全文获取类型
收费全文 | 30866篇 |
免费 | 3769篇 |
国内免费 | 4302篇 |
专业分类
化学 | 20822篇 |
晶体学 | 282篇 |
力学 | 1957篇 |
综合类 | 404篇 |
数学 | 3688篇 |
物理学 | 11784篇 |
出版年
2024年 | 44篇 |
2023年 | 411篇 |
2022年 | 570篇 |
2021年 | 764篇 |
2020年 | 850篇 |
2019年 | 826篇 |
2018年 | 707篇 |
2017年 | 715篇 |
2016年 | 1018篇 |
2015年 | 1046篇 |
2014年 | 1160篇 |
2013年 | 1670篇 |
2012年 | 1957篇 |
2011年 | 3304篇 |
2010年 | 1966篇 |
2009年 | 1941篇 |
2008年 | 1582篇 |
2007年 | 1471篇 |
2006年 | 1410篇 |
2005年 | 1401篇 |
2004年 | 2101篇 |
2003年 | 1426篇 |
2002年 | 1306篇 |
2001年 | 1006篇 |
2000年 | 672篇 |
1999年 | 708篇 |
1998年 | 693篇 |
1997年 | 620篇 |
1996年 | 596篇 |
1995年 | 495篇 |
1994年 | 490篇 |
1993年 | 751篇 |
1992年 | 757篇 |
1991年 | 545篇 |
1990年 | 497篇 |
1989年 | 452篇 |
1988年 | 251篇 |
1987年 | 112篇 |
1986年 | 171篇 |
1985年 | 109篇 |
1984年 | 90篇 |
1983年 | 59篇 |
1982年 | 48篇 |
1981年 | 29篇 |
1980年 | 32篇 |
1979年 | 19篇 |
1978年 | 11篇 |
1977年 | 11篇 |
1975年 | 8篇 |
1973年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
The Diels-Alder reaction between anthracene and tetracyanoethylene in acetonitrile does not reach a steady-state during the first half-life. The reaction follows the reversible consecutive second-order mechanism accompanied by the formation of a kinetically significant intermediate. The experimental observations consistent with this mechanism include extent of reaction-time profiles which deviate markedly from those expected for the irreversible second-order mechanism and initial pseudo first-order rate constants which differ significantly from those measured at longer times. It is concluded that the reaction intermediate giving rise to these deviations cannot be the charge-transfer (CT) complex, which is formed during the time of mixing, but rather a more intimate complex with a geometry favorable to the formation of the Diels-Alder adduct. The kinetics of the reaction were resolved into the microscopic rate constants for the individual steps. The rate constants, as shown in equation 1, at 293 K were observed to be 5.46 M(-)(1) s(-)(1) (k(f)), 14.8 s(-)(1) (k(b)), and 12.4 s(-)(1) (k(p)). Concentration profiles calculated under all conditions show that intermediate concentrations increase to maximum values early in the reaction and then continually decay during the first half-life. It is concluded that the charge-transfer complex may be an intermediate preceding the formation of the reactant complex, but due to its rapid formation and dissociation it is not detected by the kinetic measurements. 相似文献
992.
WU Jin-Gang LI Shu-BenState Key laboratory of Oxo Synthesis Selective Oxidation Ijmzhau Institute of Chemical Physics Academa Smica Lanzhou Gansu 《天然气化学杂志》1995,(1)
EPR and Raman spectroscopy have been used to characterize the catalyst. F-centers with EPR parameter of g=2. 0046 form when gas phase oxygen is admitted onto the catalyst reduced with methane at 800℃- Molecular oxygen plays an induced role in the electron transfer from W4 to the oxygen ion vacancy which is produced by methane reduction. Raman spectra give the further evidence for the production of lattice oxygen from molecular oxygen. 相似文献
993.
YUAN Song-Yue ZHAO ZhenChangchun Institute of Applied Chemistry. Academia Sinica Changchun Jilin CYU Zuo-LongChengdu Institute of Organic Chemistry. Academia Sinica Chengdu. Sichuan To whom correspondence should be addressed 《天然气化学杂志》1995,(3)
The surface basicity of Ti-La-Li multicoinponent oxides has been investigated by means of CO2-TPD. The experiment results show that C2 (C2H6 C2H4) selectivity is related to surface basic strength. The surface active oxygen species have also been characterized by means of XPS, O2-TPD and so on. It has been indicated that C2 selectivity and CH4 conversion are correlated with lattice oxygen and the adsorbed oxygen on the surface of the catalyst respectively In the O2-TPD experiments, it has also been found that there are three kinds of oxygen species on the surface of the series catalvsts, which are a (100℃ 750℃) Among them α-oxvgen causes deep oxidation whileβand γ oxygen species are related to oxidalive coupling of methane (OCM). 相似文献
994.
一阶导数光谱K系数法同时测定硝基酚钠三组分 总被引:2,自引:0,他引:2
研究和建立了同时测定硝基酚钠混合三组份的新方法——一阶导数光谱K系数法。确定了最佳实验条件和测定波长,方法简便、快速、准确。通过对动植物细胞赋活增进剂中邻硝基酚钠、对硝基酚钠、5-硝基愈创木酚钠三组份的直接测定,其相对误差小于2%,相对标准偏差小于3%,回收率为99~103%。 相似文献
995.
本文综述了利用分子对称性简化天然有机产物合成设计的策略,讨论了具有下述四种对称性的分子的合成:一、对称中心和旋转对称轴;二、对称平面;三、潜在的对称性;四、局部的对称性。 相似文献
996.
WANG Shufang SONG Cunjiang ** CHEN Guangxin LIU Jing YANG Chao ZHANG Xihui GUO Tianying ZHANG Banghua State Key Laboratory of Functional Polymer Materials for Adsorption Separation Institute of Polymer Chemistry N & T Joint Academy Nankai University Tianjin China Department of Microbiology Life Science College Nankai University Tianjin China 《Chinese Journal of Reactive Polymers》2004,(Z1)
1. INTRODUCTION Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) has been recognized as apotential environment-friendly substitute for traditional plastics. The structure, mechanicalproperties and biodegradability of PHBV as biodegradable plastic have been reported by many groups [1-3]. However, PHBV presents some problems, such as high cost, slow crystallization rate, relatively difficult processing and high degree of crystallinity. Therefore, it is difficult to use PHBV widel… 相似文献
997.
998.
Large-scale separation of metallic and semiconducting single-walled carbon nanotubes 总被引:6,自引:0,他引:6
Maeda Y Kimura S Kanda M Hirashima Y Hasegawa T Wakahara T Lian Y Nakahodo T Tsuchiya T Akasaka T Lu J Zhang X Gao Z Yu Y Nagase S Kazaoui S Minami N Shimizu T Tokumoto H Saito R 《Journal of the American Chemical Society》2005,127(29):10287-10290
In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way. 相似文献
999.
The localized molecular orbitals (LMOs) of certain quasi-aromatic organic and inor-ganic molecules with six-membered rings have been calculated by virtue of the ab initio methodusing STO-3G and 4-31G basis sets as well as the CNDO/2 method. It is shown that there existsextensively-delocalized p-pπ bonding in these quasi-aromatic systems. The localized pictures ofthe π-type LMOs for the heterocyclic and homocyclic systems from the σ-π localization schemeare discussed. The Generator Orbital approach is utilized to account for the bonding patterns. 相似文献
1000.