全文获取类型
收费全文 | 8917篇 |
免费 | 1213篇 |
国内免费 | 1280篇 |
专业分类
化学 | 5489篇 |
晶体学 | 85篇 |
力学 | 1342篇 |
综合类 | 65篇 |
数学 | 539篇 |
物理学 | 3890篇 |
出版年
2024年 | 18篇 |
2023年 | 102篇 |
2022年 | 184篇 |
2021年 | 267篇 |
2020年 | 362篇 |
2019年 | 306篇 |
2018年 | 286篇 |
2017年 | 369篇 |
2016年 | 386篇 |
2015年 | 357篇 |
2014年 | 466篇 |
2013年 | 737篇 |
2012年 | 577篇 |
2011年 | 623篇 |
2010年 | 474篇 |
2009年 | 547篇 |
2008年 | 509篇 |
2007年 | 553篇 |
2006年 | 468篇 |
2005年 | 486篇 |
2004年 | 418篇 |
2003年 | 350篇 |
2002年 | 307篇 |
2001年 | 312篇 |
2000年 | 245篇 |
1999年 | 226篇 |
1998年 | 200篇 |
1997年 | 165篇 |
1996年 | 149篇 |
1995年 | 152篇 |
1994年 | 123篇 |
1993年 | 89篇 |
1992年 | 81篇 |
1991年 | 73篇 |
1990年 | 64篇 |
1989年 | 42篇 |
1988年 | 46篇 |
1987年 | 34篇 |
1986年 | 31篇 |
1985年 | 32篇 |
1984年 | 32篇 |
1983年 | 11篇 |
1982年 | 26篇 |
1981年 | 17篇 |
1980年 | 17篇 |
1979年 | 19篇 |
1978年 | 10篇 |
1977年 | 22篇 |
1976年 | 13篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
131.
Molecular structures of three emissive annular digold compounds [Au2(dmpm)(dtc)]Cl (dmpm = Me2PCH2PMe2,dtc = S2CNEt2), 1 , [Au2(dppm)(dtc)]PF6, (dppm = Ph2PCH2PPh2),2,and [Au2(dppe)(dtc)]-(PF2) (dppe = Ph2P(CH2)2PPh2), 3, were determined. All three compounds are dimetallacycles having two gold atoms bridged by a dithiolate ligand and a diphosphine ligand, the geometry around each gold atom being almost linear. All the dimetal lacy die rings are slightly distorted from planarity with intramolecular Au-Au distances shorter than 3.0 Å. Compound 1 forms a polymeric chain through intermolecular Au-Au contacts (3.061 ? 3.135 Å). Compound 2 forms a tetramer through intermolecular Au-Au interactions (Au-Au distances ranging from 3.086 to 3.222 ). Compound 3 is monomeric. All of the compounds luminesce at 77 K in the solid state. Emissions originating from 3LMCT from dtc ligand to Au excited states are assigned. The emission maxima of 1 ? 3 are at 541,535 and 520 nm respectively and are blue shifted as the number of Au-Au interactions is decreased. 相似文献
132.
The separation of diastereomeric esters derived from (±)-pyridylethanols and 3β-acetoxyetienic acid were achieved by an extraction technique using diethyl ether and aqueous hydrochloric acid. A formal total synthesis of PNU-142721 was effectively carried out to prepare the chiral, non-racemic synthon 1-furo[2,3-c]pyridin-5-yl-ethanol (1) by means of this technique. The structure optimized using MOPAC calculations on each diastereomer suggested the presence of intramolecular CH/π interaction in only the (S)-isomer of the diastereomers. 相似文献
133.
以作者开发的从蛋白质结合部位推导出其界面所具有的疏水性质和氢键性质的计算程序PP_SITE为基础,利用蛋白质结构数据库(PDB),对蛋白质-蛋白质相互作用界面进行了统计分析.从PDB中挑出非冗余的链间相互作用对,计算出这个数据集中所有链间界面的疏水和氢键相互作用特征.对得到的界面特征进行统计分析,寻找能够明显聚类的界面特征.结果表明,界面大小、氢键和疏水相互作用在界面所占比例以及疏水相互作用的集中程度可以作为分类的依据. 相似文献
134.
