Open Access. Powered by Scholars. Published by Universities.®

Chemistry Commons

Open Access. Powered by Scholars. Published by Universities.®

Chemistry Faculty Publications and Presentations

Discipline
Institution
Keyword
Publication Year

Articles 181 - 210 of 295

Full-Text Articles in Chemistry

Coupling Fast Water Exchange To Slow Molecular Tumbling In Gd3+ Chelates: Why Faster Is Not Always Better, Stefano Avedano, Mauro Botta, Julian Saunders Haigh, Dario L. Lango, Mark Woods Jul 2013

Coupling Fast Water Exchange To Slow Molecular Tumbling In Gd3+ Chelates: Why Faster Is Not Always Better, Stefano Avedano, Mauro Botta, Julian Saunders Haigh, Dario L. Lango, Mark Woods

Chemistry Faculty Publications and Presentations

The influence of dynamics on solution state structure is a widely overlooked consideration in chemistry. Variations in Gd3+ chelate hydration with changing coordination geometry and dissociative water exchange kinetics substantially impact the effectiveness (or relaxivity) of monohydrated Gd3+ chelates as T1-shortening contrast agents for MRI. Theory shows that relaxivity is highly dependent upon the Gd3+–water proton distance (rGdH), and yet this distance is almost never considered as a variable in assessing the relaxivity of a Gd3+ chelate as a potential contrast agent. The consequence of this omission can be seen when considering …


Identification Of Cisplatin-Binding Proteins Using Agarose Conjugates Of Platinum Compounds, Takatoshi Karasawa, Martha Sibrian-Vazquez, Robert M. Strongin, Peter S. Steyger Jun 2013

Identification Of Cisplatin-Binding Proteins Using Agarose Conjugates Of Platinum Compounds, Takatoshi Karasawa, Martha Sibrian-Vazquez, Robert M. Strongin, Peter S. Steyger

Chemistry Faculty Publications and Presentations

Cisplatin is widely used as an antineoplastic drug, but its ototoxic and nephrotoxic side-effects, as well as the inherent or acquired resistance of some cancers to cisplatin, remain significant clinical problems. Cisplatin’s selectivity in killing rapidly proliferating cancer cells is largely dependent on covalent binding to DNA via cisplatin’s chloride sites that had been aquated. We hypothesized that cisplatin’s toxicity in slowly proliferating or terminally differentiated cells is primarily due to drug-protein interactions, instead of drug-DNA binding. To identify proteins that bind to cisplatin, we synthesized two different platinum-agarose conjugates, one with two amino groups and another with two chlorides …


Picture Of A Chelate In Exchange: The Crystal Structure Of Nahodotma, A 'Semi'-Hydrated Chelate, Katherine M. Payne, Edward J. Valente, Silvio Aime, Mauro Botta, Mark Woods Feb 2013

Picture Of A Chelate In Exchange: The Crystal Structure Of Nahodotma, A 'Semi'-Hydrated Chelate, Katherine M. Payne, Edward J. Valente, Silvio Aime, Mauro Botta, Mark Woods

Chemistry Faculty Publications and Presentations

Crystallography generally only provides static structural information. This can render it an ineffective technique for probing dynamic solution state processes. A crystal of HoDOTMA affords unique structures that effectively represent that of a lanthanide tetra-acetate chelate mid-way through the water exchange process.


Dimethyl Sulfoxide (Dmso) Exacerbates Cisplatin-Induced Sensory Hair Cell Death In Zebrafish (Danio Rerio), Phillip M. Uribe, Melissa A. Mueller, Julia S. Gleichman, Matthew D. Kramer, Qi Wang, Martha Sibrian-Vazquez, Robert M. Strongin, Peter S. Steyger, Douglas A. Cotanche, Jonathan I. Matsui Feb 2013

Dimethyl Sulfoxide (Dmso) Exacerbates Cisplatin-Induced Sensory Hair Cell Death In Zebrafish (Danio Rerio), Phillip M. Uribe, Melissa A. Mueller, Julia S. Gleichman, Matthew D. Kramer, Qi Wang, Martha Sibrian-Vazquez, Robert M. Strongin, Peter S. Steyger, Douglas A. Cotanche, Jonathan I. Matsui

Chemistry Faculty Publications and Presentations

Inner ear sensory hair cells die following exposure to aminoglycoside antibiotics or chemotherapeutics like cisplatin, leading to permanent auditory and/or balance deficits in humans. Zebrafish (Danio rerio) are used to study drug-induced sensory hair cell death since their hair cells are similar in structure and function to those found in humans. We developed a cisplatin dose-response curve using a transgenic line of zebrafish that expresses membrane-targeted green fluorescent protein under the control of the Brn3c promoter/enhancer. Recently, several small molecule screens have been conducted using zebrafish to identify potential pharmacological agents that could be used to protect sensory hair cells …


