全文获取类型
收费全文 | 71165篇 |
免费 | 7639篇 |
国内免费 | 14070篇 |
专业分类
化学 | 63518篇 |
晶体学 | 2639篇 |
力学 | 1296篇 |
综合类 | 595篇 |
数学 | 5059篇 |
物理学 | 19767篇 |
出版年
2024年 | 139篇 |
2023年 | 1166篇 |
2022年 | 1313篇 |
2021年 | 2357篇 |
2020年 | 2612篇 |
2019年 | 2407篇 |
2018年 | 1984篇 |
2017年 | 2615篇 |
2016年 | 2719篇 |
2015年 | 2385篇 |
2014年 | 3190篇 |
2013年 | 6435篇 |
2012年 | 4524篇 |
2011年 | 4990篇 |
2010年 | 4233篇 |
2009年 | 5013篇 |
2008年 | 4892篇 |
2007年 | 4955篇 |
2006年 | 4641篇 |
2005年 | 4153篇 |
2004年 | 3926篇 |
2003年 | 3211篇 |
2002年 | 2783篇 |
2001年 | 2217篇 |
2000年 | 2115篇 |
1999年 | 1685篇 |
1998年 | 1444篇 |
1997年 | 1269篇 |
1996年 | 1100篇 |
1995年 | 1046篇 |
1994年 | 968篇 |
1993年 | 793篇 |
1992年 | 679篇 |
1991年 | 518篇 |
1990年 | 350篇 |
1989年 | 315篇 |
1988年 | 273篇 |
1987年 | 180篇 |
1986年 | 156篇 |
1985年 | 163篇 |
1984年 | 127篇 |
1983年 | 60篇 |
1982年 | 102篇 |
1981年 | 135篇 |
1980年 | 104篇 |
1979年 | 108篇 |
1978年 | 75篇 |
1977年 | 76篇 |
1976年 | 50篇 |
1973年 | 42篇 |
排序方式: 共有10000条查询结果,搜索用时 234 毫秒
991.
本文用新方法合成了Cr(bza)_3,改进了其mer-、fac-异构体的分离方法;增大了Cr(acac)_3的化学拆分量(1.5g)。试制了DBT(二苯甲酰-d-酒石酸)吸附型手性固定相(CSP),并成功地用于色谱拆分标题配合物的对映体,mer-[Cr(bza)_3]的部分拆分是首次发现的,其他配合物的拆分结果均优于文献方法。根据mer-[Cr(bza)_3)拆分流出液前、后组分的CD光谱,指定了其对映体绝对构型。还讨论了DBT吸附型CSP的拆分效能和色谱特性。 相似文献
992.
Amorphous precursors for PbZrO3 and PbTiO3 ceramics were prepared from lead acetate and the transition metaln-propoxide inn-propanol orn-butoxide inn-butanol and hydrolysed with an excess of water.
According to GLC and TGA/EGA analyses, the type of alkoxide group influences distinctly the structure of heterometallic precursors,
i.e., oxo or acetate bridging, and the amounts of hydroxyl and organic groups bound to the metal network.
The local environments of metal atoms in the amorphous precursors were also studied by EXAFS. The analysis reveals that in
Pb−Zr precursors alkoxide groups modify the coordination spheres of the zirconium atoms. Conversely, local environments of
both lead and titanium atoms within the analysed range of 3.4 A depend weakly on the type of alkoxide used. 相似文献
993.
Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me2Si{3-But-C5H3Rh(C2H4)2}2] By reaction of [{(C2H4)2RhCl}2] with Na2[Me2Si(C5H4)2] or with Li2[Me2Si(3-But-C5H3)2] in THF the dinuclear silylene bridged complexes [Me2Si{C5H4Rh(C2H4)2}2] 1 and [Me2Si{3-But-C5H3Rh(C2H4)2}2] 2 , respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si? C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η3:η3 benzene complex [Me2Si(C5H4Rh2)2C6H6] which cannot be separated from unreacted 1 . However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3 . 相似文献
994.
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
995.
