全文获取类型
收费全文 | 4064篇 |
免费 | 145篇 |
国内免费 | 18篇 |
专业分类
化学 | 2817篇 |
晶体学 | 40篇 |
力学 | 95篇 |
数学 | 333篇 |
物理学 | 942篇 |
出版年
2024年 | 5篇 |
2023年 | 21篇 |
2022年 | 72篇 |
2021年 | 95篇 |
2020年 | 79篇 |
2019年 | 69篇 |
2018年 | 59篇 |
2017年 | 46篇 |
2016年 | 121篇 |
2015年 | 114篇 |
2014年 | 141篇 |
2013年 | 229篇 |
2012年 | 318篇 |
2011年 | 348篇 |
2010年 | 181篇 |
2009年 | 171篇 |
2008年 | 266篇 |
2007年 | 248篇 |
2006年 | 229篇 |
2005年 | 217篇 |
2004年 | 169篇 |
2003年 | 152篇 |
2002年 | 137篇 |
2001年 | 88篇 |
2000年 | 90篇 |
1999年 | 74篇 |
1998年 | 59篇 |
1997年 | 33篇 |
1996年 | 49篇 |
1995年 | 45篇 |
1994年 | 48篇 |
1993年 | 44篇 |
1992年 | 31篇 |
1991年 | 21篇 |
1990年 | 29篇 |
1989年 | 21篇 |
1988年 | 6篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 12篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 8篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 7篇 |
1973年 | 4篇 |
排序方式: 共有4227条查询结果,搜索用时 0 毫秒
91.
Ei-Ichi Terada Hiroshi Nishikawa Jinsh Cho Eishun Tsuchida 《Journal of polymer science. Part A, Polymer chemistry》1979,17(3):807-813
The equilibrium constants of the coordination reaction of chlorodimethylformamide·cobaloxime with 4-vinylpyridine–styrene copolymers (PPS) were determined. The constants for PPS, which contain 20–50% 4-vinylpyridine (4VP) unit, measured about 1.3 × 105 liter/mole larger than those in the pyridine system (6.8 × 104 liter/mole). When the polymer ligand is 4VP homopolymer or contains less than 20% 4VP unit, K values are lower. The rate constants (kf) of the coordination reactions of the cobaloxime with polymer ligands were also measured in dimethylformamide (DMF) and benzene. In DMF kf decreased with an increase in 4VP unit content of the polymer ligand; in benzene it was increased by the 4VP fraction. These results can be explained by the variation in conformation of the polymer chain in each solvent. The effect of the polymer chain on complexation was discussed on the basis of the kinetic data. 相似文献
92.
Sung-Kyu Kim Su-Dong Cho Deok-Heon Kweon Yong-Jin Yoon Jung-Ho Kim Jung-Nyoung Heo 《Journal of heterocyclic chemistry》1997,34(1):209-214
Alkylations of 4,5-dichloropyridazin-6-one (1) with dibromoalkanes 2 or 3 in the presence of potassium carbonate or tetrabutylammonium bromide/potassium hydroxide were investigated under restricted condition. Reactions of 1 with 2 or 3, except for 2b and 3b , in the presence of potassium carbonate or tetrabutylammonium bromide/potassium hydroxide gave only the N-alkylation products 3 and/or 4. Alkylation of 1 with 2b or 3b in the presence of potassium carbonate yielded the N-alkylation products 3b and/or 4b and the O-alkylation product 5 as the main product, whereas treatment of 1 with 2b or 3b in the presence of tetrabutylammonium bromide/potassium hydroxide afforded selectively the N-alkylation products 3b and/or 4b. 相似文献
93.
94.
95.
96.
Sessler JL Cho WS Lynch V Král V 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(5):1134-1143
The synthesis and structural characterization of hybrid heterocalix[4]arene analogues containing pyrrole, benzene, methoxy-substituted benzene, and pyridine subunits is described. Macrocycles 1 and 2, examples of calix[2]benzene[2]pyrrole and calix[1]benzene[3]pyrrole systems, respectively, are synthesized by the condensation of pyrrole and an appropriate phenylbis(carbinol). Macrocycles 3 and 7, examples of calix[2]benzene[1]pyridine[1]pyrrole and calix[1]pyridine[3]pyrrole, respectively, are synthesized by the use of a carbene-based pyrrole-to-pyridine ring-expansion procedure. Single-crystal X-ray analysis reveals that compounds 1a, 1b, and 2b adopt 1,3-alternate conformations in the solid state, whereas compounds 3 and 7 display structures that are best described as "flattened partial cones" in terms of their conformation. (Series a refers to pure benzene-derived systems, whereas series b indicates macrocycles containing 5-methoxyphenyl subunits). In the solid state, the methoxy-functionalized macrocycles 1b and 2b, and the chloropyridine-containing macrocycle 7 exist as dimers. In the case of 1a and 7, these compounds interact with neutral solvent in the solid state. The conformations of the macrocycles in solution were explored by temperature-dependent proton NMR and NOESY spectral analysis. At 188 K, macrocycles 1a and 2a adopt flattened 1,3-alternate conformations, whereas macrocycles 3 and 7 exist in the form of flattened partial-cone conformations. Standard proton NMR titration analyses were carried out in the case of macrocycles 1a and 2a, and reveal that at least the second of these systems is capable of binding fluoride and chloride anions in CD(2)Cl(2) solution at room temperature (K(a)=571 and 17M(-1) in the case of 2a and F(-) and Cl(-), respectively). 相似文献
97.