Aqueous Red-Emitting Silicon Nanoparticles For Cellular Imaging: Consequences Of Protecting Against Surface Passivation By Hydroxide And Water For Stable Red Emission, Sheng-Kuei Chiu, Beth Ann Manhat, William J.I. Debenedetti, Anna L. Brown, Katye Fichter, Tania Vu, Micah Eastman, Jun Jiao, Andrea Mitchell Goforth Jan 2013

Aqueous Red-Emitting Silicon Nanoparticles For Cellular Imaging: Consequences Of Protecting Against Surface Passivation By Hydroxide And Water For Stable Red Emission, Sheng-Kuei Chiu, Beth Ann Manhat, William J.I. Debenedetti, Anna L. Brown, Katye Fichter, Tania Vu, Micah Eastman, Jun Jiao, Andrea Mitchell Goforth

Chemistry Faculty Publications and Presentations

Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis and surface modification strategy that protects Si NPs and preserves red photoluminescence (PL) in water for more than 6 mo. The Si NPs were synthesized via high temperature reaction, liberated from an oxide matrix, and functionalized via hydrosilylation to yield hydrophobic particles. The hydrophobic Si NPs were phase transferred to water using the surfactant cetyltrimethylammonium bromide (CTAB) with retention of red PL. CTAB apparently serves a double role …


Evolution Of Multispectral Aerosol Optical Properties In A Biogenically-Influenced Urban Environment During The Cares Campaign, Madhu Gyawali, W. Patrick Arnott, Rahul A. Zaveri, C. Song, Mikhail Pekour, B. Flowers, Manvendra K. Dubey, Ari Setyan, Qi Zhang, Joseph Harworth, James Gregory Radney, Dean B. Atkinson, S. China, Claudio Mazzoleni, Kyle Gorkowski, R. Subramanian, B. Tom Jobson, Hans Moosmüller Jan 2013

Evolution Of Multispectral Aerosol Optical Properties In A Biogenically-Influenced Urban Environment During The Cares Campaign, Madhu Gyawali, W. Patrick Arnott, Rahul A. Zaveri, C. Song, Mikhail Pekour, B. Flowers, Manvendra K. Dubey, Ari Setyan, Qi Zhang, Joseph Harworth, James Gregory Radney, Dean B. Atkinson, S. China, Claudio Mazzoleni, Kyle Gorkowski, R. Subramanian, B. Tom Jobson, Hans Moosmüller

Chemistry Faculty Publications and Presentations

Ground-based aerosol measurements made in June 2010 within Sacramento urban area (site T0) and at a 40-km downwind location (site T1) in the forested Sierra Nevada foothills area are used to investigate the evolution of multispectral optical properties as the urban aerosols aged and interacted with biogenic emissions. Along with black carbon and non-refractory aerosol mass and composition observations, spectral absorption (abs), scattering (sca), and extinction (ext) coefficients for wavelengths ranging from 355 to 1064nm were measured at both sites using photoacoustic (PA) instruments with integrating nephelometers and using cavity ring-down (CRD) instruments. The …


Robust Visible Light Photoswitching With Ortho-Thiol Substituted Azobenzenes, Subhas Samanta, Theresa M. Mccormick, Simone K. Schmidt, Dwight S. Seferos, G. Andrew Woolley Jan 2013

Robust Visible Light Photoswitching With Ortho-Thiol Substituted Azobenzenes, Subhas Samanta, Theresa M. Mccormick, Simone K. Schmidt, Dwight S. Seferos, G. Andrew Woolley

Chemistry Faculty Publications and Presentations

Introduction of S-ethyl groups in all four ortho positions of azobenzene prevents reduction of the azo group by intracellular glutathione, while enhancing the absorptivity to ∼10000 M−1 cm−1 in the blue and green regions of the visible spectrum. cis-to-trans isomerization occurs thermally on the minutes timescale. Further, this substitution pattern permits switching with red light, a color that is more penetrating through biological tissues than other parts of the visible spectrum.


