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Full-Text Articles in Physical Sciences and Mathematics

Chemomechanical Polymers As Sensors And Actuators For Biological And Medicinal Applications, Hans-Jörg Schneider, Kazuaki Kato, Robert M. Strongin Aug 2007

Chemomechanical Polymers As Sensors And Actuators For Biological And Medicinal Applications, Hans-Jörg Schneider, Kazuaki Kato, Robert M. Strongin

Chemistry Faculty Publications and Presentations

Changes in the chemical environment can trigger large motions in chemomechanical polymers. The unique feature of such intelligent materials, mostly in the form of hydrogels, is therefore, that they serve as sensors and actuators at the same time, and do not require any measuring devices, transducers or power supplies. Until recently the most often used of these materials responded to changes in pH. Chemists are now increasingly using supramolecular recognition sites in materials, which are covalently bound to the polymer backbone. This allows one to use a nearly unlimited variety of guest (or effector) compounds in the environment for a …


Potentiometric And Relaxometric Properties Of A Gadolinium-Based Mri Contrast Agent For Sensing Tissue Ph, Ferenc K. Kálmán, Mark Woods, Peter Caravan, Paul Jurek, Marga Spiller, Gyula Tircso, Róbert Király, Ernő Brücher, A. Dean Sherry Jun 2007

Potentiometric And Relaxometric Properties Of A Gadolinium-Based Mri Contrast Agent For Sensing Tissue Ph, Ferenc K. Kálmán, Mark Woods, Peter Caravan, Paul Jurek, Marga Spiller, Gyula Tircso, Róbert Király, Ernő Brücher, A. Dean Sherry

Chemistry Faculty Publications and Presentations

The pH-sensitive contrast agent, GdDOTA-4AmP (Gd1) has been successfully used to map tissue pH by MRI. Further studies now demonstrate that two distinct chemical forms of the complex can be prepared depending upon the pH at which Gd3+ is mixed with ligand 1. The desired pH-sensitive form of this complex, referred to here as a Type II complex, is obtained as the exclusive product only when the complexation reaction is performed above pH 8. At lower pH values, a second complex is formed that, by analogy with an intermediate formed during the preparation of GdDOTA, we tentatively assign …


Albumin-Binding Paracest Agents, M. Meser Ali, Mark Woods, Eul Hyun Suh, Zoltan Kovacs, Gyula Tircsó, Piyu Zhao, Vikram D. Kodibagkar, A. Dean Sherry May 2007

Albumin-Binding Paracest Agents, M. Meser Ali, Mark Woods, Eul Hyun Suh, Zoltan Kovacs, Gyula Tircsó, Piyu Zhao, Vikram D. Kodibagkar, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Lanthanide complexes (Eu3+, Gd3+ and Yb3+) of two different 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid tetraamide derivatives containing two (2) and four (3) O-benzyl-L-serine amide substituents were synthesized and their chemical exchange saturation transfer (CEST) and relaxometric properties were examined in the presence and absence of human serum albumin (HSA). Both Eu2 and Eu3 display a significant CEST effect from a single slowly exchanging Eu3+-bound water molecule, making these PARACEST complexes potentially useful as vascular MRI agents. Yb2 also showed a detectable CEST effect from both the Yb3+-bound water protons and the …


A Bridge To Coordination Isomer Selection In Lanthanide(Iii) Dota-Tetraamide Complexes, Jeff Vipond, Mark Woods, Piyu Zhao, Gyula Tircsó, Jimin Ren, Simon G. Bott, Doug Ogrin, Garry Kiefer, Zoltan Kovacs, A. Dean Sherry Feb 2007

A Bridge To Coordination Isomer Selection In Lanthanide(Iii) Dota-Tetraamide Complexes, Jeff Vipond, Mark Woods, Piyu Zhao, Gyula Tircsó, Jimin Ren, Simon G. Bott, Doug Ogrin, Garry Kiefer, Zoltan Kovacs, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Interest in macrocyclic lanthanide complexes such as DOTA is driven largely through interest in their use as contrast agents for MRI. The lanthanide tetraamide derivatives of DOTA have shown considerable promise as PARACEST agents, taking advantage of the slow water exchange kinetics of this class of complex. We postulated that water exchange in these tetraamide complexes could be slowed even further by introducing a group to sterically encumber the space above the water coordination site, thereby hindering the departure and approach of water molecules to the complex. The ligand 8O2-bridged-DOTAM was synthesized in a 34% yield from cyclen. …


The Structure And Function Of Small Nucleolar Ribonucleoproteins, Steve Reichow, Tomoko Hamma, Adrian R. Ferré-D’Amaré, Gabriele Varani Feb 2007

The Structure And Function Of Small Nucleolar Ribonucleoproteins, Steve Reichow, Tomoko Hamma, Adrian R. Ferré-D’Amaré, Gabriele Varani

Chemistry Faculty Publications and Presentations

Eukaryotes and archaea use two sets of specialized ribonucleoproteins (RNPs) to carry out sequencespecific methylation and pseudouridylation of RNA, the two most abundant types of modifications of cellular RNAs. In eukaryotes, these protein–RNA complexes localize to the nucleolus and are called small nucleolar RNPs (snoRNPs), while in archaea they are known as small RNPs (sRNP). The C/D class of sno(s)RNPs carries out ribose- 20-O-methylation, while the H/ACA class is responsible for pseudouridylation of their RNA targets. Here, we review the recent advances in the structure, assembly and function of the conserved C/D and H/ACA sno(s)RNPs. Structures of each of the …


