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Articles 1 - 21 of 21
Full-Text Articles in Physical Sciences and Mathematics
Kohn–Sham Exchange-Correlation Potentials From Second-Order Reduced Density Matrices, Rogelio Cuevas-Saavedra, Paul W. Ayers, Viktor N. Staroverov
Kohn–Sham Exchange-Correlation Potentials From Second-Order Reduced Density Matrices, Rogelio Cuevas-Saavedra, Paul W. Ayers, Viktor N. Staroverov
Chemistry Publications
We describe a practical algorithm for constructing the Kohn–Sham exchange-correlation potential corresponding to a given second-order reduced density matrix. Unlike conventional Kohn–Sham inversion methods in which such potentials are extracted from ground-state electron densities, the proposed technique delivers unambiguous results in finite basis sets. The approach can also be used to separate approximately the exchange and correlation potentials for a many-electron system for which the reduced density matrix is known. The algorithm is implemented for configuration-interaction wave functions and its performance is illustrated with numerical examples.
Group 6 Metal Pentacarbonyl Complexes Of Air-Stable Primary, Secondary, And Tertiary Ferrocenylethylphosphines, Amir Rabiee Kenaree, Ethan R. Sauvé, Paul J. Ragogna, Joe Gilroy
Group 6 Metal Pentacarbonyl Complexes Of Air-Stable Primary, Secondary, And Tertiary Ferrocenylethylphosphines, Amir Rabiee Kenaree, Ethan R. Sauvé, Paul J. Ragogna, Joe Gilroy
Chemistry Publications
The synthesis and characterization of a series of Group 6 metal pentacarbonyl complexes of air stable primary, secondary, and tertiary phosphines containing ferrocenylethyl substituents are reported [M(CO)5L: M = Cr, Mo, W; L = PH2(CH2CH2Fc), PH(CH2CH2Fc)2, P(CH2CH2Fc)3]. The structure and composition of the complexes were confirmed by multinuclear NMR spectroscopy, IR and UV-Vis absorption spectroscopy, mass spectrometry, X-ray crystallography, and elemental analysis. The solid-state structural data reported revealed trends in M-C and M-P bond lengths that mirrored those of the …
Side-Chain Boron Difluoride Formazanate Polymers Via Ring-Opening Metathesis Polymerization, Samantha Novoa, Joseph A. Paquette, Stephanie M. Barbon, Ryan R. Maar, Joe Gilroy
Side-Chain Boron Difluoride Formazanate Polymers Via Ring-Opening Metathesis Polymerization, Samantha Novoa, Joseph A. Paquette, Stephanie M. Barbon, Ryan R. Maar, Joe Gilroy
Chemistry Publications
The synthesis, characterization, and ring-opening methathesis polymerization (ROMP) of a novel norbornene-based boron difluoride (BF2) formazante monomer are described in detail. The polymerization studies confirmed ROMP to occur in the presence of BF2 formazanates, and also demonstrated the controlled nature of the polymerization. The polymers retained many of the unique characteristics of the monomers in dichloromethane, including absorption and emission at maximum wavelengths of 518 and 645 nm, large Stoke's shifts (uST = 127 nm, 3,800 cm-1), and the ability to act as electron reservoirs to form borataverdazyl-based poly(radical anions) (E°red1 …
An Azide-Functionalized Nitronyl Nitroxide Radical: Synthesis, Characterization And Staudinger-Bertozzi Ligation Reactivity, Stephanie M. Barbon, Pierangelo Gobbo, Wilson Luo, Jacquelyn T. Price, Mark C. Biesenger, Mark S. Workentin, Joe Gilroy
An Azide-Functionalized Nitronyl Nitroxide Radical: Synthesis, Characterization And Staudinger-Bertozzi Ligation Reactivity, Stephanie M. Barbon, Pierangelo Gobbo, Wilson Luo, Jacquelyn T. Price, Mark C. Biesenger, Mark S. Workentin, Joe Gilroy
Chemistry Publications
An azide-functionalized nitronyl nitroxide was successfully synthesized and its reactivity towards the Staudinger-Bertozzi ligation was explored. While a model reaction in solution showed the conversion of the nitronyl nitroxide to an imino nitroxide radical, the same reaction at the interface of gold nanoparticles allowed for successful covalent incorporation of the nitronyl nitroxide radical onto the nanoparticles.
