Open Access. Powered by Scholars. Published by Universities.®
- Discipline
-
- Organic Chemistry (57)
- Analytical Chemistry (23)
- Materials Chemistry (22)
- Physical Chemistry (22)
- Inorganic Chemistry (16)
-
- Medicinal-Pharmaceutical Chemistry (8)
- Other Chemistry (8)
- Environmental Chemistry (7)
- Physics (7)
- Life Sciences (6)
- Engineering (4)
- Electrical and Computer Engineering (3)
- Biochemistry (2)
- Biochemistry, Biophysics, and Structural Biology (2)
- Biological and Chemical Physics (2)
- Biology (2)
- Medicine and Health Sciences (2)
- Radiochemistry (2)
- Analytical, Diagnostic and Therapeutic Techniques and Equipment (1)
- Bioimaging and Biomedical Optics (1)
- Biomedical Engineering and Bioengineering (1)
- Chemical Engineering (1)
- Earth Sciences (1)
- Electrical and Electronics (1)
- Electronic Devices and Semiconductor Manufacturing (1)
- Equipment and Supplies (1)
- Geochemistry (1)
- Geology (1)
- Keyword
-
- Nanocomposites (43)
- Polystyrene (25)
- Fire retardancy (22)
- Cone calorimetry (13)
- Spectroelectrochemistry (13)
-
- Cobalt (10)
- Iron (10)
- Kinetics (10)
- NMR (10)
- Poly(methyl methacrylate) (10)
- Thermal stability (10)
- Inelastic scattering (9)
- Ligands (9)
- Electrochemistry (8)
- Nanocomposite (8)
- Thermal degradation (8)
- Catalysis (7)
- Fire Retardancy (7)
- Ionic liquid (7)
- X-ray structures (7)
- Cellulose (6)
- Cross-linking (6)
- Crystal structure (6)
- Cyclic voltammetry (6)
- Cytochrome P450 (6)
- Layered double hydroxide (6)
- Layered double hydroxides (6)
- Molecular data (6)
- Oxidation (6)
- Ozone (6)
- Publication Year
- Publication
- Publication Type
- File Type
Articles 271 - 300 of 1110
Full-Text Articles in Chemistry
Synthesis And Characterization Of Biologically Relevant Fe(Ii) Complexes Containing Redox-Active (Hydro)Quinone Ligands, Amanda Elizabeth Baum
Synthesis And Characterization Of Biologically Relevant Fe(Ii) Complexes Containing Redox-Active (Hydro)Quinone Ligands, Amanda Elizabeth Baum
Dissertations (1934 -)
Redox-active p-(hydro)quinones work in concert with transition-metal centers to facilitate electron transfers in numerous biological contexts. While p-(hydro)quinones are known to interact with both heme and nonheme iron cofactors, the nonheme systems are particularly relevant to photosynthetic and bioremediation processes. In photosynthesis, two p-quinones facilitate an electron transfer away from the photoexcited P680 cofactor via a non-heme Fe(II) center. Based on EPR results, this interaction results in formation of transient Fe(II)/p-semiquinone (pSQ) species. In addition, a superoxo-iron(II)-pSQ species has been proposed as an intermediate of the oxidative cleavage mechanism of hydroquinone dioxygenases (HQDOs), which play a central role in the …
Synthetic And Mechanistic Studies Of Ruthenium Catalyzed C-C And C-O Bond Activation Reactions, Junghwa Kim
Synthetic And Mechanistic Studies Of Ruthenium Catalyzed C-C And C-O Bond Activation Reactions, Junghwa Kim
Dissertations (1934 -)
Etherification of alcohols is one of the most fundamental transformations in organic synthesis. Williamson ether synthesis is the most well-known synthetic method of unsymmetrical ether synthesis which is still being used in both industrial and academic laboratories. We have developed a novel catalytic etherification reaction using two different alcohols by using a well-defined cationic ruthenium catalyst. The reaction scope as well as the mechanistic study of the reaction are described.Hydroacylation is considered to be a powerful synthetic transformation for producing functionalized ketones from relatively simple olefin substrates. Despite remarkable progress in intra and intermolecular hydroacylations, the substrate scope of the …
Novel Numerical Models Of Electrostatic Interactions And Their Application To S-Nitrosothiol Simulations, Maxim Vadimovich Ivanov
Novel Numerical Models Of Electrostatic Interactions And Their Application To S-Nitrosothiol Simulations, Maxim Vadimovich Ivanov
Dissertations (1934 -)
