全文获取类型
收费全文 | 21315篇 |
免费 | 4150篇 |
国内免费 | 3198篇 |
专业分类
化学 | 15688篇 |
晶体学 | 404篇 |
力学 | 1167篇 |
综合类 | 246篇 |
数学 | 2110篇 |
物理学 | 9048篇 |
出版年
2024年 | 85篇 |
2023年 | 527篇 |
2022年 | 951篇 |
2021年 | 1049篇 |
2020年 | 1149篇 |
2019年 | 1111篇 |
2018年 | 941篇 |
2017年 | 919篇 |
2016年 | 1199篇 |
2015年 | 1265篇 |
2014年 | 1491篇 |
2013年 | 1908篇 |
2012年 | 2137篇 |
2011年 | 2119篇 |
2010年 | 1540篇 |
2009年 | 1406篇 |
2008年 | 1510篇 |
2007年 | 1230篇 |
2006年 | 1065篇 |
2005年 | 862篇 |
2004年 | 708篇 |
2003年 | 527篇 |
2002年 | 449篇 |
2001年 | 374篇 |
2000年 | 302篇 |
1999年 | 313篇 |
1998年 | 230篇 |
1997年 | 178篇 |
1996年 | 203篇 |
1995年 | 146篇 |
1994年 | 138篇 |
1993年 | 110篇 |
1992年 | 85篇 |
1991年 | 97篇 |
1990年 | 71篇 |
1989年 | 58篇 |
1988年 | 40篇 |
1987年 | 32篇 |
1986年 | 41篇 |
1985年 | 31篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 9篇 |
1980年 | 4篇 |
1978年 | 3篇 |
1969年 | 2篇 |
1959年 | 2篇 |
1957年 | 7篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Zhu XQ Cao L Liu Y Yang Y Lu JY Wang JS Cheng JP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3937-3945
Five 1-(p-substituted phenyl)-1,4-dihydronicotinamides (GPNAH-1,4-H(2)) and five 1-(p-substituted phenyl)-1,2-dihydronicotinamides (GPNAH-1,2-H(2)) were synthesized, which were used to mimic NAD(P)H coenzyme and its 1,2-dihydroisomer reductions, respectively. When the 1,4-dihydropyridine (GPNAH-1,4-H(2)) and the 1,2-dihydroisomer (GPNAH-1,2-H(2)) were treated with p-trifluoromethylbenzylidenemalononitrile (S) as a hydride acceptor, both reactions gave the same products: pyridinium derivative (GPNA(+)) and carbanion SH(-) by a hydride one-step transfer. Thermodynamic analysis on the two reactions shows that the hydride transfer from the 1,2-dihydropyridine is much more favorable than the hydride transfer from the corresponding 1,4-dihydroisomer, but the kinetic examination displays that the former reaction is remarkably slower than the latter reaction, which is mainly due to much more negative activation entropy for the former reaction. When the formed pyridinium derivative (GPNA(+)) was treated with SH(-), the major reduced product was the corresponding 1,4-dihydropyridine along with a trace of the 1,2-dihydroisomer. Thermodynamic and kinetic analyses on the hydride transfer from SH(-) to GPNA(+) all suggest that the 4-position on the pyridinium ring in GPNA(+) is much easier to accept the hydride than the 2-position, which indicates that when the 1,4-dihydropyridine is used the hydride donor to react with S, the formed pyridinium derivative GPNA(+) may return to the 1,4-dihydropyridine by a hydride transfer cycle; but when the 1,2-dihydropyridine is used as the hydride donor, the formed pyridinium derivative can not return to the 1,2-dihydropyridine by the hydride reverse transfer from SH(-) to GPNA(+). These results clearly show that the hydride-transfer cycle is favorable for the 1,4-dihydronicotinamides, but unfavorable for the corresponding 1,2-dihydroisomers. 相似文献
112.
Wender PA Hegde SG Hubbard RD Zhang L 《Journal of the American Chemical Society》2002,124(18):4956-4957
(-)-Laulimalide (1), a structurally novel macrolide isolated in trace amounts from marine sponges, promotes abnormal tubulin polymerization and apoptosis in vitro, with a similar mode of action to that of Taxol(R), but with potentially less susceptibility to multidrug resistance. Herein, a flexible and convergent asymmetric synthesis of (-)-laulimalide is described. This synthesis featured a highly diastereoselective Sakurai reaction of 2 with 3 and a regioselective macrolactonization of an unprotected vicinal diol. Laulimalide was synthesized in 25 steps (longest linear; 36 overall) in 3.5% overall yield, providing a uniquely short and efficient route to 1 and its analogues. 相似文献
113.
Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions 总被引:1,自引:0,他引:1
Ye Feng WANG Wei DENG Lei LIU Qing Xiang GUO 《中国化学快报》2005,16(9):1197-1200
Arylalkynes are important building blocks for the synthesis of natural products,pharmaceuticals,and artificial molecular devices1.They are often synthesized via the Pd-catalyzed Sonogashira coupling reactions between aryl halides and terminal alkynes2,3.Unfortunately,it remains difficult to apply the Sonogashira reaction to industrial scale and/or pharmaceutical synthesis,due to the high cost of Pd and the difficulty in removing the toxic Pd residues from the reaction products.Thus it is wor… 相似文献
114.
115.
Xiang‐Gao Meng Chun‐Shan Zhou Li Wang Chang‐Lin Liu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):o667-o670
5‐Sulfosalicylic acid (5‐SSA) and 3‐aminopyridine (3‐APy) crystallize in the same solvent system, resulting in two kinds of 1:1 proton‐transfer organic adduct, namely 3‐aminopyridinium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, C5H7N2+·C7H5O6S−·H2O or 3‐APy·5‐SSA·H2O, (I), and the anhydrous adduct, C5H7N2+·C7H5O6S− or 3‐APy·5‐SSA, (II). Both compounds have extensively hydrogen‐bonded three‐dimensional layered polymer structures, with interlayer homo‐ and heterogeneous π–π interactions in (I) and (II), respectively. 相似文献
116.
对近期发展的固体圆二色(CD)光谱测试方法进行了概述、评价和比较, 着重探讨了“浓度效应”的存在使固体CD光谱失真的原因. 通过对本课题组和其他作者已报道的四种化合物的固体CD谱再测试的反思, 强调了依手性化合物的手性光谱学性质不同, 根据浓度梯度实验选择其合适测试浓度的必要性. 对固有手性的阻转异构化合物(S)-1,1'-联二萘酚(S-BINOL)进行了成膜法固体CD谱浓度梯度测试, 发现所得固体薄膜CD谱中也存在着“浓度效应” 相似文献
117.
AbstractPoria cocos is an edible medicinal mushroom with the effects of inducing diuresis, excreting dampness, invigorating the spleen and tranquilizing the mind. The triterpenoids of Poria cocos as the main active ingredients have shown health benefits of the central nervous system of the human body. Accordingly, this study aimed at further understanding the antidepressant-like effect and a potential mechanism of the triterpenoids extracts from Poria cocos (TPC). As a result, the TPC significantly ameliorated depression-like behaviors on chronic unpredictable mild stress (CUMS) rats, and restored the levels of brain-derived neurotrophic factor and nerve growth factor in the hippocampus of rats. Gut microiota analysis revealed that TPC could increase the biodiversity and markedly regulate the relative abundance of [Prevotella], Allobaculum and Ochrobactrum of CUMS rats. The cecal contents metabolomics pointed to thirteen biomarkers associated with TPC antidepressant effect, which involved in primary bile acid biosynthesis, taurine and hypotaurine metabolism, arginine and proline metabolism. Correlation analysis further showed that there was a strong correlation relationship between the gut microbiota and the cecal contents metabolites, especially compounds involved in energy metabolism, inflammation and immunity. In conclusion, TPC showed a potential antidepressant effect, which was possibly mediated the gut microbiota and cecal contents metabolism. 相似文献
118.
119.
120.
In this text, we use inexpensive and natural amino acid, successfully obtained the asymmetric crystallization of three PTCs, [Tis(O~iPr)_(14)(μ_2-O)(μ_3-O)_2(D/L-pGlu)_2](D-PTC-53; L-PTC-53; H2 pGlu=pyroglutamic acid) and [Ti_6(O~iPr)_(14)(μ_2-O)(μ_3-O)_2(D-pGlu)_2][Ti_6(O~iPr)_(14)((μ_2-O)(μ_3-O)_2(L-pGlu)_2](D,L-PTC-53). Interestingly, in situ lactamide reaction starting from glutamic acid to pyroglutamic acid was observed. In addition,the chirality features of these PTCs have been thoroughly discussed.The two enantiomers crys tallize in chiral P21 space group.The optically pure pGlu ligands transform its chirality to the inorganic titanium oxo clusters. As a result, the stack of these inorganic clusters generates homochiral helical chains along the characteristic axial direction.Apart from the microscopic structural analysis, the macroscopic solid-state samples exhibit unusual strong circular dichroism(CD) signals,further verified the homochiral feature of the enantiomers. 相似文献