全文获取类型
收费全文 | 520篇 |
免费 | 23篇 |
专业分类
化学 | 336篇 |
晶体学 | 8篇 |
力学 | 27篇 |
综合类 | 1篇 |
数学 | 73篇 |
物理学 | 98篇 |
出版年
2023年 | 5篇 |
2022年 | 16篇 |
2021年 | 18篇 |
2020年 | 20篇 |
2019年 | 14篇 |
2018年 | 17篇 |
2017年 | 18篇 |
2016年 | 23篇 |
2015年 | 17篇 |
2014年 | 20篇 |
2013年 | 54篇 |
2012年 | 39篇 |
2011年 | 34篇 |
2010年 | 28篇 |
2009年 | 23篇 |
2008年 | 31篇 |
2007年 | 31篇 |
2006年 | 28篇 |
2005年 | 21篇 |
2004年 | 10篇 |
2003年 | 15篇 |
2002年 | 11篇 |
2001年 | 9篇 |
2000年 | 11篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
排序方式: 共有543条查询结果,搜索用时 15 毫秒
491.
The mercury complex of 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine (bdmpp) has been synthesized and characterized by X-ray diffraction, IR, UV–Vis and TGA–DTA methods. The structure consists of units in which the mercury atom is pentacoordinate with two sulfur and three nitrogen atoms. [Hg(bdmpp)(SCN)2] has a distorted square pyramid geometry. 相似文献
492.
The controversial 'near attack conformation'(NAC) effect in the important model enzyme chorismate mutase is calculated to be 3.8-4.6 kcal mol(-1) by QM/MM free energy perturbation molecular dynamics methods, showing that the NAC effect by itself does not account for catalysis in this enzyme. 相似文献
493.
Yunus KaraMetin Balci 《Tetrahedron》2003,59(12):2063-2066
The photooxygenation of trans-8-(acetyloxy)bicyclo[4.2.0]octa-2,4-dien-7-yl acetate afforded the bicyclic endoperoxide. Reduction of the endoperoxide with thiourea followed by acetylation gave the corresponding tetraacetate. The KMnO4 oxidation of the tetraacetate followed by acetylation gave dihydroxytetraacetate Ammonolysis of tetraacetate afforded the bis-homoinositol, bicyclo[4.2.0]octane-2,3,4,5,7,8-hexol. 相似文献
494.
The hydroperoxy endoperoxide 3 , obtained by photooxygenation of isotetralin (= 1,4,5,8‐tetrahydronaphthalene; 1 ), was reduced with thiourea, and the resulting intermediate 4 was converted, after acetylation with acetyl chloride, to the interesting, double‐chlorinated acetate 5 in an unprecedented tandem reaction (Scheme 1). The structures and relative configurations of 3 and 5 were determined by NMR spectroscopy and by single‐crystal X‐ray‐diffraction analyses (Figs. 1 and 2, resp.). A mechanistic rationalization for the conversion of 4 to 5 is proposed (Scheme 2). 相似文献
495.
Color removal from neutralized sunflower oil was studied with different kinds of commercial bleaching earths. The effect of changes in time (25 and 35 min), temperature (80-125 degrees C), and bleaching earth dosage (0.1-0.9% by weight) on color, chlorophyll and carotene concentrations, and oxidation degree were investigated. To obtain adsorption curves from coloring compounds adsorbed onto activated bleaching earths, the Langmuir and Freundlich equations was used, the constant parameters and correlation coefficient R were calculated for each type of bleaching earth, and color changes were explained by both adsorption isotherms. It was observed that an increase in bleaching earth dosage decreases color. Its effect on oxidation state, however, is complex and related to both primary and secondary oxidation products. In addition, an increase in temperature seems to decrease chlorophyll and carotene adsorptions. Generally, time beyond equilibrium is considered useless for the removal of unwanted components. This study also confirms this claim and reveals that the peroxide value does not indicate the oxidation state of the oil completely. 相似文献
496.
