全文获取类型
收费全文 | 21936篇 |
免费 | 821篇 |
国内免费 | 9篇 |
专业分类
化学 | 14488篇 |
晶体学 | 160篇 |
力学 | 367篇 |
数学 | 3722篇 |
物理学 | 4029篇 |
出版年
2023年 | 147篇 |
2022年 | 126篇 |
2021年 | 211篇 |
2020年 | 325篇 |
2019年 | 333篇 |
2018年 | 463篇 |
2017年 | 408篇 |
2016年 | 831篇 |
2015年 | 645篇 |
2014年 | 674篇 |
2013年 | 1449篇 |
2012年 | 1416篇 |
2011年 | 1392篇 |
2010年 | 830篇 |
2009年 | 763篇 |
2008年 | 1226篇 |
2007年 | 1262篇 |
2006年 | 1123篇 |
2005年 | 1047篇 |
2004年 | 955篇 |
2003年 | 734篇 |
2002年 | 642篇 |
2001年 | 491篇 |
2000年 | 445篇 |
1999年 | 329篇 |
1998年 | 227篇 |
1997年 | 217篇 |
1996年 | 286篇 |
1995年 | 201篇 |
1994年 | 229篇 |
1993年 | 190篇 |
1992年 | 195篇 |
1991年 | 178篇 |
1990年 | 172篇 |
1989年 | 152篇 |
1988年 | 141篇 |
1987年 | 134篇 |
1986年 | 136篇 |
1985年 | 198篇 |
1984年 | 195篇 |
1983年 | 124篇 |
1982年 | 129篇 |
1981年 | 142篇 |
1980年 | 137篇 |
1979年 | 98篇 |
1978年 | 96篇 |
1977年 | 105篇 |
1976年 | 83篇 |
1975年 | 88篇 |
1973年 | 71篇 |
排序方式: 共有10000条查询结果,搜索用时 750 毫秒
161.
A diastereoselective [4+2] annulation of vinyl carbodiimides with chiral N-alkyl imines has been developed to access the stereochemically rich tricyclic core of the batzelladine alkaloids. Its application to the asymmetric synthesis of batzelladine D permitted the use of long-range, directed hydrogenation and stereoselective intramolecular iodoamination as additional key steps to establish the remaining stereocenters within the natural product with excellent stereocontrol. 相似文献
162.
Kótai László Gács István Kazinczy Béla Sajó István E. Sreedhar B. 《Transition Metal Chemistry》2003,28(3):292-295
The theoretical investigation on the distribution of chemical species obtainable as a function of the temperature of the aqueous solutions of metal complexes containing a basic ligand, altogether with the solubility relationship of the compounds to be formed, offers a simple means of planning the preparation of various types of complexes, double and single salts of the central metal cation and onium type compounds of protonated ligand of the central ion and the anion. 相似文献
163.
A new method to improve the analysis of phytochelatins and their precursors (cysteine, gamma-Glu-Cys, and glutathione) derivatized with monobromobimane (mBrB) in complex biological samples by capillary zone electrophoresis is described. The effects of the background electrolyte pH, concentration, and different organic additives (acetonitrile, methanol, and trifluoroethanol) on the separation were studied to achieve optimum resolution and number of theoretical plates of the analyzed compounds in the electropherograms. Optimum separation of the thiol peptides was obtained with 150 mM phosphate buffer at pH 1.60. Separation efficiency was improved when 2.5% v/v methanol was added to the background electrolyte. The electrophoretic conditions were 13 kV and capillary dimensions with 30 cm length from the inlet to the detector (38 cm total length) and 50 microm inner diameter. The injection was by pressure at 50 mbar for 17 s. Under these conditions, the separation between desglycyl-peptides and phytochelatins was also achieved. We also describe the optimum conditions for the derivatization of biological samples with mBrB to increase electrophoretic sensitivity and number of theoretical plates. The improved method was shown to be simple, reproducible, selective, and accurate in measuring thiol peptides in complex biological samples, the detection limit being 2.5 microM glutathione at a wavelength of 390 nm. 相似文献
164.
Macroporous poly(methyl methacrylate) produced by phase separation during polymerisation in solution
A. Serrano Aroca M. Monleón Pradas J. L. Gómez Ribelles 《Colloid and polymer science》2007,285(7):753-760
Polymethyl methacrylate (PMMA) sponges were obtained by polymerization in a solution with monomer/ethanol ratios up to 20:80.
