全文获取类型
收费全文 | 10457篇 |
免费 | 1643篇 |
国内免费 | 1349篇 |
专业分类
化学 | 7608篇 |
晶体学 | 107篇 |
力学 | 445篇 |
综合类 | 151篇 |
数学 | 1172篇 |
物理学 | 3966篇 |
出版年
2024年 | 27篇 |
2023年 | 225篇 |
2022年 | 380篇 |
2021年 | 392篇 |
2020年 | 437篇 |
2019年 | 450篇 |
2018年 | 365篇 |
2017年 | 372篇 |
2016年 | 504篇 |
2015年 | 512篇 |
2014年 | 637篇 |
2013年 | 795篇 |
2012年 | 946篇 |
2011年 | 929篇 |
2010年 | 631篇 |
2009年 | 572篇 |
2008年 | 701篇 |
2007年 | 668篇 |
2006年 | 528篇 |
2005年 | 487篇 |
2004年 | 338篇 |
2003年 | 272篇 |
2002年 | 265篇 |
2001年 | 230篇 |
2000年 | 239篇 |
1999年 | 206篇 |
1998年 | 190篇 |
1997年 | 153篇 |
1996年 | 165篇 |
1995年 | 150篇 |
1994年 | 111篇 |
1993年 | 102篇 |
1992年 | 83篇 |
1991年 | 64篇 |
1990年 | 65篇 |
1989年 | 41篇 |
1988年 | 38篇 |
1987年 | 32篇 |
1986年 | 27篇 |
1985年 | 37篇 |
1984年 | 15篇 |
1983年 | 15篇 |
1982年 | 16篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 4篇 |
1976年 | 6篇 |
1962年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
61.
62.
63.
过渡金属酞等配合物(MPC)用手均相液相氧化中作催化剂已有不少报导,象许多均相催化剂一样,MPC用于均相反应存在着难于从反应体系中分离出来的问题.把均相配合物催化剂固载在无机氧化物如硅股或有机高分子载体上是解决这一问题的一种方法.我们曾尝试把MP。固载在分子筛载体和硅胶载体上,并用ESR研究其对O2的活化作用[1,2].本文报导MPc通过共价键键联固载在SiO2上,并研究其对O2的活化作用.1实验部分1.1试剂HSIC13为日本东京化成株式会社产品,二级试剂·发烟硫酸(SO。质量分数大于20%)为分析纯试剂.PCl5为化学纯试… 相似文献
64.
The new isocyanato carborane anion, [7-OCN-7-CB10H12]− was prepared by the reaction of 7-H3N-7-CB10H12 with triphosgene in the presence of triethylamine. The structure of this compound was established by 1H, 11B and 13C NMR as well as IR spectroscopy. The reactivigty of this compound with a series of organic amines was investigated. The resulting ureas were obtained in good to excellent yields. This approach is suitable for development of compounds for use in tumor selective Boron Neutron Capture Therapy (BNCT). 相似文献
65.
Two new compounds from Zingiber officinale 总被引:1,自引:0,他引:1
Yu Zhao Qiao Feng Tao Rong Ping Zhang Chang Xin Zhou Hui Dou Shu Yun Shi Ye Cheng Xiao Lian Li Sun Su Zeng Ke Xin Huang Xiao Dong Zhang Xiao Kun Li 《中国化学快报》2007,18(10):1247-1249
A new cyclic diarylheptanoid,1,5-epoxy-3-hydroxy-1-(3-methoxy-4,5-dihydroxyphenyl)-7-(4-hydroxyphenyl)-heptane (1),as well as a new monoterpene,10-O-β-D-glucopyranosyl-hydroxy cineole (2) were isolated from the rhizomes of Zingiber officinale. The structures of compounds 1 and 2 were established based on their spectral data.In addition,the antioxidant activities of these compounds were also measured. 相似文献
66.
Enantioselective transition metal catalysis directed by chiral cations is the amalgamation of chiral cation catalysis and organometallic catalysis. Thus far, three strategies have been revealed: ligand scaffolds incorporated on chiral cations, chiral cations paired with transition metal ‘ate’-type complexes, and ligand scaffolds incorporated on achiral anions. Chiral cation ion-pair catalysis has been successfully applied to alkylation, cycloaddition, dihydroxylation, oxohydroxylation, sulfoxidation, epoxidation and C–H borylation. This development represents an effective approach to promote the cooperation between chiral cations and transition metals, increasing the versatility and capability of both these forms of catalysts. In this review, we present current examples of the three strategies and suggest possible inclusions for the future.Enantioselective transition metal catalysis directed by chiral cations is the amalgamation of chiral cation catalysis and organometallic catalysis. 相似文献
67.
68.
Haralampus-Grynaviski N Ransom C Ye T Rôzanowska M Wrona M Sarna T Simon JD 《Journal of the American Chemical Society》2002,124(13):3461-3468
Urocanic acid, UCA, is characterized by two electronic transitions in the UV-B (280-320 nm) which comprise its broad absorption spectrum and give rise to wavelength-dependent isomerization quantum yields. The absorption spectrum of UCA extends into the UV-A (320-400 nm). Given the UV-A component of sunlight is significantly greater than the UV-B component it is hypothesized even weak UV-A photochemistry of UCA could be important for in vivo responses to UV radiation. Degenerate pump-probe experiments performed on t-UCA at several wavelengths in the UV-A reveal an excited-state absorption that undergoes a rapid, approximately 1 ps decay. Photoacoustic experiments performed on both the cis and trans isomers reveal the formation of a long-lived intermediate following UV-A excitation. The efficiency and action spectra for this latter photoactive process are presented and are similar for both isomers of UCA. Cholesterol hydroperoxide assays designed to investigate the nature of the UV-A photoreactivity of t-UCA confirm the production of reactive oxygen species. The bimolecular rate constant for the quenching of singlet oxygen by t-UCA is determined to be 3.5 x 10(6) M(-1) s(-1). Taking into consideration recent theoretical calculations and jet expansion studies of the electronic structure of gas-phase t-UCA, a model is proposed to explain the isomerization and photoreactivity of t-UCA in solution over the UV-A region. 相似文献
69.
The use of acidic mobile phase additives allows the chiral separation of underivatized phenylalanine analogs on a common amylosic column. In addition to decreasing retention and band-broadening arising from non-ideal interactions, acidic additives may also increase selectivity. This appears to be due to the minimization of non-selective binding in the recognition site. Effects of the additives are related to additive pKa and size. Ethanesulfonic acid was typically the most effective additive with trifluoroacetic acid being one of the least effective. 相似文献
70.
用X-射线荧光光谱法,测定了387例内蒙古牧区蒙古族、汉族成人和儿童的发中铜(Cu)、锌(Zn)、铁(Fe)、锶(St)及钙(Ca)的含量,对同一地区蒙、汉族成人间,成人及儿童间发中五种元素含量进行了比较分析。结果表明:蒙汉族成人发中Cu,Zn、Fe含量不受种族及饮食习惯的影响,其含量无显著性差异;蒙汉族成人发中Sr和Ca含量存在着相平行的显著差异;牧区儿童发Zn含量与牧区成人发Zn含量差异无显著性意义,提示牧区儿童不缺Zn,可能与多动物性食物有关;牧区儿童发中Cu、Fe、Sr、Ca均显著低于牧区成人、可能与儿童发育旺盛和Zn摄入量高对Cu、Fe吸收发生抑制有关。 相似文献