全文获取类型
收费全文 | 2937篇 |
免费 | 94篇 |
国内免费 | 15篇 |
专业分类
化学 | 2398篇 |
晶体学 | 28篇 |
力学 | 29篇 |
数学 | 206篇 |
物理学 | 385篇 |
出版年
2023年 | 18篇 |
2022年 | 22篇 |
2021年 | 21篇 |
2020年 | 42篇 |
2019年 | 43篇 |
2018年 | 27篇 |
2017年 | 23篇 |
2016年 | 56篇 |
2015年 | 54篇 |
2014年 | 91篇 |
2013年 | 184篇 |
2012年 | 142篇 |
2011年 | 177篇 |
2010年 | 123篇 |
2009年 | 107篇 |
2008年 | 182篇 |
2007年 | 163篇 |
2006年 | 186篇 |
2005年 | 187篇 |
2004年 | 171篇 |
2003年 | 137篇 |
2002年 | 143篇 |
2001年 | 50篇 |
2000年 | 41篇 |
1999年 | 26篇 |
1998年 | 39篇 |
1997年 | 30篇 |
1996年 | 26篇 |
1995年 | 17篇 |
1994年 | 31篇 |
1993年 | 15篇 |
1992年 | 24篇 |
1991年 | 18篇 |
1989年 | 13篇 |
1988年 | 15篇 |
1986年 | 15篇 |
1985年 | 33篇 |
1984年 | 46篇 |
1983年 | 27篇 |
1982年 | 37篇 |
1981年 | 43篇 |
1980年 | 28篇 |
1979年 | 26篇 |
1978年 | 17篇 |
1977年 | 21篇 |
1976年 | 19篇 |
1975年 | 17篇 |
1974年 | 17篇 |
1973年 | 11篇 |
1972年 | 8篇 |
排序方式: 共有3046条查询结果,搜索用时 10 毫秒
41.
Katsuhiko Saido Takeshi Kuroki Tadashi Ikemura Makoto Kirisawa 《Journal of Analytical and Applied Pyrolysis》1985,9(1):29-34
In order to clarify the mechanism conferring heat resistance on phthalate esters, those with a substituent on the β-carbon atom, such as bis(2-aminobutyl) phthalate, bis(2-nitrobutyl) phthalate, bis(2,4-diphenylbutyl) phthalate and dineopentyl phthalate, were synthesized and their thermal stabilities were studied by thermogravimetry and differential thermal analysis. The analytical results for these phthalate esters were compared with those for dibutyl phthalate, with a straight alkyl chain. As the temperatures required for a 3% weight loss of phthalate esters with a substituent, an electron-donating group (amino group) or an electron-accepting group (nitro group) on the β-carbon atom move to the higher end of the range, the effect of the adjacent group was recognized. The presence of a phenyl group in phthalate esters considerably improved the heat resistance. It is considered that the high heat resistance of bis(2,4-diphenylbutyl) phthalate is due to the obstruction of the planar configuration for cis elimination by the phenyl group and hindrance by the phenyl group of the formation of the six-membered cyclic transition state owing to the interaction between non-bondable molecules. 相似文献
42.
Cobalt(II) complexes of poly(aryl ester) dendrimer porphyrins [(m-[Gn]TPP)Co(II)] (generation number n=0-4), in the presence of azobisisobutyronitrile (AIBN) at 60 degrees C, underwent alkenylation with several alkynes at the metal center. A complete inhibition of double-bond migration (secondary transformation) was observed for [(m-[Gn]TPP)Co(II)] (n=3 and 4), which gave [(m-[Gn]TPP)Co(III)-C(=CH(2))R] (n=3 and 4) exclusively. Overall reaction rates for [(m-[Gn]TPP)Co(II)] (n=0-3) were hardly dependent on the size of the dendritic substituents, while a notable retardation was observed for the largest dendrimer, [(m-[G4]TPP)Co(II)]. Mechanistic studies on double-bond migration with pure [(m-[Gn]TPP)Co(III)-C(=CH(2))Bu] (n=0-4) demonstrated that the secondary transformation involves participation of [(m-[Gn]TPP)Co(III)H] (n=0-4), derived from [(m-[Gn]TPP)Co(II)] and AIBN, rather than [(m-[Gn]TPP)Co(II)] alone. Crossover experiments using [(m-[Gn]TPP)Co(III)-C(=CH(2))Bu] (n=2-4), in combination with nondendritic [(m-[G0]TPP)Co(II)] and AIBN, indicated a high level of steric protection of the active center by a robust [G4]-dendritic cage, as suggested by a (1)H NMR pulse relaxation time profile of m-[G4]TPPH(2). 相似文献
43.
