全文获取类型
收费全文 | 66280篇 |
免费 | 22056篇 |
国内免费 | 3108篇 |
专业分类
化学 | 71794篇 |
晶体学 | 415篇 |
力学 | 3411篇 |
综合类 | 189篇 |
数学 | 5197篇 |
物理学 | 10438篇 |
出版年
2024年 | 215篇 |
2023年 | 4414篇 |
2022年 | 2244篇 |
2021年 | 3459篇 |
2020年 | 5595篇 |
2019年 | 3395篇 |
2018年 | 3139篇 |
2017年 | 1449篇 |
2016年 | 6619篇 |
2015年 | 6695篇 |
2014年 | 6386篇 |
2013年 | 6936篇 |
2012年 | 5408篇 |
2011年 | 3388篇 |
2010年 | 5023篇 |
2009年 | 4870篇 |
2008年 | 2748篇 |
2007年 | 2257篇 |
2006年 | 1460篇 |
2005年 | 1189篇 |
2004年 | 887篇 |
2003年 | 709篇 |
2002年 | 666篇 |
2001年 | 497篇 |
2000年 | 466篇 |
1999年 | 386篇 |
1998年 | 335篇 |
1997年 | 343篇 |
1996年 | 322篇 |
1995年 | 327篇 |
1994年 | 307篇 |
1993年 | 381篇 |
1992年 | 254篇 |
1991年 | 179篇 |
1990年 | 164篇 |
1989年 | 178篇 |
1988年 | 173篇 |
1980年 | 213篇 |
1979年 | 191篇 |
1978年 | 194篇 |
1977年 | 312篇 |
1976年 | 373篇 |
1975年 | 463篇 |
1974年 | 480篇 |
1973年 | 291篇 |
1972年 | 371篇 |
1971年 | 359篇 |
1970年 | 542篇 |
1969年 | 417篇 |
1968年 | 461篇 |
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
81.
In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation. 相似文献
82.
83.
Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport 下载免费PDF全文
B. Sc. Eduard Puig Prof. Dr. Beat Ernst Prof. Dr. Horst Kessler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8023-8027
Recently, oral absorption of cyclic hexapeptides was improved by N‐methylation of their backbone amides. However, the number and position of N‐methylations or of solvent exposed NHs did not correlate to intestinal permeability, measured in a Caco‐2 model. In this study, we investigate enantiomeric pairs of three polar and two lipophilic peptides to demonstrate the participation of carrier‐mediated transporters. As expected, all the enantiomeric peptides exhibited identical lipophilicity (logD7.4) and passive transcellular permeability determined by the parallel artificial membrane permeability assay (PAMPA). However, the enantiomeric polar peptides exhibited different Caco‐2 permeability (Papp) in both directions a–b and b–a. The same trend was observed for one of the lipophilic peptide, whereas the second lipophilic enantiomer pair showed identical Caco‐2 permeability (within the errors). These findings provide the first evidence for the involvement of carrier‐mediated transport for peptides, especially for those of polar nature. 相似文献
84.
Cover Picture: Coordination Chemistry of N‐Heterocyclic Nitrenium‐Based Ligands (Chem. Eur. J. 19/2015) 下载免费PDF全文
85.
Dr. Yogesh Kumar Maurya Dr. Pingchun Wei Takahide Shimada Dr. Kazuhisa Yamasumi Dr. Shigeki Mori Prof. Dr. Ko Furukawa Dr. Hajime Kusaba Prof. Dr. Tatsumi Ishihara Prof. Dr. Yongshu Xie Dr. Masatoshi Ishida Prof. Dr. Hiroyuki Furuta 《化学:亚洲杂志》2021,16(7):743-747
A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials. 相似文献
86.
Mariam Hakami Dr. Geetanjali Deokar Jasmin Smajic Dr. Nitin M. Batra Prof. Pedro M. F. J. Costa 《化学:亚洲杂志》2021,16(11):1466-1474
In the last decade, catalytic chemical vapor deposition (CVD) has been intensively explored for the growth of single-layer graphene (SLG). Despite the scattering of guidelines and procedures, variables such as the surface texture/chemistry of catalyst metal foils, carbon feedstock, and growth process parameters have been well-scrutinized. Still, questions remain on how best to standardize the growth procedure. The possible correlation of procedures between different CVD setups is an example. Here, two thermal CVD reactors were explored to grow graphene on Cu foil. The design of these setups was entirely distinct, one being a “showerhead” cold-wall type, whereas the other represented the popular “tubular” hot-wall type. Upon standardizing the Cu foil surface, it was possible to develop a procedure for cm2-scale SLG growth that differed only by the carrier gas flow rate used in the two reactors. 相似文献
87.
