全文获取类型
收费全文 | 77897篇 |
免费 | 15601篇 |
国内免费 | 6632篇 |
专业分类
化学 | 70245篇 |
晶体学 | 845篇 |
力学 | 3306篇 |
综合类 | 483篇 |
数学 | 7271篇 |
物理学 | 17980篇 |
出版年
2024年 | 109篇 |
2023年 | 795篇 |
2022年 | 1182篇 |
2021年 | 1548篇 |
2020年 | 2756篇 |
2019年 | 3951篇 |
2018年 | 2326篇 |
2017年 | 1944篇 |
2016年 | 5113篇 |
2015年 | 5210篇 |
2014年 | 5593篇 |
2013年 | 6958篇 |
2012年 | 6653篇 |
2011年 | 6214篇 |
2010年 | 5451篇 |
2009年 | 5380篇 |
2008年 | 5210篇 |
2007年 | 4367篇 |
2006年 | 3839篇 |
2005年 | 3557篇 |
2004年 | 2874篇 |
2003年 | 2517篇 |
2002年 | 3235篇 |
2001年 | 2358篇 |
2000年 | 2213篇 |
1999年 | 1386篇 |
1998年 | 892篇 |
1997年 | 844篇 |
1996年 | 905篇 |
1995年 | 722篇 |
1994年 | 601篇 |
1993年 | 524篇 |
1992年 | 487篇 |
1991年 | 442篇 |
1990年 | 344篇 |
1989年 | 282篇 |
1988年 | 219篇 |
1987年 | 186篇 |
1986年 | 180篇 |
1985年 | 158篇 |
1984年 | 112篇 |
1983年 | 90篇 |
1982年 | 63篇 |
1981年 | 50篇 |
1980年 | 26篇 |
1979年 | 23篇 |
1978年 | 25篇 |
1977年 | 25篇 |
1975年 | 33篇 |
1974年 | 32篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Electrostatic interactions of proteins, including bovine serum albumin (BSA), human serum albumin (HSA), γ-globulin (γ-IgG), α-chymotrypsin (Chy), lysozyme (Lys) and cellulase (Cel), with multiply negatively charged chromophores were investigated based on the measurements of the enhanced resonance light scattering (RLS) signals. Using triply negatively charged water blue (WB) as an example, the factors were discussed that affect the enhanced resonance light scattering signals of the interactions between proteins and the negatively charged chromophores. It was found that the enhanced RLS signals with the maximum light scattering peak at 346.0 nm in these interacting systems are strongly dependent on the isoelectric points of proteins and show adverse linear relationships with increasing ionic strength depending on the positive charges of the inorganic metal ions used to control the ionic strength of the medium, sufficiently disclosing that the electrostatic attraction performs an important role in the combination of proteins with WB. Linear responses were discovered between the enhanced RLS signals and the protein molecular weights (Mw), displaying the dimensions of scattered particles formed by proteins and WB make a key contribution to the RLS enhancements. An empirical equation is proposed which possibly displays the factors affecting the enhanced RLS signals of the interactions between proteins with negatively charged chromophores. 相似文献
992.
A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO4 (pH1.6), 6.0×10?3 mol/L GA, 3.0×10?3 mol/L V(IV), 4.0×10?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10?11 to 1.0×10?8 mol/L and the detection limit is 2×10?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results. 相似文献
993.
The concentration polarization phenomena in ion exchange membrane electrodialysis have been studied with single exchange membrane cell. The limiting current densities of Asahi ion-permselective membranes CK-1 and CK-2, Selemion ion-exchange membranes CMV, AMV, DMV and ASV have been measured with Ag-AgCl reversible electrode in various electrolyte solutions under 25°C and constant flow rate. In sodium chloride solution, the cation exchange membrane is easier to occur concentration polarization than the anion exchange membrane. The limiting current density increases as the concentration of solution increases for the same kind of ion exchange membrane. The experimental limiting current densities of Selemion CMV and AMV in NaCl, KCl, MgCl2, CaCl2, BaCl2, Na2SO4, NaOH and HCl aqueous solutions are measured. The results show that the limiting current density increases as the ion mobility and diffusivity increase, and is affected by the transference number of ion. For the mixture of electrolyte solution, there are linear relationship between limiting current density and equivalent fraction of electrolytes. 相似文献
994.
