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Marquette University

2015

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Articles 1 - 30 of 85

Full-Text Articles in Physical Sciences and Mathematics

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 Dec 2015

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 …


Maximal Class P-Groups With Large Character Degree Gaps, Michael Slattery Dec 2015

Maximal Class P-Groups With Large Character Degree Gaps, Michael Slattery

Mathematics, Statistics and Computer Science Faculty Research and Publications

In Mann (More on normally monomial p-groups, 2015), he proves some bounds on the size of gaps between character degrees of maximal class p-groups. In this note we construct a family of examples that shows that one of these bounds is sharp.


Unveiling The Crucial Intermediates In Androgen Production, Piotr J. Mak, Michael C. Gregory, Ilia G. Denisov, Stephen G. Sligar, James R. Kincaid Dec 2015

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 …


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 Dec 2015

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 Nov 2015

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 …


Reversible Peg Solitaire On Graphs, John Engbers, Christopher Stocker Nov 2015

Reversible Peg Solitaire On Graphs, John Engbers, Christopher Stocker

Mathematics, Statistics and Computer Science Faculty Research and Publications

The game of peg solitaire on graphs was introduced by Beeler and Hoilman in 2011. In this game, pegs are initially placed on all but one vertex of a graph G. If xyz forms a path in G and there are pegs on vertices x and y but not z, then a jump places a peg on z and removes the pegs from x and y. A graph is called solvable if, for some configuration of pegs occupying all but one vertex, some sequence of jumps leaves a single peg. We study the game of reversible peg …


The Homo Nodal Arrangement In Polychromophoric Molecules And Assemblies Controls The Interchromophoric Electronic Coupling, Marat R. Talipov, Tushar Navale, Rajendra Rathore Nov 2015

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 …


The Kumaraswamy Marshal-Olkin Family Of Distributions, Morad Alizadeh, M. H. Tahir, Gauss M. Cordeiro, M. Mansoor, Muhammad Zubair, Gholamhossein Hamedani Oct 2015

The Kumaraswamy Marshal-Olkin Family Of Distributions, Morad Alizadeh, M. H. Tahir, Gauss M. Cordeiro, M. Mansoor, Muhammad Zubair, Gholamhossein Hamedani

Mathematics, Statistics and Computer Science Faculty Research and Publications

We introduce a new family of continuous distributions called the Kumaraswamy Marshal-Olkin generalized family of distributions. We study some mathematical properties of this family. Its density function is symmetrical, left-skewed, right-skewed and reversed-J shaped, and has constant, increasing, decreasing, upside-down bathtub, bathtub and S-shaped hazard rate. We present some special models and investigate the asymptotics and shapes of the family. We derive a power series for the quantile function and obtain explicit expressions for the moments, generating function, mean deviations, two types of entropies and order statistics. Some useful characterizations of the family are also proposed. The method of maximum …


Sequencing Of 15 622 Gene-Bearing Bacs Clarifies The Gene-Dense Regions Of The Barley Genome, María Muñoz-Amatriaín, Stefano Lonardi, Mingcheng Luo, Kavitha Madishetty, Jan T. Svensson, Matthew J. Moscou, Steve Wanamaker, Tao Jiang, Andris Kleinhofs, Gary J. Muehlbauer, Roger P. Wise, Nils Stein, Shane Ma, Edmundo Rodriguez, Dave Kudrna, Prasanna R. Bhat, Shiaoman Chao, Pascal Condamine, Shane Heinen, Josh Resnik, Rod Wing, Heather N. Witt, Matthew Alpert, Marco Beccuti, Serdar Bozdag, Francesca Cordero, Hamid Mirebrahim, Rachid Ounit, Yonghui Wu, Frank You, Jie Zheng, Hana Simková, Jaroslav Dolezel, Jane Grimwood, Jeremy Schmutz, Denisa Duma, Lothar Altschmied, Tom Blake, Phil Bregitzer, Laurel Cooper, Muharrem Dilbirligi, Anders Falk, Leila Feiz, Andreas Graner, Perry Gustafson, Patrick M. Hayes, Peggy Lemaux, Jafar Mammadov, Timothy J. Close Oct 2015

