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991.
Romeiro NC Albuquerque MG de Alencastro RB Ravi M Hopfinger AJ 《Journal of computer-aided molecular design》2005,19(6):385-400
The p38-mitogen-activated protein kinase (p38-MAPK) plays a key role in lipopolysaccharide-induced tumor necrosis factor-alpha (TNF-alpha) and interleukin-1 (IL-1) release during the inflammatory process, emerging as an attractive target for new anti-inflammatory agents. Four-dimensional quantitative structure-activity relationship (4D-QSAR) analysis [Hopfinger et al., J. Am. Chem. Soc., 119 (1997) 10509] was applied to a series of 33 (a training set of 28 and a test set of 5) pyridinyl-imidazole and pyrimidinyl-imidazole inhibitors of p38-MAPK, with IC50 ranging from 0.11 to 2100 nM [Liverton et al., J. Med. Chem., 42 (1999) 2180]. Five thousand conformations of each analogue were sampled from a molecular dynamics simulation (MDS) during 50 ps at a constant temperature of 303 K. Each conformation was placed in a 2 angstroms grid cell lattice for each of three trial alignments. 4D-QSAR models were constructed by genetic algorithm (GA) optimization and partial least squares (PLS) fitting, and evaluated by leave-one-out cross-validation technique. In the best models, with three to six terms, the adjusted cross-validated squared correlation coefficients, Q2adj, ranged from 0.67 to 0.85. Model D (Q2adj = 0.84) was identified as the most robust model from alignment 1, and it is representative of the other best models. This model encompasses new molecular regions as containing pharmacophore sites, such as the amino-benzyl moiety of pyrimidine analogs and the N1-substituent in the imidazole ring. These regions of the ligands should be further explored to identify better anti-inflammatory inhibitors of p38-MAPK. 相似文献
992.
Reisner E Arion VB Rufińska A Chiorescu I Schmid WF Keppler BK 《Dalton transactions (Cambridge, England : 2003)》2005,(14):2355-2364
Reaction of the antitumor complex trans-[Ru(III)Cl4(Hind)2]- (Hind = indazole) with an excess of dimethyl sulfoxide (dmso) in acetone afforded the complex trans,trans,trans-[Ru(II)Cl2(dmso)2(Hind)2] (1). Two other isomeric compounds trans,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (2) and cis,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (3) have been obtained on refluxing cis-[Ru(II)Cl(2)(dmso)(4)] with 2 equiv. of indazole in ethanol and methanol, respectively. Isomers 1 and 2 react with acetonitrile yielding the complexes trans-[Ru(II)Cl2(dmso)(Hind){HN=C(Me)ind}].CH3CN (4.CH3CN) and trans,cis-[Ru(II)Cl2(dmso)2{HN=C(Me)ind}].H2O (5.H2O), respectively, containing a cyclic amidine ligand resulting from insertion of the acetonitrile C triple bond N group in the N1-H bond of the N2-coordinated indazole ligand in the nomenclature used for 1H-indazole. These are the first examples of the metal-assisted iminoacylation of indazole. The products isolated have been characterized by elemental analysis, IR spectroscopy, UV-vis spectroscopy, electrospray mass-spectrometry, thermogravimetry, differential scanning calorimetry, 1H NMR spectroscopy, and solid-state 13C CP MAS NMR spectroscopy. The isomeric structures of 1-3 and the presence of a chelating amidine ligand in 4 and 5 have been confirmed by X-ray crystallography. The electrochemical behavior of 1-5 and the formation of 5 have been studied by cyclic voltammetry. 相似文献
993.
Steen Br?ndsted Nielsen Tapas Chakraborty S?ren Vr?nning Hoffmann 《Chemphyschem》2005,6(12):2619-2624
Synchrotron radiation circular dichroism (SRCD) spectra of ribose and deoxyribose sugars, adenosine, AMP and dAMP nucleotides and cyclic derivatives were measured in the vacuum ultraviolet region (down to 168 nm for sugars and 175 nm for adenine derivatives) and at different pH values (3, 6-7, 9-10) and temperatures (between 5 and 45 degrees C). The information content in the VUV region is important since the CD bands strongly depend on the chemical structure of the sugar, the presence and orientation of a phosphate group and the protonation state of adenine. On the other hand, single or double deprotonation of the phosphoric acid group has no influence on the spectra. We assign the vacuum ultraviolet (VUV) CD bands of the nucleoside and nucleotides to be due mainly to n-->pi* transitions in the adenine nucleobase based on a comparison with the absorption spectra. The CD bands of the sugars are due to n(O -->sigma*) transitions and are much smaller than the CD signal from the nucleotides in the VUV region. Bands are assigned to both pyranose and open-chain forms. 相似文献
994.