Differential Effects Of The Hydrophobic Surfactant Proteins On The Formation Of Inverse Bicontinuous Cubic Phases, Mariya Chavarha, Ryan W. Loney, Kamlesh Kumar, Shankar B. Rananavare, Stephen B. Hall Nov 2012

Differential Effects Of The Hydrophobic Surfactant Proteins On The Formation Of Inverse Bicontinuous Cubic Phases, Mariya Chavarha, Ryan W. Loney, Kamlesh Kumar, Shankar B. Rananavare, Stephen B. Hall

Chemistry Faculty Publications and Presentations

Prior studies have shown that the biological mixture of the two hydrophobic surfactant proteins, SP-B and SP-C, produces faster adsorption of the surfactant lipids to an air/water interface, and that they induce 1-palmitoyl-2-oleoyl phosphatidylethanolamine (POPE) to form inverse bicontinuous cubic phases. SP-B has a much greater effect than SP-C on adsorption. If the two proteins induce formation of the bicontinuous structures and faster adsorption by similar mechanisms, then they should also have differential ability to form the cubic phases. To test this hypothesis, we measured small angle X-ray scattering on the individual proteins combined with POPE. SP-B replicated the doserelated …


Progress Toward Red And Near-Infrared (Nir) Emitting Saccharide Sensors, Martha Sibrian-Vazquez, Jorge O. Escobedo, Mark Lowry, Robert M. Strongin Nov 2012

Progress Toward Red And Near-Infrared (Nir) Emitting Saccharide Sensors, Martha Sibrian-Vazquez, Jorge O. Escobedo, Mark Lowry, Robert M. Strongin

Chemistry Faculty Publications and Presentations

Red-shifted and near-infrared (NIR)-active rhodamine analogs and their boronic acid derivatives were synthesized and studied. These latter compounds function as fluorogenic NIR active substrates for sugar sensing. The effects of benzannulation and boronic acid functionalization on fluorophore optical and sensing properties are described.


A Fast Response Highly Selective Probe For The Detection Of Glutathione In Human Blood Plasma, Yixing Guo, Xiaofeng Yang, Lovemore Hakuna, Aabha Barve, Jorge O. Escobedo, Mark Lowry, Robert M. Strongin May 2012

A Fast Response Highly Selective Probe For The Detection Of Glutathione In Human Blood Plasma, Yixing Guo, Xiaofeng Yang, Lovemore Hakuna, Aabha Barve, Jorge O. Escobedo, Mark Lowry, Robert M. Strongin

Chemistry Faculty Publications and Presentations

A fluorescent probe for glutathione (GSH) detection was developed. Our study indicates a possible mechanism which couples a conjugate addition and micelle-catalyzed large membered ring formation/elimination sequence. This method enables excellent selectivity towards GSH over other biological thiols such as cysteine (Cys) and homocysteine (Hcy). The proposed method is precise with a relative standard deviation (R.S.D) lower than 6% (n = 3) and has been successfully applied to determine GSH in human plasma with recoveries between 99.2% and 102.3%.


Chemical Exchange Saturation Transfer Is Unaffected By Modest Changes In Pressure, Benjamin Charles Webber, Christiane A. Carney, Mark Woods Apr 2012

Chemical Exchange Saturation Transfer Is Unaffected By Modest Changes In Pressure, Benjamin Charles Webber, Christiane A. Carney, Mark Woods

Chemistry Faculty Publications and Presentations

ParaCEST (paramagnetic Chemical Exchange Saturation Transfer) agents offer an unparalleled opportunity to perform quantitative molecular imaging by MRI. Agents that can alter the image contrast they generate in response to changes in local environmental parameters such as pH, glucose concentration or lactate concentration can be used ratiometrically to quantitatively describe the local tissue environment. However, when performing such quantitative measurements it is important that the results are not confounded by changes in a second environmental parameter. In vivo pressure varies quite considerably, both through the respiratory cycle and from tissue to tissue (tumors in particular have high interstitial pressures). Since …


Reversed Chloroquine Molecules As A Strategy To Overcome Resistance In Malaria, David H. Peyton Mar 2012

Reversed Chloroquine Molecules As A Strategy To Overcome Resistance In Malaria, David H. Peyton

Chemistry Faculty Publications and Presentations

This short review tells the story of how Reversed Chloroquine drugs (RCQs) were developed. These are hybrid molecules, made by combining the quinoline nucleus from chloroquine (CQ) with moieties which are designed to inhibit efflux via known transporters in the membrane of the digestive vacuole of the malaria parasite. The resulting RCQ drugs can have potencies exceeding that of CQ, while at the same time having physical chemical characteristics that may make them favorable as partner drugs in combination therapies. The need for such novel antimalarial drugs will continue for the foreseeable future.