Sequencing Of 15 622 Gene-Bearing Bacs Clarifies The Gene-Dense Regions Of The Barley Genome, María Muñoz-Amatriaín, Stefano Lonardi, Mingcheng Luo, Kavitha Madishetty, Jan T. Svensson, Matthew J. Moscou, Steve Wanamaker, Tao Jiang, Andris Kleinhofs, Gary J. Muehlbauer, Roger P. Wise, Nils Stein, Shane Ma, Edmundo Rodriguez, Dave Kudrna, Prasanna R. Bhat, Shiaoman Chao, Pascal Condamine, Shane Heinen, Josh Resnik, Rod Wing, Heather N. Witt, Matthew Alpert, Marco Beccuti, Serdar Bozdag, Francesca Cordero, Hamid Mirebrahim, Rachid Ounit, Yonghui Wu, Frank You, Jie Zheng, Hana Simková, Jaroslav Dolezel, Jane Grimwood, Jeremy Schmutz, Denisa Duma, Lothar Altschmied, Tom Blake, Phil Bregitzer, Laurel Cooper, Muharrem Dilbirligi, Anders Falk, Leila Feiz, Andreas Graner, Perry Gustafson, Patrick M. Hayes, Peggy Lemaux, Jafar Mammadov, Timothy J. Close

Mathematics, Statistics and Computer Science Faculty Research and Publications

Barley (Hordeum vulgare L.) possesses a large and highly repetitive genome of 5.1 Gb that has hindered the development of a complete sequence. In 2012, the International Barley Sequencing Consortium released a resource integrating whole-genome shotgun sequences with a physical and genetic framework. However, because only 6278 bacterial artificial chromosome (BACs) in the physical map were sequenced, fine structure was limited. To gain access to the gene-containing portion of the barley genome at high resolution, we identified and sequenced 15 622 BACs representing the minimal tiling path of 72 052 physical-mapped gene-bearing BACs. This generated ~1.7 Gb of genomic …


Lpcoms: Towards A Low Power Wireless Smart-Shoe System For Gait Analysis In People With Disabilities, Ishmat Zerin Oct 2015

Lpcoms: Towards A Low Power Wireless Smart-Shoe System For Gait Analysis In People With Disabilities, Ishmat Zerin

Master's Theses (2009 -)

Gait analysis using smart sensor technology is an important medical diagnostic process and has many applications in rehabilitation, therapy and exercise training. In this thesis, we present a low power wireless smart-shoe system (LPcomS) to analyze different functional postures and characteristics of gait while walking. We have designed and implemented a smart-shoe with a Bluetooth communication module to unobtrusively collect data using smartphone in any environment. With the design of a shoe insole equipped with four pressure sensors, the foot pressure is been collected, and those data are used to obtain accurate gait pattern of a patient. With our proposed …


Students’ Perceptions Of And Responses To Teaching Assistant And Peer Feedback, Kelsey Joy Rodgers, Aladar K. Horvath, Hyunyi Jung, Amanda S. Fry, Heidi A. Diefes-Dux, Monica E. Cardella Oct 2015

Students’ Perceptions Of And Responses To Teaching Assistant And Peer Feedback, Kelsey Joy Rodgers, Aladar K. Horvath, Hyunyi Jung, Amanda S. Fry, Heidi A. Diefes-Dux, Monica E. Cardella

Mathematics, Statistics and Computer Science Faculty Research and Publications

Authentic open-ended problems are increasingly appearing in university classrooms at all levels. Formative feedback that leads to learning and improved student work products is a challenge, particularly in large enrollment courses. This is a case study of one first-year engineering student team’s experience with teaching assistant and peer feedback during a series of open-ended mathematical modeling problems called Model-Eliciting Activities. The goal of this study was to gain deep insight into the interactions between students, feedback providers, and written feedback by examining one team’s perceptions of the feedback they received and the changes they made to their solutions based on …


