全文获取类型
收费全文 | 9055篇 |
免费 | 1708篇 |
国内免费 | 947篇 |
专业分类
化学 | 6073篇 |
晶体学 | 87篇 |
力学 | 735篇 |
综合类 | 67篇 |
数学 | 1136篇 |
物理学 | 3612篇 |
出版年
2024年 | 39篇 |
2023年 | 185篇 |
2022年 | 313篇 |
2021年 | 345篇 |
2020年 | 358篇 |
2019年 | 330篇 |
2018年 | 299篇 |
2017年 | 298篇 |
2016年 | 440篇 |
2015年 | 431篇 |
2014年 | 473篇 |
2013年 | 650篇 |
2012年 | 771篇 |
2011年 | 845篇 |
2010年 | 560篇 |
2009年 | 541篇 |
2008年 | 627篇 |
2007年 | 489篇 |
2006年 | 527篇 |
2005年 | 394篇 |
2004年 | 323篇 |
2003年 | 256篇 |
2002年 | 237篇 |
2001年 | 201篇 |
2000年 | 192篇 |
1999年 | 191篇 |
1998年 | 185篇 |
1997年 | 175篇 |
1996年 | 171篇 |
1995年 | 137篇 |
1994年 | 121篇 |
1993年 | 113篇 |
1992年 | 91篇 |
1991年 | 69篇 |
1990年 | 75篇 |
1989年 | 61篇 |
1988年 | 44篇 |
1987年 | 34篇 |
1986年 | 34篇 |
1985年 | 22篇 |
1984年 | 18篇 |
1983年 | 14篇 |
1982年 | 15篇 |
1981年 | 3篇 |
1980年 | 7篇 |
1979年 | 2篇 |
1975年 | 1篇 |
1959年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
972.
Ling Yang Rong-Zhen Liao Wan-Jian Ding Kai Liu Jian-Guo Yu Ruo-Zhuang Liu 《Theoretical chemistry accounts》2012,131(9):1-12
Mechanisms for the formation of the Schiff base from acetaldehyde and butylamine, glycine and phosphatidylethanolamine based on Dmol3/DFT calculations were realized. For the case of phosphatidylethanolamine, calculations were done under periodic boundary conditions, in an amine-phospholipid monolayer model with two molecules of phosphatidylethanolamine by cell. All models contained explicit aqueous solvent. In the three cases, a neutral amino group is used to model the nucleophilic attack on the carbonyl group of acetaldehyde, and water molecules form hydrogen bond networks. These networks were involved in the reactions by performing as proton-transfer carriers, important in some steps of reactions, and stabilizing reaction intermediates. In all the studied reactions, they take place in two steps, namely: (1) formation of a carbinolamine and (2) its dehydration to the Schiff base, being the dehydration the rate-determining step of the process, consistent with available experimental evidence for similar reactions. The main difference between the studied reactions is found in the value for relative free energy for the intermediates and transition states in the second step; these values are lower in the cases of glycine and phosphatidylethanolamine in comparison with butylamine, due the influence of their molecular environments. Based on the results, the aminophospholipid surface environment and carboxylic group of glycine may boost Schiff base formation via a neighboring catalyst effect. 相似文献
973.
974.
975.
A series of Fe(III), Co(II) and Cu(II) complexes of 8‐quinolinol were encapsulated into the supercages of zeolite? Y and characterized by X‐ray diffraction, SEM, N2 adsorption/desorption, FT‐IR, UV–vis spectroscopy, elemental analysis, ICP‐AES and TG/DSC measurements. The encapsulation was achieved by a flexible ligand method in which the transition metal cations were first ion‐exchanged into zeolite Y and then complexed with 8‐quinolinol ligand. The metal‐exchanged zeolites, metal complexes encapsulated in zeolite–Y plus non‐encapsulated homogeneous counterparts were all screened as catalysts for the aerobic oxidation of styrene under mild conditions. It was found that the encapsulated complexes always showed better activity than their respective non‐encapsulated counterparts. Moreover, the encapsulated iron complex showed good recoverability without significant loss of activity and selectivity within successive runs. Heterogeneity test for this catalyst confirmed its high stability against leaching of active complex species into solution. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
976.
Gang Feng Yongguang Jia Lingyan Liu Weixing Chang Jing Li 《Journal of polymer science. Part A, Polymer chemistry》2010,48(24):5992-6002
A series of novel organotin‐containing core‐cross‐linked knedels and shell‐cross‐linked knedels were first synthesized facilely from poly(styrene)‐b‐poly(acrylate acid) nanoparticles in different selective solvents [Tetrahydrofuran (THF)/H2O or THF/n‐octane] by using organotin compound 1,3‐dichloro‐tetra‐n‐butyl‐distannoxane as a new cross‐linker. The formation of the 1‐chloro‐3‐carboxylato‐tetra‐n‐butyl‐distannoxane layer in our cross‐linking reaction was supported by Fourier transform infrared (FT‐IR) and inductive coupled plasma emission spectrometer (ICP) analysis of the resulting shell‐cross‐linked knedels and core‐cross‐linked knedels. Transmission electron microscopy (TEM) study showed the spherical morphology and the size of the core‐cross‐linked knedels and shell‐cross‐linked knedel. Especially, the layer structure of the core‐cross‐linked knedels was clearly displayed in TEM image. The increase of extent of cross‐linking lead to the increasing of diameter for the shell‐cross‐linked knedels, whereas there was no significant effect on the core‐cross‐linked knedels. Dynamic light scattering (DLS) measurements gave hydrodynamic diameters of the core‐cross‐linked knedels that were in agreement with the TEM diameters. Moreover, the wall thickness of the shell layer of the core‐cross‐linked knedels could be easily modified by varying the block copolymer composition. Notably, the organotin‐containing core‐cross‐linked knedel exhibited highly efficient catalytic activity for the aqueous esterification reaction under nearly neutral conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
977.
对DEPT实验技术的一点改进 总被引:2,自引:0,他引:2
将DEPT -1 3 5实验的 1 3 5° -脉冲分成一个 90°脉冲和一个 4 5°脉冲 ,通过相位循环 ,设计了两个新的DEPT实验分别称为DEPT-90 -4 5和DEPT -90 +4 5。DEPT -90 -4 5谱中只有 -CH3的吸收峰。DEPT -90 +4 5谱中没有 >CH -的吸收峰 ,其 -CH3为正信号 ,-CH2 -为负信号。实验结果显示 ,对比DEPT -90谱 ,这两个新的DEPT谱中完全没有所选基团之外的残余干扰信号 ,而且DEPT -90 -4 5谱比DEPT-90 +4 5谱更好。 相似文献
978.
建议了一个新的双线性旋转去偶序列 ,称为反BIRD (inverse -BIRD) ,其去偶作用与碳连质子的数目有关。将反BIRD结合到INEPT实验中 ,得到了INEPT -iBIRD实验技术 ,它可用于核磁共振碳谱的编辑与简化 相似文献
979.
980.
JPC – Journal of Planar Chromatography – Modern TLC - Two new types of reversed-phase sintered plate have been prepared used in planar electrochromatography (PEC). One was bonded with... 相似文献