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71.
Wladyslaw Reimschüssel Halina Abramczyk Jacek Michalak 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):201-211
Abstract 2-Chloro-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane has been studied in CCl4, CHCl3 and CD3CN solutions by IR and Raman line shape analysis. Equilibrium process of dimerization and ring conversion in CCl4 solutions have been considered. On the contrary to the commonly expected dominance of the conformer with the equatorial oriented P[dbnd]O bond for 2-halo-2-oxo-1,3,2-dioxaphosphorinanes, it was found that for the 2-chloro derivative both conformers are nearly equally distributed. It has been shown that the interactions induced absorption is an important mechanism of relaxation in the studied compound and this mechanism gives significant contribution to the total IR band broadening, while the interaction induced light scattering is negligible. The obtained results show that the molecular dynamics method can be useful in studying cyclic compounds in solutions. 相似文献
72.
Jacek E. Nycz 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2605-2612
The present study shows new aspects of the synthesis of polyhalogenoarylphosphanes. The sterically hindered anions Ph(R)P-Y? (1a–c, Y = O, lone pair; R = Ph, But) have been used to show the complexity of the reaction between phosphorus nucleophiles and hexahalogenobenzenes or 9-bromofluorene (E3). The Ph(But)P-O? (1a) anion reacts with hexachlorobenzene (E1), hexafluorobenzene (E2), or E3 to give Ph(R)P(O)X (4a–c, X = F, Cl, Br) with the release of the corresponding carbanion as a nucleofuge, followed by side reactions. In contrast, the lithium phosphides Ph(R)PLi (1b,c) react with hexahalogenobenzenes to give the corresponding diphosphanes 5a,b as the main product and traces of P-arylated products, i.e., Ph(R)P-C6X5 (10a,b, X = Cl, F). Unexpectedly, Ph(But)PLi (1b) reacts with an excess of 9-bromofluorene to give only halogenophosphane Ph(But)P-X. 相似文献
73.
Annia H. Kycia Kallum Koczkur J. Jay Leitch Jacek Lipkowski Vlad Zamlynny Michael W. P. Petryk 《Analytical and bioanalytical chemistry》2013,405(5):1537-1546
Polarization modulation–infrared reflection absorption spectroscopy (PM-IRRAS) was employed to analyze two unique samples: (1) an industrially prepared alkoxysilane-pretreated aluminum alloy (AA6111) in the absence and presence of a ~600-nm-thick lubricant coating and (2) a chemical warfare agent simulant, triethyl phosphate (TEP), on glass. For the pretreated aluminum samples, PM-IRRAS spectra were analyzed for three distinct regions; the SiO stretching vibration around 1120 cm?1, the NH2 bending mode at ~1600 cm?1 and the CH stretching region around 2900 cm?1. Our results showed that increasing the curing temperature (from 55 to 100 °C) improved the overall extent of cross-linking within the siloxane network. In addition, the spectra of lubricant (top coating) and the underlying siloxane layer for the aluminum samples with lubricant were collected for the same sample. Our results show that the nature of the siloxane film remains intact and unaltered after deposition of the lubricant top-coat. For detection of TEP on glass, the band at 1268 cm?1, corresponding to the P═O vibration, was monitored. A droplet of TEP solution in dichloromethane was deposited on glass. After solvent evaporation had occurred, the intensity of the P═O vibration band was used to construct calibration curves to determine the experimental limit of detection, which was found to be ~200 μg for TEP on glass. Figure
Schematic of a akoxysilane network and PM-IRRAS spectrum of the alkoxysilane film at aluminum surface 相似文献
74.
Abstract: Synthesis of bis(2-chlorosulfonylphenyl) diselenide (11) from 2-amino-benzenesulfonic acid was elaborated. It was shown that (11) is a good starting material for synthesis of the organoselenium sulfonamides, such as bis(2-sulfamoylphenyl) diselenides (3) and benz-2,3-azaselenathiophene 1,1-dioxides (4), being potential immunostimulants and oxidation catalysts. 相似文献
75.
Synthesis of two new groups of organoselenium compounds: 2-acyl-and sulfonylbenzisoselenazol-3(2H)-ones (3, 4), potential immunostimulants, in two alternative ways was elaborated. One of them was based on the reaction of 2-chlorobenzoyl chloride (2) with primary amides while the second one involved N-acylation or N-sulfonylation of benzisoselenazol-3(2H)-one (5) with acid chlorides. Two exceptions from general reaction of dichloride 2 with amides were observed. Thioacetamide produced 2,1-benzothiaselenophenone (6), and urea gave 6,7-benzo-2,4-diaza-1-selenacyclohepta-3,5-dione (7). 相似文献
76.
