全文获取类型
收费全文 | 53931篇 |
免费 | 4837篇 |
国内免费 | 8793篇 |
专业分类
化学 | 49514篇 |
晶体学 | 1674篇 |
力学 | 914篇 |
综合类 | 335篇 |
数学 | 2817篇 |
物理学 | 12307篇 |
出版年
2024年 | 96篇 |
2023年 | 537篇 |
2022年 | 1288篇 |
2021年 | 1231篇 |
2020年 | 1473篇 |
2019年 | 2371篇 |
2018年 | 1424篇 |
2017年 | 2460篇 |
2016年 | 1947篇 |
2015年 | 1790篇 |
2014年 | 2396篇 |
2013年 | 4559篇 |
2012年 | 3207篇 |
2011年 | 3682篇 |
2010年 | 2897篇 |
2009年 | 3328篇 |
2008年 | 3580篇 |
2007年 | 3612篇 |
2006年 | 3380篇 |
2005年 | 3083篇 |
2004年 | 2891篇 |
2003年 | 2366篇 |
2002年 | 2001篇 |
2001年 | 1701篇 |
2000年 | 1647篇 |
1999年 | 1280篇 |
1998年 | 1126篇 |
1997年 | 988篇 |
1996年 | 817篇 |
1995年 | 818篇 |
1994年 | 663篇 |
1993年 | 580篇 |
1992年 | 491篇 |
1991年 | 342篇 |
1990年 | 213篇 |
1989年 | 200篇 |
1988年 | 174篇 |
1987年 | 106篇 |
1986年 | 101篇 |
1985年 | 103篇 |
1984年 | 81篇 |
1983年 | 46篇 |
1982年 | 75篇 |
1981年 | 81篇 |
1980年 | 63篇 |
1979年 | 80篇 |
1978年 | 49篇 |
1977年 | 40篇 |
1976年 | 29篇 |
1973年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
R.-L. Yun Y.-M. Chang C.-H. Lin K.-H. Hu C.-M. Shu 《Journal of Thermal Analysis and Calorimetry》2006,85(1):107-113
In industrial processes, information
on the safety property of chemicals is essentially crucial for safe handling
during unit operations. Ensuring the safe use of combustible or flammable
substances in processes is unlikely without detailed investigations of their
flammability characteristics and related hazards. We studied 3-methyl pyridine
(3-picoline), e.g., flammability limits (LFL/UFL), maximum explosion pressure
(P
max), maximum
explosion pressure rise (dP/dt)max, minimum oxygen concentration
(MOC), vapor deflagration index (K
g),
and characterized the influence of inert steam (H2O)
on critical parameters for 3-picoline/water mixtures at 270°C, 1 atm,
various oxygen concentrations, and vapor mixing ratios (100/0, 30/70, 10/90
and 5/95 vol.%) with a 20-L-Apparatus in simulated conditions, respectively.
The results showed that the flammability characteristics
of 3-picoline(aq) all increased with the oxygen concentration.
However, as the composition of inert steam increased, the flammability parameters
and the degree of fire and explosion hazards were significantly reduced, instead.
This study elucidated the flammability properties of 3-picoline mixed with
inert steam. The conclusions could be applied to proactively prevent the relevant
processes from incurring fire and explosion accidents. 相似文献
942.
《Tetrahedron letters》2004,45(27):5203-5205
The first synthesis of polyfunctionalized 4-ferrocenyl-4H-pyran and 4-ferrocenyl-1,4-dihydropyridine derivatives, as well as some of their relevant properties, including an electrochemical study and some aspects of their biological profile have been described. 相似文献
943.
制备了负载铬酸氢根的季铵树脂,研究了以该树脂为氧化剂将糠醇氧化为糠醛的反应,考察了温度,时间、溶剂,树脂与醇的摩尔比对该氧化反应的影响。在优化反应条件下,即以苯为溶剂,n(树脂):n(醇)=3.5:1,反应回流10h,糠醛产率达75%,实验中铬酸氢根季铵树脂选择性地将糠醇氧化为糠醛,表明它是一种有效的、可套用的氧化剂。 相似文献
944.
Masafumi Kobayashi Tetsuya Inoguchi Takashi Iida Takashi Tanioka Hiroshi Kumase Yasushi Fukai 《Journal of fluorine chemistry》2003,120(2):2838-110
Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride. 相似文献
945.
