全文获取类型
收费全文 | 7034篇 |
免费 | 1137篇 |
国内免费 | 479篇 |
专业分类
化学 | 4516篇 |
晶体学 | 24篇 |
力学 | 815篇 |
综合类 | 55篇 |
数学 | 366篇 |
物理学 | 2183篇 |
无线电 | 691篇 |
出版年
2024年 | 18篇 |
2023年 | 77篇 |
2022年 | 247篇 |
2021年 | 340篇 |
2020年 | 307篇 |
2019年 | 201篇 |
2018年 | 220篇 |
2017年 | 219篇 |
2016年 | 343篇 |
2015年 | 341篇 |
2014年 | 364篇 |
2013年 | 635篇 |
2012年 | 404篇 |
2011年 | 437篇 |
2010年 | 306篇 |
2009年 | 401篇 |
2008年 | 408篇 |
2007年 | 411篇 |
2006年 | 405篇 |
2005年 | 366篇 |
2004年 | 334篇 |
2003年 | 305篇 |
2002年 | 261篇 |
2001年 | 180篇 |
2000年 | 177篇 |
1999年 | 121篇 |
1998年 | 120篇 |
1997年 | 118篇 |
1996年 | 103篇 |
1995年 | 86篇 |
1994年 | 66篇 |
1993年 | 55篇 |
1992年 | 68篇 |
1991年 | 41篇 |
1990年 | 33篇 |
1989年 | 12篇 |
1988年 | 23篇 |
1987年 | 13篇 |
1986年 | 10篇 |
1985年 | 10篇 |
1984年 | 15篇 |
1983年 | 2篇 |
1982年 | 16篇 |
1981年 | 9篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
排序方式: 共有8650条查询结果,搜索用时 671 毫秒
141.
DTA/TG and TG/DTG thermal studies and XRD investigations were carried out on pastes of lime-pozzolan binders to examine the
relative hydration process. The binders were prepared with two natural pozzolans and hydrated lime, mixed together in different
proportions. The main hydrated phases formed in the pastes are calcium silicate hydrate (CSH) and mono-carboaluminate. The
growth of CSH was greater for the paste of the pozzolan richer in reactive constituents. For pastes with a higher lime/pozzolan
ratio, a slowing of the formation of CSH was observed, while the formation of monocarboaluminate was more intense. The calcium
hydroxide contents of the pastes obtained by thermogravimetric analysis made it possible to determine the pozzolanic activities
of the two pozzolans under examination. The mortars for the various lime-pozzolan binders displayed characteristic hardening.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
142.
Quantum chemical calculations at mPW1PW91 level, with full geometry optimization, using the 6-31g(d) basis set, and GIAO (gauge including atomic orbitals) 13C NMR chemical shifts using the 6-31g(d,p) basis set, are here utilized as a support to define the configurational features of the natural product passifloricin A, whose previously proposed relative configuration has been recently shown, by synthetic studies, to be incorrect. This study suggests that the relative stereostructure for passifloricin A corresponds to the δ-lactone of the (5R,7R,9S,11R)-tetrahydroxyhexacos-2-enoic acid. 相似文献
143.
Francisco Sarabia 《Tetrahedron letters》2003,44(41):7671-7675
A synthetic approach to the [15]-membered stevastelins, a novel class of immunosuppressant agents, is reported based on a macrolactamization route to the 2,3-epoxy derivative 6. The synthesis of this compound was achieved via a stereoselective epoxidation of the allylic alcohol 13, followed by a coupling reaction with a variety of peptide derivatives to give the epoxy peptides 7-10. After an extensive study of cyclizations with these precursors, the best result was achieved with the macrolactamization of 8 in the presence of DEPC, to obtain the epoxy cyclic depsipeptide 6 in 42% yield. From this product, an epoxy analogue of stevastelin B, compound 27, was prepared. Finally, the synthesis of the natural product was attempted through the opening of the oxirane ring contained in 6 and 26, with a variety of methyl cuprate reagents, but without success. 相似文献
144.