Jacek Grodner 《合成通讯》2013,43(7):919-924
The main component of the sex pheromone of many lepidopteran pests, (2E,13Z)‐2,13‐octadecadienyl acetate (1), has been synthesized following a simple route using 12‐(2‐tetrahydropyranyloxy)‐1‐dodecyne (2) as the starting material. 相似文献
77.
The catalytic oxidative domino degradation of phenols was investigated. Hydrogen peroxide (30% aq.) was used as an oxidant and 2,2′-dinitro-4,4′-ditrifluoromethyldiphenyl diselenide 4e as a catalyst. The products were muconic acid 5, and muconolactones muconolactones—5-carboxymethylfuran-2(5H)-ones 7 and 9. Phenols with alkyl groups at 2 or 4 positions of the benzene ring were converted regioselectively to corresponding muconolactones substituted at alkenylene ring carbon atoms. The reaction mechanism is proposed. 相似文献
78.
Magdalena Olak-Kucharczyk Jacek S. Miller Stanisław Ledakowicz 《Chemical Papers》2013,67(9):1157-1163
The decomposition of meta-phenylphenol (m-PP) and para-phenylphenol (p-PP) in a heterogeneous gas-liquid system using ozone was investigated. The influence of different reaction parameters such as ozone and PP isomers concentration as well as pH and temperature of the reaction mixture on the PP decay rate was determined. The second-order rate constants for the direct reaction of molecular ozone, determined in a homogeneous system, were (5.85 ± 0.35) × 102 M?1 s?1 and (8.90 ± 0.33) × 102 M?1 s?1 for m-PP and p-PP, respectively. The rate constants for the reaction of m-PP and p-PP with ozone increased with increasing pH. The reaction rate constants with ozone were found to be (1.75 ± 0.02) × 109 M?1 s?1 and (1.86 ± 0.02) × 109 M?1 s?1 for m-PP and p-PP anions, respectively. 相似文献
79.
Dr. Jacek Cieślak Dr. Cristina Ausín Dr. Andrzej Grajkowski Dr. Serge L. Beaucage 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(14):4623-4632
The reaction of 2‐cyano‐2‐methyl propanal with 2′‐O‐aminooxymethylribonucleosides leads to stable and yet reversible 2′‐O‐(2‐cyano‐2,2‐dimethylethanimine‐N‐oxymethyl)ribonucleosides. Following N‐protection of the nucleobases, 5′‐dimethoxytritylation and 3′‐phosphitylation, the resulting 2′‐protected ribonucleoside phosphoramidite monomers are employed in the solid‐phase synthesis of three chimeric RNA sequences, each differing in their ratios of purine/pyrimidine. When the activation of phosphoramidite monomers is performed in the presence of 5‐benzylthio‐1H‐tetrazole, coupling efficiencies averaging 99 % are obtained within 180 s. Upon completion of the RNA‐chain assemblies, removal of the nucleobase and phosphate protecting groups and release of the sequences from the solid support are carried out under standard basic conditions, whereas the cleavage of 2′‐O‐(2‐cyano‐2,2‐dimethylethanimine‐N‐oxymethyl) protective groups is effected (without releasing RNA alkylating side‐products) by treatment with tetra‐n‐butylammonium fluoride (0.5 m) in dry DMSO over a period of 24–48 h at 55 °C. Characterization of the fully deprotected RNA sequences by polyacrylamide gel electrophoresis (PAGE), enzymatic hydrolysis, and matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry confirmed the identity and quality of these sequences. Thus, the use of 2′‐O‐aminooxymethylribonucleosides in the design of new 2′‐hydroxyl protecting groups is a powerful approach to the development of a straightforward, efficient, and cost‐effective method for the chemical synthesis of high‐quality RNA sequences in the framework of RNA interference applications. 相似文献
80.
Antoni W. Morawski Ewelina Kusiak-Nejman Jacek Przepiórski Roksana Kordala Juliusz Pernak 《Cellulose (London, England)》2013,20(3):1293-1300
TiO2/N-cellulose nanocomposite was successfully prepared in the (cyclohexyl)hexyl-dimethylammonium acetate–dimethyl sulfoxide solution. The obtained composite was characterized with various techniques like UV–Vis/DR, FTIR/DRS, X-ray diffraction, thermogravimetric analysis, DLS method and BET SSA measurements. TiO2/N-cellulose nanocomposite exhibited high UV–Vis light absorption with energy gap shifted to the visible region. Additive of TiO2/N photocatalyst to cellulose-IL-DMSO solution leads to obtaining the material with higher thermostability and limited photoactivity. 相似文献