Functional Promiscuity Of The Cog0720 Family, Gabriela Phillips, Laura L. Grochowski, Shilah Bonnett, Huimin Xu, Marc Bailly, Crysten Haas-Blaby, Basma El Yacoubi, Dirk Iwata-Reuyl, Robert H. White, Valérie De Crécy-Lagard Jan 2012

Functional Promiscuity Of The Cog0720 Family, Gabriela Phillips, Laura L. Grochowski, Shilah Bonnett, Huimin Xu, Marc Bailly, Crysten Haas-Blaby, Basma El Yacoubi, Dirk Iwata-Reuyl, Robert H. White, Valérie De Crécy-Lagard

Chemistry Faculty Publications and Presentations

The biosynthesis of GTP derived metabolites such as tetrahydrofolate (THF), biopterin (BH4), and the modified tRNA nucleosides queuosine (Q) and archaeosine (G+) relies on several enzymes of the Tunnel-fold superfamily. A subset of these proteins include the 6-pyruvoyl-tetrahydropterin (PTPS-II), PTPS-III, and PTPS-I homologs, all members of the COG0720 family, that have been previously shown to transform 7,8-dihydroneopterin triphosphate (H2NTP) into different products. PTPS-II catalyzes the formation of 6-pyruvoyltetrahydropterin in the BH4 pathway. PTPS-III catalyzes the formation of 6-hydroxylmethyl-7,8-dihydropterin in the THF pathway. PTPS-I catalyzes the formation of 6-carboxy-5,6,7,8-tetrahydropterin in the Q pathway. Genes of these …


Surfactant-Free Hybridization Of Transition Metal Oxide Nanoparticles With Conductive Graphene For High-Performance Supercapacitor, Wen Qian, Zhiqiang Chen, Steven Cottingham, William Alexander Merrill, Natasja A. Swartz, Andrea Goforth, Tami Lasseter Clare, Jun Jiao Jan 2012

Surfactant-Free Hybridization Of Transition Metal Oxide Nanoparticles With Conductive Graphene For High-Performance Supercapacitor, Wen Qian, Zhiqiang Chen, Steven Cottingham, William Alexander Merrill, Natasja A. Swartz, Andrea Goforth, Tami Lasseter Clare, Jun Jiao

Chemistry Faculty Publications and Presentations

In order to improve specific capacitance and limit electrical resistance, high-quality exfoliatedgraphene decorated with transition metal (Fe, Mn, Co) oxide nanoparticles (NPs) has been successfully synthesized without the use of surfactant via a simple, general, environmentally-friendly chemical process. The specific capacitance of as-prepared graphene/Mn3O4 composite reach 239.6 F/g, when employed as the anode material in neutral NaCl electrolyte solutions (cf. 98.2 F/g for pristine graphene and 141.4 F/g for pure Mn3O4 NPs), which indicate the synergetic effects from both graphene and attached Mn3O4 NPs. Moreover, the high conductivity of …


Diversity Of Archaeosine Synthesis In Crenarchaeota, Gabriela Phillips, Manal A. Swairjo, Kirk W. Gaston, Marc Bailly, Patrick A. Limbach, Dirk Iwata-Reuyl, Valérie De Crécy-Lagard Jan 2012

Diversity Of Archaeosine Synthesis In Crenarchaeota, Gabriela Phillips, Manal A. Swairjo, Kirk W. Gaston, Marc Bailly, Patrick A. Limbach, Dirk Iwata-Reuyl, Valérie De Crécy-Lagard

Chemistry Faculty Publications and Presentations

Archaeosine (G+) is found at position 15 of many archaeal tRNAs. In Euryarchaeota, the G+ precursor, 7-cyano-7-deazaguanine (preQ0), is inserted into tRNA by tRNA-guanine transglycosylase (arcTGT) before conversion into G+ by ARChaeosine Synthase (ArcS). However, many Crenarchaeota known to harbor G+ lack ArcS homologs. Using comparative genomics approaches, two families that could functionally replace ArcS in these organisms were identified: 1) GAT-QueC, a two-domain family with an N-terminal glutamine amidotransferase class-II domain fused to a domain homologous to QueC, the enzyme that produces preQ0; 2) QueF-like, a family homologous to the bacterial enzyme catalyzing the reduction of preQ0 to 7- …


Advanced Nanohybrid Materials: Surface Modification And Applications, Li-Hung Liu, Rémi Métivier, Shanfeng Wang, Hui Wang Jan 2012

Advanced Nanohybrid Materials: Surface Modification And Applications, Li-Hung Liu, Rémi Métivier, Shanfeng Wang, Hui Wang

Chemistry Faculty Publications and Presentations

The field of functional nanoscale hybrid materials is one of the most promising and rapidly emerging research areas in materials chemistry. Nanoscale hybrid materials can be broadly defined as synthetic materials with organic and inorganic components that are linked together by noncovalent bonds (Class I, linked by hydrogen bond, electrostatic force, or van der Waals force) or covalent bonds (Class II) at nanometer scale. The unlimited possible combinations of the distinct properties of inorganic, organic, or even bioactive components in a single material, either in molecular or nanoscale dimensions, have attracted considerable attention. This approach provides an opportunity to create …


A Seminaphthofluorescein-Based Fluorescent Chemodosimeter For The Highly Selective Detection Of Cysteine, Xiaofeng Yang, Yixing Guo, Robert M. Strongin Jan 2012

A Seminaphthofluorescein-Based Fluorescent Chemodosimeter For The Highly Selective Detection Of Cysteine, Xiaofeng Yang, Yixing Guo, Robert M. Strongin

Chemistry Faculty Publications and Presentations

A fluorescent chemodosimeter for cysteine detection was developed based on a tandem conjugate addition and intramolecular cyclization reaction. The method exhibited an excellent selectivity for cysteine over other biothiols such as homocysteine and glutathione.


