全文获取类型
收费全文 | 90596篇 |
免费 | 16362篇 |
国内免费 | 9191篇 |
专业分类
化学 | 61622篇 |
晶体学 | 916篇 |
力学 | 5746篇 |
综合类 | 512篇 |
数学 | 10096篇 |
物理学 | 37257篇 |
出版年
2024年 | 344篇 |
2023年 | 2044篇 |
2022年 | 3293篇 |
2021年 | 3563篇 |
2020年 | 3928篇 |
2019年 | 3510篇 |
2018年 | 3218篇 |
2017年 | 2866篇 |
2016年 | 4585篇 |
2015年 | 4363篇 |
2014年 | 5320篇 |
2013年 | 6765篇 |
2012年 | 8215篇 |
2011年 | 8400篇 |
2010年 | 5547篇 |
2009年 | 5381篇 |
2008年 | 5780篇 |
2007年 | 5069篇 |
2006年 | 4762篇 |
2005年 | 3821篇 |
2004年 | 2947篇 |
2003年 | 2295篇 |
2002年 | 2111篇 |
2001年 | 1816篇 |
2000年 | 1604篇 |
1999年 | 1840篇 |
1998年 | 1591篇 |
1997年 | 1576篇 |
1996年 | 1563篇 |
1995年 | 1322篇 |
1994年 | 1150篇 |
1993年 | 996篇 |
1992年 | 858篇 |
1991年 | 783篇 |
1990年 | 643篇 |
1989年 | 501篇 |
1988年 | 370篇 |
1987年 | 308篇 |
1986年 | 323篇 |
1985年 | 261篇 |
1984年 | 151篇 |
1983年 | 117篇 |
1982年 | 100篇 |
1981年 | 57篇 |
1980年 | 42篇 |
1979年 | 15篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1957年 | 31篇 |
1922年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
971.
972.
973.
Yongqiang Zhang ShengzhengWang Zhenyuan Miao Jianzhong Yao Wannian Zhang Chunquan Sheng 《中国化学》2013,(9):1139-1143
Iodiconazole is a novel antifungal agent that was developed in its racemic form. In order to investigate the ef- fects of the chiral center on the antifungal activity, R- and S-isomers of iodiconazole were prepared on the basis of the asymmetric Sharpless epoxidation. (S)-Iodiconazole was proved to have better antifungal activity than the (R)- isomer. The binding modes of the two isomers with lanosterol 14~z-demethylase were clarified by molecular dock- ing. 相似文献
974.
An effective approach for the direct benzylhalogenation with in situ generation of hypervalent halides has been developed.A variety of benzyl halides are produced in moderate to excellent yields(up to 99%) with high regioselectivities.UV absorption spectrum is employed to detect the formation of ferr-butyl hypoiodite. 相似文献
975.
Well-dispersed graphene materials reduced by Ac under hydrothermal condition were used as conductive additives to improve intrisic disadvantage of promising LiFePO4 battery materials, which was synthesized at surface of graphene sheets. The as-prepared LiFePO4/graphene composites were characterized by X-ray powder diffraction (XRD), scan electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge tests. The results show that, compared with conventional LiFePO4 platelets, the composite deliver excellent electrochemical performances, due to flexible graphene-based porous conducting network. We believe that such a facile process will provide a new pathway for further enhancing its energy storage efficiency. 相似文献
976.
Ying Zhang Wei Shen Zhongping Ou Weihua Zhu Yuangyuan Fang Karl M. Kadish 《Electroanalysis》2013,25(6):1513-1518
Two iron(I) porphyrins were electrogenerated and then utilized as catalysts for the reductive dechlorination of 1,1‐bis(4‐chlorophenyl)‐2,2,2‐trichloroethane (DDT) in N,N′‐dimethylformamide. No reaction is observed between DDT and the Fe(III) or Fe(II) forms of the porphyrin, but the electrogenerated Fe(I) porphyrin efficiently catalyzes the electroreduction of DDT to give (1,1‐bis(4‐chlorophenyl)‐2,2‐dichloroethane) DDD, (1,1‐bis(4‐chlorophenyl)‐2,2‐dichloroethylene) DDE and (1,1‐bis(4‐chlorophenyl)‐2‐dichloroethane) DDMU as determined by GC‐MS analysis. The reductive dechlorination was monitored by electrochemistry, controlled potential electrolysis and spectroelectrochemistry and a mechanism for the reaction involving the reduced porphyrins and DDT is proposed. Comparisons are also made between the catalytic properties of metalloporphyrins containing iron, cobalt and manganese central metal ions under the same solution conditions. 相似文献
977.
