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911.
The electrophoretic mobility and catalytic activity of individual molecules of Escherichia coli beta-galactosidase were measured using CE-LIF detection. Both the mobility and activity were reproducible for each molecule but differed between individual molecules. Assays were performed using uncoated capillaries and capillaries coated with different polymers, using enzymes from different sources and by three different experimental protocols. In all cases the observed ranges in electrophoretic mobilities were similar. The observed range in the electrophoretic mobility may be explained by structural microheterogeneity resulting in a gain or loss of up to 1.6 suppressed charge units. There was no observed relationship between the observed activities and electrophoretic mobilities. If the finding that individual beta-galactosidase molecules have heterogeneous electrophoretic mobility can be extended to other proteins, this may limit the resolution possible for capillary zone electrophoresis protein separations. 相似文献
912.
Photodynamic therapy (PDT) is a promising treatment modality for malignant tumors but it is also immunosuppressive which may reduce its therapeutic efficacy. The purpose of our study was to elucidate the role of CD4+ and CD8+ T cells in PDT immunosuppression. Using silicon phthalocyanine 4 (Pc4) as photosensitizer, nontumor-bearing CD4 knockout (CD4-/-) mice and their wild type (WT) counterparts were subjected to Pc4-PDT in a manner identical to that used for tumor regression (1 cm spot size, 0.5 mg kg(-1) Pc4, 110 J cm(-2) light) to assess the effect of Pc4-PDT on cell-mediated immunity. There was a decrease in immunosuppression in CD4-/- mice compared with WT mice. We next examined the role of CD8+ T cells in Pc4-PDT-induced immunosuppression using CD8-/- mice following the same treatment regimen used for CD4-/- mice. Similar to CD4-/- mice, CD8-/- mice exhibited less immunosuppression than WT mice. Pc4-PDT-induced immunosuppression could be adoptively transferred with spleen cells from Pc4-PDT treated donor mice to syngenic naive recipients (P < 0.05) and was mediated primarily by T cells, although macrophages were also found to play a role. Procedures that limit PDT-induced immunosuppression but do not affect PDT-induced regression of tumors may prove superior to PDT alone in promoting long-term antitumor responses. 相似文献
913.
Michael R. Webb Catherine M. Crawforth Xavier Franci Craig Donald 《Tetrahedron》2008,64(21):4778-4791
The Stille coupling between a common oxazole vinyl iodide and stereodefined stannyl-diene units is described as the cornerstone of a unified synthetic route to the inthomycin family of bioactive Streptomyces metabolites. This procedure has been utilised to prepare (+)-inthomycin B and (+)-inthomycin C for the first time; in these examples the stereogenic centre was introduced using the Kiyooka ketene acetal/amino acid-derived oxazaborolidinone variant of the Mukaiyama aldol reaction. In addition, a convenient preparation of rac-inthomycin A is described based on the same strategy. 相似文献
914.
Engel S Skoumbourdis AP Childress J Neumann S Deschamps JR Thomas CJ Colson AO Costanzi S Gershengorn MC 《Journal of the American Chemical Society》2008,130(15):5115-5123
Virtual screening has become a major focus of bioactive small molecule lead identification, and reports of agonists and antagonists discovered via virtual methods are becoming more frequent. G protein-coupled receptors (GPCRs) are the one class of protein targets for which success with this approach has been limited. This is likely due to the paucity of detailed experimental information describing GPCR structure and the intrinsic function-associated structural flexibility of GPCRs which present major challenges in the application of receptor-based virtual screening. Here we describe an in silico methodology that diminishes the effects of structural uncertainty, allowing for more inclusive representation of a potential docking interaction with exogenous ligands. Using this approach, we screened one million compounds from a virtual database, and a diverse subgroup of 100 compounds was selected, leading to experimental identification of five structurally diverse antagonists of the thyrotropin-releasing hormone receptors (TRH-R1 and TRH-R2). The chirality of the most potent chemotype was demonstrated to be important in its binding affinity to TRH receptors; the most potent stereoisomer was noted to have a 13-fold selectivity for TRH-R1 over TRH-R2. A comprehensive mutational analysis of key amino acid residues that form the putative binding pocket of TRH receptors further verified the binding modality of these small molecule antagonists. The described virtual screening approach may prove applicable in the search for novel small molecule agonists and antagonists of other GPCRs. 相似文献
915.
A convergent enantioselective total synthesis of (+)-pinnatoxin A is described. The synthesis capitalizes on the highly diastereoselective Ireland-Claisen rearrangement of an acyclic alpha-branched allylic ester to set the quaternary stereogenic center at the core of the spiroimine ring system along with the adjacent tertiary stereocenter. The all-carbon macrocyclic ring system was formed by ring-closing metathesis. 相似文献
916.