Oxidative Cyclization Of Tertiary Pentenol Derivatives Forming 2,5,5-Trisubstituted Thf Rings And The Total Synthesis Of Cyclocapitelline, Geoffrey A. Phillips, Cory Palmer, Andrew C. Stevens, Mattew L. Piotrowski, Daryyl Sr Dekruyf, Brian Pagenkopf
Oxidative Cyclization Of Tertiary Pentenol Derivatives Forming 2,5,5-Trisubstituted Thf Rings And The Total Synthesis Of Cyclocapitelline, Geoffrey A. Phillips, Cory Palmer, Andrew C. Stevens, Mattew L. Piotrowski, Daryyl Sr Dekruyf, Brian Pagenkopf
Chemistry Publications
The synthesis of 2,5,5-trisubstituted tetrahydrofuran rings was accomplished via the Mukaiyama aerobic oxidative cyclization of tertiary 5-pentenols employing the Co(nmp)2catalyst. A variety of THFs were formed in moderate to good yield and diastereoselectivity. The method developed herein was successfully applied to an enantioselective total synthesis of cyclocapitelline.
Evaluation Of Anisole-Substituted Boron Difluoride Formazanate Complexes For Fluorescence Cell Imaging, Ryan R. Maar, Stephanie M. Barbon, Neha Sharma, Hilary Groom, Leonard G. Luyt, Joe Gilroy
Evaluation Of Anisole-Substituted Boron Difluoride Formazanate Complexes For Fluorescence Cell Imaging, Ryan R. Maar, Stephanie M. Barbon, Neha Sharma, Hilary Groom, Leonard G. Luyt, Joe Gilroy
Chemistry Publications
The evaluation of three subclasses of boron difluoride formazanate complexes bearing o-, m-, and p-anisole N-aryl substituents (Ar) as readily accessible alternatives to boron dipyrromethene (BODIPY) dyes for cell imaging applications is described. While the wavelengths of maximum absorption (lmax) and emission (lem) observed for each subclass of complexes, which differed by their carbon-bound substituents (R), were similar, the emission quantum yields for 7a-c (R = cyano) were enhanced relative to 8a-c (R = nitro) and 9a-c (R = phenyl). Complexes 7a-c and 8a-c were also significantly …
Substrate-Mediated Deactivation Of A Ru(PTBu2nBn2) Cooperative Complex, John Paul J. Bow, Paul D. Boyle, Johanna M. Blacquiere
Substrate-Mediated Deactivation Of A Ru(PTBu2nBn2) Cooperative Complex, John Paul J. Bow, Paul D. Boyle, Johanna M. Blacquiere
Chemistry Publications
Ligand design for metal-ligand cooperative (MLC) catalysis is inherently more complex than that for traditional non-cooperative ligands. The basicity, sterics and structure of the acid/base group in MLC proton-transfer (PT) complexes, for instance, undoubtedly influence catalyst performance. Herein, we evaluate the highly tunable PR2NR′2 (1,5-R′-3,7-R-1,5-diaza-3,7-diphosphacyclooctane) ligand family for the first time in an organic transformation. With [Ru(Cp)(PtBu2NBn2)(MeCN)][PF6] as the catalyst, no turnover was observed in the anti-Markovnikov hydration of alkynes, a known PT MLC reaction. Treatment of the cooperative complex with phenylacetylene affords a vinylammonium product in which the pendant nitrogen atom of the PtBu2NBn2 ligand forms a Lewis acid-base …
Synthesis And Characterization Of A Family Of Air-Stable Ferrocene- And Ruthenocene-Containing Primary, Secondary, And Tertiary Phosphines, Amir Rabiee Kenaree, Tyler J. Cuthbert, Stephanie M. Barbon, Paul D. Boyle, Elizabeth R. Gillies, Paul J. Ragogna, Joe Gilroy
Synthesis And Characterization Of A Family Of Air-Stable Ferrocene- And Ruthenocene-Containing Primary, Secondary, And Tertiary Phosphines, Amir Rabiee Kenaree, Tyler J. Cuthbert, Stephanie M. Barbon, Paul D. Boyle, Elizabeth R. Gillies, Paul J. Ragogna, Joe Gilroy
Chemistry Publications
The synthesis and characterization of a family of air-stable primary, secondary, and tertiary phosphines containing all possible combinations of ethylferrocene and ethylruthenocene substituents are reported. Each phosphine was characterized by 1H, 13C, and 31P NMR spectroscopy, IR and UV-vis absorption spectroscopy, mass spectrometry, and elemental analysis. With the exception of primary ethylruthenocene phosphine 8a, all of the title compounds have been studied by single crystal X-ray crystallography. Ferrocene-containing phosphines showed maximum absorption at wavelengths of ca. 440 nm and qualitatively reversible oxidation waves in their cyclic voltammograms with intensities scaling to the number of ferrocene units …
Enhanced Rates Of Photoinduced Molecular Orientation In A Series Of Molecular Glassy Thin Films., Kristen E Snell, Renjie Hou, Eléna Ishow, François Lagugné-Labarthet
Enhanced Rates Of Photoinduced Molecular Orientation In A Series Of Molecular Glassy Thin Films., Kristen E Snell, Renjie Hou, Eléna Ishow, François Lagugné-Labarthet