Kitano H Tada S Mori T Takaha K Gemmei-Ide M Tanaka M Fukuda M Yokoyama Y 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11932-11940
The structure and hydrogen bonding of water in the vicinity of carboxybetaine homopolymer (poly[1-carboxy-N,N-dimethyl-N-(2'-methacryloyloxyethyl)methanaminium inner salt] (PolyCMB), and a random copolymer of CMB and n-butyl methacrylate, Poly(CMB-r-BMA), with various molecular weights were analyzed in their aqueous solutions and thin film with contours of O-H stretching of Raman and attenuated total reflection infrared (ATR-IR) spectra, respectively. The relative intensity of the collective band (C value) corresponding to a long-range coupling of O-H stretchings of the Raman spectra for aqueous solution of Poly(CMB-r-BMA) was very close to that for pure water, which is in contrast with the smaller C value in aqueous solution of ordinary polyelectrolytes. The number of hydrogen bonds collapsed by the presence of one monomer residue (N(corr) value) of PolyCMB and Poly(CMB-r-BMA) (CMB, 45 mol %) (M(w), 1.14 x 10(4) and 1.78 x 10(4), respectively) could be calculated from the C value. The N(corr) values were much smaller than those for ordinary polyelectrolytes and close to those for nonionic water-soluble polymers such as poly(ethylene glycol) and poly(N-vinylpyrrolidone). Furthermore, a water-insoluble Poly(CMB-r-BMA) with a large BMA content (M(w) = 347 kD, CMB 27 mol %) could be cast as a thin film (thickness, ca. 10 microm) on a ZnSe crystal for the ATR-IR analyses. At an early stage of sorption of water into the Poly(CMB-r-BMA) film, the O-H stretching band of IR spectra for the water incorporated in the film was similar to that for free water, which is in contrast with the drastic change in the O-H stretching band of water incorporated in polymer films such as poly(methyl methacrylate) (PMMA) and poly(n-butyl methacrylate) (PBMA). The theoretical vibrational frequency for water molecules hydrating a betaine molecule calculated by using a density functional method supported the experimental results. The adhesion of human platelets to Poly(CMB-r-BMA) films was much less than that to PMMA and PBMA. With an increase in the content of CMB residue, the number of platelets adhered to the Poly(CMB-r-BMA) film drastically decreased and then gradually increased, probably due to the increase in the roughness of the film surface. These results suggest that the carboxybetaine monomer residues with a zwitterionic structure do not significantly disturb the hydrogen bonding between water molecules in both aqueous solution and thin film systems, resulting in the excellent blood-compatibility of the carboxybetaine polymers. 相似文献
44.
45.
Numerical Algorithms - In this paper, we propose an infeasible arc-search interior-point algorithm for solving nonlinear programming problems. Most algorithms based on interior-point methods are... 相似文献
46.
A bioassay-directed fractionation of the cytotoxic constituents of the Japanese sea hare Dolabella auricularia resulted in the isolation of two 35-membered depsipeptides dolastatin G (1) and nordolastatin G (2), which showed cytotoxicity against HeLa S(3) cells with IC(50) values of 1.0 and 5.3 &mgr;g/mL, respectively. The gross structures of these substances were established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure of 1 was determined by chiral HPLC analysis of amino acid components obtained from acid hydrolysis of 1 and by the enantioselective syntheses of two degradation products arising from polyketide portions. Nordolastatin G (2) is a congener that has the same absolute stereochemistry as that of 1. 相似文献
47.
Sung Il Hong Toshikazu Kurosaki Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1972,10(11):3405-3419
Polyoxime-urethanes have been synthesized from dioximes and diisocyanates, and their structures have been ascertained by elemental analysis and infrared spectroscopy. They can be represented by the general formula: These polymer films were photolyzed by using a high-pressure 100-W mercury lamp, and the rate of decomposition of the N? O bond was determined by use of ultraviolet and infrared spectra, or comparing the photochemical behavior with that of corresponding model compounds. Upon irradiating these polymers in the presence or absence of sensitizers or a hydrogen donor, there were obtained photolyzed polymers of low molecular weight, of which the molecular weights were estimated by observing the viscosity changes. To deduce the mechanism of photodegradation of polyoxime-urethane, photolysis of benzophenone oxime-phenyl urethane was investigated as a model compound. 相似文献
48.
Yoko Nambu Takeshi Endo Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1981,19(8):1937-1943
Reductive S-monoacylation of lipoamide with some carboxylic acids and tri-n-butylphosphine was carried out in acetonitrile to obtain the corresponding S-monoacylated compounds in excellent yield. This method was applied to the preparation of S-monoacylated dihydrolipoyl polymer with a neighboring thiol group. The acyl transfer from the polymer to cyclohexylamine was enhanced as much as 64 times by adding silver perchlorate. 相似文献
49.
The proposed structures of patellamides B and C, cytotoxic lipophilic cyclic peptides from a marine tunicate, have been revised on the basis of the spectral data of their partial hydrolysates, and their revised structures have been synthetically confirmed by the use of diphenyl phosphorazidate(DPPA) and diethyl phosphorocyanidate(DEPC). 相似文献
50.
Makoto Oba 《Journal of organometallic chemistry》2006,691(6):1151-1153
A novel [2.2]metacyclophane in which two benzene rings are linked together with a carbon-carbon double bond and a disilane unit was prepared. Photolysis of the cyclophane in the presence of oxygen afforded the 4,5-dihydro-4,5-disilapyrene derivative via a transannular dehydrogenation reaction. 相似文献