Atom-centered point charge model of the molecular electrostatics remains a major workhorse in the atomistic biomolecular simulations. However, this approximation fails to reproduce anisotropic features of the molecular electrostatic potential (MEP), and the existing methods of the charge derivation are often associated with the numerical instabilities. This work provides an in-depth analysis of these limitations and offers a novel approach to describe electrostatic interactions that paves the way toward efficient next-generation force fields. By analyzing the charge fitting problem from first principles, as an example of the mathematical inverse problem, we show that the numerical instabilities of the charge-fitting problem …
Fluorescence Of Supported Phospholipid Bilayers Recorded In A Conventional Horizontal-Beam Spectrofluorometer, Elizaveta A. Kovrigina, Evgeni L. Kovrigin
Fluorescence Of Supported Phospholipid Bilayers Recorded In A Conventional Horizontal-Beam Spectrofluorometer, Elizaveta A. Kovrigina, Evgeni L. Kovrigin
Chemistry Faculty Research and Publications
Supported phospholipid bilayers are a convenient model of cellular membranes in studies of membrane biophysics and protein-lipid interactions. Traditionally, supported lipid bilayers are formed on a flat surface of a glass slide to be observed through fluorescence microscopes. This paper describes a method to enable fluorescence detection from the supported lipid bilayers using standard horizontal-beam spectrofluorometers instead of the microscopes. In the proposed approach, the supported lipid bilayers are formed on the inner optical surfaces of the standard fluorescence microcell. To enable observation of the bilayer absorbed on the cell wall, the microcell is placed in a standard fluorometer cell …
Influence Of Rtil Nanodomains On The Voltammetry And Spectroelectrochemistry Of Fullerene C60 In Benzonitrile/Room Temperature Ionic Liquids Mixtures, Abderrahman Atifi, Michael D. Ryan
Influence Of Rtil Nanodomains On The Voltammetry And Spectroelectrochemistry Of Fullerene C60 In Benzonitrile/Room Temperature Ionic Liquids Mixtures, Abderrahman Atifi, Michael D. Ryan
Chemistry Faculty Research and Publications
The cyclic voltammetry of fullerene C60 was examined in mixed benzonitrile/RTIL solvents in order to probe the effect of nanodomains in the mixed RTIL/benzonitrile solutions and their effect upon the voltammetry. In probing the interactions of the fullerides (up to C603−) with RTILs, BMIm+ (1-butyl-3-methylimidazolium, mostly planar) and tetraalkylammonium (more spherical/flexible) salts were used. In order to investigate these shifts in more detail, the ΔE12° (=E°1–E°2) and ΔE23° (=E°2–E°3) values, which were independent of the reference potential, were used. At higher concentrations of …
Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations With Phosphonate Stabilized Nucleophiles: Application To The Synthesis Of Oxygenated Metabolites Of Carvone, Do W. Lee, Charles Felix Manful, Jayapal Reddy Gone, Yuzhi Ma, William A. Donaldson
Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations With Phosphonate Stabilized Nucleophiles: Application To The Synthesis Of Oxygenated Metabolites Of Carvone, Do W. Lee, Charles Felix Manful, Jayapal Reddy Gone, Yuzhi Ma, William A. Donaldson
Chemistry Faculty Research and Publications
The addition of phosphonate stabilized carbon nucleophiles to acyclic (pentadienyl)iron(1+) cations proceeds predominantly at an internal carbon to afford (pentenediyl)iron complexes. Those complexes bearing an electron withdrawing group at the σ-bound carbon (i.e., 13/14) are stable and isolable, while complexes which do not contain an electron withdrawing group at the σ-bound carbon undergo CO insertion, reductive elimination and conjugation of the double bond to afford cyclohexenone products (21/22). Deprotonation of the phosphonate 13/14 or 21 and reaction with paraformaldehyde affords the olefinated products. This methodology was utilized to prepare oxygenated carvone metabolites (±)-25 and (±)-26.