Overview Of The 2010 Carbonaceous Aerosols And Radiative Effects Study (Cares), Rahul A. Zaveri, William J. Shaw, Daniel J. Cziczo, Beat Schmid, Richard Ferrare, M. Lizabeth Alexander, Raul Alvarez, W. Patrick Arnott, Dean B. Atkinson, Sunil Baidar, Robert M. Banta, James Barnard, Josef Beranek, Larry K. Berg, Fred Brechtel, W. Alan Brewer, John F. Cahill, Brian Cairns, Christopher D. Cappa, D. Chand, S. China, Jennifer M. Comstock, Manvendra K. Dubey, Robert C. Easter, M. H. Erickson, Jerome Fast, Cody Floerchinger, B. Flowers, Edward C. Fortner, Jeffrey S. Gaffney, Mary K. Gilles, Kyle Gorkowski, William Gustafson, Madhu Gyawali, J. Hair, R. M. Hardesty, Joseph Harworth, Scott C. Herndon, Naruki Hiranuma, Chris Hostetler, John M. Hubbe, John T. Jayne, H. Jeong, B. Tom Jobson, Evgueni Kassianov, Lawrence I. Kleinman, C. Kluzek, W. Berk Knighton, Katheryn R. Kolesar, Chongai Kuang, Alena Kubátová, Andrew O. Langford, Alexander Laskin, N. Laulainen, Richard D. Marchbanks, Claudio Mazzoleni, Fan Mei, Ryan C. Moffet, Dan Nelson, Michael Obland, Hilke Oetjen, Timothy B. Onasch, I. Ortega, Matteo Ottaviani, Mikhail Pekour, Kimberly A. Prather, James Gregory Radney, Raymond R. Rogers, Scott P. Sandberg, Arthur J. Sedlacek, Christoph J. Senff, Gunnar I. Senum, Ari Setyan, John E. Shilling, Manishkumar Shrivastava, C. Song, Stephen R. Springston, R. Subramanian, Kaitlyn Suski, Jason Tomlinson, Rainer M. Volkamer, H. W. Wallace, Jian Wang, A. M. Weickmann, Douglas R. Worsnop, Xiao-Ying Yu, Alla Zelenyuk, Qi Zhang Jan 2012

Overview Of The 2010 Carbonaceous Aerosols And Radiative Effects Study (Cares), Rahul A. Zaveri, William J. Shaw, Daniel J. Cziczo, Beat Schmid, Richard Ferrare, M. Lizabeth Alexander, Raul Alvarez, W. Patrick Arnott, Dean B. Atkinson, Sunil Baidar, Robert M. Banta, James Barnard, Josef Beranek, Larry K. Berg, Fred Brechtel, W. Alan Brewer, John F. Cahill, Brian Cairns, Christopher D. Cappa, D. Chand, S. China, Jennifer M. Comstock, Manvendra K. Dubey, Robert C. Easter, M. H. Erickson, Jerome Fast, Cody Floerchinger, B. Flowers, Edward C. Fortner, Jeffrey S. Gaffney, Mary K. Gilles, Kyle Gorkowski, William Gustafson, Madhu Gyawali, J. Hair, R. M. Hardesty, Joseph Harworth, Scott C. Herndon, Naruki Hiranuma, Chris Hostetler, John M. Hubbe, John T. Jayne, H. Jeong, B. Tom Jobson, Evgueni Kassianov, Lawrence I. Kleinman, C. Kluzek, W. Berk Knighton, Katheryn R. Kolesar, Chongai Kuang, Alena Kubátová, Andrew O. Langford, Alexander Laskin, N. Laulainen, Richard D. Marchbanks, Claudio Mazzoleni, Fan Mei, Ryan C. Moffet, Dan Nelson, Michael Obland, Hilke Oetjen, Timothy B. Onasch, I. Ortega, Matteo Ottaviani, Mikhail Pekour, Kimberly A. Prather, James Gregory Radney, Raymond R. Rogers, Scott P. Sandberg, Arthur J. Sedlacek, Christoph J. Senff, Gunnar I. Senum, Ari Setyan, John E. Shilling, Manishkumar Shrivastava, C. Song, Stephen R. Springston, R. Subramanian, Kaitlyn Suski, Jason Tomlinson, Rainer M. Volkamer, H. W. Wallace, Jian Wang, A. M. Weickmann, Douglas R. Worsnop, Xiao-Ying Yu, Alla Zelenyuk, Qi Zhang

