全文获取类型
收费全文 | 22180篇 |
免费 | 1983篇 |
国内免费 | 4380篇 |
专业分类
化学 | 12629篇 |
晶体学 | 207篇 |
力学 | 773篇 |
综合类 | 162篇 |
数学 | 339篇 |
物理学 | 3048篇 |
综合类 | 11385篇 |
出版年
2024年 | 142篇 |
2023年 | 429篇 |
2022年 | 849篇 |
2021年 | 790篇 |
2020年 | 804篇 |
2019年 | 667篇 |
2018年 | 592篇 |
2017年 | 719篇 |
2016年 | 845篇 |
2015年 | 857篇 |
2014年 | 1067篇 |
2013年 | 1383篇 |
2012年 | 1276篇 |
2011年 | 1336篇 |
2010年 | 1105篇 |
2009年 | 1315篇 |
2008年 | 1259篇 |
2007年 | 1489篇 |
2006年 | 1387篇 |
2005年 | 1321篇 |
2004年 | 1192篇 |
2003年 | 958篇 |
2002年 | 848篇 |
2001年 | 703篇 |
2000年 | 729篇 |
1999年 | 621篇 |
1998年 | 545篇 |
1997年 | 498篇 |
1996年 | 434篇 |
1995年 | 395篇 |
1994年 | 338篇 |
1993年 | 328篇 |
1992年 | 290篇 |
1991年 | 203篇 |
1990年 | 189篇 |
1989年 | 173篇 |
1988年 | 161篇 |
1987年 | 101篇 |
1986年 | 51篇 |
1985年 | 42篇 |
1984年 | 27篇 |
1983年 | 19篇 |
1982年 | 20篇 |
1981年 | 15篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1977年 | 2篇 |
1971年 | 1篇 |
1957年 | 4篇 |
1955年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
变性剂诱导的多结构域蛋白质变性现象的研究 总被引:1,自引:0,他引:1
从蛋白质变性的构象渐变模型出发,分析了多结构域蛋白质变性过程的特点,用吸附动力学方法得到了可描述多个结构域变性的关系表示式,特别对典型双结构域蛋白质变性过程予以较详细的讨论。通过对比理论计算结果与实验观测结果,发现在一定参数条件下两者符合较好,从构象渐变的观点,对双结构域蛋白质变性过程中出现双S形变性曲线的原因做出了解释,同时对变性过程中可能出现的一些情况进行了预测和分析。 相似文献
72.
G. N. Merrill 《Journal of Physical Organic Chemistry》2007,20(1):19-29
Ab initio molecular orbital calculations were carried out on epibromohydrin (EBH) and epichlorohydrin (ECH) in an attempt to elucidate their reactivity with respect to a hard nucleophile, hydroxide. These systems were modeled in both the gas phase and a polar solvent under basic conditions. In the gas phase, it was determined that a direct displacement mechanism (nucleophilic attack at the C1 position) was operative for EBH, while an indirect pathway (nucleophilic attack at the C3 position and subsequent intramolecular displacement) was followed for ECH. In an acetone solution, only the indirect displacement mechanism was found to occur. An electrostatic argument is advanced to account for this behavior in polar solution. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
73.
74.
N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods
in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization
of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly
accepted. Bridged TS are formed by both the substitution mechanism S
N
2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise
N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized
upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates
of N-acylalkylation, as was demonstrated by localization of the corresponding TS.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007. 相似文献
75.