Towards Mhealth Solutions For Asthma Patients, Nahid Negar Oct 2015

Towards Mhealth Solutions For Asthma Patients, Nahid Negar

Master's Theses (2009 -)

With the recent, rapid growth in mobile-computing technology, mobile health (mHealth) is becoming a popular research topic. mHealth is one of several examples of how using technology in the health sector is being more advanced every day. mHealth is being applied to the care of a broad spectrum of diseases from acute to chronic, such as the flu, asthma, and cancer. Due to the easy-to-understand and friendly user interfaces, mobility and cost effectiveness; a mobile application can be a powerful tool to collect patient information. Asthma is a common disease around the globe. Collecting the proper symptom, trigger, peak-flow and …


Anaerobic Membrane Bioreactors To Treat Municipal Wastewater At Ambient Temperatures, Matthew D. Seib Oct 2015

Anaerobic Membrane Bioreactors To Treat Municipal Wastewater At Ambient Temperatures, Matthew D. Seib

Dissertations (1934 -)

Anaerobic biotechnology is viewed as a sustainable alternative to aerobic biotechnology for municipal wastewater recovery. However, anaerobic processes have not been successful in cold climates. Past examples have not been able to meet low organic effluent concentrations, or have failed due to biomass washout resulting from low temperature operation and short hydraulic residence time. Recently, the anaerobic membrane bioreactor (AnMBR) has been shown to achieve low effluent organic concentrations and maintain stable anaerobic biomass. However, shortcomings have included high energy demands for membrane operation and poor understanding of microbial community structures within AnMBRs. This dissertation describes efforts to improve AnMBRs …


Mixed Valent Metal Pincer Complexes And Reactivity Of Metal Complexes Of Extended Pincer Ligands, Jeewantha Sampath Hewage Oct 2015

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 Oct 2015

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 Oct 2015

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 …


Computational Approaches For Remote Monitoring Of Symptoms And Activities, Ferdaus Kawsar Oct 2015

Computational Approaches For Remote Monitoring Of Symptoms And Activities, Ferdaus Kawsar

Dissertations (1934 -)

We now have a unique phenomenon where significant computational power, storage, connectivity, and built-in sensors are carried by many people willingly as part of their life style; two billion people now use smart phones. Unique and innovative solutions using smart phones are motivated by rising health care cost in both the developed and developing worlds. In this work, development of a methodology for building a remote symptom monitoring system for rural people in developing countries has been explored. Design, development, deployment, and evaluation of e-ESAS is described. The system’s performance was studied by analyzing feedback from users. A smart phone …


With Vibrationally Excited Thiophosgene Molecule And Double-Well Ion Traps, Dmytro Shyshlov Oct 2015

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 Oct 2015

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 …


An Analytical Method For Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles, Zachary R. Osner, Richard C. Holz, Daniel P. Becker Sep 2015

An Analytical Method For Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles, Zachary R. Osner, Richard C. Holz, Daniel P. Becker

Chemistry Faculty Research and Publications

Cyclotriveratrylene-oxime (CTV-oxime) derivatives that terminate with a dithiolate linker were synthesized enabling the supramolecular scaffold to adhere to gold nanoparticles (AuNPs) with the bowl-shaped cavity of the CTV scaffold exposed for utilization in host–guest chemistry. Exposure of these CTV functionalized AuNPs to varying concentrations of di- and trivalent metal cations resulted in the formation of large CTV-AuNP polymeric clusters and an accompanying a shift in the plasmon resonance. These interactions between the CTV-AuNPs and the metal cations in solution provides proof-of-concept that supramolecular functionalized AuNPs can be used as a simple and straightforward, on-site detection system for toxic metal cations …


