全文获取类型
收费全文 | 1749篇 |
免费 | 89篇 |
国内免费 | 14篇 |
专业分类
化学 | 1322篇 |
晶体学 | 12篇 |
力学 | 39篇 |
数学 | 193篇 |
物理学 | 286篇 |
出版年
2023年 | 16篇 |
2022年 | 57篇 |
2021年 | 54篇 |
2020年 | 32篇 |
2019年 | 35篇 |
2018年 | 39篇 |
2017年 | 19篇 |
2016年 | 61篇 |
2015年 | 66篇 |
2014年 | 68篇 |
2013年 | 108篇 |
2012年 | 109篇 |
2011年 | 161篇 |
2010年 | 81篇 |
2009年 | 86篇 |
2008年 | 132篇 |
2007年 | 122篇 |
2006年 | 86篇 |
2005年 | 102篇 |
2004年 | 70篇 |
2003年 | 48篇 |
2002年 | 48篇 |
2001年 | 19篇 |
2000年 | 15篇 |
1999年 | 23篇 |
1998年 | 19篇 |
1997年 | 9篇 |
1996年 | 13篇 |
1995年 | 13篇 |
1994年 | 10篇 |
1993年 | 15篇 |
1992年 | 13篇 |
1991年 | 6篇 |
1990年 | 11篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 7篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 6篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1977年 | 2篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1973年 | 7篇 |
1972年 | 2篇 |
1971年 | 2篇 |
排序方式: 共有1852条查询结果,搜索用时 0 毫秒
61.
Gregory B. Kharas Sonia E. Chavez Harrison S. Browning Jennifer A. Sepe Mario E. Romanelli Melissa K. Susnis 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):751-755
Electrophilic trisubstituted ethylenes, ring-disubstituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO2CH3, where R is 2,5-dichloro, 3,5-dichloro, 2,3-difluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro, 2-chloro-5-nitro, and 2-chloro-6-nitro were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and methyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. The order of relative reactivity (1/r1) for the monomers is 4-Cl-3-F (4.87) > 2,3-F2 (4.49) > 3-Cl-4-F (3.50) > 3-Cl-2-F (2.96) > 2-Cl-5-NO2 (2.02) > 2,5-Cl2 (1.54) > 2-Cl-6-NO2 (1.00) > 3,5-Cl2 (0.41). Relatively high Tg of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500ºC range with residue (1.5–34.5% wt), which then decomposed in the 500-800ºC range. 相似文献
62.
Gregory B. Kharas Sonia E. Chavez Alex C. Mast Mark Krzeszowiec Stan Mazo 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):451-454
Novel copolymers of trisubstituted ethylene monomers, ring-substituted 1,1-dicyano-2-(1-naphthyl)ethylenes, RC10H6CH?C(CN)2 (where R is H, 2-OCH3, 4-OCH3) and 4-fluorostyrene were prepared by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C-NMR. The order of relative reactivity (1/r 1) for the monomers is (5.86) > 2-CH3O (4.28) > 4-CH3O (2.87). Relatively high Tg of the copolymers in comparison with that of poly(4-fluorostyrene) indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (7.3–7.7% wt.), which then decomposed in the 500–800°C range. 相似文献
63.
Sonia Degeratu P. Rotaru S. Rizescu N. G. Bîzdoacă 《Journal of Thermal Analysis and Calorimetry》2013,111(2):1255-1262
The study concerns an experimental model using a SMA spring actuator for improving the whole performance of a barrier structure. The study is, specifically, focused on the thermal analysis of the SMA spring material and on determination of the SMA spring working time periods at different values of the activating electric current inducing different phase changing speeds. 相似文献
64.
Manuel Alberto Flores‐Hidalgo Daniel Glossman‐Mitnik D. H. Galvan Diana Barraza‐Jimenez 《中国化学会会志》2013,60(8):1082-1091
Density Functional Theory employing hybrid and M06 functionals in combination with three different basis sets is used to calculate the ground state of a cage like (ZnO)12 nanocluster which has been consistently reported as the more stable cluster for its particular size. B3LYP and B3PW91 hybrid functionals combined with 6‐31+G*, Lanl2dz and SDD basis sets are employed to treat the ZnO molecular system. Alternatively, three M06 functionals in combination with three basis sets are employed in the nanostructure calculations. Results obtained by treating ZnO sodalite cage nanocluster with M06 functionals demonstrated comparable quality to results obtained with hybrid functionals. Within this study, efficient theoretical DFT methods with the widely known hybrid and the recently created M06 meta‐hybrid functionals are employed to study nanostructured ZnO. Our resulting parameters provide a fresh approach performance wise on the different theoretical methods to treat transition metal nanostructures, particularly, ZnO nanoclusters geometry and electronic structure. 相似文献
65.