A new synthesis of 6‐carbomethoxy‐1,2,3,5‐tetrahydroirnidazo[2,3‐b][1,3]benzodiazocines 13 by the intramolecular cycloaddition reaction of methyl 2‐(1‐aziridinylmethyl)‐3‐(2‐ureidophenyl)propenoates 10 under Appel's dehydration conditions is described. The latter were readily obtained from 2‐nitrobenzalde‐hyde with methyl acrylate through the Baylis‐Hillman reaction. 相似文献
98.
Wenjie Jin Sungbo Cho Namujila Laxi Terigele Bao Lili Dai Hongzhen Yu Rigeer Qi Junqing Zhang Genna Ba Minghai Fu 《Molecules (Basel, Switzerland)》2022,27(10)
Ixeris chinensis (Thunb.) Nakai (IC) is a folk medicinal herb used in Mongolian medical clinics for the treatment of hepatitis and fatty liver diseases even though its pharmacological mechanism has not been well characterized. This study investigated the hepatoprotective mechanism of IC on mice with nonalcoholic fatty liver disease (NAFLD) by integrating gut microbiota and metabolomic analysis. A high-fat diet (HFD) was used to develop nonalcoholic fatty liver disease, after which the mice were treated with oral IC (0.5, 1.5 and 3.0 g/kg) for 10 weeks. HFD induced NAFLD and the therapeutic effects were characterized by pathological and histological evaluations, and the serum indicators were analyzed by ELISA. The gut microbial and metabolite profiles were studied by 16S rRNA sequencing and untargeted metabolomic analysis, respectively. The results showed that the administration of IC resulted in significant decreases in body weight; liver index; serum biomarkers such as ALT, TG, and LDL-C; and the liver inflammatory factors IL-1β, IL-6, and TNF-α. The 16S rRNA sequencing results showed that administration of IC extract altered both the composition and abundance of the gut microbiota. Untargeted metabolomic analysis of liver samples detected a total of 212 metabolites, of which 128 were differentially expressed between the HFD and IC group. IC was found to significantly alter the levels of metabolites such as L-glutamic acid, pyridoxal, ornithine, L-aspartic acid, D-proline, and N4-acetylaminobutanal, which are involved in the regulation of glutamine and glutamate, Vitamin B6 metabolism, and arginine and proline metabolic pathways. Correlation analysis indicated that the effects of the IC extract on metabolites were associated with alterations in the abundance of Akkermansiaceae, Lachnospiraceae, and Muribaculaceae. Our study revealed that IC has a potential hepatoprotective effect in NAFLD and that its function might be linked to improvements in the composition of gut microbiota and their metabolites. 相似文献
99.
Kyung-Hyun Cho 《Molecules (Basel, Switzerland)》2022,27(13)
Human serum amyloid A (SAA) is an exchangeable apolipoprotein (apo) in high-density lipoprotein (HDL) that influences HDL quality and functionality, particularly in the acute phase of inflammation. On the other hand, the structural and functional correlations of HDL containing SAA and apoA-I have not been reported. The current study was designed to compare the change in HDL quality with increasing SAA content in the lipid-free and lipid-bound states in reconstituted HDL (rHDL). The expressed recombinant human SAA1 (13 kDa) was purified to at least 98% and characterized in the lipid-free and lipid-bound states with apoA-I. The dimyristoyl phosphatidylcholine (DMPC) binding ability of apoA-I was impaired severely by the addition of SAA, while SAA alone could not bind with DMPC. The recombinant human SAA1 was incorporated into the rHDL (molar ratio 95:5:1, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC): cholesterol: apoA-I) with various apoA-I:SAA molar ratios from 1:0 to 1:0.5, 1:1 and 1:2. With increasing SAA1 content, the rHDL particle size was reduced from 98 Å to 93 Å, and the α-helicity of apoA-I:SAA was decreased from 73% to 40% for (1:0) and (1:2), respectively. The wavelength maximum fluorescence (WMF) of tryptophan in rHDL was red-shifted from 339 nm to 345 nm for (1:0) and (1:2) of apoA-I:SAA, respectively, indicating that the addition of SAA to rHDL destabilized the secondary structure of apoA-I. Upon denaturation by urea treatment from 0 M to 8 M, SAA showed only a 3 nm red-shift in WMF, while apoA-I showed a 16 nm red-shift in WMF, indicating that SAA is resistant to denaturation and apoA-I had higher conformational flexibility than SAA. The glycation reaction of apoA-I in the presence of fructose was accelerated up to 1.8-fold by adding SAA in a dose-dependent manner than that of apoA-I alone. In conclusion, the incorporation of SAA in rHDL impaired the structural stability of apoA-I and exacerbated glycation of HDL and apoA-I. 相似文献
100.