Rabindra N. Roy Lakshmi N. Roy Jason G. Grant Mason P. Cummins Bennett J. Tabor III Sarah J. Richards Curtis A. Himes Bret R. Lively Penny L. Blackwell Ashley N. Simon 《Journal of solution chemistry》2002,31(11):861-872
The values of the second dissociation constant, pK
2, for the dissociation of the NH+ charge center of the zwitterionic buffer compounds 4-(N-morpholino)butanesulfonic acid (MOBS), and N-(2-hydroxyethyl)piperazine-N-4-butanesulfonic acid (HEPBS) have been determined from 5 to 55°C, including, 37°C at intervals of 5°C. The electromotive-force (emf) measurements have been made utilizing hydrogen electrodes and silver–silver chloride electrodes. The value of pK
2 for MOBS was found to be 7.702 ± 0.0005, and 8.284 ± 0.0004 for HEPBS, at 25°C, respectively. The related thermodynamic quantities, G
o, H
o, S
o, and C
p
o for the dissociation processes of MOBS and HEPBS have been derived from the temperature coefficients of pK
2. Both the MOBS and HEPBS buffer materials are useful as primary pH standards for the control of pH 7.3 to 8.6 in the region close to that of physiological fluids. 相似文献
996.
碳苷合成研究——3-β-D-吡喃木糖基-1,2,4-氧杂二唑类化合物的合成 总被引:1,自引:0,他引:1
本文研究了1-(2,3,4-三-O-苯甲酰-β-D-吡喃木糖基)-偕氨基肟与酸酐及酰氯的缩合反应,探讨了不同缩合剂、不同取代基对环合反应的影响,与酸酐反应可以一步完成,且收率较好;与酰氯反应分两步进行,第一步酰化,第二步脱水环合,芳环上取代基的电性效应,决定环合反应的难易,并证明了该环系的碳苷对酸、碱、热具有化学稳定性,本文合成了12个氧杂二唑类木糖碳苷及2个木糖基化的开环产物,通过光谱及元素分析,确定了它们的结构。 相似文献
997.
D. V. Soldatov J. A. Ripmeester 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(1-2):81-84
Inclusion of tert-butylbenzeneinto the l-D channel of the titlehost matrix results in a-[CuL2]1/3(tert-butylbenzene)inclusion compound(trigonal, space groupR =3;a = 24.495(3),c = 10.510(2) Å,V = 5461(1) Å3,Z = 9;R = 0.049). The observed guest–host mole ratio of 1/3 was confirmed by X-ray diffraction and arises from the stoichiometric filling of the larger wide segments of the channel. This contrasts with the benzene inclusion compound studied previously, where both the larger and smaller wide segments were occupied to give a 2/3 guest–host stoichiometry. A comparison of these two structures explains the experimental fact that the guest–host mole ratios for inclusions of the title host lie between values of 1/3 and 2/3for 20 different benzene derivatives. 相似文献
998.
B. Misra 《Journal of statistical physics》1987,48(5-6):1295-1320
It is widely recognized that for highly unstable dynamical systems there exists a fundamental limitation on predictability and determinism. An important class of such highly unstable systems is the class of K-flow, which is further characterized by the existence of time-asymmetric objects in the form of K-partition. Our recent approach to the problem of irreversibility has shown that when the implications of the limitation on determinism arising from strong form of instability and those of the existence of K-partition are consistently taken into account, one is naturally led from the physically unrealizable deterministic evolution of phase points to an entropy-increasing stochastic Markovian evolution. Furthermore, this transition is not the result of extraneously imposed coarse graining and/or approximation schemes, but can be brought about by an invertible transformation whose existence and construction are determined by the nature of the instability of the dynamical system itself. After a brief review of this theory which also contains some relatively new remarks, we prove that classical Klein-Gordon field (both massive and massless) possess the structure of K-flow. This seems to provide the first examples of relativistic systems that are K-flows. Some of the implications of this result are briefly discussed. From a mathematical point of view, this seems to be a first step toward an ergodic theory of partial differential equations. In the process, we also provide an independant group-theoretic proof of the existence of incoming and outgoing subspaces of the scattering theory of Lax and Phillips for the wave equation. 相似文献
999.
M. P. Sassi A. Godone F. Bertinetto 《International Journal of Infrared and Millimeter Waves》1987,8(3):291-297
Point contact MIM diodes of different materials have been tested as harmonic mixers at 29 THz and 88 THz. From the analysis of the I-V static characteristic quantitative informations have been obtained about the effectiveness of the diodes as high order mixers. 相似文献
1000.
G. R. Sudhakaran J. C. Sarker R. L. Bhattacharjee L. H. Johnston 《International Journal of Infrared and Millimeter Waves》1987,8(12):1531-1540
Submillimeter laser-Stark spectra have been observed for the isotopic species of methyl fluoride,13CH3F, using the 337 m line of the HCN laser. We have identified the multiplet transitions as JK=18K17K in the ground vibrational state. Ten distinct families with K=8, 9, 10, 11, 12, 13, 14, 15, 16 and 17 have been observed. Zero-field frequencies for all the transitions are given and in most cases with better accuracy than predicted from the previous constants. 相似文献