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11.
Merkx M Kopp DA Sazinsky MH Blazyk JL Müller J Lippard SJ 《Angewandte Chemie (International ed. in English)》2001,40(15):2725
The cover picture shows in the background the whole cell of a methanotrophic bacterium on which are superimposed components of methane monooxygenase (the structure of the hydroxylase component (top), one of the two four-helix bundles that house the catalytic diiron centers (left)) and a schematic diagram of the catalytic cycle by which the enzyme converts dioxygen and methane into methanol and water. More about this unusual enzyme system is reported by Lippard et al. on p. 2782 ff. 相似文献
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Formation and Crystal Structure of an Oxygen Bridged Titanium Amino Bisphenoxide Di‐(μ‐oxo)‐titan‐bis[aminobisphenoxide] ( 3 ) was obtained by reaction of (i‐Prop)2TiL* ( 2 ) {L* = O‐4, 6‐(t‐Bu)2C6H2‐2‐CH2‐[1, 4‐N2C5H10]‐2'‐CH2‐4', 6'‐(t‐Bu)2C6H2O] with water in a molar ratio 1:1 in diethylether. Both i‐Propyl moieties are substituted yielding the dimeric oxygen bridged amino bisphenoxide complex. The six coordinate Ti atoms are a result of Ti—N and Ti—O interactions of the corresponding atoms of the amino bisphenoxide ligand and the bridging O atoms. The central planar Ti2O2 ring may be considered as the general structural feature of the title compound: Space group P1¯, Z = 1, lattice dimensions at —60°C: a = 11.6899(4), b = 11.7873(4), c = 12.6462(4) Å, α = 98.070(1), β = 99.660(1), γ = 95.343(1)°, R1 = 0.0469, wR2 = 0.1049, GooF = 0.939. 相似文献
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15.
Leva S Lichte A Burmeister J Muhn P Jahnke B Fesser D Erfurth J Burgstaller P Klussmann S 《Chemistry & biology》2002,9(3):351-359
Mirror-image oligonucleotide ligands (Spiegelmers) that bind to the pharmacologically relevant target gonadotropin-releasing hormone I (GnRH) with high affinity and high specificity have been identified using the Spiegelmer technology. GnRH is a decapeptide that plays an important role in mammalian reproduction and sexual maturation and is associated with several benign and malignant diseases. First, aptamers that bind to D-GnRH with dissociation constants of 50-100 nM were isolated out of RNA and DNA libraries. The respective enantiomers of the DNA and RNA aptamers were synthesized, and their binding to L-GnRH was shown. These Spiegelmers bind to L-GnRH with similar affinity to that of the corresponding aptamers that bind to D-GnRH. We further demonstrated dose-dependent inhibition of GnRH-induced Ca(2+) release in Chinese hamster ovary cells that were stably transfected with the human GnRH receptor. 相似文献
16.
The photoprocesses of a series of N-substituted dibenz[b,f]azepines (iminostilbenes) were studied by absorption and emission spectroscopy, by laser flash photolysis, and by preparative irradiation with NMR analysis. In solutions, 2pi+2pi photodimers of N-cyano and N-acyl dibenzazepines are formed via the triplet state upon acetone- or benzophenone-sensitized energy transfer. T-T absorption spectra were measured and absorption coefficients were determined. The triplet energy transfer is equally efficient for N-alkyl dibenzazepines, which do not dimerize. Excited states of npi* character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 21 dibenzazepine derivatives, photodimers of N-acyl and N-cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0.01-0.1 mol dm(-3)) as well as in the solid state. A selective anti-configuration of the photodimers was found throughout. 相似文献
17.
Hainer?Wackerbarth Rodolphe?Marie Mikala?Grubb Jingdong?Zhang Allan?G.?Hansen Ib?Chorkendorff Claus?B.?V.?Christensen Anja?Boisen Jens?UlstrupEmail author 《Journal of Solid State Electrochemistry》2004,8(7):474-481
We provide a comprehensive study of single- (ss) and double-strand (ds) oligonucleotides with either 25 or 10 bases or base pairs (bp) immobilized on polycrystalline and single-crystal Au(111) surfaces. The study is based on X-ray photoelectron spectroscopy, cyclic and differential pulse voltammetry, interfacial capacitance data, and electrochemical scanning tunnelling microscopy (in situ STM). The sequences used were the 25-bp sequence from the BRCA1 gene (25-mer), while the 10-bp oligonucleotides contained solely linear adenine and thymine sequences. The oligonucleotides were modified by the dimethoxytrityl group (DMT) via a disulfide group [DMT-S-S-ss25-mer and DMT-S-S-ds(AT)10], a pure disulfide group (A10-S-S-T10), or a thiol group [HS-ss25-mer and HS-ds-(AT)10], all via a hexamethylene linker. The overall pattern suggests strategies for controlled adsorption of DNA-based molecules and recognition of complementary strands or other molecules. 相似文献
18.