Chemistry Faculty Publications and Presentations

Substantial uncertainties still exist in the scientific understanding of the possible interactions between urban and natural (biogenic) emissions in the production and transformation of atmospheric aerosol and the resulting impact on climate change. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) program’s Carbonaceous Aerosol and Radiative Effects Study (CARES) carried out in June 2010 in Central Valley, California, was a comprehensive effort designed to improve this understanding. The primary objective of the field study was to investigate the evolution of secondary organic and black carbon aerosols and their climate-related properties in the Sacramento urban plume as it was …


Towards The Rational Design Of Mri Contrast Agents: Δ-Substitution Of Lanthanide(Iii) Nb-Dota-Tetraamide Chelates Influences But Does Not Control Coordination Geometry, Christiane E. Carney, Anh D. Tran, Jing Wang, Matthias C. Schabel, A. Dean Sherry, Mark Woods Sep 2011

Towards The Rational Design Of Mri Contrast Agents: Δ-Substitution Of Lanthanide(Iii) Nb-Dota-Tetraamide Chelates Influences But Does Not Control Coordination Geometry, Christiane E. Carney, Anh D. Tran, Jing Wang, Matthias C. Schabel, A. Dean Sherry, Mark Woods

Chemistry Faculty Publications and Presentations

LnDOTA-tetraamide chelates (DOTA=1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) have received considerable recent attention as a result of their potential to act as PARACEST contrast agents for magnetic resonance imaging (MRI). Although PARACEST agents afford several advantages over conventional contrast agents they suffer from substantially higher detection limits; thus, improving the effectiveness of LnDOTA-tetraamide chelates is an important goal. In this study we investigate the potential to extend conformational control of LnDOTA-type ligands to those applicable to PARACEST. Furthermore, the question of whether δ- rather than α-substitution of the pendant arms could be used to control the chelate coordination geometry is addressed. Although δ-substitution does …


Properties, Solution State Behavior, And Crystal Structures Of Chelates Of Dotma, Silvio Aime, Mauro Botta, Zoltán Garda, Benjamin E. Kucera, Gyula Tircso, Victor G. Young, Mark Woods Sep 2011

Properties, Solution State Behavior, And Crystal Structures Of Chelates Of Dotma, Silvio Aime, Mauro Botta, Zoltán Garda, Benjamin E. Kucera, Gyula Tircso, Victor G. Young, Mark Woods

Chemistry Faculty Publications and Presentations

The chemistry of polyamino carboxylates and their use as ligands for Ln(3+) ions is of considerable interest from the point of view of the development of new imaging agents. Of particular interest is the chemistry of the macrocyclic ligand 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and its derivatives. Herein we report that the tetramethylated DOTA derivative, DOTMA, possess several properties that, from an imaging agent development point of view, are more advantageous than those of the parent DOTA. In particular, the Ln(3+) chelates of DOTMA exhibit a marked preference for the monocapped twisted square antiprismatic coordination isomer which imparts more rapid water exchange …


Bis Photobase Generator, Hoang Tran, Shankar B. Rananavare Aug 2011

Bis Photobase Generator, Hoang Tran, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

The extension of 193nm technology is desirable due to the magnitude of past investments. Since “optical” advancements are increasingly difficult, there is a strong demand for more sophisticated “smart” resists to increase pattern density. Many studies have proven double pattering can be used for the extension of 193nm lithography. In this study, a new class of two stage photo base generators will be introduced along with the synthetic procedure and molecular characterization. The characterizations for exposure study by NMR have shown typical characteristics to stage decomposition under the exposure of 254nm light as well as promising pitch division. GCMS was …


Positional Control Over Nanoparticle Deposition Into Nanoholes, Moshood K. Morakinyo, Shankar B. Rananavare Aug 2011

Positional Control Over Nanoparticle Deposition Into Nanoholes, Moshood K. Morakinyo, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

Controlled deposition of metal nanoparticles (NPs) into lithographic patterned nanoholes has been a major challenge. Electrostatic attraction was employed in directing gold NPs of precise size into e-beam lithographically patterned holes. Citrate stabilized gold NPs with a net negative surface charge were deposited on a positively charged well-bottom surface generated by adsorption of long-chain amino-terminated organosilane N-(2-aminoethyl)-11-aminoundecyltrimethoxy- silane (AATMS). Scanning electron microscopy (SEM) results indicate that deposition of NPs into patterned holes is a function of deposition time and NPs concentration. Other factors affecting NP fill fraction are thickness of silane and resist layer and spacing between the nanoholes.