A sensitive and selective solid phase spectrophotometric method for the determination of trace amounts of inorganic mercury is described. Hg2+ was sorbed on a silica gel-packed column as an Hg2+–N,N-bis(2-mercaptophenyl)ethanediamide (H2L) complex. The Hg2+ complex was eluted from the column using 7mL of acetone. Various parameters including pH, column flow rate, and ligand concentration were optimized. The complex was found to obey Beers law from 2.3 to 73.7µgmL–1 within the optimum range when the preconcentration factor was two. The effective molar absorption coefficient at 523nm was 1.17×103Lmol–1cm–1 at 523nm. The concentration limits in Beers law dropped from 0.09 to 2.95µgmL–1 within the optimum range when the preconcentration factor was 50. The relative standard deviation at a concentration level of 5µgmL–1 Hg2+ (9 repetitive determinations) was 1.6%. The detection limits are 0.34µgmL–1 and 0.015µgmL–1 when the preconcentration factors are 2 and 50, respectively. The method has been used for routine determination of trace levels of Hg2+ in natural waters. The potential application of this method for the removal of Hg2+ from natural samples (sea water and lake water) spiked with 100ngmL–1 of Hg2+ was studied. In order to validate the proposed method, LGC 6156 (harbour sediment – extractable metals) was analysed by this method. The results proved that excellent extraction of Hg2+ from both natural water samples was obtained by solid phase extraction using N,N-bis(2-mercaptophenyl) ethanediamide. 相似文献
497.
Yunus Akcamur Gerhard Penn Erich Ziegler Heinz Sterk Gert Kollenz Karl Peters Eva-Maria Peters Hans Georg von Schnering 《Monatshefte für Chemie / Chemical Monthly》1986,117(2):231-245
4-Benzoyl-5-phenyl-furan-2,3-dione (1) reacts with various phenylhydrazones2 at 60–80°C to the pyrazole carboxylic acid3 a, which then can be decarboxylated to 4-benzoyl-1,5-diphenyl-pyrazole (5).1 and phenylhydrazine combine again yielding3 a as the main product and the isomeric pyridazinone6 as by-product. At higher temperatures (120–140°C) the reaction of1 with2 a leads to the formation of dibenzoyl acetic acid hydrazide derivatives8.The structures of all products were confirmed by IR, MS,15N- and13C-NMR spectroscopic measurements, in the case of the pyridazinone6 also by an X-ray study.6 crystallizes with one moleDMSO monoclinically in space group P 21/n (Nr. 14) with 4 molecules6 andDMSO per cell.The reaction pathways leading to the compounds3, 6 and8 are discussed. 相似文献
498.
The reaction between BrO2(-) and excess HOCl (p[H+] 6-7, 25.0 degrees C) proceeds through several pathways. The primary path is a multistep oxidation of HOCl by BrO(2)(-) to form ClO(3)(-) and HOBr (85% of the initial 0.15 mM BrO(2)(-)). Another pathway produces ClO(2) and HOBr (8%), and a third pathway produces BrO(3)(-) and Cl(-) (7%). With excess HOCl concentrations, Cl(2)O also is a reactive species. In the proposed mechanism, HOCl and Cl(2)O react with BrO(2)(-) to form steady-state species, HOClOBrO(-) and ClOClOBrO(-). Acid facilitates the conversion of HOClOBrO(-) and ClOClOBrO(-) to HOBrOClO(-). These reactions require a chainlike connectivity of the intermediates with alternating halogen-oxygen bonding (i.e. HOBrOClO(-)) as opposed to Y-shaped intermediates with a direct halogen-halogen bond (i.e. HOBrCl(O)O(-)). The HOBrOClO(-) species dissociates into HOBr and ClO(2)(-) or reacts with general acids to form BrOClO. The distribution of products suggests that BrOClO exists as a BrOClO.HOCl adduct in the presence of excess HOCl. The primary products, ClO(3)(-) and HOBr, are formed from the hydrolysis of BrOClO.HOCl. A minor hydrolysis path for BrOClO.HOCl gives BrO(3)(-) and Cl(-). An induction period in the formation of ClO(2) is observed due to the buildup of ClO(2)(-), which reacts with BrOClO.HOCl to give 2 ClO(2) and Br(-). Second-order rate constants for the reactions of HOCl and Cl(2)O with BrO(2)(-) are k(1)(HOCl) = 1.6 x 10(2) M(-1) s(-1) and k(1)(Cl)()2(O) = 1.8 x 10(5) M(-)(1) s(-)(1). When Cl(-) is added in large excess, a Cl(2) pathway exists in competition with the HOCl and Cl(2)O pathways for the loss of BrO(2)(-). The proposed Cl(2) pathway proceeds by Cl(+) transfer to form a steady-state ClOBrO species with a rate constant of k(1)(Cl2) = 8.7 x 10(5) M(-1) s(-1). 相似文献
499.