Robertson CM Leitch AA Cvrkalj K Reed RW Myles DJ Dube PA Oakley RT 《Journal of the American Chemical Society》2008,130(26):8414-8425
Synthetic methods have been developed to generate the complete series of resonance-stabilized heterocyclic thia/selenazyl radicals 1a-4a. X-ray crystallographic studies confirm that all four radicals are isostructural, belonging to the tetragonal space group P42(1)m. The crystal structures consist of slipped pi-stack arrays of undimerized radicals packed about 4 centers running along the z direction, an arrangement which gives rise to a complex lattice-wide network of close intermolecular E2---E2' contacts. Variable temperature conductivity (sigma) measurements reveal an increase in conductivity with increasing selenium content, particularly so when selenium occupies the E2 position, with sigma(300 K) reaching a maximum (for E1 = E2 = Se) of 3.0 x 10(-4) S cm(-1). Thermal activation energies E(act) follow a similar profile, decreasing with increasing selenium content along the series 1a (0.43 eV), 3a (0.31 eV), 2a (0.27 eV), 4a (0.19 eV). Variable temperature magnetic susceptibility measurements indicate that all four radicals exhibit S = 1/2 Curie-Weiss behavior over the temperature range 20-300 K. At lower temperatures, the three selenium-based radicals display magnetic ordering. Radical 3a, with selenium positioned at the E1 site, undergoes a phase transition at 14 K to a weakly spin-canted (phi = 0.010 degrees) antiferromagnetic state. By contrast, radicals 2a and 4a, which both possess selenium in the E2 position, order ferromagnetically, with Curie temperatures of T(c) = 12.8 and 17.0 K, respectively. The coercive fields H(c) at 2 K of 2a (250 Oe) and 4a (1370 Oe) are much larger than those seen in conventional light atom organic ferromagnets. The transport properties of the entire series 1a-4a are discussed in the light of Extended Hückel Theory band structure calculations. 相似文献
917.
Time and distance dependence of reversible polymer bridging followed by single-molecule force spectroscopy 总被引:1,自引:0,他引:1
Serpe MJ Rivera M Kersey FR Clark RL Craig SL 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):4738-4742
Polymer bridging between surfaces plays an important role in a range of fundamental processes in the material and life sciences. Bridges formed by main-chain reversible polymers differ from their covalent analogs in that they can dynamically adjust their size and shape in response to external stimuli and have the potential to reform following bond scission. In this work, the time and distance dependence of main-chain reversible polymer bridge formation are studied using an atomic force microscope. The bridging process was studied using single-molecule force spectroscopy, and its dependence on the distance between surfaces and equilibration time was probed. The number of bridges formed decreases as the gap width increases, from approximately 2 bridges per 14 s equilibration at separations of 5-15 nm to approximately 0.5 bridges per 14 s equilibration at separations of 35-45 nm. The kinetics of bridge formation appear to be slightly faster at smaller separations. 相似文献
918.
van Zwol PJ Palasantzas G van de Schootbrugge M de Hosson JT Craig VS 《Langmuir : the ACS journal of surfaces and colloids》2008,24(14):7528-7531
We have investigated the morphology and surface roughness of several commercially available microspheres to determine their suitability for force measurements using the atomic force microscope. The roughness varies considerably, depending on sphere size and material, ranging from nearly ideally flat up to micrometer-sized features. Because surface roughness significantly influences the magnitude and accuracy of measurement of surface forces, the results presented here should be helpful for colloid physicists and in particular for those performing force measurements. 相似文献
919.
Increasing the density of adsorbed hydrogen with coordinatively unsaturated metal centers in metal-organic frameworks 总被引:1,自引:0,他引:1
Liu Y Kabbour H Brown CM Neumann DA Ahn CC 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):4772-4777
Storing molecular hydrogen in porous media is one of the promising avenues for mobile hydrogen storage. In order to achieve technologically relevant levels of gravimetric density, the density of adsorbed H2 must be increased beyond levels attained for typical high surface area carbons. Here, we demonstrate a strong correlation between exposed and coordinatively unsaturated metal centers and enhanced hydrogen surface density in many framework structures. We show that the MOF-74 framework structure with open Zn(2+) sites displays the highest surface density for physisorbed hydrogen in framework structures. Isotherm and neutron scattering methods are used to elucidate the strength of the guest-host interactions and atomic-scale bonding of hydrogen in this material. As a metric with which to compare adsorption density with other materials, we define a surface packing density and model the strength of the H(2-)surface interaction required to decrease the H(2)-H(2) distance and to estimate the largest possible surface packing density based on surface physisorption methods. 相似文献
920.
Tang M Ramos AV Jud E Chung SY Gautier-Soyer M Cannon RM Carter WC Chiang YM 《Langmuir : the ACS journal of surfaces and colloids》2008,24(5):1891-1896
Despite the extremely broad technical applications of the Si/SiO2 structure, the equilibrium wetting properties of silicon oxide on silicon are poorly understood. Here, we produce new results in which a solid-state buffer method is used to systematically titrate oxygen activity about the Si/SiO2 coexistence value. The equilibrium morphology at the Si(001) surface over >8 decades of PO2 about coexistence is revealed to be a uniform sub-stoichiometric SiOx film of sub-nanometer thickness, coexisting with secondary island structures which coarsen with annealing time. A new thermodynamic method using chemical potential to stabilize and control surficial oxides in nanoscale devices is suggested. 相似文献