A new diamine monomer containing flexible sulfone, sulfide, and amide units was prepared via three steps. Nucleophilic chloro displacement reaction of 4‐aminothiophenol with 4‐nitrobenzoyl chloride in the presence of propylene oxide afforded N‐(4‐mercapto‐phenyl)‐4‐nitrobenzamide and subsequent reduction of the nitro intermediate led to 4‐amino‐N‐(4‐mercapto‐phenyl)benzamide. Two moles of this amino thiophenol compound was reacted with bis‐(4‐chloro phenyl)sulfone to provide a novel diamine monomer. The diamine was reacted with aromatic dianhydrides to form polyimides via a two‐step polycondensation method, formation of poly(amic acid)s, followed by chemical imidization. The resulting polymers were characterized and their physical properties including thermal behavior, thermal stability, solubility and inherent viscosity were studied. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
995.
TU Shu-Jianga② WANG Qiana ZOU Xianga b SHI Fenga MIAO Chun-Baoa FANG Fanga XU Jia-Ninga a 《结构化学》2005,24(3):255-258
1 INTRODUCTION 1,4-Dihydropyridines (1,4-DHPs) are well-knowncompounds because of their pharmacological pro-perty as calcium channel modulators[1, . The che- 2]mical modifications, such as the introduction of dif-ferent substituents[3, or heteroatoms[5], of the DHP 4]ring have allowed the expansion of researches onthe structure-activity relationship to gain new in-sights into the molecular interactions at the receptorlevel. In fact, it is well established th… 相似文献
996.
A rhodium-catalyzed ortho-CH functionalization and annulation between enaminones and sulfoxonium ylides was developed, affording a series of multi-substituted naphthalenes in good to moderate yields with excellent functional group compatibility. The procedure featured with enaminone acting as both a directing and cyclization bifunctional group, and the application of sulfoxonium ylide in CH functionalization. 相似文献
997.
[structure: see text] The catalytic asymmetric dihydroxylation of olefins has been accomplished with high enantioselectivities using a proline-based catalyst. The pre-transition-state assembly for styrene is shown. 相似文献
998.
The desymmetrization ring opening of meso epoxides using trimethylsilyl cyanide catalyzed by organogallium and indium complexes with binaphthol monoether derivatives as chiral ligands gave beta-isocyanohydrins with moderate to excellent enantioselectivities of up to 95% ee. 相似文献
999.
Catalina Soriano‐Correa Rodolfo O. Esquivel Robin P. Sagar 《International journal of quantum chemistry》2003,94(3):165-172
A theoretical study at the Hartree–Fock and density functional theory levels is performed on sulfonamide‐type bacteriostatic compounds with the aim to provide an insight into their structure–activity relationship. The basicity of the p‐amino group is analyzed by means of the proton affinities and the protonation energies, showing that molecules presenting bacteriostatic activity are less basic, i.e., they are characterized by larger protonation energies and smaller proton affinities. The acidity of the amide group is analyzed through the deprotonation energy. The results reveal that the more acidic molecules present a larger bacteriostatic activity. This result is also confirmed from a study of bond orders. A bond order analysis of the amide group suggests that the electron attracting group in these molecules is responsible for the increase in acidity. The charge of the SO2 group is also shown to be affected by the presence of the electron attracting group and consequently related to the acidity of the molecules. A geometric analysis shows that structures in which the amino group is more coplanar with respect to the benzenic ring possess larger bacteriostatic activity. A conformational analysis of these molecules illustrates that active molecules have relatively larger torsion energy barriers. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 165–172, 2003 相似文献
1000.