fung Mui, Jacob FernáNdez-Gallardo, Benelita T. Elie, Ahmed Gubran, Irene Maluenda, Mercedes Sanau, Marıá Contel

Publications and Research

We report on the synthesis, characterization, and stability studies of new titanocene complexes containing a methyl group and a carboxylate ligand (mba = −OC(O)-p-C6H4-S−) bound to gold(I)−N-heterocyclic carbene fragments through the thiolate group: [(η5-C5H5)2TiMe(μ-mba)Au(NHC)]. The cytotoxicities of the heterometallic compounds along with those of novel monometallic gold−N-heterocyclic carbene precursors [(NHC)Au(mbaH)] have been evaluated against renal, prostate, colon, and breast cancer cell lines. The highest activity and selectivity and a synergistic effect of the resulting heterometallic species was found for the prostate and colon cancer cell lines. The colocalization of both titanium and gold metals (1:1 ratio) in PC3 prostate cancer …


Discovery And Characterisation Of A Novel Toxin From Dendroaspis Angusticeps, Named Tx7335, That Activates The Potassium Channel Kcsa, Ivan O. Rivera-Torres, Tony B. Jin, Martine Cadene, Brian T. Chait, Sébastien F. Poget Apr 2016

Discovery And Characterisation Of A Novel Toxin From Dendroaspis Angusticeps, Named Tx7335, That Activates The Potassium Channel Kcsa, Ivan O. Rivera-Torres, Tony B. Jin, Martine Cadene, Brian T. Chait, Sébastien F. Poget

Publications and Research

Due to their central role in essential physiological processes, potassium channels are common targets for animal toxins. These toxins in turn are of great value as tools for studying channel function and as lead compounds for drug development. Here, we used a direct toxin pull-down assay with immobilised KcsA potassium channel to isolate a novel KcsA-binding toxin (called Tx7335) from eastern green mamba snake (Dendroaspis angusticeps) venom. Sequencing of the toxin by Edman degradation and mass spectrometry revealed a 63 amino acid residue peptide with 4 disulphide bonds that belongs to the three-finger toxin family, but with a unique modification …


Glass Polymorphism In Glycerol–Water Mixtures: Ii. Experimental Studies, Johannes Bachler, Violeta Fuentes-Landete, David A. Jahn, Jessina Wong, Nicolas Giovambattista, Thomas Loerting Mar 2016

Glass Polymorphism In Glycerol–Water Mixtures: Ii. Experimental Studies, Johannes Bachler, Violeta Fuentes-Landete, David A. Jahn, Jessina Wong, Nicolas Giovambattista, Thomas Loerting

Publications and Research

We report a detailed experimental study of (i) pressure-induced transformations in glycerol–water mixtures at T = 77 K and P = 0–1.8 GPa, and (ii) heating-induced transformations of glycerol–water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s1–10 K h1) and for the whole range of glycerol mole fractions, wg. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (wg Z 0.20), ice (wg r 0.32), and/or ‘‘distorted ice’’ (0 o wg r 0.38). Upon compression, we …


Sulfur-Mediated Photochemical Energy Harvesting In Nanoporous Carbons, Alicia Gomis-Berenguer, Mykola Seredych, Jesus Iniesta, Joao C. Lima, Teresa J. Bandosz, Conchi O. Ania Mar 2016

Sulfur-Mediated Photochemical Energy Harvesting In Nanoporous Carbons, Alicia Gomis-Berenguer, Mykola Seredych, Jesus Iniesta, Joao C. Lima, Teresa J. Bandosz, Conchi O. Ania

Publications and Research

This work provides new insights in the field of applied photochemistry based on semiconductor-free nanoporous carbons and its application to sunlight energy harvesting. Using carbon materials of increasing average pore size, chemical functionalization to introduce a variety of O- and S-containing functional groups and monochromatic light, we have shown the dependence of the photochemical conversion of phenol in the confinement of the carbons nanopore space with the wavelength of the irradiation source, the dimensions of the pore voids and their surface chemistry. The photochemical conversion of phenol inside the carbons pore space was found to be very sensitive to the …