Chemistry Publications
Photoinduced orientation in a series of molecular glasses made of small push-pull azo derivatives is dynamically investigated for the first time. Birefringence measurements at 632.8 nm are conducted with a temporal resolution of 100 ms to probe the fast rate of the azo orientation induced under polarized light and its temporal stability over several consecutive cycles. To better evaluate the influence of the azo chemical substituents and their electronic properties on the orientation of the whole molecule, a series of push-pull azo derivatives involving a triphenylaminoazo core substituted with distinct electron-withdrawing moieties is studied. All resulting thin films are probed …
Synthesis And Characterization Of Conjugated/Cross-Conjugated Benzene-Bridged Boron Difluoride Formazanate Dimers, Stephanie M. Barbon, Jacquelyn T. Price, Umesh Yogarajah, Joe Gilroy
Synthesis And Characterization Of Conjugated/Cross-Conjugated Benzene-Bridged Boron Difluoride Formazanate Dimers, Stephanie M. Barbon, Jacquelyn T. Price, Umesh Yogarajah, Joe Gilroy
Chemistry Publications
One of the most common strategies for the production of molecular materials with optical properties in the far-red/near-IR regions of the electromagnetic spectrum is their incorporation into dimeric architectures. In this paper, we describe the synthesis and characterization (1H, 11B, 13C and 19F NMR spectroscopy, IR and UV-Vis absorption and emission spectroscopy, mass spectrometry and X-ray crystallography) of the first examples of boron difluoride (BF2) formazanate dimers. Specifically, the properties of meta- and para-substituted benzene-bridged dimers p-10 and m-10 were compared to closely related boron difluoride triphenyl formazanate complex …
Synthesis Of Tetrahydro-1,2-Oxazines And Pyrrolidines Via Cycloadditions Of Donor-Acceptor Cyclobutanes And Nitrosoarenes, Naresh Vemula, Brian L Pagenkopf
Synthesis Of Tetrahydro-1,2-Oxazines And Pyrrolidines Via Cycloadditions Of Donor-Acceptor Cyclobutanes And Nitrosoarenes, Naresh Vemula, Brian L Pagenkopf
Chemistry Publications
During efforts to expand the scope of Lewis-acid-catalyzed [4+2] cycloaddition between donor–acceptor cyclobutanes and nitrosoarenes, an unexpected formation of pyrrolidine products was discovered when 50 mol-% of MgI2 was used as a Lewis acid. It was also observed that the electronics of the nitrosoarene and judicious selection of the Lewis acid catalyst have a profound effect on the regioselectivity of the reaction.
The Effect Of Extended Π-Conjugation On The Spectroscopic And Electrochemical Properties Of Boron Difluoride Formazanate Complexes, Stephanie M. Barbon, Viktor N. Staroverov, Joe Gilroy
The Effect Of Extended Π-Conjugation On The Spectroscopic And Electrochemical Properties Of Boron Difluoride Formazanate Complexes, Stephanie M. Barbon, Viktor N. Staroverov, Joe Gilroy
Chemistry Publications
The effect of extended π-conjugation on the spectroscopic and electrochemical properties of boron difluoride (BF2) formazanate complexes was studied by the systematic comparison of phenyl- and naphthyl-substituted derivatives. Each of the BF2 complexes described was characterized by 1H, 13C, 11B and 19F NMR spectroscopy, cyclic voltammetry, infrared spectroscopy, UV-vis absorption and emission spectroscopy and mass spectrometry. X-ray crystallography and electronic structure calculations were used to rationalize the trends observed, including direct comparison of 3-cyano-, 3-nitro- and 3-phenyl-substituted BF2 formazanate complexes. In all cases, the wavelength of maximum absorption and emission were red-shifted …
Computational Study Of The Visible Spectrum Of Curcumin's Protonation States, Peter Braegelmann, Joseph D. Alia
Computational Study Of The Visible Spectrum Of Curcumin's Protonation States, Peter Braegelmann, Joseph D. Alia
Chemistry Publications
Curcumin, the main dye in the important Indian spice turmeric, has received much attention recently for its potential anti-cancer and anti-Alzheimer properties.1 Our study computes the thermodynamics and spectroscopic properties of curcumin’s various protonation states using several methods and compares the results to experiment. M06/3-21G* gave the best thermodynamic results, while M06 with 3-21G* and 6-31G* gave good spectroscopic results for the neutral and dianionic forms of curcumin. However, applying diffuse functions appears to be necessary for the trianionic form. Interestingly, M06 and B3LYP with 6-31+G* gave good spectroscopic results for the singly anionic form.
