全文获取类型
收费全文 | 33489篇 |
免费 | 6344篇 |
国内免费 | 8162篇 |
专业分类
化学 | 24700篇 |
晶体学 | 899篇 |
力学 | 2209篇 |
综合类 | 684篇 |
数学 | 4403篇 |
物理学 | 15100篇 |
出版年
2024年 | 88篇 |
2023年 | 518篇 |
2022年 | 1176篇 |
2021年 | 1222篇 |
2020年 | 1324篇 |
2019年 | 1313篇 |
2018年 | 1131篇 |
2017年 | 1308篇 |
2016年 | 1396篇 |
2015年 | 1653篇 |
2014年 | 2044篇 |
2013年 | 2646篇 |
2012年 | 2899篇 |
2011年 | 3125篇 |
2010年 | 2605篇 |
2009年 | 2664篇 |
2008年 | 2854篇 |
2007年 | 2539篇 |
2006年 | 2448篇 |
2005年 | 2010篇 |
2004年 | 1649篇 |
2003年 | 1229篇 |
2002年 | 1231篇 |
2001年 | 1127篇 |
2000年 | 1126篇 |
1999年 | 752篇 |
1998年 | 518篇 |
1997年 | 479篇 |
1996年 | 444篇 |
1995年 | 351篇 |
1994年 | 352篇 |
1993年 | 293篇 |
1992年 | 213篇 |
1991年 | 196篇 |
1990年 | 195篇 |
1989年 | 159篇 |
1988年 | 145篇 |
1987年 | 119篇 |
1986年 | 84篇 |
1985年 | 55篇 |
1984年 | 55篇 |
1983年 | 50篇 |
1982年 | 48篇 |
1981年 | 42篇 |
1980年 | 28篇 |
1979年 | 13篇 |
1976年 | 8篇 |
1975年 | 9篇 |
1965年 | 11篇 |
1959年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
The reaction of alkali metal hexacyanoferrate(II/III) with (CH2)6N4 (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK2[Fe111(CN)6]·2HMT·4H2O, H2K2[Fe11(CN)6]·2HMT·4H2O, and HNa2[Fe111(CN)6]· 2HMT·5H2O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)6]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate. 相似文献
72.
High-level computations at G3, CBS-Q, and G3B3 levels were conducted, and good-quality C-H and N-H bond dissociation energies (BDEs) were obtained for a variety of saturated and unsaturated strained hydrocarbons and amines for the first time. From detailed NBO analyses, we found that the C-H BDEs of hydrocarbons are determined mainly by the hybridization of the parent compound, the hybridization of the radical, and the extent of spin delocalization of the radical. The ring strain has a significant effect on the C-H BDE because it forces the parent compound and radical to adopt certain undesirable hybridization. A structure-activity relationship equation (i.e., BDE (C-H) = 61.1-227.8 (p(parent)% - 0.75)(2) + 152.9 (p(radical)% - 1.00)(2) + 40.4 spin) was established, and it can predict the C-H BDEs of a variety of saturated and unsaturated strained hydrocarbons fairly well. For the C-H BDEs associated with the bridgehead carbons of the highly rigid strained compounds, we found that the strength of the C-H bond can also be predicted from the H-C-C bond angles of the bridgehead carbon. Finally, we found that N-H BDEs show less dependence on the ring strain than C-H BDEs. 相似文献
73.
Porous ceria-zirconia composite with narrow particle size distribution and large specific surface area was synthesized by a sol-gel process. Chromatographic properties of the native supports was investigated in normal phase mode for the separation of test mixtures of basic, neutral and acidic compounds. The new packing material exhibited polar and basic properties, which are suitable for the separation of basic compounds. Lypophilic packing has been obtained by the modification of the ceria-zirconia with stearic acid, which exhibited strong hydrophobicity relative to the native packing. Therefore, the modified ceria-zirconia behaves as a reversed-phase packing material. Different selectivity towards basic compounds was observed on the new packing compared to the native ceria-zirconia and conventional ODS stationary phase. 相似文献
74.
