全文获取类型
收费全文 | 90410篇 |
免费 | 6991篇 |
国内免费 | 8095篇 |
专业分类
化学 | 44649篇 |
晶体学 | 1391篇 |
力学 | 5619篇 |
综合类 | 832篇 |
数学 | 13451篇 |
物理学 | 39554篇 |
出版年
2025年 | 238篇 |
2024年 | 1090篇 |
2023年 | 1231篇 |
2022年 | 2275篇 |
2021年 | 2602篇 |
2020年 | 3428篇 |
2019年 | 3290篇 |
2018年 | 2660篇 |
2017年 | 2580篇 |
2016年 | 3013篇 |
2015年 | 2964篇 |
2014年 | 3969篇 |
2013年 | 6285篇 |
2012年 | 5197篇 |
2011年 | 4984篇 |
2010年 | 4040篇 |
2009年 | 5088篇 |
2008年 | 5271篇 |
2007年 | 5116篇 |
2006年 | 4456篇 |
2005年 | 3669篇 |
2004年 | 3263篇 |
2003年 | 3281篇 |
2002年 | 3790篇 |
2001年 | 2769篇 |
2000年 | 2634篇 |
1999年 | 2196篇 |
1998年 | 2396篇 |
1997年 | 1533篇 |
1996年 | 1479篇 |
1995年 | 1124篇 |
1994年 | 1121篇 |
1993年 | 847篇 |
1992年 | 909篇 |
1991年 | 590篇 |
1990年 | 556篇 |
1989年 | 419篇 |
1988年 | 379篇 |
1987年 | 359篇 |
1986年 | 299篇 |
1985年 | 298篇 |
1984年 | 277篇 |
1983年 | 178篇 |
1982年 | 242篇 |
1981年 | 205篇 |
1980年 | 148篇 |
1979年 | 172篇 |
1978年 | 148篇 |
1977年 | 126篇 |
1976年 | 90篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Padavattan Govindaswamy Patrick J. Carroll Yurij A. Mozharivskyj Mohan Rao Kollipara 《Journal of Chemical Sciences》2006,118(4):319-326
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl2(κ1-P-PPh2Py)]3 and [(η5-C5Me5) IrCl2(ϰ1-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+
5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+
8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3 and [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+
7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3, [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+
6 are established by single-crystal X-ray diffraction methods 相似文献
2.
We derive a test problem for evaluating the ability of time-steppingmethods to preserve the statistical properties of systems inmolecular dynamics. We consider a family of deterministic systemsconsisting of a finite number of particles interacting on acompact interval. The particles are given random initial conditionsand interact through instantaneous energy- and momentum-conservingcollisions. As the number of particles, the particle density,and the mean particle speed go to infinity, the trajectory ofa tracer particle is shown to converge to a stationary Gaussianstochastic process. We approximate this system by one describedby a system of ordinary differential equations and provide numericalevidence that it converges to the same stochastic process. Wesimulate the latter system with a variety of numerical integrators,including the symplectic Euler method, a fourth-order Runge-Kuttamethod, and an energyconserving step-and-project method. Weassess the methods' ability to recapture the system's limitingstatistics and observe that symplectic Euler performs significantlybetter than the others for comparable computational expense. 相似文献
3.
Raymond Mackay Jie Zhang Qi Wu Yuzhuo Li 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):343-348
The longitudinal relaxation times (T1) of water in concentrated silica and alumina slurries were measured as a function of solids content. It was shown that the results could be fit very well with a two-phase fast-exchange model between free and surface-bound water. As expected, values of T1 for bound water were in the order of 20–2000 times lower than that for free water, indicating a higher effective viscosity of the surface-bound water. The strength of the interaction depended on the particular surface, and all of the aluminas examined interacted more strongly with water than the two silicas studied, which themselves differed considerably. The chemical mechanical polishing (CMP) removal rate of tantalum by silica slurries was shown to be directly correlated with the interaction parameters, derived from the NMR relation times rather than with total surface hydroxyl group concentration. 相似文献
4.
本文是[1,12]的继续,研究描述架中概念的结构;本文讨论后半部分,内容涉及概念内涵与外延的转换,清晰关系的内投影与内变换,概念的结构*以及有关问题的注记。 相似文献
5.
本文首先提出逆(反)对策这一新问题,给出了数学模型;探讨了“奇门遁甲”预测理论(术)中的数学问题;通过系统分析“专门遁甲”预测过程,可知它的预测过程隐含着一个特殊的逆(反)对策问题;最后指出逆(反)对策问题的广泛存在并给出案例分析. 相似文献
6.
Semi-empirical molecular orbital calculations were carried out for the compounds (C2H5)3As, (C2H5)3Ga and RAsH2 (R = C2H5, i-C3H7, i-C4H9, and t-C4H9) by using the CNDO/2-U program, and their capability of β-elimination reaction is compared on the basis of the torsion energy to the transition state, electrostatic interactions and orbital overlapping between the central atom and the β-hydrogen, and bond order of the metal-carbon, and carbon-hydrogen bond. In the comparison of (C2H5)3As with (C2H5)3Ga, we found that the β-elimination of (C2H5)3As could hardly be expected to take place in the thermal decomposition. The capability of β-elimination would be smaller in C2H5AsH2 than that in (C2H5)3As. Moreover when the ethyl group is replaced by a t-butyl group in RAsH2, the β-elimination reaction appears to become more difficult and a large possibility for a radical process is suggested. 相似文献
7.
The phase behavior of binary blends of poly(ether ether ketone) (PEEK), sulfonated PEEK, and sulfamidated PEEK with aromatic polyimides is reported. PEEK was determined to be immiscible with a poly(amide imide) (TORLON 4000T). Blends of sulfonated and sulfamidated PEEK with this poly(amide imide), however, are reported here to be miscible in all proportions. Blends of sulfonated PEEK and a poly(ether imide) (ULTEM 1000) are also reported to be miscible. Spectroscopic investigations of the intermolecular interactions suggest that formation of electron donoracceptor complexes between the sulfonated/sulfamidated phenylene rings of the PEEKs and the n-phenylene units of the polyimides are responsible for this miscibility. © 1993 John Wiley & Sons, Inc. 相似文献
8.
《Journal of Chemical Sciences》2005,117(5):525-531
The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It
has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated
compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of
the silicon atom for SiH
n
F4−n
and SiH
n
F
5−n
1−
. The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the
tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version
of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft
nucleophiles preferably react with SiH
n
F
5−n
1−
, and hard nucleophiles with SiH
n
F4−n
. 相似文献
9.
Pál Sohár Gábor Bernáth Géza Stájer Angela E. Szabo 《Magnetic resonance in chemistry : MRC》1989,27(9):872-876
Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of 1H and 13C NMR spectroscopy and DNOE experiments. 相似文献
10.
《Magnetic resonance in chemistry : MRC》2003,41(8):585-588
A novel, radical responsive MRI contrast agent based on a gadolinium chelate conjugated to a liposome through a disulfide linker was synthesized, with the aim of pursuing the in vivo mapping of radicals. The liposome was prepared by incorporating a thiol‐activated phospholipid, which was subsequently reacted with a gadolinium chelate containing a free thiol group. The long reorientational motion of the supramolecular adduct endows the paramagnetic agent with a relaxivity significantly higher than that of the free complex. The disulfide bond represents a radical‐sensitive moiety and a large decrease in contrast efficacy (T1 relaxivity) is shown upon its cleavage. A preliminary assessment of the system was made by means of in vitro gamma‐irradiation and thiol–disulfide bond exchange with dithiothreitol. Both methods showed a clear dose‐dependent decrease in T1‐relaxivity. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献