Pore Structure And Synergy In Antimicrobial Peptides Of The Magainin Family, Almudena Pino-Angeles, John M. Leveritt Iii, Themis Lazaridis Jan 2016

Pore Structure And Synergy In Antimicrobial Peptides Of The Magainin Family, Almudena Pino-Angeles, John M. Leveritt Iii, Themis Lazaridis

Publications and Research

Magainin 2 and PGLa are among the best-studied cationic antimicrobial peptides. They bind preferentially to negatively charged membranes and apparently cause their disruption by the formation of transmembrane pores, whose detailed structure is still unclear. Here we report the results of 5–9 μs all-atom molecular dynamics simulations starting from tetrameric transmembrane helical bundles of these two peptides, as well as their stoichiometric mixture, and the analog MG-H2 in DMPC or 3:1 DMPC/DMPG membranes. The simulations produce pore structures that appear converged, although some effect of the starting peptide arrangement (parallel vs. antiparallel) is still observed on this timescale. The peptides …


Self-Assembly Of Gold Supraparticles With Crystallographically Aligned And Strongly Coupled Nanoparticle Building Blocks For Sers And Photothermal Therapy, S. Paterson, S. A. Thompson, J. Gracie, A. W. Wark, R. De La Rica Jan 2016

Self-Assembly Of Gold Supraparticles With Crystallographically Aligned And Strongly Coupled Nanoparticle Building Blocks For Sers And Photothermal Therapy, S. Paterson, S. A. Thompson, J. Gracie, A. W. Wark, R. De La Rica

Publications and Research

A new method is introduced for self-assembling citrate-capped gold nanoparticles into supraparticles with crystallographically aligned building blocks. It consists in confining gld nanoparticles inside a cellulose acetate membrane. The constituent nanoparticles are in close contact in the superstructure, and therefore generate hot spots leading to intense Surface-Enhanced Raman Scattering (SERS) signals. They also generate more plasmonic heat than the nanoparticle building blocks. The supraparticles are internalized by cells and show low cytotoxicity, but can kill cancer cells when irradiated with a laser. This, along with the improved plasmonic properties arising from their assembly, makes the gold supraparticles promising materials for …


Quantitative Model For Rationalizing Solvent Effect In Noncovalent Ch-Aryl Interactions, Bright C. Emenike, Sara N. Bey, Brianna C. Bigelow, Srinivas V.S. Chakravartula Jan 2016

Quantitative Model For Rationalizing Solvent Effect In Noncovalent Ch-Aryl Interactions, Bright C. Emenike, Sara N. Bey, Brianna C. Bigelow, Srinivas V.S. Chakravartula

Publications and Research

The strength of CH–aryl interactions (ΔG) in 14 solvents was determined via the conformational analysis of a molecular torsion balance. The molecular balance adopted folded and unfolded conformers in which the ratio of the conformers in solution provided a quantitative measure of ΔG as a function of solvation. While a single empirical solvent parameter based on solvent polarity failed to explain solvent effect in the molecular balance, it is shown that these ΔG values can be correlated through a multiparameter linear solvation energy relationship (LSER) using the equation introduced by Kamlet and Taft. The resulting LSER …


Density Functional Investigation Of The Inclusion Of Gold Clusters On A Ch3s Self-Assembled Lattice On Au(111), Darnel J. Allen, Wayne E. Archibald, John A. Harper, John C. Saputo, Daniel Torres Jan 2016

Density Functional Investigation Of The Inclusion Of Gold Clusters On A Ch3s Self-Assembled Lattice On Au(111), Darnel J. Allen, Wayne E. Archibald, John A. Harper, John C. Saputo, Daniel Torres

Publications and Research

We employ first-principles density functional theoretical calculations to address the inclusion of gold (Au) clusters in a well-packed CH3S self-assembled lattice. We compute CH3S adsorption energies to quantify the energetic stability of the self-assembly and gold adsorption and dissolution energies to characterize the structural stability of a series of Au clusters adsorbed at the SAM-Au interface. Our results indicate that the inclusion of Au clusters with less than four Au atoms in the SAM-Au interface enhances the binding of CH3S species. In contrast, larger Au clusters destabilize the self-assembly.We attribute this effect to the low-coordinated gold atoms in the cluster. …