Coon JJ Shabanowitz J Hunt DF Syka JE 《Journal of the American Society for Mass Spectrometry》2005,16(6):880-882
Ion/ion reactions of multiply deprotonated peptide anions with xenon radical cations result in electron abstraction to generate
charge-reduced peptide anions containing a free-radical site. Peptide backbone cleavage then occurs by hydrogen radical abstraction
from a backbone amide N to facilitate cleavage of the adjacent C-C bond, thereby producing a- and x-type product ions. Introduction
of free-radical sites to multiply charged peptides allows access to new fragmentation pathways that are otherwise too costly
(e. g., lowers activation energies). Further, ion/ion chemistry, namely electron transfer reactions, presents a rapid and
efficient means of generating odd-electron multiply charged peptides; these reactions can be used for studying gas-phase chemistries
and for peptide sequence analysis. 相似文献
995.
A structure and kinetic stability study on some complexes with the general formula MN5, where M are the alkali-metal atoms, Li, Na, K, and Rb, has been carried by using hybrid density functional methods. Complex B (C2v) with two points of attachment to the N5 ring is the most energetically favored for all metals considered here. Pyramidal structures A (C5v) are kinetically unstable and they rapidly rearrange to the most stable planar structures B. At the QCISD(T)/6-311 + G*//B3LYP/6-311 + G* + ZPE (B3LYP/6-311 + G*) level, the decomposition barrier heights of LiN5-B, NaN5–B, KN5-B, and RbN5-B are predicted to be 19.9, 22.0, 22.5, and 23.0 kcal/mol, respectively. In addition, the rate constants of the decomposition reaction MN5-B MN3 + N2 (M + Li, Na, K, and Rb) are also predicted using conventional transition state theory and canonical variational transition state theory, respectively. 相似文献
996.
Hanne?Heiberg Odd?GropenEmail author Jon K.?Laerdahl Ole?Swang Ulf?Wahlgren 《Theoretical chemistry accounts》2003,110(3):118-125
Different density functional theory (DFT) functionals have been evaluated by studying geometries and bond strengths of YbH, YbF, EuF, GdF, and NdF and compared with accurate CCSD(T) results and, when available, experiment. The agreement between the CCSD(T) results and experiment, when available, is good. The agreement is also good between bond strengths calculated at the DFT level using relativistic effective core potentials and the CCSD(T) results. However, the all-electron ADF calculations systematically overestimate binding energies. The geometries obtained by both the all-electron and the effective-core-potential-based DFT calculations are generally in good agreement with the CCSD(T) results.Contribution to the Björn Roos Honorary Issue 相似文献
997.
Bodwell GJ Bridson JN Cyrañski MK Kennedy JW Krygowski TM Mannion MR Miller DO 《The Journal of organic chemistry》2003,68(6):2089-2098
998.
The π-π stacking interactions between maleimide's and nitrone's aromatic rings during the 1,3-dipolar cycloaddition were assumed to control the exo-endo selectivity of the reaction. The exo-endo ratios change during the reactions until they reach a constant value, which depends on the substituent. Electron-withdrawing groups favour the exo adduct while electron-donating groups favour the endo adduct. The nitrone ZnBr2 complexes react much more slowly than the free nitrone and the cycloaddition is exo selective in all cases independent of the substituents on the maleimide's aromatic ring. Thermal retrocycloaddition of the cycloadducts produce the corresponding nitrones. The ring opening in the presence of secondary amines did not induce imine formation. endo Adducts were shown for the first time to be the stable paramagnetic compounds. 相似文献
999.
In the work the procedure of chromium(VI) determination by catalytic adsorptive stripping voltammetry (CAdSV) with application of fumed silica, is presented. Two variants of the method are proposed: in the first fumed silica is put directly to the electrolytic cell containing tested solution, in the second the silica is shaken with the sample and next centrifuged. The effectiveness of many surface‐active substances removal from synthetic solutions as well as natural water samples, is studied. In the experiments the fumed silica (Sigma‐Aldrich) of the specific surface area in the range 200–390 m2 g?1 was used. Two types of the working electrodes were applied, i.e., hanging mercury drop electrode (HMDE) and cyclic renewable mercury film electrode (Hg(Ag)FE). In the silica presence i) the relative standard deviation (RSD) for 0.1 μg L?1 Cr(VI) is <2% (HMDE) and <5% (Hg(Ag)FE), n=7, ii) the detection limits estimated deposition time 20 s were respectively 14 ng L?1 (HMDE) and 22 ng L?1 (Hg(Ag)FE). The accuracy of the method was tested by studying the recovery of Cr(VI) from spiked natural water samples. 相似文献
1000.
Andreas?HeintzEmail author Dagmar?Klasen Jochen?K.?Lehmann Christiane?Wertz 《Journal of solution chemistry》2005,34(10):1135-1144
Experimental densities were measured for the system 1-methyl-3-octyl-imidazolium tetrafluoroborate [OMIM][BF4] + butan-1-ol, + pentan-1-ol at 298.15 K and ambient pressure using a vibrating tube densimeter, taking into account the
influence of the viscosity correction. Excess molar volumes VE have been determined. VE is quite small and negative in the alcohol-rich range of the mixture composition and positive in the alcohol-poor range.
LLE data of [OMIM][BF4] + pentan-1-ol have been measured using a laser light scattering cell for detecting cloud points at different compositions
in the temperature range of 282–292 K. A miscibility gap with an upper critical solution temperature (UCST) of 292 K has been
found. 相似文献