The adsorption behavior (capacity, density distribution and packing density) and the isosteric heat versus loading in a slit pore whose walls contain defective graphene layers are investigated in this paper. The defective wall is characterized by the extent and size of the defect. Simulation results obtained with the Grand Canonical Monte Carlo method reveal complex patterns of isosteric heat, and this complex behavior is a result of the interplay between three factors: (i) the surface heterogeneity (solid-fluid interaction, sites with varying degree of affinity), (ii) fluid-fluid interaction and (iii) the overlapping of potentials exerted by the two defective walls. We illustrate this with argon adsorption in pores of various sizes, and results obtained from the simulation agree qualitatively with the experimental data at 77 K on Saran microporous S600H and micro-mesoporous S84 charcoals of Beebe et al. [R.A. Beebe, B. Millard, J. Cynarski, J. Am. Chem. Soc. 75 (1953) 839]. The S600H was found to contain pores predominantly in the neighborhood of 7 Å with 30% of defect and a defective size of 2.84 Å. This is consistent with the argument made by Beebe et al. that this sample is a microporous solid and most pores can accommodate only one layer. The other sample, S84, has larger pores than S600H, and it is found that it has a wider pore size distribution and the pore width is centered at about 12 Å. 相似文献
76.
By using the tools of statistical physics and recent investigations of the scaling properties of different complex networks,
the structural and evolving properties of the Chinese railway network (CRN) is studied. It has been verified that the CRN
has the same small-world properties of the Indian railway network (IRN). According to the class of small-world networks, we
believe the CRN is a single scale. In addition, a novel result is obtained. Measurements on the CRN indicate that the rate
at which nodes acquire links depends on the node’s degree and follows a power law.
相似文献
77.
Summary The enzymes a-amylase, invertase and glucoamylase were immobilized on acid activated montmorillonite using two techniques,
viz. adsorption and covalent binding, and their activities were tested in a batch and packed-bed reactor and were compared. The
packed-bed reactor showed an improved performance for all immobilized enzymes, which was attributed to lowering of diffusional
restrictions to mass transfer. Lower activity in case of batch reactor for immobilized invertase was due to a combined effect
of loss of native conformation of enzyme on account of immobilization and mass transfer resistances due to improper diffusion
of substrate to the active site of enzyme. For immobilized glucoamylase, the packed-bed reactor demonstrated exceptionally
high activity that was very close to the free enzyme. Covalently bound glucoamylase showed higher activity than the free enzyme. 相似文献
78.
现场拉曼光谱研究乙腈在金电极上的解离吸附行为 总被引:2,自引:1,他引:1
利用共焦显微拉曼系统、结合合适的电极表面粗糙方法研究了非水体系 0 1mol/LLiClO4 /CH3CN溶液中 ,乙腈分子在金表面的吸附和解离行为。结果表明非水体系中乙腈可在金表面发生还原反应 ,产物CN- 离子与电极表面作用形成的表面配合物可在较宽的电位区间吸附于电极表面。溶液中的微量水、激光照射以及电极电位均对该反应有较大的影响。通过拉曼谱图的比较得出乙腈分子解离出的CN- 在金电极表面比在银电极表面有更强的吸附作用。 相似文献
79.
采用从头算CCSD(T)/6-311 G(2d,2p)//B3LYP/6-311G(d,p)方法,研究了自由基-分子反应F CH2CHCH3的各种不同的反应通道.该反应主要是通过复合物形成机制进行,即F分别加到碳碳双键的两端形成自由基复合物1和2.这两种亚稳态自由基会解离成三种产物:H C3H5F、CH3 C2H3F和HF C3H5.理论计算结果表明,生成CH3 C2H3F是反应的主要通道,而生成H C3H5F和HF C3H5对产物也有一定的贡献.这一结果和实验符合得很好. 相似文献
80.
The mechanism of the asymmetric hydrogenation of 2-acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines, the first reported reaction with the Noyori-Takaya Ru(CH3COO)2(binap) complex, has been investigated by means of deuterium labeling, kinetics, and NMR analysis. A series of experiments has revealed that (1) a monohydride-unsaturated mechanism operates involving the initial formation of RuH followed by reaction with the enamide substrate, (2) the hydride transfer from RuH to the olefinic double bond is endothermic and reversible, and (3) the rate is determined in the hydrogenolysis step. This view is consistent with that of proposed for the BINAP-Ru catalyzed Kagan reaction. 相似文献