Tuning the Basicity of Cyano‐Containing Ionic Liquids to Improve SO2 Capture through Cyano–Sulfur Interactions 下载免费PDF全文
Dr. Guokai Cui Fengtao Zhang Xiuyuan Zhou Prof. Haoran Li Prof. Jianji Wang Prof. Congmin Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5632-5639
A new approach has been developed to improve SO2 sorption by cyano‐containing ionic liquids (ILs) through tuning the basicity of ILs and cyano–sulfur interaction. Several kinds of cyano‐containing ILs with different basicity were designed, prepared, and used for SO2 capture. The interaction between these cyano‐containing ILs and SO2 was investigated by FTIR and NMR methods. Spectroscopic investigations and quantum chemical calculations showed that dramatic effects on SO2 capacity originate from the basicity of the ILs and enhanced cyano–sulfur interaction. Furthermore, the captured SO2 was easy to release by heating or bubbling N2 through the ILs. This efficient and reversible process, achieved by tuning the basicity of ILs, is an excellent alternative to current technologies for SO2 capture. 相似文献
88.
In the present research, hierarchical structure observation and mechanical property characterization for a type of biomaterial are carried out. The investigated biomaterial is Hyriopsis cumingii, a typical limnetic shell, which consists of two different structural layers, a prismatic "pillar"structure and a nacreous "brick and mortar" structure. The prismatic layer looks like a "pillar forest" with variationsection pillars sized on the order of several tens of microns.The nacreous material looks like a "brick wall" with bricks sized on the order of several microns. Both pillars and bricks are composed of nanoparticles. The mechanical properties of the hierarchical biomaterial are measured by using the nanoindentation test. Hardness and modulus are measured for both the nacre layer and the prismatic layer, respectively.The nanoindentation size effects for the hierarchical structural materials are investigated experimentally. The results show that the prismatic nanostructured material has a higher stiffness and hardness than the nacre nanostructured material.In addition, the nanoindentation size effects for the hierarchical structural materials are described theoretically, by using the trans-scale mechanics theory considering both strain gradient effect and the surface/interface effect. The modeling results are consistent with experimental ones. 相似文献
89.
Studies on metabolites and metabolic pathways of bulleyaconitine A in rat liver microsomes using LC‐MSn combined with specific inhibitors 下载免费PDF全文
Hongbin Zhu Fengrui Song Zhiqiang Liu Shuying Liu 《Biomedical chromatography : BMC》2015,29(7):1027-1034
Bulleyaconitine A (BLA) from Aconitum bulleyanum plants is usually used as anti‐inflammatory drug in some Asian countries. It has a variety of bioactivities, and at the same time some toxicities. Since the bioactivities and toxicities of BLA are closely related to its metabolism, the metabolites and the metabolic pathways of BLA in rat liver microsomes were investigated by HPLC–MSn. In this research, the 12 metabolites of BLA were identified according to the results of HPLC‐MSn data and the relevant literature. The results showed that there are multiple metabolites of BLA in rat liver microsomes, including demethylation, deacetylation, dehydrogenation deacetylation and hydroxylation. The major metabolic pathways of BLA in rat liver microsomes were clarified by HPLC‐MS combined with specific inhibitors of CYP450 isoforms. As a result, CYP3A and 2C were found to be the principal CYP isoforms contributing to the metabolism of BLA. Moreover, CYP2D6 and 2E1 are also more important CYP isoforms for the metabolism of BLA. While CYP1A2 only affected the formation rate of M11, its effect on the metabolism of BLA is very small. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
90.
Marius Lupu Adnana Zaulet Prof. Dr. Francesc Teixidor Prof. Dr. Eliseo Ruiz Prof. Dr. Clara Viñas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6888-6897
The metallacarborane [3,3′‐Co(1,2‐closo‐C2B9H11)2]? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C2B9H7I4)2]? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed. 相似文献