Recent Advances In Development And Applications Of The Mixed Quantum/Classical Theory For Inelastic Scattering, Dmitri Babikov, Alexander Semenov
Recent Advances In Development And Applications Of The Mixed Quantum/Classical Theory For Inelastic Scattering, Dmitri Babikov, Alexander Semenov
Chemistry Faculty Research and Publications
A mixed quantum/classical approach to inelastic scattering (MQCT) is developed in which the relative motion of two collision partners is treated classically, and the rotational and vibrational motion of each molecule is treated quantum mechanically. The cases of molecule + atom and molecule + molecule are considered including diatomics, symmetric-top rotors, and asymmetric-top rotor molecules. Phase information is taken into consideration, permitting calculations of elastic and inelastic, total and differential cross sections for excitation and quenching. The method is numerically efficient and intrinsically parallel. The scaling law of MQCT is favorable, which enables calculations at high collision energies and for …
A Search For Blues Brothers: X-Ray Crystallographic/Spectroscopic Characterization Of The Tetraarylbenzidine Cation Radical As A Product Of Aging Of Solid Magic Blue, Marat R. Talipov, Mohammad M. Hossain, Anitha Boddeda, Khushabu Thakur, Rajendra Rathore
A Search For Blues Brothers: X-Ray Crystallographic/Spectroscopic Characterization Of The Tetraarylbenzidine Cation Radical As A Product Of Aging Of Solid Magic Blue, Marat R. Talipov, Mohammad M. Hossain, Anitha Boddeda, Khushabu Thakur, Rajendra Rathore
Chemistry Faculty Research and Publications
Magic blue (MB+˙ SbCl6− salt), i.e. tris-4-bromophenylamminium cation radical, is a routinely employed one-electron oxidant that slowly decomposes in the solid state upon storage to form so called ‘blues brothers’, which often complicate the quantitative analyses of the oxidation processes. Herein, we disclose the identity of the main ‘blues brother’ as the cation radical and dication of tetrakis-(4-bromophenyl)benzidine (TAB) by a combined DFT and experimental approach, including isolation of TAB+˙ SbCl6− and its X-ray crystallography characterization. The formation of TAB in aged magic blue samples occurs by a Scholl-type …
X-Ray Structure And Properties Of The Ferrous Octaethylporphyrin Nitroxyl Complex, Nagabhushanam Kundakarla, Sergey V. Lindeman, Hafiz Md. Rahman, Michael D. Ryan
X-Ray Structure And Properties Of The Ferrous Octaethylporphyrin Nitroxyl Complex, Nagabhushanam Kundakarla, Sergey V. Lindeman, Hafiz Md. Rahman, Michael D. Ryan
Chemistry Faculty Research and Publications
The preparation and characterization of the iron octaethylporphyrin nitroxyl ion, [Fe(OEP)(NO)−], is reported. The complex was synthesized by the one-electron reduction of Fe(OEP)(NO) using anthracenide as the reducing agent. The compound was isolated as the potassium (2.2.2)cryptand salt. The anion was characterized using X-ray analysis with visible and infrared spectroscopy. The spectral features of the iron nitroxyl complex were consistent with previous literature reports. The important structural changes upon reduction were a significant decrease in the Fe–N–O bond angle from 142° to 127° and an increase in the N–O bond length from that in the starting nitrosyl moiety. …
One-Pot Synthesis Of Biocompatible Silver Nanoparticle Composites From Cellulose And Keratin: Characterization And Antimicrobial Activity, Chieu D. Tran, Franja Prosenc, Mladen Franko, Gerald Benzi
One-Pot Synthesis Of Biocompatible Silver Nanoparticle Composites From Cellulose And Keratin: Characterization And Antimicrobial Activity, Chieu D. Tran, Franja Prosenc, Mladen Franko, Gerald Benzi
Chemistry Faculty Research and Publications
A novel, simple method was developed to synthesize biocompatible composites containing 50% cellulose (CEL) and 50% keratin (KER) and silver in the form of either ionic (Ag+) or Ag0 nanoparticles (Ag+NPs or Ag0NPs). In this method, butylmethylimmidazolium chloride ([BMIm+Cl–]), a simple ionic liquid, was used as the sole solvent and silver chloride was added to the [BMIm+Cl–] solution of [CEL+KER] during the dissolution process. The silver in the composites can be maintained as ionic silver (Ag+) or completely converted to metallic silver (Ag …
Accessing Spin-Crossover Behaviour In Iron(Ii) Complexes Of N-Confused Scorpionate Ligands, James R. Gardinier, Alexander Richard Treleven, Kristin J. Meise, Sergey V. Lindeman
Accessing Spin-Crossover Behaviour In Iron(Ii) Complexes Of N-Confused Scorpionate Ligands, James R. Gardinier, Alexander Richard Treleven, Kristin J. Meise, Sergey V. Lindeman
Chemistry Faculty Research and Publications
The first examples of a class of N-confused tris(pyrazolyl)methane ‘scorpionate’ ligands have been prepared. The magnetic properties of their iron(II) tetrafluoroborate complexes are dictated by changing one substituent per ligand rather than three as is typical for normal scorpionate ligands.