使用疏水作用色谱研究蛋白质的构象变化 总被引:2,自引:0,他引:2
研究了高效疏水作用液相色谱中(HIC)色谱条件改变对蛋白质构象的影响。发现固定相配体的疏水性、温度及流动相中盐的阴离子、阳离子和pH值都影响蛋白质的构象。 相似文献
135.
The enthalpies of dilution of l-cystine in solutions of two strong alkalis and one strong acid have been determined by isothermal flow-mix calorimetry at the temperatures 298.15 K, 303.15 K, 308.15 K, 313.15 K and 318.15 K. Equations of apparent enthalpies of dilution have been obtained from the experimental data in terms of the improved McMillan-Mayer theory. Enthalpic interaction coefficients, h2, h3, and h4, are obtained and the values of pair-wise enthalpic interaction coefficient, h2, discussed in the light of solute-solute and solute-solvent interactions. 相似文献
136.
The interaction energy of a molecule M with a point-like charge q can be partitioned into simpler contributions, two of which can be expressed in terms of the charge distribution M of the sole M. The first term, qV(r), represents the interaction of q with the undistorted charge
M
0
of M while the second q
2
P(r) gives the additional contributions due to the polarization of
M
0
under the influence of the charge q placed at the point r. In this paper we investigate the possibility of getting an inexpensive and sufficiently accurate analytical representation of P(r) over the whole space outside the van der Waals volume of M. 相似文献
137.
Summary A set of algorithms designed to enhance the display of protein binding cavities is presented. These algorithms, collectively entitled CAVITY SEARCH, allow the user to isolate and fully define the extent of a particular cavity. Solid modeling techniques are employed to produce a detailed cast of the active site region, which can then be color-coded to show electrostatic and steric interactions between the protein cavity and a bound ligand. 相似文献
138.
将微透析(microdialysis)高效液相色谱法(high performance liquid chromatography,HPLC)联用技术应用于定量研究超氧化物歧化酶(superoxide dismutase)与组氨酸和组氨酸-金属离子配合物的相互作用。实验结果表明: Cu2Zn2SOD酶不仅与组氨酸,而且还可以与组氨酸-Co(Ⅱ)和组氨酸-Ni(Ⅱ)相互 作用,Cu2Zn2SOD酶中的部分Cu(Ⅱ)和Zn(Ⅱ)被诱导和置换出来,并相应地影响了 酶的活性;组氨酸-金属离子配合物的作用比组氨酸强,酶活性降低也更明显;酶 中结合的外来金属离子的量比从酶上被诱导和顶替下来的金属离子的量要少,说明 在溶液中有脱辅基酶的存在。 相似文献
139.
140.
T. Kimura Y. Takahashi T. Kamiyama M. Fujisawa 《Journal of Thermal Analysis and Calorimetry》2007,88(2):587-595
Excess enthalpies (H
E)
of 17 binary mixtures of o- and m-isomers of dichlorobenzene, difluorobenzene, methoxymethylbenzene,
dimethylbenzene, dimethoxybenzene, aminofluorobenzene, fluoronitrobenzene,
diethylbenzene, chlorofluorobenzene, fluoroiodobenzene, bromofluorobenzene,
chloromethylbenzene, fluoromethylbenzene, bromomethylbenzene, iodomethylbenzene,
fluoromethoxybenzene, dibromobenzene at 298.15 K were measured. All excess
enthalpies measured were very small, and those of o-+m-isomers of aminofluorobenzene, dibromobenzene and
iodomethylbenzene were negative but 14 other binary mixtures of isomers were
positive over the whole range of mole fractions. H
E
of o-+m-isomers
of dimethoxybenzene showed the largest enthalpic instability and those of
aminofluorobenzene showed the largest enthalpic stability. There was a correlation
between dipole–dipole interaction, dipole–induced dipole interaction
or entropies of vaporization and excess partial molar enthalpies at infinite
dilution. 相似文献