Antibacterial Targets In Fatty Acid Biosynthesis, H. Tonie Wright, Kevin A. Reynolds Jan 2007

Antibacterial Targets In Fatty Acid Biosynthesis, H. Tonie Wright, Kevin A. Reynolds

Chemistry Faculty Publications and Presentations

The fatty acid biosynthesis pathway is an attractive but still largely unexploited target for development of new anti-bacterial agents. The extended use of the anti-tuberculosis drug isoniazid and the antiseptic triclosan, which are inhibitors of fatty acid biosynthesis, validates this pathway as a target for anti-bacterial development. Differences in subcellular organization of the bacterial and eukaryotic multi-enzyme fatty acid synthase systems offer the prospect of inhibitors with host vs. target specificity. Platensimycin, platencin, and phomallenic acids, newly discovered natural product inhibitors of the condensation steps in fatty acid biosynthesis, represent new classes of compounds with antibiotic potential. An almost complete …


Probing Reactivity And Substrate Specificity Of Both Subunits Of The Dimeric Mycobacterium Tuberculosis Fabh Using Alkyl-Coa Disulfide Inhibitors And Acyl-Coa Substrates, Sarbjot Sachdeva, Faik Musayev, Mamoun M. Alhamadsheh, J. Neel Scarsdale, H. Tonie Wright, Kevin A. Reynolds Jan 2007

Probing Reactivity And Substrate Specificity Of Both Subunits Of The Dimeric Mycobacterium Tuberculosis Fabh Using Alkyl-Coa Disulfide Inhibitors And Acyl-Coa Substrates, Sarbjot Sachdeva, Faik Musayev, Mamoun M. Alhamadsheh, J. Neel Scarsdale, H. Tonie Wright, Kevin A. Reynolds

Chemistry Faculty Publications and Presentations

The dimeric Mycobacterium tuberculosis FabH (mtFabH) catalyses a Claisen-type condensation between an acyl-CoA and malonyl-acyl carrier protein (ACP) to initiate the Type II fatty acid synthase cycle. To analyze the initial covalent acylation of mtFabH with acyl-CoA, we challenged it with mixture of C6-C20 acyl-CoAs and the ESI-MS analysis showed reaction at both subunits and a strict specificity for C12 acyl CoA. Crystallographic and ESI-MS studies of mtFabH with a decyl-CoA disulfide inhibitor revealed a decyl chain bound in acyl-binding channels of both subunits through disulfide linkage to the active site cysteine. These data provide the first unequivocal evidence that …


Dna Multiplex Hybridization On Microarrays And Thermodynamic Stability In Solution: A Direct Comparison, Daniel J. Fish, M. Todd Horne, Greg P. Brewood, Jim P. Goodarzi, Saba Alemayehu, Ashwini Bhandiwad, Robert P. Searles, Albert S. Benight Jan 2007

Dna Multiplex Hybridization On Microarrays And Thermodynamic Stability In Solution: A Direct Comparison, Daniel J. Fish, M. Todd Horne, Greg P. Brewood, Jim P. Goodarzi, Saba Alemayehu, Ashwini Bhandiwad, Robert P. Searles, Albert S. Benight

Chemistry Faculty Publications and Presentations

Hybridization intensities of 30 distinct short duplex DNAs measured on spotted microarrays, were directly compared with thermodynamic stabilities measured in solution. DNA sequences were designed to promote formation of perfect match, or hybrid duplexes containing tandem mismatches. Thermodynamic parameters DeltaH degrees , DeltaS degrees and DeltaG degrees of melting transitions in solution were evaluated directly using differential scanning calorimetry. Quantitative comparison with results from 63 multiplex microarray hybridization experiments provided a linear relationship for perfect match and most mismatch duplexes. Examination of outliers suggests that both duplex length and relative position of tandem mismatches could be important factors contributing to …


Modular Polyketide Synthases And Cis Double Bond Formation:  Establishment Of Activated Cis-3-Cyclohexylpropenoic Acid As The Diketide Intermediate In Phoslactomycin Biosynthesis, Mamoun M. Alhamadsheh, Nadaraj Palaniappan, Suparna Daschouduri, Kevin A. Reynolds Jan 2007

Modular Polyketide Synthases And Cis Double Bond Formation:  Establishment Of Activated Cis-3-Cyclohexylpropenoic Acid As The Diketide Intermediate In Phoslactomycin Biosynthesis, Mamoun M. Alhamadsheh, Nadaraj Palaniappan, Suparna Daschouduri, Kevin A. Reynolds

Chemistry Faculty Publications and Presentations

The majority of modular polyketide synthase (PKS) systems which generate unsaturated products do so with trans double bonds. Phoslactomycin B (PLM B) presents a class of antitumor and antiviral natural polyketide products that have unique structural features, including a linear unsaturated backbone with one trans and three cis double bonds. There is substantial evidence that trans double bonds are established by ketoreductase-dehydratase (KR-DH) didomains within a PKS module. In cases where modules containing these didomains appear to generate product containing a cis double bond there is no experimental evidence to determine if they do so directly, or if they also …