On Stabilization Of Scattering Resonances In Recombination Reaction That Forms Ozone, Mikhail V. Ivanov, Dmitri Babikov
On Stabilization Of Scattering Resonances In Recombination Reaction That Forms Ozone, Mikhail V. Ivanov, Dmitri Babikov
Chemistry Faculty Research and Publications
Calculations of energy transfer in the recombination reaction that forms ozone are carried out within the framework of the mixed quantum/classical theory and using the dimensionally reduced 2D-model of ozone molecule, with bending motion neglected. Recombination rate coefficients are obtained at room temperature for symmetric and asymmetric isotopomers of singly and doubly substituted isotopologues. The processes of resonance formation, spontaneous decay, collisional dissociation, and stabilization by bath gas (Ar) are all characterized and taken into account within the steady-state approximation for kinetics. The focus is on stabilization step, where the mysterious isotopic η-effect was thought to originate from. Our results …
Does Koopmans’ Paradigm For 1-Electron Oxidation Always Hold? Breakdown Of Ip/EOx Relationship For P-Hydroquinone Ethers And The Role Of Methoxy Group Rotation, Marat R. Talipov, Anitha Boddeda, Sergey V. Lindeman, Rajendra Rathore
Does Koopmans’ Paradigm For 1-Electron Oxidation Always Hold? Breakdown Of Ip/EOx Relationship For P-Hydroquinone Ethers And The Role Of Methoxy Group Rotation, Marat R. Talipov, Anitha Boddeda, Sergey V. Lindeman, Rajendra Rathore
Chemistry Faculty Research and Publications
Koopmans’ paradigm states that electron loss occurs from HOMO, thus forming the basis for the observed linear relationships between HOMO/IP, HOMO/Eox, and IP/Eox. In cases where a molecule undergoes dramatic structural reorganization upon 1-electron oxidation, the IP/Eoxrelationship does not hold, and the origin of which is not understood. For example, X-ray crystallography of the neutral and cation radicals of bicyclo[2.2.1]heptane-annulated p-hydroquinone ethers (THE and MHE) showed that they undergo electron-transfer-induced conformational reorganization and show breakdown of the IP/Eox relationship. DFT calculations revealed that Koopmans’ paradigm …
Design And Synthesis Of Oxazoline-Based Scaffolds For Hybrid Lewis Acid/Lewis Base Catalysis Of Carbon–Carbon Bond Formation, Dennis Wiedenhoeft, Adam R. Benoit, Jacob D. Porter, Yibiao Wu, Rajdeep S. Virdi, Alaa Shanaa, Chris Dockendorff
Design And Synthesis Of Oxazoline-Based Scaffolds For Hybrid Lewis Acid/Lewis Base Catalysis Of Carbon–Carbon Bond Formation, Dennis Wiedenhoeft, Adam R. Benoit, Jacob D. Porter, Yibiao Wu, Rajdeep S. Virdi, Alaa Shanaa, Chris Dockendorff
Chemistry Faculty Research and Publications
A new class of hybrid Lewis acid/Lewis base catalysts has been designed and prepared with an initial objective of promoting stereoselective direct aldol reactions. Several scaffolds were synthesized that contain amine moieties capable of enamine catalysis, connected to heterocyclic metal-chelating sections composed of an oxazole–oxazoline or thiazole–oxazoline. Early screening results have identified oxazole–oxazoline-based systems capable of promoting a highly diastereo- and enantioselective direct aldol reaction of propionaldehyde with 4-nitrobenzaldehyde, when combined with Lewis acids such as zinc triflate.