Synthesis And Characterization Of N- And P- Doped Tin Oxide Nanowires, Hoang Tran, Shankar B. Rananavare Aug 2011

Synthesis And Characterization Of N- And P- Doped Tin Oxide Nanowires, Hoang Tran, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

Bulk-scale synthetic methods for preparing doped tin oxide (SnO2) nanowires (NWs) are presented. n-and p-doping is achieved through insertion of Antimony and Lithium in tin oxide lattice, respectively. We also present a comparison of the structural and optical properties of SnO2 nanoparticles (NPs), and SnO2 NWs. Both n-type and p- type NWs display a characteristic red shift in their photoluminescence (PL) spectra. Surface plasmons observed in these systems imply high carrier concentrations. These corrosion resistant materials are useful in fabricating ultra-sensitive gas detectors and transparent electronics.


Analysis Of The Conformational Behavior And Stability Of The Sap And Tsap Isomers Of Lanthanide(Iii) Nb-Dota-Type Chelates, Gyula Tircso, Benjamin Charles Webber, Benjamin E. Kucera, Victor G. Young, Mark Woods Aug 2011

Analysis Of The Conformational Behavior And Stability Of The Sap And Tsap Isomers Of Lanthanide(Iii) Nb-Dota-Type Chelates, Gyula Tircso, Benjamin Charles Webber, Benjamin E. Kucera, Victor G. Young, Mark Woods

Chemistry Faculty Publications and Presentations

Controlling the water exchange kinetics of macrocyclic Gd(3+) chelates, a key parameter in the design of improved magnetic resonance imaging (MRI) contrast media, may be facilitated by selecting the coordination geometry of the chelate. The water exchange kinetics of the mono- capped twisted square antiprism (TSAP) being much closer to optimal than those of the mono capped square antiprism (SAP) render the TSAP isomer more desirable for high relaxivity applications. Two systems have been developed that allow for selection of the TSAP coordination geometry in 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-type Gd(3+) chelates, both based upon the macrocycle nitrobenzyl cyclen. In this paper …


Hiv-1 Matrix Protein Binding To Rna, Ayna Alfadhli, Henry Mcnett, Seyram Tsagli, Hans Peter Bachinger, David H. Peyton Jul 2011

Hiv-1 Matrix Protein Binding To Rna, Ayna Alfadhli, Henry Mcnett, Seyram Tsagli, Hans Peter Bachinger, David H. Peyton

Chemistry Faculty Publications and Presentations

The matrix (MA) domain of the HIV-1 precursor Gag (PrGag) protein plays multiple roles in the viral replication cycle. One essential role is to target PrGag proteins to their lipid raft-associated phosphatidylinositol-(4,5)-bisphosphate (PI[4,5]P2) assembly sites at the plasma membranes (PMs) of infected cells. In addition to this role, several reports have implicated nucleic acid binding properties to retroviral MAs. Evidence indicates that RNA binding enhances the binding specificity of MA to PI(4,5)P2-containing membranes, and supports a hypothesis in which RNA binding to MA acts as a chaperone that protects MA from associating with inappropriate cellular membranes prior to PrGag delivery …


Investigations Into Whole Water, Prototropic And Amide Proton Exchange In Lanthanide(Iii) Dota-Tetraamide Chelates, Mark Woods, Azhar Pasha, Piyu Zhao, Gyula Tircso, Somdatta Chowdhury, Garry Kiefer, Donald E. Woessner, A. Dean Sherry Jul 2011

Investigations Into Whole Water, Prototropic And Amide Proton Exchange In Lanthanide(Iii) Dota-Tetraamide Chelates, Mark Woods, Azhar Pasha, Piyu Zhao, Gyula Tircso, Somdatta Chowdhury, Garry Kiefer, Donald E. Woessner, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Lanthanide(III) chelates of DOTA-tetraamide ligands have been an area of particular interest since the discovery that water exchange kinetics are dramatically affected by the switch from acetate to amide side-chain donors. More recently these chelates have attracted interest as potential PARACEST agents for use in MRI. In this paper we report the results of studies using chemical exchange saturation transfer (CEST) and some more recently reported chelates to re-examine the exchange processes in this class of chelate. We find that the conclusions of Parker and Aime are, for the most part, solid; water exchange is slow and a substantial amount …


Tension Directly Stabilizes Reconstituted Kinetochore-Microtubule Attachments, Bungo Akiyoshi, Krishna K. Sarangapani, Andrew F. Powers, Christian R. Nelson, Steve Reichow, Hugo Arellano-Santoyo, Tamir Gonen, Jeffrey A. Ranish, Charles L. Asbury, Sue Biggins Jun 2011

Tension Directly Stabilizes Reconstituted Kinetochore-Microtubule Attachments, Bungo Akiyoshi, Krishna K. Sarangapani, Andrew F. Powers, Christian R. Nelson, Steve Reichow, Hugo Arellano-Santoyo, Tamir Gonen, Jeffrey A. Ranish, Charles L. Asbury, Sue Biggins