芦荟中多糖的光度测定新方法 总被引:3,自引:0,他引:3
利用正交试验考察了芦荟多糖与刚果红显色反应的最佳条件;研究了麦芽糖糊精等多糖、蔗糖等低聚糖和葡萄糖等单糖对显色反应的影响;建立了简便快速、常见糖类基本无干扰的测定芦荟多糖含量的吸光光度法。对芦荟鲜叶和芦荟制品中的多糖进行分析,加标回收率在92%~96%范围内,相对标准偏差≤5%。 相似文献
75.
在pH5.0的NaOAc-HOAc缓冲溶液中,过量的硝酸银完全沉淀叶酸,用原子吸收光谱法测定剩余的硝酸银,间接计算出叶酸的含量。方法简单快速,回收率在98%~104%之间,相对标准偏差为2.4%。 相似文献
76.
羧甲基壳聚糖/聚乙烯醇/甘油环氧树脂蛇笼型复合螯合膜的制备及对金属离子的吸附性能 总被引:4,自引:0,他引:4
以交联甘油环氧树脂交联的聚乙烯醇(PVA)为笼树脂,羧甲基壳聚糖(CCTS)为蛇树脂制备了具有蛇笼结构的复合螯合膜,研究了其对Cu^2 、Ni^2 、Pb^2 、Fe^3 、Zn^2 ,Hg”^2 、Cd^2 等金属离子的吸附性能,研究表明,该树脂对Cu^2 、Ni^2 、Pb^2 有较好的吸附性能,其中PVA是对Cu^2 的吸附的主要贡献者,而CCTS则是在对Ni^2 的吸附中起主要作用。该树脂可以用于含Cu^2 废水的处理。 相似文献
77.
Enol and keto tautomers of methyl 3-oxo pentanoate could be separated on a HP-5 capillary column. The chromatographic peaks
were identified by examining characteristic mass ions arose from the corresponding enol and keto molecular ions. The study
showed that the area percentage of enol tautomer is a function of temperature of the column. Treating the column as a reactor,
the energy of activation for the on-column tautomerization could be extracted (35.1 kJ mol−1) by monitoring the loss of the enol tautomer, because the reaction is found to obey pseudo first-order kinetics. The enthalpy
and the entropy changes (ΔH = −3.98 kJ mol−1, ΔS = −7.89 J K−1mol−1) for the enol-to-keto reaction in the stationary phase were also obtained. 相似文献
78.
Protein-ligand interactions may lead to the formation of multiple molecular complexes in dynamic exchange, affecting the kinetic and thermodynamic characteristics of the binding equilibrium. We followed the dissociation kinetics of the transient and specific complex of an antithrombotic peptide N-acetyl-Asp(55)-Phe-Glu-Glu-Ile-Pro(60)-Glu-Glu-Tyr-Leu-Gln(65) with human prothrombin by use of (15)N NMR relaxation dispersion spectroscopy of the peptide. Every one of the five (15)N-labeled adjacent residues of the peptide exhibited apparently different kinetic exchange and relaxation behaviors, which were especially evident at different concentrations of prothrombin. Binding-induced (15)N relaxation dispersion of residues Phe(56), Glu(57), Glu(58), and Ile(59) can be fitted phenomenologically to a two-site on-and-off exchange mechanism with physically feasible relaxation and kinetic parameters obtained for residues Phe(56), Glu(58), and Ile(59), independent of the prothrombin concentration. The apparent kinetic parameters of Glu(57) show some dependence on the concentration of prothrombin and the extracted transverse relaxation rate for Glu(57) in the bound state was severalfold higher than that expected for a protein-peptide complex with a size of approximately 72 kDa. In addition, the equilibrium population of the bound peptide obtained for Glu(57) was inconsistent with those for Phe(56), Glu(58), and Ile(59) and with the prothrombin/peptide ratios used in the experiments. These discrepancies can be explained by the presence of two conformations for the peptide-protein complex exchanging at a rate of approximately 100 s(-)(1). In all, our study shows that fast dissociation of protein-peptide complexes can be studied quantitatively using peptide (15)N NMR relaxation dispersion measurements without a precise knowledge of the peptide and protein concentrations. In addition, protein titration was found to improve the accuracy of quantitative analysis and may make it possible to determine the rate of conformational changes within the protein-peptide complex. 相似文献
79.
80.