Inelastic Scattering Of Identical Molecules Within Framework Of The Mixed Quantum/Classical Theory: Application To Rotational Excitations In H2 + H2, Alexander Semenov, Dmitri Babikov
Inelastic Scattering Of Identical Molecules Within Framework Of The Mixed Quantum/Classical Theory: Application To Rotational Excitations In H2 + H2, Alexander Semenov, Dmitri Babikov
Chemistry Faculty Research and Publications
Theoretical foundation is laid out for description of permutation symmetry in the inelastic scattering processes that involve collisions of two identical molecules, within the framework of the mixed quantum/classical theory (MQCT). In this approach, the rotational (and vibrational) states of two molecules are treated quantum-mechanically, whereas their translational motion (responsible for scattering) is treated classically. This theory is applied to H2 + H2 system, and the state-to-state transition cross sections are compared versus those obtained from the full-quantum calculations and experimental results from the literature. Good agreement is found in all cases. It is also found that results of MQCT, …
From Wires To Cables: Attempted Synthesis Of 1,3,5-Trifluorenylcyclohexane As A Platform For Molecular Cables, Marat R. Talipov, Sameh H. Abdelwahed, Khushabu Thakur, Scott A. Reid, Rajendra Rathore
From Wires To Cables: Attempted Synthesis Of 1,3,5-Trifluorenylcyclohexane As A Platform For Molecular Cables, Marat R. Talipov, Sameh H. Abdelwahed, Khushabu Thakur, Scott A. Reid, Rajendra Rathore
Chemistry Faculty Research and Publications
Multiple molecular wires braided together in a single assembly, termed as molecular cable, are promising next-generation materials for effective long-range charge transport. As an example of the platform for constructing molecular cables, 1,3,5-trifluorenylcyclohexane (TFC) and its difluorenyl analogues (DFCs) were systematically investigated both experimentally (X-ray crystallography) and theoretically (DFT calculations). Although the syntheses of DFCs were successfully achieved, the synthesis of TFC, which involved a similar intramolecular Friedel–Crafts cyclization as the last step, was unsuccessful. An exhaustive study of the conformational landscape of cyclohexane ring of TFC and DFCs revealed that TFC is …
Reactivity Of (3-Methylpentadienyl)Iron(1+) Cation: Late-Stage Introduction Of A (3-Methyl-2z,4-Pentadien-1-Yl) Side Chain, Subhabrata Chaudhury, Shukun Li, William A. Donaldson
Reactivity Of (3-Methylpentadienyl)Iron(1+) Cation: Late-Stage Introduction Of A (3-Methyl-2z,4-Pentadien-1-Yl) Side Chain, Subhabrata Chaudhury, Shukun Li, William A. Donaldson
Chemistry Faculty Research and Publications
The 3-methyl-2Z,4-pentadien-1-yl sidechain is found in various sesquiterpenes and diterpenes. A route for the late stage introduction of this functionality was developed which relies on nucleophilic attack on the (3-methylpentadienyl)iron(1+) cation, followed by oxidative decomplexation. This methodology was applied to the synthesis of the proposed structure of heteroscyphic acid A methyl ester. Realization of this synthesis led to a correction of the proposed structure.
