全文获取类型
收费全文 | 7927篇 |
免费 | 835篇 |
国内免费 | 529篇 |
专业分类
化学 | 5584篇 |
晶体学 | 96篇 |
力学 | 419篇 |
综合类 | 46篇 |
数学 | 692篇 |
物理学 | 2454篇 |
出版年
2024年 | 18篇 |
2023年 | 121篇 |
2022年 | 226篇 |
2021年 | 297篇 |
2020年 | 276篇 |
2019年 | 270篇 |
2018年 | 206篇 |
2017年 | 212篇 |
2016年 | 315篇 |
2015年 | 287篇 |
2014年 | 370篇 |
2013年 | 560篇 |
2012年 | 703篇 |
2011年 | 696篇 |
2010年 | 491篇 |
2009年 | 432篇 |
2008年 | 544篇 |
2007年 | 459篇 |
2006年 | 433篇 |
2005年 | 370篇 |
2004年 | 319篇 |
2003年 | 263篇 |
2002年 | 260篇 |
2001年 | 166篇 |
2000年 | 126篇 |
1999年 | 121篇 |
1998年 | 104篇 |
1997年 | 83篇 |
1996年 | 85篇 |
1995年 | 74篇 |
1994年 | 48篇 |
1993年 | 54篇 |
1992年 | 50篇 |
1991年 | 53篇 |
1990年 | 27篇 |
1989年 | 24篇 |
1988年 | 23篇 |
1987年 | 20篇 |
1986年 | 15篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1973年 | 4篇 |
1971年 | 6篇 |
1970年 | 6篇 |
排序方式: 共有9291条查询结果,搜索用时 20 毫秒
91.
A kind of inorganic‐organic hybrid 18‐molybdodiphosphate nanoparticles ([(C4H9)4N]6P2Mo18Q62·4H2O) was firstly used as a bulk‐modifier to fabricate a three‐dimensional chemically modified carbon paste electrode (CPE) by direct mixing. The electrochemical behavior of the solid nanoparticles dispersed in the CPE in acidic aqueous solution was characterized by cyclic and square‐wave voltammetry. The hybrid 18‐molybdodiphosphate nanoparticles bulk‐modified CPE (MNP‐CPE) displayed a high electrocatalytic activity towards the reduction of nitrite, bromate and hydrogen peroxide. The remarkable advantages of the MNP‐CPE over the traditional polyoxometalates‐modified electrodes are their excellent reproducibility of surface‐renewal and high stability owing to the insolubility of the hybrid 18‐molybdodiphosphate nanoparticles. 相似文献
92.
As a new type of foldamers, oligoindoles containing 4, 6, and 8 indole rings were synthesized, and their folding properties were characterized by a combination of 1H NMR techniques and UV/visible titration experiments. When chloride was added, the NH signals of the oligoindoles were downfield shifted as a result of hydrogen-bond formation, and the aromatic signals were upfield shifted by stacking between two indoles. Moreover, the ROESY experiment provided definitive NOE evidence for the helical stacking in the presence of chloride. Finally, the UV/visible titration experiments demonstrated that the oligoindoles formed 1:1 complexes with chloride, and the association constants greatly increased with increasing the number of the indole NHs. These observations are all consistent with the fact that oligoindoles adopt a helical conformation when complexed with chloride by hydrogen-bonding interactions. 相似文献
93.
Kang HS 《The journal of physical chemistry. A》2005,109(3):478-483
Using density functional theory, we have theoretically studied the formation of neutral lithium-aromatic complexes R-nLi and R-nLi-R, where R is benzene, naphthalene, or pyrene. We first find that the maximum number of lithium atoms n in the complexes increases with the size of R. In addition, pyrene favors the sandwich compound R-4Li-R over R-4Li more than three times that of the corresponding tendency for benzene, strongly suggesting the possible existence of oligomer (R-4Li)x. We have also investigated energetics and band structures of infinite one-dimensional crystals of R-nLi, finding them metallic. Detailed analysis of the electronic structure shows that all these observations are related to the strong electrostatic interaction among the species, which is originated from the charge transfer from Li atoms to the aromatic rings. In addition, it is shown that the pyrene crystal is mechanically stable with respect to deformation. This also suggests the possibility of its existence, which, in turn, holds potential application in lithium storage in respect to its large Li/C ratio. 相似文献
94.
Photoreaction of 2,3-benzo-1,1-diphenyl(or dimethyl)-1-sila-2-cyclobutene with an aldehyde or ketone results in 1:1 cycloadduct of [4+2] type, the formation of which is accountd for in terms of SH2 process, i.e., attack of a triplet carbonyl compound on the silicon of the benzosilacyclobutene. 相似文献
95.
Hyoung Sik Kim Min Kang Min Woo Song Jin Won Park Byoung Ryul Min 《Reaction Kinetics and Catalysis Letters》2004,81(2):251-257
Pt-Pd bimetallic catalysts were prepared in order to develop and investigate catalysts having excellent activity and stability
for benzene destruction. The effect of Pt addition to Pd catalysts is studied by XPS analysis.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
96.