Study Of The Protonation States Of The Curcumin Molecule And Their Visible Absorption Spectra In Aqueous Solution Using M06, Smd, And Tddft And Compared To Experiment, Joseph D. Alia, Peter Braegelmann, Timothy Roettgen, Hannah Goemann
Study Of The Protonation States Of The Curcumin Molecule And Their Visible Absorption Spectra In Aqueous Solution Using M06, Smd, And Tddft And Compared To Experiment, Joseph D. Alia, Peter Braegelmann, Timothy Roettgen, Hannah Goemann
Chemistry Publications
Curcumin, the primary natural dye from the spice turmeric, has been of recent interest due to its possible health benefits as an antioxidant and possible anti cancer and anti Alzheimer's properties. Limited solubility and instability in water are of primary importance when considering curcumin's possible uses as a pharmaceutical. DFT computations were carried out using B3LYP and MO6 density functionals and the SMD solvent model for water. TDDFT computations were carried out on geometries optimized in water as described by the SMD solvent model. It is found that M06 with the 3-21G* basis set and SMD solvent model gives accurate …
Au Nanostructured Surfaces For Electrochemical And Localized Surface Plasmon Resonance-Based Monitoring Of Α-Synuclein-Small Molecule Interactions., Xin R Cheng, Gregory Q Wallace, François Lagugné-Labarthet, Kagan Kerman
Au Nanostructured Surfaces For Electrochemical And Localized Surface Plasmon Resonance-Based Monitoring Of Α-Synuclein-Small Molecule Interactions., Xin R Cheng, Gregory Q Wallace, François Lagugné-Labarthet, Kagan Kerman
Chemistry Publications
In this proof-of-concept study, the fabrication of novel Au nanostructured indium tin oxide (Au-ITO) surfaces is described for the development of a dual-detection platform with electrochemical and localized surface plasmon resonance (LSPR)-based biosensing capabilities. Nanosphere lithography (NSL) was applied to fabricate Au-ITO surfaces. Oligomers of α-synuclein (αS) were covalently immobilized to determine the electrochemical and LSPR characteristics of the protein. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were performed using the redox probe [Fe(CN)6](3-/4-) to detect the binding of Cu(II) ions and (-)-epigallocatechin-3-gallate (EGCG) to αS on the Au-ITO surface. Electrochemical and LSPR data were complemented by Thioflavin-T (ThT) …
Au Nanostructured Surfaces For Electrochemical And Localized Surface Plasmon Resonance-Based Monitoring Of Α-Synuclein-Small Molecule Interactions., Xin R Cheng, Gregory Q Wallace, François Lagugné-Labarthet, Kagan Kerman
Au Nanostructured Surfaces For Electrochemical And Localized Surface Plasmon Resonance-Based Monitoring Of Α-Synuclein-Small Molecule Interactions., Xin R Cheng, Gregory Q Wallace, François Lagugné-Labarthet, Kagan Kerman
Chemistry Publications
In this proof-of-concept study, the fabrication of novel Au nanostructured indium tin oxide (Au-ITO) surfaces is described for the development of a dual-detection platform with electrochemical and localized surface plasmon resonance (LSPR)-based biosensing capabilities. Nanosphere lithography (NSL) was applied to fabricate Au-ITO surfaces. Oligomers of α-synuclein (αS) were covalently immobilized to determine the electrochemical and LSPR characteristics of the protein. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were performed using the redox probe [Fe(CN)6](3-/4-) to detect the binding of Cu(II) ions and (-)-epigallocatechin-3-gallate (EGCG) to αS on the Au-ITO surface. Electrochemical and LSPR data were complemented by Thioflavin-T (ThT) …
Genetic Encoding Of The Post-Translational Modification 2-Hydroxyisobutyryl-Lysine, William A. Knight, Thomas A. Cropp
Genetic Encoding Of The Post-Translational Modification 2-Hydroxyisobutyryl-Lysine, William A. Knight, Thomas A. Cropp
Chemistry Publications
We report the synthesis and genetic encoding of a recently discovered posttranslational modification, 2-hydroxyisobutryl-lysine, to the genetic code of E. coli. The production of homogeneous proteins containing this amino acid will facilitate the study of modification in full-length proteins.