The Kumaraswamy-G Poisson Family Of Distributions, Manoel Wallace A. Ramos, Pedro Rafael D. Marinho, Gauss M. Cordeiro, Ronaldo V. Da Silva, Gholamhossein Hamedani Sep 2015

The Kumaraswamy-G Poisson Family Of Distributions, Manoel Wallace A. Ramos, Pedro Rafael D. Marinho, Gauss M. Cordeiro, Ronaldo V. Da Silva, Gholamhossein Hamedani

Mathematics, Statistics and Computer Science Faculty Research and Publications

For any baseline continuous G distribution, we propose a new generalized family called the Kumaraswamy-G Poisson (denoted with the prefix “Kw-GP”) with three extra positive parameters. Some special distributions in the new family such as the Kw-Weibull Poisson, Kw-gamma Poisson and Kw-beta Poisson distributions are introduced. We derive some mathematical properties of the new family including the ordinary moments, generating function and order statistics. The method of maximum likelihood is used to fit the distributions in the new family. We illustrate its potentiality by means of an application to a real data set.


The Ras G Domain Lacks The Intrinsic Propensity To Form Dimers, Elizaveta A. Kovrigina, Azamat R. Galiakhmetov, Evgueni Kovriguine Sep 2015

The Ras G Domain Lacks The Intrinsic Propensity To Form Dimers, Elizaveta A. Kovrigina, Azamat R. Galiakhmetov, Evgueni Kovriguine

Chemistry Faculty Research and Publications

Ras GTPase is a molecular switch controlling a number of cellular pathways including growth, proliferation, differentiation, and apoptosis. Recent reports indicated that Ras undergoes dimerization at the membrane surface through protein-protein interactions. If firmly established this property of Ras would require profound reassessment of a large amount of published data and modification of the Ras signaling paradigm. One proposed mechanism of dimerization involves formation of salt bridges between the two GTPase domains (G domains) leading to formation of a compact dimer as observed in Ras crystal structures. In this work, we interrogated the intrinsic ability of Ras to self-associate in …


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 Lindeman, Rajendra Rathore Sep 2015

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 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/Eox relationship 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’ …


Identification Of Inhibitors That Target Dual-Specificity Phosphatase 5 Provide New Insights Into The Binding Requirements For The Two Phosphate Pockets, Terrence S. Neumann, Elise A. Span, Kelsey S. Kalous, Robert D. Bongard, Adam Gastonguay, Michael A. Lepley, Raman G. Kutty, Jaladhi Nayak, Chris Bohl, Rachel G. Lange, Majher I. Sarker, Marat R. Talipov, Rajendra Rathore, Ramani Ramchandran, Daniel S. Sem Aug 2015

Identification Of Inhibitors That Target Dual-Specificity Phosphatase 5 Provide New Insights Into The Binding Requirements For The Two Phosphate Pockets, Terrence S. Neumann, Elise A. Span, Kelsey S. Kalous, Robert D. Bongard, Adam Gastonguay, Michael A. Lepley, Raman G. Kutty, Jaladhi Nayak, Chris Bohl, Rachel G. Lange, Majher I. Sarker, Marat R. Talipov, Rajendra Rathore, Ramani Ramchandran, Daniel S. Sem

Chemistry Faculty Research and Publications

Background: Dual-specificity phosphatase-5 (DUSP5) plays a central role in vascular development and disease. We present a p-nitrophenol phosphate (pNPP) based enzymatic assay to screen for inhibitors of the phosphatase domain of DUSP5.