A Full-Dimensional Model Of Ozone Forming Reaction: The Absolute Value Of The Recombination Rate Coefficient, Its Pressure And Temperature Dependencies, Alexander Teplukhin, Dmitri Babikov
A Full-Dimensional Model Of Ozone Forming Reaction: The Absolute Value Of The Recombination Rate Coefficient, Its Pressure And Temperature Dependencies, Alexander Teplukhin, Dmitri Babikov
Chemistry Faculty Research and Publications
Rigorous calculations of scattering resonances in ozone are carried out for a broad range of rotational excitations. The accurate potential energy surface of Dawes is adopted, and a new efficient method for calculations of ro–vibrational energies, wave functions and resonance lifetimes is employed (which uses hyper-spherical coordinates, the sequential diagonalization/truncation approach, grid optimization and complex absorbing potential). A detailed analysis is carried out to characterize distributions of resonance energies and lifetimes, their rotational/vibrational content and their positions with respect to the centrifugal barrier. Emphasis is on the contribution of these resonances to the recombination process that forms ozone. It is …
A Flipped Classroom Redesign In General Chemistry, Scott A. Reid
A Flipped Classroom Redesign In General Chemistry, Scott A. Reid
Chemistry Faculty Research and Publications
The flipped classroom continues to attract significant attention in higher education. Building upon our recent parallel controlled study of the flipped classroom in a second-term general chemistry course (J. Chem. Educ., 2016, 93, 13–23), here we report on a redesign of the flipped course aimed at scaling up total enrollment while keeping discussion sizes small (i.e.,students), and maintaining equivalent contact hour load for faculty and workload for students. To that end, the course format featured lecture contact pushed outside of the classroom in the form of video lectures (mean duration 13 minutes) paired with online …
Hydrogen-Atom Attack On Phenol And Toluene Is Ortho-Directed, Olha Krechkivska, Callan M. Wilcox, Tyler P. Troy, Klaas Nauta, Bun Chan, Rebecca Jacob, Scott A. Reid, Leo Radom, Timothy W. Schmidt, Scott H. Kable
Hydrogen-Atom Attack On Phenol And Toluene Is Ortho-Directed, Olha Krechkivska, Callan M. Wilcox, Tyler P. Troy, Klaas Nauta, Bun Chan, Rebecca Jacob, Scott A. Reid, Leo Radom, Timothy W. Schmidt, Scott H. Kable
Chemistry Faculty Research and Publications
The reaction of H + phenol and H/D + toluene has been studied in a supersonic expansion after electric discharge. The (1 + 1′) resonance-enhanced multiphoton ionization (REMPI) spectra of the reaction products, at m/z = parent + 1, or parent + 2 amu, were measured by scanning the first (resonance) laser. The resulting spectra are highly structured. Ionization energies were measured by scanning the second (ionization) laser, while the first laser was tuned to a specific transition. Theoretical calculations, benchmarked to the well-studied H + benzene → cyclohexadienyl radical reaction, were performed. The spectrum arising from the …
Unveiling The Crucial Intermediates In Androgen Production, Piotr J. Mak, Michael C. Gregory, Ilia G. Denisov, Stephen G. Sligar, James R. Kincaid
Unveiling The Crucial Intermediates In Androgen Production, Piotr J. Mak, Michael C. Gregory, Ilia G. Denisov, Stephen G. Sligar, James R. Kincaid
Chemistry Faculty Research and Publications
Significance: The human enzyme cytochrome P450 17A1 (CYP17A1) catalyzes the critical step in the biosynthesis of the male sex hormones, and, as such, it is a key target for the inhibition of testosterone production that is necessary for the progression of certain cancers. CYP17A1 catalyzes two distinct types of chemical transformations. The first is the hydroxylation of the steroid precursors pregnenolone and progesterone. The second is a different reaction involving carbon–carbon (C-C) bond cleavage, the mechanism of which has been actively debated in the literature. Using a combination of chemical and biophysical methods, we have been able to trap and …
A Circle Has No End: Role Of Cyclic Topology And Accompanying Structural Reorganization On The Hole Distribution In Cyclic And Linear Poly‑P‑Phenylene Molecular Wires, Marat R. Talipov, Ramesh Jasti, Rajendra Rathore
A Circle Has No End: Role Of Cyclic Topology And Accompanying Structural Reorganization On The Hole Distribution In Cyclic And Linear Poly‑P‑Phenylene Molecular Wires, Marat R. Talipov, Ramesh Jasti, Rajendra Rathore
