全文获取类型
收费全文 | 172533篇 |
免费 | 30250篇 |
国内免费 | 17601篇 |
专业分类
化学 | 130660篇 |
晶体学 | 2029篇 |
力学 | 9915篇 |
综合类 | 1063篇 |
数学 | 18508篇 |
物理学 | 58209篇 |
出版年
2024年 | 457篇 |
2023年 | 2726篇 |
2022年 | 4863篇 |
2021年 | 5427篇 |
2020年 | 6447篇 |
2019年 | 7445篇 |
2018年 | 5540篇 |
2017年 | 5181篇 |
2016年 | 9560篇 |
2015年 | 9643篇 |
2014年 | 11075篇 |
2013年 | 13943篇 |
2012年 | 15184篇 |
2011年 | 14806篇 |
2010年 | 11371篇 |
2009年 | 11152篇 |
2008年 | 11240篇 |
2007年 | 9810篇 |
2006年 | 8919篇 |
2005年 | 7841篇 |
2004年 | 6124篇 |
2003年 | 5109篇 |
2002年 | 5704篇 |
2001年 | 4456篇 |
2000年 | 3856篇 |
1999年 | 3184篇 |
1998年 | 2391篇 |
1997年 | 2197篇 |
1996年 | 2282篇 |
1995年 | 1851篇 |
1994年 | 1774篇 |
1993年 | 1428篇 |
1992年 | 1304篇 |
1991年 | 1170篇 |
1990年 | 974篇 |
1989年 | 673篇 |
1988年 | 571篇 |
1987年 | 456篇 |
1986年 | 459篇 |
1985年 | 376篇 |
1984年 | 276篇 |
1983年 | 188篇 |
1982年 | 155篇 |
1981年 | 120篇 |
1980年 | 85篇 |
1979年 | 64篇 |
1978年 | 40篇 |
1976年 | 41篇 |
1975年 | 39篇 |
1974年 | 50篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
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
982.
The magneto-structural correlation between a Mn(ll) ion, coordinated in an octahedral environment, and two nitronyl nitroxide
radical ligands in trans- and cis-metal-radical complexes is investigated by the broken symmetry (BS) approach within density functional theory (DFT).
The dependences of coupling constants J on three structural parameters: (i) bond angle θ (Mn-O-N (nitroxide)); (ii) rotating angle ψ, defined by the nitronyl nitroxide radical plane rotating around the axial Mn-O (nitroxide); (iii) bond distance R (Mn-O (nitroxide)) are directly calculated. Our calculations showed that both trans- and cis-Mn(ll)-radical complexes behave a stronger antiferromagnetic interaction, consistent with experiments. In view of
molecular orbital theory, the direct exchanges, including σ-type and π-type exchanges, are responsible for the magnetic exchange
pathways. There is a preferable linear correlation between the calculated coupling constants J and the overlap integral squares S b between the local magnetic orbitals at the various rotating angle ψ at the fixed bond angle θ and bond distance R, in both trans- and cis-Mn(ll)-radical complexes. 相似文献
983.
The drug-loaded alginate/poly-L-arginine/chitosan ternary complex microcapsules were prepared by mixing method, absorption method and the combined method of mixing and absorption, respectively. The effect of drug-loading methods on drug load, the encapsulation efficiency and the release properties of the complex microcapsules were investigated. The results showed that the absorption process is a dominating factor to greatly increase the drug load of Hb into microcapsules. Upon loading Hb into microcapsules by combined method of mixing and absorption, the drug load (19.9%) is up to the maximum value, and the encapsulation efficiency is 93.8%. Moreover, the drug release is a zero-order kinetics process for the ternary complex microcapsules made by mixing. For the complex microcapsules made by absorption, the drug release is a first-order kinetics. However, for the complex microcapsules made by combining the mixing and the absorption, the drug release obeys a first-order kinetics during the first eighteen hours, changing afterwards to a zero-order kinetics process. Effect of drug-loading methods on drug load and encapsulation efficiency of alginate/poly-L-arginine/chitosan ternary complex microcapsules. 相似文献
984.
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
985.
使用双沸点仪测定了丙酮、乙酸乙酯、对二氧六环、乙腈或三乙胺与甲醇或1,2→二氯乙烷以及二者混合物等十一组二元体系在99.3 kPa下的汽液平衡数据(T,x,p), 计算了有关体系的过量吉布斯自由能。结果表明, 六种非质子溶剂与甲醇组成的二元系GE>0; 乙腈或三乙胺与1,2-二氯乙烷组成的二元系GE>0, 而丙酮、乙酸乙酯或对二氧六环与1,2-二氯乙烷的二元混合物GE<0。从同种分子间或不同种分子间的缔合作用对上述结果进行了讨论。本文还在固定极性非质子溶剂(第三组分)物质的量浓度的条件下, 测定了非质子溶剂+1,2-二氯乙烷+甲醇三元混合物的汽液平衡数据, 考察了非质子溶剂的加入对甲醇+1,2-二氯乙烷二元系GE的影响。 相似文献
986.
建立了耐硫甲烷化循环式反应器的拟均相一维模型,考察了床层直径,循环比,入口气体温度及压力和温度范围对反应器操作的影响,结果表明:循环比和温度操作范围是反应器操作的决定因素,对日产5万标准立方煤气的反应器进行了优化设计分析。 相似文献
987.
Analytical methodologies for aluminium speciation in environmental and biological samples--a review 总被引:1,自引:0,他引:1
Bi SP Yang XD Zhang FP Wang XL Zou GW 《Fresenius' Journal of Analytical Chemistry》2001,370(8):984-996
It is recognized that aluminium (Al) is a potential environmental hazard. Acidic deposition has been linked to increased Al concentrations in natural waters. Elevated levels of Al might have serious consequences for biological communities. Of particular interest is the speciation of Al in aquatic environments, because Al toxicity depends on its forms and concentrations. In this paper, advances in analytical methodologies for Al speciation in environmental and biological samples during the past five years are reviewed. Concerns about the specific problems of Al speciation and highlights of some important methods are elucidated in sections devoted to hybrid techniques (HPLC or FPLC coupled with ET-AAS, ICP-AES, or ICP-MS), flow-injection analysis (FIA), nuclear magnetic resonance (27Al NMR), electrochemical analysis, and computer simulation. More than 130 references are cited. 相似文献
988.
(Z)-3-丁烯基苯酞和它的衍生物广泛地存在于微形科植物,如当归、川芎等,这些植物有些是重要的中药材。(Z)-3-丁烯基-4,5-二羟基苯酞是(Z)-3-丁烯基苯酞的类似物;它对前列腺素F2α具有抑制作用。本文以3,4-二甲氧基苯甲醇(2)或价廉易得的胡椒醇(6)为起始原料,分别经四步反应顺利地合成了(Z)-3-丁烯基-4,5羟基苯酞(1)。和一步是本方法的关键,即利用杂原子诱导的区域选择性的芳环 相似文献
989.
990.
Ung-Ping Wang 《中国化学会会志》1973,20(2):57-73
Vinyl monomers such as vinyl acetate, vinyl chloride, methyl methacrylate and styrene etc., can be polymerized without catalyst into the composites of bagasse material by gamma-radiation induced in situ liquid polymerization process. The fundamental factors, such as polymerization-rate, effect of swelling agent, molecular weight of vinyl polymers and graft reaction between bagasse cellulose and vinyl polymers, have been investigated and discussed. The use of suitable low G-value polar swelling agents and the application of suitable gamma dose-rate are two key factors found to control the smooth in situ liquid polymerization system of vinyl monomers in bagasse. 相似文献