Methods: pNPP is a mimic of the phosphorylated tyrosine on the ERK2 substrate (pERK2) and binds the DUSP5 phosphatase domain with a Km of 7.6 ± 0.4 mM. Docking followed by inhibitor verification using the pNPP assay identified a series of polysulfonated aromatic inhibitors that occupy the DUSP5 active site in the region that is likely occupied by the dual-phosphorylated ERK2 substrate tripeptide (pThr-Glu-pTyr). Secondary assays …


Inhibition Of The Dape-Encoded N-Succinyl- ʟ, ʟ-Diaminopimelic Acid Desuccinylase From Neisseria Meningitidis By ʟ-Captopril, Anna Starus, Boguslaw Nocek, Brian Bennett, James A. Larrabee, Daniel L. Shaw, Wisath Sae-Lee, Marie T. Russo, Danuta M. Gillner, Magdalena Makowska-Grzyska, Andzrej Joachimiak, Richard C. Holz Aug 2015

Inhibition Of The Dape-Encoded N-Succinyl- ʟ, ʟ-Diaminopimelic Acid Desuccinylase From Neisseria Meningitidis By ʟ-Captopril, Anna Starus, Boguslaw Nocek, Brian Bennett, James A. Larrabee, Daniel L. Shaw, Wisath Sae-Lee, Marie T. Russo, Danuta M. Gillner, Magdalena Makowska-Grzyska, Andzrej Joachimiak, Richard C. Holz

Physics Faculty Research and Publications

Binding of the competitive inhibitor ʟ-captopril to the dapE-encoded N-succinyl-ʟ, ʟ-diaminopimelic acid desuccinylase from Neisseria meningitidis (NmDapE) was examined by kinetic, spectroscopic, and crystallographic methods. ʟ-Captopril, an angiotensin-converting enzyme (ACE) inhibitor, was previously shown to be a potent inhibitor of the DapE from Haemophilus influenzae (HiDapE) with an IC50 of 3.3 μM and a measured Ki of 1.8 μM and displayed a dose-responsive antibiotic activity toward Escherichia coli. ʟ-Captopril is also a competitive inhibitor of NmDapE with a Ki of 2.8 μM. To examine the nature of the interaction …


Di- And Trinuclear Mixed-Valence Copper Amidinate Complexes From Reduction Of Iodine, Andrew C. Lane, Charles L. Barnes, William E. Antholine, Denan Wang, Adam T. Fiedler, Justin R. Walensky Aug 2015

Di- And Trinuclear Mixed-Valence Copper Amidinate Complexes From Reduction Of Iodine, Andrew C. Lane, Charles L. Barnes, William E. Antholine, Denan Wang, Adam T. Fiedler, Justin R. Walensky

Chemistry Faculty Research and Publications

Molecular examples of mixed-valence copper complexes through chemical oxidation are rare but invoked in the mechanism of substrate activation, especially oxygen, in copper-containing enzymes. To examine the cooperative chemistry between two metals in close proximity to each other we began studying the reactivity of a dinuclear Cu(I) amidinate complex. The reaction of [(2,6-Me2C6H3N)2C(H)]2Cu2, 1, with I2 in tetrahydrofuran (THF), CH3CN, and toluene affords three new mixed-valence copper complexes [(2,6-Me2C6H3N)2C(H)]2Cu2(μ2-I3)(THF)2, 2, [(2,6-Me2C6H3N)2C(H)]2Cu2(μ2-I) (NCMe)2, 3, and [(2,6-Me2C6H3N)2C(H)]3Cu3(μ3-I)2, 4, respectively. The first two compounds were characterized by UV-vis and electron paramagnetic resonance spectroscopies, and their molecular structure was determined by X-ray crystallography. Both …


Scope And Mechanistic Analysis For Chemoselective Hydrogenolysis Of Carbonyl Compounds Catalyzed By A Cationic Ruthenium Hydride Complex With A Tunable Phenol Ligand, Nishantha Kumara Kalutharage, Chae S. Yi Aug 2015

Scope And Mechanistic Analysis For Chemoselective Hydrogenolysis Of Carbonyl Compounds Catalyzed By A Cationic Ruthenium Hydride Complex With A Tunable Phenol Ligand, Nishantha Kumara Kalutharage, Chae S. Yi