Chemistry Faculty Research and Publications
π-Conjugated organic oligomers/polymers hold great promise as long-range charge-transfer materials for modern photovoltaic applications. However, a set of criteria for the rational design of functional materials is not yet available, in part because of a lack of understanding of charge distribution in extended π-conjugated systems of different topologies, and concomitant effects on redox and optical properties. Herein we demonstrate the role of cyclic versus linear topology in controlling the redox/optical properties and hole distribution in poly-p-phenylenes (PPs) with the aid of experiment, computation, and our recently developed multistate parabolic model (MPM). It is unequivocally shown that the hole …
Direct Observation Of Photoinduced Charge Separation In Ruthenium Complex/Ni(Oh)2 Nanoparticle Hybrid, Yu Tang, Brian Pattengale, John Ludwig, Abderrahman Atifi, Alexander V. Zinovev, Bin Dong, Qingyu Kong, Xiaobing Zuo, Xiaoyi Zhang, Jier Huang
Direct Observation Of Photoinduced Charge Separation In Ruthenium Complex/Ni(Oh)2 Nanoparticle Hybrid, Yu Tang, Brian Pattengale, John Ludwig, Abderrahman Atifi, Alexander V. Zinovev, Bin Dong, Qingyu Kong, Xiaobing Zuo, Xiaoyi Zhang, Jier Huang
Chemistry Faculty Research and Publications
Ni(OH)2 have emerged as important functional materials for solar fuel conversion because of their potential as cost-effective bifunctional catalysts for both hydrogen and oxygen evolution reactions. However, their roles as photocatalysts in the photoinduced charge separation (CS) reactions remain unexplored. In this paper, we investigate the CS dynamics of a newly designed hybrid catalyst by integrating a Ru complex with Ni(OH)2 nanoparticles (NPs). Using time resolved X-ray absorption spectroscopy (XTA), we directly observed the formation of the reduced Ni metal site (~60 ps), unambiguously demonstrating CS process in the hybrid through ultrafast electron transfer from Ru complex to …
Spectroscopic Evidence Of Nanodomains In Thf/Rtil Mixtures: Spectroelectrochemical And Voltammetric Study Of Nickel Porphyrins, Abderrahman Atifi, Michael D. Ryan
Spectroscopic Evidence Of Nanodomains In Thf/Rtil Mixtures: Spectroelectrochemical And Voltammetric Study Of Nickel Porphyrins, Abderrahman Atifi, Michael D. Ryan
Chemistry Faculty Research and Publications
The presence and effect of RTIL nanodomains in molecular solvent/RTIL mixture were investigated by studying the spectroelectrochemistry and voltammetry of nickel octaethylporphyrin (Ni(OEP)) and nickel octaethylporphinone (Ni(OEPone)). Two oxidation and 2–3 reduction redox couples were observed, and the UV–visible spectra of all stable products in THF and RTIL mixtures were obtained. The E° values for the reduction couples that were studied were linearly correlated with the Gutmann acceptor number, as well as the difference in the E° values between the first two waves (ΔE12° = |E1° – E2°|). The Δ …
The Homo Nodal Arrangement In Polychromophoric Molecules And Assemblies Controls The Interchromophoric Electronic Coupling, Marat R. Talipov, Tushar Navale, Rajendra Rathore
The Homo Nodal Arrangement In Polychromophoric Molecules And Assemblies Controls The Interchromophoric Electronic Coupling, Marat R. Talipov, Tushar Navale, Rajendra Rathore
Chemistry Faculty Research and Publications
Triptycenes spontaneously assemble into two-dimensional networks in which long-range charge transport is facilitated by the extensive electronic coupling through the triptycene framework (intramolecularly) and by cofacial π-stacking (intermolecularly). While designing and synthesizing next-generation triptycenes containing polyaromatic chromophores, the electronic coupling amongst the chromophores was observed to be highly dependent on the nature and position of the substituents. Herein, we demonstrate using hexaalkoxytriptycenes that the electronic coupling amongst the chromophores is switched on and off by a simple repositioning of the substituents, which alters the nodal arrangement of the HOMOs of the individual chromophores. A visual inspection of the HOMOs can …
Mixed Valent Metal Pincer Complexes And Reactivity Of Metal Complexes Of Extended Pincer Ligands, Jeewantha Sampath Hewage
Mixed Valent Metal Pincer Complexes And Reactivity Of Metal Complexes Of Extended Pincer Ligands, Jeewantha Sampath Hewage
Dissertations (1934 -)