Massari AM Finkelstein IJ McClain BL Goj A Wen X Bren KL Loring RF Fayer MD 《Journal of the American Chemical Society》2005,127(41):14279-14289
Spectrally resolved infrared stimulated vibrational echo measurements are used to measure the vibrational dephasing of the CO stretching mode of carbonmonoxy-hemoglobin (HbCO), a myoglobin mutant (H64V), and a bacterial cytochrome c(552) mutant (Ht-M61A) in aqueous solution and trehalose glasses. The vibrational dephasing of the heme-bound CO is significantly slower for all three proteins embedded in trehalose glasses compared to that of aqueous protein solutions. All three proteins exhibit persistent but notably slower spectral diffusion when the protein surface is fixed by the glassy solvent. Frequency-frequency correlation functions (FFCFs) of the CO are extracted from the vibrational echo data to reveal that the structural dynamics, as sensed by the CO, of the three proteins in trehalose and aqueous solution are dominated by fast (tens of femtoseconds), motionally narrowed fluctuations. MD simulations of H64V in dynamic and "static" water are presented as models of the aqueous and glassy environments. FFCFs are calculated from the H64V simulations and qualitatively reproduce the important features of the experimentally extracted FFCFs. The suppression of long time scale (picoseconds to tens of picoseconds) frequency fluctuations (spectral diffusion) in the glassy solvent is the result of a damping of atomic displacements throughout the protein structure and is not limited to structural dynamics that occur only at the protein surface. The analysis provides evidence that some dynamics are coupled to the hydration shell of water, supporting the idea that the bioprotection offered by trehalose is due to its ability to immobilize the protein surface through a thin, constrained layer of water. 相似文献
500.
A direct and stereospecific capillary zone electrophoresis (CZE) method for quantification ibuprofen enantiomers in biological matrices: human serum and urine, has been developed. Chiral separation of the enantiomers of ibuprofen and (+)-S-indobufen [(+)-S-INDB, internal standard, IS] was obtained in an uncoated silica capillary filled with a background electrolyte (BGE), consisted of heptakis 2,3,6-tri-O-methyl-β-cyclodextrin (TM-β-CD) in buffer of pH 5.0. The complete enantioselective analysis of ibuprofen and its 1-hydroxy metabolite confirmed appropriate specificity of the method. The electrophoretic parameters: electroosmotic (μEOF) and electrophoretic (μep) mobility and resolution factor (Rs) were determined. Extraction procedures with organic solvent and solid phase extraction (SPE) with C18 stationary phase for isolation of enantiomers from biological fluids were compared. SPE method for further studies was chosen. Stereoselective extraction of IBP enantiomers from serum at basic pH has been discovered. Validation of the method was carried out. Calibration curves of ibuprofen enantiomers were linear in the range of 0.1-25.0 μg/ml in serum and of 0.5-250.0 μg/ml in urine. Recovery of both enantiomers from serum and urine amounted 74-86 and 90-98%, respectively. Intra- and inter-day measurement precision and accuracy were below 15%. Limits of detection for IBP enantiomers amounted 0.05 and 0.25 μg/ml in samples of serum and urine, respectively. Limit of quantitation was also estimated. IBP enantiomers proved to be stable following three freeze and thaw cycles and during storage in autosampler at ambient temperature. The validated methods enable pharmacokinetic studies of enantiomers in both media. The elaborated HPCE method can be alternative to HPLC. 相似文献