Kang Y Zyryanov GV Rudkevich DM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(6):1924-1932
The use of simple calix[4]arenes for chemical conversion of NO2/N2O4 gases is demonstrated in solution and in the solid state. Upon reacting with these gases, calixarenes 1 encapsulate nitrosonium (NO+) cations within their cavities with the formation of stable calixarene-NO+ complexes 2. These complexes act as encapsulated nitrosating reagents; cavity effects control their reactivity and selectivity. Complexes 2 were effectively used for nitrosation of secondary amides 5, including chiral derivatives. Unique size-shape selectivity was observed, allowing for exclusive nitrosation of less crowded N-Me amides 5 a-e (up to 95 % yields). Bulkier N-Alk (Alk>Me) substrates 5 did not react due to the hindered approach to the encapsulated NO+ reagents. Robust, silica gel based calixarene material 3 was prepared, which reversibly traps NO2/N2O4 with the formation of NO+-storing silica gel 4. With material 4, similar size-shape selectivity was observed for nitrosation. The N-Me-N-nitroso derivatives 6 d,e were obtained with approximately 30 % yields, while bulkier amides were nitrosated with much lower yields (<8 %). Enantiomerically pure encapsulating reagent 2 d was tested for nitrosation of racemic amide 5 t, showing modest but reproducible stereoselectivity and approximately 15 % ee. Given high affinity to NO+ species, which can be generated by a number of NOX gases, these supramolecular reagents and materials may be useful for NOX entrapment and separation in the environment and biomedical areas. 相似文献
97.
Reaction of 1,6-enynes with a hydrosilane in the presence of immobilized cobalt/rhodium bimetallic nanoparticles gives 2-methyl-1-silylmethylidene-2-cyclopentanes in the absence of carbon monoxide and 2-formylmethyl-1-silylmethylidene-2-cyclopentanes under 1 atm of carbon monoxide, respectively. [reaction: see text] 相似文献
98.
Tae?Shin?Chung Young?Mee?Na Shin?Won?Kang Ok-Sang?JungEmail author Young-A?Lee 《Transition Metal Chemistry》2005,30(5):541-545
Hydrogen peroxide oxidation of platinum(II) compounds containing labile groups such as Cl, OH, and alkene moieties has been carried out and the products characterized. The reactions of [PtII (X)2 (N–N)] (X = Cl, OH, X2 = isopropylidenemalorate (ipm); N–N 2,2-dimethyl-1,3-propanediamine [(dmpda), N-isopropyl-1,3-propanediamine (ippda)] with hydrogen peroxide in an appropriate solvent at room temperature affords [PtIV (OH)(Y)(X)2(N–N)] (Y = OH, OCH3). The crystal structures of [PtIV(OH)(OCH3)(Cl)2(dmpda)]·2H2O (P-1 bar, a = 6.339(2) Å , b = 9.861(1) Å, c = 11.561(1) Å, a = 92.078(9)°, β = 104.78(1)°, γ=100.54(1)°, V = 684.3(2) Å3, Z = 2R = 0.0503) and [PtIV(OH)2(ipm)(ippda)]·3H2O (C 2/c, a = 27.275(6) Å, b=6.954(2) Å, c = 22.331(4) Å, β = 118.30(2)°, V = 3729(2) Å3, Z = 8, R = 0.0345) have been solved and refined. The local geometry around the platinum(IV) atom approximates to a typical octahedral arrangement with two added groups (OH and OCH3; OH and OH) in a transposition. The platinum(IV) compounds with potential labile moieties may be important intermediate species for further reactions. 相似文献
99.
Catalytic oxidation of alcohols with polymer-supported ruthenium complex under mild conditions 总被引:1,自引:0,他引:1
Qiao-xiang Kang Ju-jie Luo Yan-bin Bai Zhi-wang Yang Zi-qiang Lei 《Journal of organometallic chemistry》2005,690(26):6309-6313
Polymer-supported ruthenium-containing complex PS–Phen–Ru was synthesized (where PS = chloromethyl polystyrene resin, Phen = 1,10-phenanthroline) and was characterized by FT-IR, ICP, and XPS. The supported complex was used to catalyze the oxidation of primary aliphatic alcohols as well as aromatic alcohols in the presence of iodosylbenzene. The oxidations were carried out in acetonitrile solution, affording the corresponding aldehydes or ketones in high substrate conversion and high selectivities under mild reaction conditions. The catalyst can be easily prepared and can be recycled. 相似文献
100.
Nam-Sook Kang Seok-Joo Hong Chong-Hak Chae Sung-Eun Yoo 《Journal of Molecular Structure》2007,820(1-3):58-64
A comparative molecular field analysis (CoMFA) for phosphodiesterase (PDE) IV inhibitors has been performed to correlate their chemical structures with their observed biological activity. In this study, CoMFA model based on docking mode for active site of PDE IV can describe the relative change in magnitude of the steric and electrostatic fields as a function of the compounds. Pyridine N-oxide and pyridine group of each compound are aligned toward the metal ion in S2-sub pocket of PDE IV. The study provided a statistically valid model with good correlation and predictive power, and consequently we identified some key features that may be used to design new derivatives. 相似文献