Historically, the study of mixed valence complexes has been critical for advancing our understanding of electron transfer processes in biological and abiological systems. The recent use of mixed valence complexes in electrochromic materials, and the promise of their use in future technological or molecular electronic applications, has spurred further interest in this class of compound. Previous studies by our research group have shown that gallium(III) or tricarbonylrhenium(I) complexes of pincer-type ligands with diarylamido anchors and either pyrazol-1-yl (pz) or diarylphosphino (PAr2) flanking donors are electroactive species with quasi reversible ligand-centered oxidations. Moreover, the one-electron oxidized derivative with pz flankers, [Ga(L)(L+)]2+ …
Ligand Frameworks For Transition-Metal Complexes That Model Metalloenzyme Active, Denan Wang
Ligand Frameworks For Transition-Metal Complexes That Model Metalloenzyme Active, Denan Wang
Dissertations (1934 -)
Advances in the field of biomimetic inorganic chemistry require the design of sophisticated ligand frameworks that reflect the amazing complexity of metalloenzyme active sites. For instance, most active sites feature extensive hydrogen-bonding interactions between ligands bound to the metal center (the “first” coordination sphere) and nearby units in the outer (or “second”) sphere. Since these interactions modify the structural and electronic properties of the active sites, a number of inorganic chemists have sought to design ligands that permit outer-sphere functional groups to interact with first-sphere donors. This dissertation describes our contribution to these broader efforts to model the second coordination …
S-Nitrosothiols: Electronic Structure And Substituent Effects, Matthew Flister
S-Nitrosothiols: Electronic Structure And Substituent Effects, Matthew Flister
Dissertations (1934 -)
S-nitrosothiols (RSNOs) are biologically important molecules involved in the storage and transport of nitric oxide (NO) and account for much of its signaling activity in living organisms. RSNOs have significant impact on NO signaling through, S-nitrosation, a major post-translational modification of proteins. These unstable thiol derivatives readily undergo homolytic dissociation of the S–N bond to release NO. RSNOs have potential therapeutic applications as NO donors, although the development of novel RSNOs has been slow due to the complex electronic structure of the –SNO group. A specific focus on the impact of the –R group on RSNO properties via substituent effect …
With Vibrationally Excited Thiophosgene Molecule And Double-Well Ion Traps, Dmytro Shyshlov
With Vibrationally Excited Thiophosgene Molecule And Double-Well Ion Traps, Dmytro Shyshlov
Dissertations (1934 -)
For practical realization of quantum information processing we need a quantum system that provides reliable preparation of the initial state, high-fidelity quantum gate operations, error tolerance, readout of the result of quantum computation and scalability of the system to increase the number of qubits. In this dissertation we show how these requirements can be addressed for molecular quantum computer. For computational study of quantum information processing with molecules we employ thiophosgene (SCCl2) molecule that has been used as a test system for quantum control experiments [Mol. Phys. 105, 1999 (2007)]. We investigate the gateway scheme of control in which transitions …
A Deeper Insight Into Strain For The Sila-Bi[6]Prismane (Si18H12) Cluster With Its Endohedrally Trapped Silicon Atom, Si19H12, Vach Holger, Lena V. Ivanova, Qadir K. Timerghazin, Fatme Jardali, Ha-Linh Thi Le
A Deeper Insight Into Strain For The Sila-Bi[6]Prismane (Si18H12) Cluster With Its Endohedrally Trapped Silicon Atom, Si19H12, Vach Holger, Lena V. Ivanova, Qadir K. Timerghazin, Fatme Jardali, Ha-Linh Thi Le
Chemistry Faculty Research and Publications
A new family of over-coordinated hydrogenated silicon nanoclusters with outstanding optical and mechanical properties has recently been proposed. For one member of this family, namely the highly symmetric Si19H12 nanocrystal, strain calculations have been presented with the goal to question its thermal stability and the underlying mechanism of ultrastability and electron-deficiency aromaticity. Here, the invalidity of these strain energy (SE) calculations is demonstrated mainly based on a fundamentally wrong usage of homodesmotic reactions, the miscounting of atomic bonds, and arithmetic errors. Since the article in question is entirely anchored on those erroneous SE values, all of its …