Qiongbo Zhou Xuzhuo Sun Haibo Zhang Chunlan Xia Xiaohai Zhou 《Journal of Cluster Science》2013,24(4):969-977
A crystal structure of {H2O@CB[5]·(NH4PF6)2}·9(H2O) which consists of supramolecular chains self-assembled by water clusters and water capsules alternately was demonstrated. A water molecule is encapsulated in the cavity of CB[5] whose portals are occupied by two NH4 +, resulting in the formation of water capsule. The water clusters are made up of (H2O)4 and (H2O)5 clusters. The (H2O)4 cluster forms zigzag line and (H2O)5 features “Y-shape” structure. Moreover, anion channels consisting of six parallel supramolecular chains are occupied by PF6 ?. 相似文献
978.
Computational investigation of the heat of formation, detonation properties of furazan-based energetic materials 总被引:1,自引:0,他引:1
The heats of formation (HOFs) for a series of furazan-based energetic materials were calculated by density functional theory. The isodesmic reaction method was employed to estimate the HOFs. The result shows that the introductions of azo and azoxy groups can increase the HOF, but the introduction of azo group can increase the more HOF, when compared with azoxy group. The detonation velocities and detonation pressures of the furazan-based energetic materials are further evaluated at B3LYP/6-31G* level. Dioxoazotetrafurazan and azoxytetrafurazan may be regarded as the potential candidates of high-energy density materials because of good detonation performance. In addition, there are good linear correlations between OB and detonation velocities, and OB and detonation pressures. The energy gaps between the HOMO and LUMO of the studied compounds are also investigated. These results provide basic information for the molecular design of novel high-energy density materials. 相似文献
979.
Yue Zhang Guowen Zhang Xiaoyue Zhou Yu Li 《Analytical and bioanalytical chemistry》2013,405(27):8871-8883
Acetamiprid (ACT) is an insecticide widely used for controlling a variety of insect pests. The binding mode associated with calf thymus DNA (ctDNA) upon interaction with ACT was determined using spectroscopic, chemometrics, and molecular docking techniques to clarify the interaction mechanism at the molecular level. Fluorescence titration suggested that the fluorescence quenching of ACT by ctDNA is a static procedure. The binding constants between ACT and ctDNA at different temperatures were calculated to be of the order 103?104 L mol?1. The positive values of enthalpy and entropy change suggested that the binding process is primarily driven by hydrophobic interactions. Multivariate curve resolution?alternating least squares (MCR?ALS), a chemometrics approach, was used to resolve the expanded UV–visible spectral data matrix. The concentration profiles and the spectra for the three reaction components (ACT, ctDNA, and ACT?ctDNA complex) of the system, which formed a highly overlapping composite response, were then successfully obtained and used to evaluate the progress of ACT interacting with ctDNA. The results of the single-stranded ctDNA and iodide quenching experiments, ctDNA-melting investigations, and viscosity measurements indicated that ACT binds to ctDNA by means of a partial intercalation. Molecular docking studies showed that the specific binding site is mainly located between the ACT and G–C base pairs of ctDNA. This docking prediction was confirmed by use of Fourier-transform infrared (FT-IR) spectral analysis. Results from circular dichroism (CD) spectroscopy revealed that ACT induced a conformational change from the B–ctDNA form to the A–ctDNA form. Figure
Acetamiprid partialintercalative binding to ctDNA 相似文献
980.
F. Yang J. Mao X. W. He L. X. Chen Y. K. Zhang 《Analytical and bioanalytical chemistry》2013,405(21):6639-6648
In this study, a boronate-silica hybrid affinity monolith was prepared for specific capture of glycoproteins at neutral pH condition. The monolith was synthesized via a facile one-pot procedure in a stainless steel column by concurrently mixing hydrolyzed alkoxysilanes tetramethoxysilane and vinyltrimethoxysilane, organic monomer 3-acrylamidophenylboronic acid and initiator 2,2′-azobisisobutyronitrile together. The polycondensation of alkoxysilanes and copolymerization of organic monomer and vinyl-silica monolith were carried out successively by reacting at different temperatures. After optimizing the preparation conditions, the resulting hybrid affinity monolith was systematically characterized and exhibited excellent affinity to both cis-diol-containing small molecules and glycoproteins at neutral and physiological pH, including adenosine, horseradish peroxidase, transferrin and ovalbumin. The binding capacity of ovalbumin on monolith was measured to be 2.5 mg g?1 at pH 7.0. Furthermore, the hybrid affinity monolith was applied to the separation of transferrin from bovine serum sample at a physiological condition. Good repeatability was obtained and the relative standard deviations of retention time were 1.15 and 4.77 % (n?=?5) for run-to-run and column-to-column, respectively. 相似文献