Chemistry Faculty Publications and Presentations

Kinetochores are macromolecular machines that couple chromosomes to dynamic microtubule tips during cell division, thereby generating force to segregate the chromosomes. Accurate segregation depends on selective stabilization of correct ‘bi-oriented’ kinetochore-microtubule attachments, which come under tension due to opposing forces exerted by microtubules. Tension is thought to stabilize these bi-oriented attachments indirectly, by suppressing the destabilizing activity of a kinase, Aurora B. However, a complete mechanistic understanding of the role of tension requires reconstitution of kinetochore-microtubule attachments for biochemical and biophysical analyses in vitro. Here we show that native kinetochore particles retaining the majority of kinetochore proteins can be …


Organometallic Iron(Iii)-Salophene Exerts Cytotoxic Properties In Neuroblastoma Cells Via Mapk Activation And Ros Generation, Kyu Kwang Kim, Rakesh K. Singh, Robert M. Strongin, Richard G. Moore, Laurent Brard, Thilo S. Lange Apr 2011

Organometallic Iron(Iii)-Salophene Exerts Cytotoxic Properties In Neuroblastoma Cells Via Mapk Activation And Ros Generation, Kyu Kwang Kim, Rakesh K. Singh, Robert M. Strongin, Richard G. Moore, Laurent Brard, Thilo S. Lange

Chemistry Faculty Publications and Presentations

The objective of the present study was to investigate the specific effects of Iron(III)-salophene (Fe-SP) on viability, morphology, proliferation, cell cycle progression, ROS generation and pro-apoptotic MAPK activation in neuroblastoma (NB) cells. A NCI-DTP cancer screen revealed that Fe-SP displayed high toxicity against cell lines of different tumor origin but not tumor type-specificity. In a viability screen Fe-SP exhibited high cytotoxicity against all three NB cell lines tested. The compound caused cell cycle arrest in G1 phase, suppression of cells progressing through S phase, morphological changes, disruption of the mitochondrial membrane depolarization potential, induction of apoptotic markers as well as …


Imaging The Extracellular Ph Of Tumors By Mri After Injection Of A Single Cocktail Of T1 And T2 Contrast Agents, Gary V. Martinez, Xiaomeng Zhang, María L. García-Martín, David L. Morse, Mark Woods, A. Dean Sherry, Robert J. Gillies Jan 2011

Imaging The Extracellular Ph Of Tumors By Mri After Injection Of A Single Cocktail Of T1 And T2 Contrast Agents, Gary V. Martinez, Xiaomeng Zhang, María L. García-Martín, David L. Morse, Mark Woods, A. Dean Sherry, Robert J. Gillies

Chemistry Faculty Publications and Presentations

The extracellular pH (pH(e) ) of solid tumors is acidic, and there is evidence that an acidic pH(e) is related to invasiveness. Herein, we describe an MRI single-infusion method to measure pH(e) in gliomas using a cocktail of contrast agents (CAs). The cocktail contained gadolinium-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaminophosphonate (GdDOTA-4AmP) and dysprosium-1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetrakis(methylenephosphonic acid) (DyDOTP), whose effects on relaxation are sensitive and insensitive to pH, respectively. The Gd-CA dominated the spin-lattice relaxivity ΔR(1) , whereas the Dy-CA dominated the spin-spin relaxivity ΔR(2)*. The ΔR(2)* effects were used to determine the pixel-wise concentration of [Dy] which, in turn, was used to calculate a value for [Gd] …


Strategies For Labeling Proteins With Paracest Agents, Olga Vasalatiy, Piyu Zhao, Mark Woods, Andrei Marconescu, Aminta Castillo-Muzquiz, Philip Thorpe, Garry Kiefer, A. Dean Sherry Jan 2011

Strategies For Labeling Proteins With Paracest Agents, Olga Vasalatiy, Piyu Zhao, Mark Woods, Andrei Marconescu, Aminta Castillo-Muzquiz, Philip Thorpe, Garry Kiefer, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Reactive surface lysine groups on the chimeric monoclonal antibody (3G4) and on human serum albumin (HSA) were labeled with two different PARACEST chelates. Between 7.4 – 10.1 chelates were added per 3G4 molecule and between 5.6 – 5.9 chelates per molecule of HSA, depending upon which conjugation chemistry was used. The immunoreactivity of 3G4 as measured by ELISA assays was highly dependent upon the number of attached chelates: 88% immunoreactivity with 7.4 chelates per antibody versus only 17% immunoreactivity with 10.1 chelates per antibody. Upon conjugation to 3G4, the bound water lifetime of Eu-1 increased only marginally, up from …