Alex F. C. Flores Juliana L. Malavolta Leandro M. Frigo Morgana Doneda Darlene C. Flores 《合成通讯》2013,43(10):1198-1204
We develop an efficient method to synthesize novel propionyl-spaced bisheterocyclic compounds. It entails cyclocondensation of 3-(5-trifluoromethyl-1H-pyrazol-3-yl)propanoyl hydrazide obtained from levulinic acid, with 1,1,1-trifluoro-4-methoxy-3-alken-2-ones proceeding regiospecifically to 1-[(5-trifluoromethyl-5-hydroxy-3-substituted-4,5-dihydro-1H-pyrazol-1-yl)-3-(5-trifluoromethyl-1H-pyrazol-3-yl)propan-1-one derivatives. 相似文献
66.
Parthasarathy Saravanan Suparna Gupta Arpita DattaGupta Sonia Gupta Vinod K. Singh 《合成通讯》2013,43(15):2695-2699
The cleavage of α-hydroxy tert-butyldimethylsilyl ether to diol takes place efficiently with LAH. It has been proposed that the reaction proceeds via intramolecular hydride transfer from the alkoxy aluminium hydride. In order to substantiate this, reduction of TBDMS ether with LAH in a variety of substrates was studied. 相似文献
67.
Alex F. C. Flores Luciana A. Piovesan Alynne A. Souto Mariano A. Pereira Marcos A. P. Martins Tatiane L. Balliano 《合成通讯》2013,43(17):2326-2336
Two series of 5-trichloromethylisoxazoles were synthesized from the cyclocondensation of 1,1,1-trichloro-4-methoxy-3-alken-2-ones [Cl3CC(O)C(R2) = C(R1)OMe, where R1 = H, Me, Et, Pr, iso-Pr, cyclo-Pr, Bu, terc-Bu, CH2Br, CHBr2, CH(Me)SMe, (CH2)2Ph, and Ph, and R2 = H; R1 = H and R2 = Me and Et; R1 and R2 = -(CH2)4- and -(CH2)5-; and R1 = Et and Ph and R2 = Me] with hydroxylamine hydrochloride through a rapid one-pot reaction in water. The 5-trichloromethyl-4,5-dihydroisoxazoles were aromatized by reaction with concentrated sulfuric acid to obtain the respective 5-trichloromethylisoxazoles. Their structures were confirmed by elemental analysis, 1H/13C nuclear magnetic resonance, and electron impact mass spectroscopy. Crystal structure analysis for 5-triclhoromethyl-5-hydroxy-3-propyl-4,5-dihydroisoxazole (2d) and 5-trichloromethyl-5-hydroxy-3,4-hexamethylene-4,5-dihydroisoxazole (2o) is presented. The antimicrobial activities of the 5-trichloromethyl-4,5-dihydroisoxazole derivatives were examined using the standard twofold dilution method against Gram-positive bacteria (Staphylococcus aureus), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa), and yeasts (Candida spp. and Cryptococcus neoformans). All of the tested 5-trichloromethyldihydroisoxazoles exhibited antibacterial and antifungal activities at the tested concentrations. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
68.
Roberta Del Sole Anna Scardino Maria Rosaria Lazzoi Lucia Mergola Sonia Scorrano Giuseppe Vasapollo 《Mikrochimica acta》2013,180(15-16):1401-1409
A molecularly imprinted polymer (MIP) for the specific retention of neopterin has been developed. A set of 6 polymers was prepared by radical polymerization under different experimental condition using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker, with the aim to understand their influence on the efficiency of the MIP. The performance of each MIP was tested in batch experiments via their binding capacity. The MIP prepared in the presence of nickel ions in dimethylsulfoxide-acetonitrile mixture (P4) exhibited the highest binding capacity for neopterin (260 μmol per gram of polymer). A selectivity study with two other pteridines demonstrated the polymer P4 also to possess the best selectivity. Figure
A molecularly imprinted polymer for the specific retention of neopterin was developed. A set of 6 polymers was prepared under different experimental condition. The performance of each MIP was tested through their binding capacity. The MIP P4 prepared in the presence of nickel ions exhibited the highest binding capacity 相似文献
69.
The reactions of 2,2,2-trichloro-1-phenylethanone with various oxygen, carbon and sulfur nucleophiles were investigated with a view of widening the use of trichloroethanones as acylating agents. 相似文献
70.
Quentin Vanbellingen Paul Servin Anaïs Coinaud Sonia Mallet-Ladeira Rgis Laurent Anne-Marie Caminade 《Molecules (Basel, Switzerland)》2021,26(8)
Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers and dendrimers towards palladium(II) has been assayed. The corresponding complexes have been either isolated or prepared in situ. In both cases, the monomeric and dendritic complexes have been tested as catalysts in Heck couplings and in Sonogashira couplings. In some cases, a positive dendritic effect has been observed, that is, an increase of the catalytic efficiency proportional to the dendrimer generation. 相似文献