Chemistry Faculty Research and Publications

A cationic ruthenium hydride complex, [(C6H6)(PCy3)(CO)RuH]+BF4 (1), with a phenol ligand was found to exhibit high catalytic activity for the hydrogenolysis of carbonyl compounds to yield the corresponding aliphatic products. The catalytic method showed exceptionally high chemoselectivity toward the carbonyl reduction over alkene hydrogenation. Kinetic and spectroscopic studies revealed a strong electronic influence of the phenol ligand on the catalyst activity. The Hammett plot of the hydrogenolysis of 4-methoxyacetophenone displayed two opposite linear slopes for the catalytic system 1/p-X-C6H4OH (ρ = …


Generation Of Molecular Complexity From Cyclooctatetraene: Preparation Of Aminobicyclo[5.1.0]Octitols, Mohamed F. El-Mansy, Matthew Flister, Sergey Lindeman, Kelsey S. Kalous, Daniel S. Sem, William Donaldson Jul 2015

Generation Of Molecular Complexity From Cyclooctatetraene: Preparation Of Aminobicyclo[5.1.0]Octitols, Mohamed F. El-Mansy, Matthew Flister, Sergey Lindeman, Kelsey S. Kalous, Daniel S. Sem, William Donaldson

Chemistry Faculty Research and Publications

A series of eight stereoisomeric N-(tetrahydroxy bicyclo-[5.1.0]oct-2S*-yl)phthalimides were prepared in one to four steps from N-(bicyclo[5.1.0]octa-3,5-dien-2-yl)phthalimide (±)-7, which is readily available from cyclooctatetraene (62 % yield). The structural assignments of the stereoisomers were established by 1H NMR spectral data as well as X-ray crystal structures for certain members. The outcomes of several epoxydiol hydrolyses, particularly ring contraction and enlargement, are of note. The isomeric phthalimides as well as the free amines did not exhibit β-glucosidase inhibitory activity at a concentration of less than 100 μM.


Crystal Structure Of Cis-2-(2-Carboxycyclopropyl)-Glycine (Ccg-Iii) Monohydrate, Sergey V. Lindeman, Nathaniel J. Wallock, William A. Donaldson Jul 2015

Crystal Structure Of Cis-2-(2-Carboxycyclopropyl)-Glycine (Ccg-Iii) Monohydrate, Sergey V. Lindeman, Nathaniel J. Wallock, William A. Donaldson

Chemistry Faculty Research and Publications

The title compound, C6H9NO4·H2O [systematic name: (αR,1R,2S)-rel-α-amino-2-carb­oxy­cyclo­propane­acetic acid monohydrate], crystallizes with two organic mol­ecules and two water mol­ecules in the asymmetric unit. The space group is P21 and the organic mol­ecules are enanti­omers, thus this is an example of a `false conglomerate' with two mol­ecules of opposite handedness in the asymmetric unit (r.m.s. overlay fit = 0.056 Å for one mol­ecule and its inverted partner). Each mol­ecule exists as a zwitterion, with proton transfer from the amino acid carb­oxy­lic acid group to …


Characterizations Of Levy Distribution Via Sub-Independence Of The Random Variables And Truncated Moments, Gholamhossein G. Hamedani, M. Ahsanullah, Seyed Morteza Najibi Jul 2015

Characterizations Of Levy Distribution Via Sub-Independence Of The Random Variables And Truncated Moments, Gholamhossein G. Hamedani, M. Ahsanullah, Seyed Morteza Najibi

Mathematics, Statistics and Computer Science Faculty Research and Publications

The concept of sub-independence is based on the convolution of the distributions of the random variables. It is much weaker than that of independence, but is shown to be sufficient to yield the conclusions of important theorems and results in probability and statistics. It also provides a measure of dissociation between two random variables which is much stronger than uncorrelatedness. Following Ahsanullah and Nevzorov (2014), we present certain characterizations of Levy distribution based on: (i) the sub-independence of the random variables; (ii) a simple relationship between two truncated moments; (iii) conditional expectation of certain function of the random variable. In …