N. G. Komissarova N. G. Belenkova L. V. Spirikhin O. V. Shitikova M. S. Yunusov 《Chemistry of Natural Compounds》2002,38(1):58-61
Oxidation of betulin by pyridinium dichromate, pyridinium chlorochromate, and K2Cr2O7 -H2SO4 in the presence of tetrabutylammonium bromide was studied. Products of regioselective C-3, C-28-, and exhaustive oxidation, 28-hydroxylup-20(29)-3-one, 3-hydroxy- and 3-oxolup-20(29)-en-28-al were obtained. 相似文献
946.
Hiratake J 《Chemical record (New York, N.Y.)》2005,5(4):209-228
Carefully designed molecules that are intimately related to the reaction mechanism of enzymes are often highly selective and potent inhibitors that serve as extremely useful chemical probes for understanding the reaction mechanism and structure of enzymes. This article describes the design, synthesis, and applications of specific inhibitors of two mechanistically distinct groups of enzymes, ATP-dependent amide ligases and Ser- and Thr-hydrolases. Our strategy is based on the premise that stable analogues of the transition state (transition-state analogues) are highly potent inhibitors that serve as good mechanistic probes, and that a key structure of a good inhibitor of one enzyme is also utilized for the inhibitors of other enzymes that share the same chemistry in their catalyzed reactions, irrespective of the degree of structural similarity and evolutionary link between the enzymes. According to these principles, we designed and synthesized a series of phosphinate- and sulfoximine-based transition-state analogue inhibitors of glutathione synthetase, gamma-glutamylcysteine synthetase and asparagine synthetase. For the second group of enzymes, we synthesized a gamma-monofluorophosphono glutamate analogue for mechanism-based affinity labeling of gamma-glutamyltranspeptidase and fluorescent phosphonic acid esters for the active-site titration of lipase. These inhibitors were used successfully as ligands for detailed kinetic analyses, X-ray crystallography, and mass analysis of the enzymes to identify the key amino acid residues responsible for catalysis and substrate recognition in the transition state. 相似文献
947.
以4-N,N-二乙基氨基水杨醛为原料,制备了2-(苯并噻唑-2-基)-5-(N,N-二乙基氨基)苯酚衍生物(探针L),并对其结构进行了表征。在DMSO/PBS(体积比3∶7,pH=7.4)溶液中,探针L具有高选择性并可荧光"关-开"识别H_2S,在365nm紫外灯照射下,由无荧光变成蓝色荧光。实验表明,探针L识别H_2S的检测限为2.05×10~(-6)mol/L,pH适用范围为6~9,可用于检测实际水样中的H_2S。 相似文献
948.
V. V. Nikitenko A. I. Martynenko S. A. Ostrovsky V. V. Rusak V. V. Kryuchkov D. A. Topchiev 《Russian Chemical Bulletin》1993,42(2):378-380
3-Methyl-l-vinylpyrazole (M3VP) and 5-methyl-1-vinylpyrazole (M5VP) were isolated as individual substances by vacuum rectification of their mixture (M3VP: M5VP 60 40). For each of them the kinetics of free-radical polymerization in MeOH were measured at low conversions. In both cases the rate of polymerization is proportional to 0.5 order with respect to the initiator (AIBN) concentration. On the other hand, a first order of reaction with respect to monomer concentration is observed only when the latter is relatively low (3M). At higher initial concentrations of monomers the order of reaction becomes less than unity. The overall rate of polymerization for M5VP was higher than for M3VP, whereas the initiation rate remained constant in the whole range of monomer concentrations and did not depend on the exact structure of the monomer. The difference in the rates of polymerization observed for M3VP and M5VP is probably connected with the difference in the key parameterk
p/k
t
1/2
for each of the two isomers. It is concluded that the correct kinetic information about homo- and co-polymerization of M3VP and M5VP cannot be obtained without their adequate separation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 413–415, February, 1993. 相似文献
949.
1,2,4-三嗪类化合物具有抗癌、抗病毒、杀虫、抑制中枢神经系统等多种作用。前文用苯甲酰基硫代甲酰胺直接与氨基脲反应,制备了8种新的4,6-二取代-3-酮-5-硫酮-1,2,4-三嗪类化合物(a—h),本文测定了其电子轰击质谱、高分辨质谱及联动扫描质谱,以了解其质谱裂解途径。 相似文献
950.
高效液相色谱法测定小麦幼苗中植物生长调节剂 总被引:3,自引:0,他引:3
介绍了高效液相色谱法测定麦苗中植物生长调节剂(赤霉素GA3),3-吲哚乙酸(IAA)的方法,用国产预处理小柱处理样品,并以甲醇:1%,冰乙酸=12:88(V/V)为流动相,色谱柱为ZorbaxC18,在210nm紫外检测。 相似文献