全文获取类型
收费全文 | 1966篇 |
免费 | 70篇 |
国内免费 | 13篇 |
专业分类
化学 | 1570篇 |
晶体学 | 31篇 |
力学 | 35篇 |
数学 | 101篇 |
物理学 | 312篇 |
出版年
2022年 | 13篇 |
2021年 | 18篇 |
2020年 | 29篇 |
2019年 | 24篇 |
2018年 | 15篇 |
2017年 | 21篇 |
2016年 | 41篇 |
2015年 | 44篇 |
2014年 | 61篇 |
2013年 | 108篇 |
2012年 | 99篇 |
2011年 | 132篇 |
2010年 | 59篇 |
2009年 | 62篇 |
2008年 | 120篇 |
2007年 | 130篇 |
2006年 | 126篇 |
2005年 | 141篇 |
2004年 | 113篇 |
2003年 | 103篇 |
2002年 | 93篇 |
2001年 | 31篇 |
2000年 | 25篇 |
1999年 | 28篇 |
1998年 | 17篇 |
1997年 | 14篇 |
1996年 | 14篇 |
1995年 | 19篇 |
1994年 | 17篇 |
1993年 | 14篇 |
1992年 | 18篇 |
1991年 | 17篇 |
1990年 | 15篇 |
1989年 | 21篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 13篇 |
1985年 | 29篇 |
1984年 | 21篇 |
1983年 | 13篇 |
1982年 | 13篇 |
1981年 | 18篇 |
1980年 | 12篇 |
1979年 | 15篇 |
1978年 | 11篇 |
1977年 | 12篇 |
1976年 | 11篇 |
1975年 | 13篇 |
1974年 | 15篇 |
1973年 | 11篇 |
排序方式: 共有2049条查询结果,搜索用时 15 毫秒
91.
Yutaka Hitomi Masakazu Higuchi Tsunehiro Tanaka Takuzo Funabiki 《Journal of molecular catalysis. A, Chemical》2005,240(1-2):207-213
We examined the oxygenative degradation of 4-chlorocatechol and 4-tert-butylcatechol catalyzed by iron(III)-tris(pyridin-2-yl)amine complex from the standpoint of repressing the formation of 4-chlorocatechol esters of the oxygenated products that causes the incomplete degradation of 4-chlorocatechol. Analysis of the products revealed that 4-chlorocatechol esters are formed by the reaction of muconic anhydride, which is the monooxygenated product, with catechols. It was found that the use of MeOH as the solvent instead of MeCN completely suppressed the catechol ester formation through the methanolysis of muconic anhydride, which greatly improves the degradation efficiency of 4-chlorocatechol. 相似文献
92.
Iida T Satoh H Maeda K Yamamoto Y Asakawa K Sawada N Wada T Kadowaki C Itoh T Mase T Weissman SA Tschaen D Krska S Volante RP 《The Journal of organic chemistry》2005,70(23):9222-9229
[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1. 相似文献
93.
Momchilova S Tsuji K Itabashi Y Nikolova-Damyanova B Kuksis A 《Journal of separation science》2004,27(12):1033-1036
The ability of reversed-phase high-performance liquid chromatography (RP-HPLC) to separate some positionally isomeric disaturated and monounsaturated triacylglycerols (TAGs) as intact species is demonstrated for the first time. Mobile phases of acetonitrile modified with methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, acetone, or dichloromethane were tested for the separation of POP-PPO, PLP-PPL, PEP-PPE, and PDP-PPD (P-palmitic, O-oleic, L-linoleic, E-eicosapentaenoic, D-docosahexaenoic acid residue) on a single RP-HPLC column. The resolution improved with increasing number of double bonds in the acyl residues. While POP and PPO were only partially resolved, PDP and PPD were fully separated with all tested mobile phases, except those containing methanol. Also separated were the four TAGs having the same equivalent carbon number (ECN = 42), PEP, PPE, PDP, and PPD, on a single RP-HPLC column with mobile phase acetonitrile-2-propanol (70:30, v/v) at 0.8 mL/min. In all cases the isomer with the unsaturated acyl residue in either 1- or 3-position was retained more strongly than the respective 2-isomer. 相似文献
94.
Jinno K Sawada H Catabay AP Watanabe H Sabli NB Pesek JJ Matyska MT 《Journal of chromatography. A》2000,887(1-2):479-487
Packed column capillary electrochromatography (CEC), open-tubular CEC and microcolum liquid chromatography (LC) using a cholesteryl silica bonded phase have been studied to compare the retention behavior for benzodiazepines. It has been found that packed column CEC gives better resolution, faster analysis time than microcolumn LC for benzodiazepines maintaining similar selectivity except for some solutes which are charged species under the separation conditions. However, open-tubular CEC gave different selectivities to a larger extent for charged benzodiazepines from that which should be produced by the chromatographic properties of the cholesteryl silica phase. Charged species migration times are mainly influenced by electrophoretic mobility rather than the chromatographic interactions. 相似文献
95.
Yutaka Ono 《Tetrahedron letters》2006,47(4):421-424
The epoxidation of alkenylphosphorus compounds with hydrogen peroxide was systematically studied, revealing that while alkenylphosphine oxides failed to produce the corresponding epoxides, alkenylphosphonates, or phosphinates having a phenyl group at α-position reacted with H2O2/K2CO3 or alkenylphosphonic acids or phosphinic acids having an aliphatic group at α- or β-positions reacted with H2O2/Na2WO4/Et3N to produce high yields of the corresponding epoxides. 相似文献
96.