Ionizable residues play important roles in protein structure and activity, and proton binding is a valuable reporter of electrostatic interactions in these systems. We use molecular dynamics free energy simulations (MDFE) to compute proton pKa shifts, relative to a model compound in solution, for three aspartate side chains in two proteins. Simulations with explicit solvent and with an implicit, dielectric continuum solvent are reported. The implicit solvent simulations use the generalized Born (GB) model, which provides an approximate, analytical solution to Poisson's equation. With explicit solvent, the direction of the pKa shifts is correct in all three cases with one force field (AMBER) and in two out of three cases with another (CHARMM). For two aspartates, the dielectric response to ionization is found to be linear, even though the separate protein and solvent responses can be nonlinear. For thioredoxin Asp26, nonlinearity arises from the presence of two substates that correspond to the two possible orientations of the protonated carboxylate. For this side chain, which is partly buried and has a large pKa upshift, very long simulations are needed to correctly sample several slow degrees of freedom that reorganize in response to the ionization. Thus, nearby Lys57 rotates to form a salt bridge and becomes buried, while three waters intercalate along the opposite edge of Asp26. Such strong and anisotropic reorganization is very difficult to predict with Poisson-Boltzmann methods that only consider electrostatic interactions and employ a single protein structure. In contrast, MDFE with a GB dielectric continuum solvent, used for the first time for pKa calculations, can describe protein reorganization accurately and gives encouraging agreement with experiment and with the explicit solvent simulations. 相似文献
19.
Jens Beckmann Dainis Dakternieks Andrew Duthie Naomi A. Lewcenko Cassandra Mitchell Markus Schürmann 《无机化学与普通化学杂志》2005,631(10):1856-1862
The reaction of (p‐MeOC6H4)2TeO with two equivalents of HO3SCF3 and HO2PPh2 provided the tetraorganoditelluroxanes (F3CSO3)(p‐MeOC6H4)2TeOTe(p‐MeOC6H4)2(O3SCF3) ( 1 ) and (Ph2PO2)(p‐MeOC6H4)2TeOTe(p‐MeOC6H4)2(O2PPh2)·2 Ph2PO2H ( 2 ) in good yields. Compounds 1 and 2 were characterized by solution and solid‐state 31P and 125Te NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry, conductivity measurements and single crystal X‐ray diffraction. In solution, compound 1 undergoes an electrolytic dissociation and reversibly reacts with traces of water to give the mononuclear cation [(p‐MeOC6H4)2TeOH]+ and triflate anions. Theoretical aspects of the protonation and hydration of model telluroxanes R2TeO (R = H, Me, Ph) were investigated by preliminary DFT calculations and compared to the corresponding selenoxanes R2SeO. The tellurium dihydroxides R2Te(OH)2 seem to be more stable than the hydrogen‐bonded complexes R2TeO·H2O. 相似文献
20.
Pozzoli L Bolzacchini E Van Dingenen R Hjiorth J Dentener F Perrone G Rindone B Librando V 《Annali di chimica》2003,93(4):447-456
The model BAGS (Boxmodel for Aerosol and Gasphase Simulations) has been developed. It is composed of two major modules: the first one describes the system of the chemical reactions in the gaseous phase, the second one calculates the aerosol chemical composition and the dimensional distribution of the particles. The boxmodel has been developed with the introduction of new chemical and physical processes, not previously included, in particular the formation of Secondary Organic Aerosol. The other implemented processes are a module for the dynamic of the particle population, nucleation, coagulation and dry deposition. The last phase of the work has been a check of the BAGS capabilities by a series of tests, that have permitted to compare it with other models (MAPS and MADM). The tests in particular have concerned the aerosol water content prediction, the photochemistry, the condensation of the inorganic compounds and the formation of Secondary Organic Aerosol. 相似文献