Electrolyte Pore/Solution Partitioning By Expanded Grand Canonical Ensemble Monte Carlo Simulation, F. Moucka, D. Bratko, A. Luzar
Electrolyte Pore/Solution Partitioning By Expanded Grand Canonical Ensemble Monte Carlo Simulation, F. Moucka, D. Bratko, A. Luzar
Chemistry Publications
Using a newly developed grand canonical Monte Carlo approach based on fractional exchanges of dissolved ions and water molecules, we studied equilibrium partitioning of both components between laterally extended apolar confinements and surrounding electrolyte solution. Accurate calculations of the Hamiltonian and tensorial pressure components at anisotropic conditions in the pore required the development of a novel algorithm for a self-consistent correction of nonelectrostatic cut-off effects. At pore widths above the kinetic threshold to capillary evaporation, the molality of the salt inside the confinement grows in parallel with that of the bulk phase, but presents a nonuniform width-dependence, being depleted at …
Dynamic Control Of Nanopore Wetting In Water And Saline Solutions Under An Electric Field, D. Vanzo, D. Bratko, A. Luzar
Dynamic Control Of Nanopore Wetting In Water And Saline Solutions Under An Electric Field, D. Vanzo, D. Bratko, A. Luzar
Chemistry Publications
Field-induced nanopore wetting by aqueous solutions, including electrolytes, provides opportunities for a variety of applications. Con!icting porosity requirements have so far precluded direct implementations of a two-way control: the pores have to be su"ciently wide to allow water in#ltration at experimentally relevant voltages but should not exceed the kinetic threshold for spontaneous expulsion in the absence of the #eld. Applicable widths are restricted below a few nanometers. Only a narrow window of #elds and pore geometries can simultaneously satisfy both of the above requirements. Accurate accounts of wetting equilibria and dynamics at nanoscale porosity require molecular level descriptions. Here we …
Salt And Water Uptake In Nanocon!Nement Under Applied Electric Field: An Open Ensemble Monte Carlo Study, F. Moucka, D. Bratko, A. Luzar
Salt And Water Uptake In Nanocon!Nement Under Applied Electric Field: An Open Ensemble Monte Carlo Study, F. Moucka, D. Bratko, A. Luzar
Chemistry Publications
Permeation of electrolytes in nanoporous materials underlies many applications in energy and materials technologies. Wetting of apolar nanopores can be enhanced by electric !eld, attracting water and ions from unperturbed electrolyte bath. We study absorption of water and NaCl in the pores by Expanded Ensemble Grand Canonical Monte Carlo simulation, which implements particle insertions and deletions through incremental changes in particles’ coupling with the system. We determine the uptake of water and ions in the pores, and concomitant changes in pore thermodynamics, as functions of !eld strength in the pore and salinity in the external bath. Pressure increase and reduction …
Tunable 3d Plasmonic Cavity Nanosensors For Surface-Enhanced Raman Spectroscopy With Sub Femtomolar Limit Of Detection, Mohammadali Tabatabei, Mohamadreza Najiminaini, Kiefer Davieau, Bozena Kaminska, Mahi Singh, Jeff Carson, Francois Lagugne-Labarthet
Tunable 3d Plasmonic Cavity Nanosensors For Surface-Enhanced Raman Spectroscopy With Sub Femtomolar Limit Of Detection, Mohammadali Tabatabei, Mohamadreza Najiminaini, Kiefer Davieau, Bozena Kaminska, Mahi Singh, Jeff Carson, Francois Lagugne-Labarthet
Chemistry Publications
Metallic nanohole arrays (NHAs) with a high hole density have emerged with potential applications for surface-enhanced Raman spectroscopy (SERS) including the detection of analytes at ultra-low concentrations. However, these NHA structures generally yield weak localized surface plasmon resonance (LSPR) which is a prerequisite for SERS measurements. In this work, a compact three-dimensional (3D) tunable plasmonic cavity with extraordinary optical transmission properties serves as a molecular sensor with sub-femtomolar detection. The 3D nanosensor consists of a gold film containing a NHA with an underlying cavity and a gold nanocone array at the bottom of the cavity. These nanosensors provide remarkable surface …