The paper represents a further development of our hydrate hypothesis of simplest living matter origination (SLMO) from inorganic and simplest organic mineral substances. It is supposed that the sources of SLMO are simplest aliphatic hydrocarbons, niters, and phosphates. Thermodynamic calculations demonstrating a principal possibility for simultaneous syntheses of different nitrogen bases, d-ribose, and desoxy-d-ribose from these source substances are presented. The most probable principal mechanism of SLMO and the principal conditions necessary for realization of the proposed chemism of SLMO in the framework of the proposed mechanism are considered. A principal means for testing the hypothesis is proposed. 相似文献
145.
G. S. M. Moore 《Journal of Thermal Analysis and Calorimetry》1993,40(1):115-120
The bacground to the supposed development of the ‘Beilby layer’ on fine-grinding quartz is briefly reviewed. It is shown, using single crucible thermal analysis and sub-milligram DTA, that grinding quartz can cause a dispersion of the α-β inversion over a temperature range of several degrees; this is a crystallographic effect rather than an impurity effect. The sub-milligram DTA apparatus used is described and some thermal effects, such as impurity zoning, are illustrated. 相似文献
146.
Drahl C Cravatt BF Sorensen EJ 《Angewandte Chemie (International ed. in English)》2005,44(36):5788-5809
Researchers in the post-genome era are confronted with the daunting task of assigning structure and function to tens of thousands of encoded proteins. To realize this goal, new technologies are emerging for the analysis of protein function on a global scale, such as activity-based protein profiling (ABPP), which aims to develop active site-directed chemical probes for enzyme analysis in whole proteomes. For the pursuit of such chemical proteomic technologies, it is helpful to derive inspiration from protein-reactive natural products. Natural products use a remarkably diverse set of mechanisms to covalently modify enzymes from distinct mechanistic classes, thus providing a wellspring of chemical concepts that can be exploited for the design of active-site-directed proteomic probes. Herein, we highlight several examples of protein-reactive natural products and illustrate how their mechanisms of action have influenced and continue to shape the progression of chemical proteomic technologies like ABPP. 相似文献
147.
3d‐Metal mononitrides are studied using the density functional theory method. The lowest spin state for these dimers is obtained using the B3LYP hybrid functional with the 6‐311+G* basis set. The equilibrium geometries, vibrational frequencies, binding energies, Mulliken, and natural orbital population analysis charges, natural orbital electronic configuration, electron affinity, and ionization potential are obtained. Mulliken as well as natural orbital population analysis charges indicate that for all dimers, in cations most of the positive charge localized on the transition metal atom where in anions most of the negative charge localized on nitrogen atom. The binding energies for 3d‐metal mononitrides are higher than those for monocarbides and monoxides. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
148.
149.
C30卡宾三叶结分子结构与稳定性的理论研究 总被引:1,自引:0,他引:1
三叶结分子是最简单的非平凡纽结分子, C30卡宾三叶结分子是由一条闭合的(C≡C—)15 sp杂化碳链组成的, 是具有D3对称性的拓扑手性分子. 本文用密度泛函方法[DFT/RB3LYP/6-31G(D)]对分子结构和光谱性质进行了研究, 在优化构型的基础上通过自然键轨道(NBO)方法和轨道能级研究了它的共轭性、成键情况和稳定性, 并与平面型C30卡宾环分子进行了比较. 计算结果表明三叶结分子的三叶弧上形成了非平面的C≡C共轭和扭曲的内螺旋结构, 交叉处具有弱成键作用, 且分子轨道也发生了扭曲; 三叶结分子比卡宾环的共轭性和赝Jahn-Teller效应都明显小, 而总能量高. 因此, 分子打结是一个能量升高的过程. 相似文献
150.
Quantum equations of motion describing the energy transfer dynamics via intramolecular anharmonic coupling are presented and solved numerically. Dynamical features of the average excitations of a homogeneous system (SF6) and a heterogeneous system (H/W) are quantitatively discussed in terms of the intramolecular vibrational relaxation (IVR) rates. Possible mechanisms of surface-enhanced desorption via low-power laser radiation are proposed.This work was supported in part by the Office of Naval Research, the Air Force Office of Scientific Research (AFSC), United States Air Force, under Grant AFOSR-82-0046 and the National Science Foundation under Grant No. CHE-8022874Camille and Henry Dreyfus Teacher-Scholar (1975–82) 相似文献