A biosynthetic gene cluster containing five genes, alt1-5, was cloned from Alternaria solani, a causal fungus of early blight disease to tomato and potato. Homology searching indicated that the alt1, 2, and 3 genes code for cytochrome P450s and the alt4 gene for a FAD-dependent oxygenase/oxidase. The alt5 gene encodes a polyketide synthase (PKS), named PKSN, that was found to be an iterative type I complex reduced-type PKS with a C-methyltransferase domain. To identify the PKSN function, the alt5 gene was introduced into the fungal host Aspergillus oryzae under an alpha-amylase promoter. The transformant produced a polyketide compound, named alternapyrone, whose structure is shown to be 3,5-dimethyl-4-hydroxy-6-(1,3,5,7,11,13-hexamethyl-3,5,11-pentadecatrienyl)-pyran-2-one. Labeling experiments confirmed that alternapyrone is a decaketide with octa-methylation from methionine on every C(2) unit except the third unit. 相似文献
97.
Hwang IW Park M Ahn TK Yoon ZS Ko DM Kim D Ito F Ishibashi Y Khan SR Nagasawa Y Miyasaka H Ikeda C Takahashi R Ogawa K Satake A Kobuke Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(12):3753-3761
The excitation-energy-hopping (EEH) times within two-dimensional cyclic zinc(II)-porphyrin arrays 5 and 6, which were prepared by intermolecular coordination and ring-closing metathesis reaction of olefins, were deduced by modeling the EEH process based on the anisotropy depolarization as well as the exciton-exciton annihilation dynamics. Assuming the number of energy-hopping sites N = 5 and 6, the two different experimental observables, that is, anisotropy depolarization and exciton-excition annihilation times, consistently give the EEH times of 8.0 +/- 0.5 and 5.3 +/- 0.6 ps through the 1,3-phenylene linkages of 5 and 6, respectively. Accordingly, the self-assembled cyclic porphyrin arrays have proven to be well-defined two-dimensional models for natural light-harvesting complexes. 相似文献
98.
Hato M Yamashita I Kato T Abe Y 《Langmuir : the ACS journal of surfaces and colloids》2004,20(26):11366-11373
Temperature- and concentration-dependent aqueous phase diagram of a novel alkylglycoside, 1-O-phytanyl-beta-D-xyloside (beta-Xyl(Phyt)), was studied using small-angle X-ray scattering, polarizing optical microscopy, and differential scanning calorimetry. The phases found in this system include an Lc phase, an Lalpha phase, an HII phase, two inverted cubic phases of crystallographic space groups Pn3m and Ia3d, and a fluid isotropic phase, FI. The phase diagram of the beta-Xyl(Phyt)/water system is similar to that for the 1-monooleylglycerol (MO)/water system, suggesting that the phase behavior is largely determined by the overall molecular shape rather than the details of surfactant molecular structure. Moreover, the structural parameters of the beta-Xyl(Phyt) liquid crystals are also similar to those of the MO/water, due primarily to the similar molecular dimensions of two molecules. As compared to the MO/water system, however, the beta-Xyl(Phyt)/water system displays a lower value of TK ( approximately 8.(5) degrees C) and a wider temperature window for the mesophases (8.(5)-120 degrees C). Moreover, beta-Xyl(Phyt) is chemically more robust than MO, as the ether linkage is more stable against hydrolysis than the ester linkage and the phytanyl chain is fully saturated. 相似文献
99.
Using a technique of laser flash photolysis coupled with vacuum ultraviolet laser-induced fluorescence spectroscopy, the rate coefficients of O(1D) reactions with N2, O2, N2O, and H2O at 295 ± 2 K have been determined to be , kO2=(4.06±0.24)×10-11, kN2O=(1.35±0.08)×10-10 and . The quoted uncertainties include estimated errors and are the 95% confidence level. The kN2 and kN2O values obtained are larger than the current NASA/JPL recommendations by 26% and 16%, respectively, although they are still within the error limits associated with the recommendations. 相似文献
100.
Miyazaki A Fujisawa Y Shiotani K Fujita Y Li T Tsuda Y Yokoi T Bryant SD Lazarus LH Okada Y 《Chemical & pharmaceutical bulletin》2005,53(9):1152-1158
1,2-Dihydropyrazin-2-one derivatives, which have two aminoalkyl groups at the positions 3 and 6, were found to be efficient tools for the construction of potent, selective and long-acting opioid mimetics. During the course of preparation, we found that the catalytic hydrogenation of 3,6-bis(benzyloxycarbonylaminomethyl)-5-methyl-1,2-dihydropyrazin-2-one to remove the benzyloxycarbonyl groups resulted in a side reaction. By MS and NMR studies and by preparation of additional 1,2-dihydropyrazin-2-one derivatives, the structure of the by-product was identified as 3-aminomethyl-5,6-dimethyl-1,2-dihydropyrazin-2-one. Preparation of additional compounds substituted with deuterium provided us with sufficient information to confirm the structure of the product and to support a cyclization mechanism in its formation. 相似文献