The material obtained after the elimination of the solvent present a homogeneous distribution of dispersed pores up to a monomer/ethanol
ratio lower than 40:60. For higher ethanol contents in the reacting mixture, the morphology of the sponge corresponds to a
network of PMMA microparticles, leaving large empty spaces leading to highly porous structure. The monomer/ethanol ratio during
polymerization has a large influence on the porosity, thermal, and mechanical properties of the material and, for large solvent
contents, on the size of the polymer microparticles. 相似文献
165.
M. Piñeiro-Iglesias M. Miñones-Vázquez E. Vázquez-Blanco S. Muniategui-Lorenzo P. López-Mahía D. Prada-Rodríguez 《Chromatographia》2002,56(7-8):483-488
Summary The aim of this work is to establish the best conditions for concentration and purification steps in the trace analysis of
aliphatic and polycyclic aromatic hydrocarbons (PAH) from atmospheric particulate matter by gas chromatography-flame ionisation
detection (GC-FID) and high performance liquid chromatography with ultraviolet and fluorescence detection (HPLC-UV-FL). The
best results for the more volatile compound were obtained with a combination of rotary evaporation and a stream of nitrogen
(near to 100% for aliphatic hydrocarbons and from 70 to 105% for PAH). Two types of solid phase extraction (SPE)cartridges
(Supelclean
tm
LC-Silica SPE tubes and Sep-Pak? Plus silica cartridges) and glass column were examined for the purification and fractionation step. Blank chromatograms of
both types of cartridges analysed by GC-FID made this study difficult, because a PSS (programmed split-splitless) injector
was employed thereby increasing the sensitivity. This problem was not observed in the HPLC-UV-FL blank chromatograms of these
cartridges. Glass columns filled with silica and alumina were chosen because no interference was found in the GC-FID blank
chromatograms and the best recoveries in the fractionation of both aliphatic hydrocarbons and PAH were achieved. This is especially
important when aliphatic hydrocarbons concentrations are lower than 1 μg mL−1. Finally, the selected conditions were applied to the analysis of hydrocarbons in real atmospheric particulate samples. 相似文献
166.
167.
Irina Odinets Tamás Körtvélyesi Tamás Kégl László Kollár György Keglevich 《Transition Metal Chemistry》2007,32(3):299-303
In the series of 1-(2,4,6-trialkylphenyl-)3-methyl-1H-phospholes (1a–c) that are to a certain extent of aromaticity, only the isopropyl substituted one (1a) entered into reaction with dimeric (pentamethylcyclopentadienyl)rhodium dichloride to afford Rh(III) complex (2a) in a reversible manner. After a careful workup, (2a) could be prepared and characterized whose stereostructure was elucidated by B3LYP/3–21G*, B3LYP/6–31G* and LANL2DZ calculations.
Complex (2a) as a preformed catalyst, as well as the Rh(acac)(CO)2 + 2(1a) in situ catalytic system were useful in the hydroformylation of styrene and gave the branched aldehyde in regioselectivities of 65–96%. 相似文献
168.
Gáti T Simon A Tóth G Magiera D Moeller S Duddeck H 《Magnetic resonance in chemistry : MRC》2004,42(7):600-604
Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group. 相似文献
169.
P. Miranda Jr. J. Zukerman-Schpector J. R. Matos M. F. Máduar E. M. Aricó M. Linardi L. B. Zinner G. Vicentini 《Journal of Thermal Analysis and Calorimetry》2004,75(2):577-582
The complexes [Ln(pic)3(DTSO)3] (Ln=La, Lu and Y; pic=picrate; DTSO=1,3-dithiane-1-oxide) were synthesized and characterized. Indirect structural determination by far infrared
spectroscopy is presented. Results from thermal decomposition of these complexes by TG/DTG and DSC techniques are reported.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
170.
Summary The novel theoretical scheme IMOMM, integrating ab initio and molecular mechanics contributions in a single geometry optimization process, is applied to the structural determination of different [OsO4(NR3)] (NR3 = bulky chiral alkaloid derivative) species closely related to active catalysts for the asymmetric dihydroxylation of olefins. Computed values compare in a satisfactory way with available X-ray data, the relationship between the Os-N distance and the nature of the NR3, ligand being properly reproduced. The computational scheme allows the separate quantification of electronic and steric effects, as well as the identification of the specific steric repulsions responsible for the difference. 相似文献