全文获取类型
收费全文 | 2550篇 |
免费 | 113篇 |
国内免费 | 15篇 |
专业分类
化学 | 1943篇 |
晶体学 | 22篇 |
力学 | 37篇 |
综合类 | 16篇 |
数学 | 230篇 |
物理学 | 430篇 |
出版年
2023年 | 20篇 |
2022年 | 14篇 |
2021年 | 41篇 |
2020年 | 54篇 |
2019年 | 56篇 |
2018年 | 38篇 |
2017年 | 31篇 |
2016年 | 60篇 |
2015年 | 57篇 |
2014年 | 64篇 |
2013年 | 132篇 |
2012年 | 170篇 |
2011年 | 166篇 |
2010年 | 93篇 |
2009年 | 104篇 |
2008年 | 184篇 |
2007年 | 158篇 |
2006年 | 163篇 |
2005年 | 155篇 |
2004年 | 131篇 |
2003年 | 109篇 |
2002年 | 105篇 |
2001年 | 38篇 |
2000年 | 46篇 |
1999年 | 30篇 |
1998年 | 33篇 |
1997年 | 31篇 |
1996年 | 29篇 |
1995年 | 16篇 |
1994年 | 21篇 |
1993年 | 16篇 |
1992年 | 23篇 |
1991年 | 12篇 |
1990年 | 22篇 |
1989年 | 13篇 |
1988年 | 15篇 |
1987年 | 20篇 |
1986年 | 12篇 |
1985年 | 26篇 |
1984年 | 22篇 |
1983年 | 19篇 |
1982年 | 20篇 |
1981年 | 22篇 |
1980年 | 21篇 |
1979年 | 11篇 |
1978年 | 9篇 |
1977年 | 10篇 |
1976年 | 10篇 |
1975年 | 5篇 |
1974年 | 6篇 |
排序方式: 共有2678条查询结果,搜索用时 15 毫秒
91.
Yoshihiko Ohishi Tomonori Kawabata Tetsuya Shishido Ken Takaki Qinghong Zhang Ye Wang Katsuomi Takehira 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):49-58
M-MCM-41 catalysts (M: V, Cr, Fe, and Ga) prepared by direct hydrothermal synthesis (DHT) have been tested for dehydrogenation of ethylbenzene with CO2. The synthesized materials were characterized by X-ray diffraction (XRD), N2 adsorption (77 K), and diffuse reflectance UV–vis spectroscopic measurements. Cr-MCM-41 showed the highest activity among M-MCM-41 catalysts tested, resulting in the production of styrene with the conversion of 65% and the selectivity above 90%. The rate of styrene formation increased with increasing Cr loading up to 1.7 wt.%. It is suggested that Cr(VI)O4 in tetrahedral coordination is formed as an active monochromate species and reduced to Cr(III)O6 in octahedral coordination as a less active polychromate species during the reaction. Deactivated catalyst was regenerated by a treatment with gaseous oxygen or CO2, during which redistribution as well as reoxidation of polymeric Cr(III)O6 octahedra to monomeric Cr(VI)O4 tetrahedra was observed. The rate of CO formation increased together with that of styrene formation, while the rate of H2 formation decreased, with increasing partial pressure of CO2. It was confirmed that reverse water-gas shift reaction took place over Cr-MCM-41 by a separate experiment. The rate of CO formation during the dehydrogenation of ethylbenzene with CO2 over Cr-MCM-41 was well accounted for by assuming parallel occurrence of two reactions, i.e., direct oxidative dehydrogenation of ethylbenzene with CO2 and simple dehydrogenation of ethylbenzene thermodynamically assisted by reverse water-gas shift reaction. 相似文献
92.
The second method for the synthesis of cis-[Ru(III)Cl(2)(cyclam)]Cl (1) (cyclam = 1,4,8,11-tetraazacyclotetradecane), with use of cis-Ru(II)Cl(2)(DMSO)(4) (DMSO = dimethyl sulfoxide) as a starting complex, is reported together with the synthesis of [Ru(II)(cyclam)(bpy)](BF(4))(2).H(2)O (2) (bpy = 2,2'-bipyridine) from 1. The syntheses of Ru complexes of tris(2-aminoethyl)amine (tren) are also reported. A reaction between K(3)[Ru(III)(ox)(3)] (ox = oxalate) and tren affords fac-[Ru(III)Cl(3)(trenH)]Cl.(1)/(2)H(2)O (3) (trenH = bis(2-aminoethyl)(2-ammonioethyl)amine = monoprotonated tren) and (H(5)O(2))(2)[K(tren)][Ru(III)Cl(6)] (4) as major products and gives fac-[Ru(III)Cl(ox)(trenH)]Cl.(3)/(2)H(2)O (5) in very low reproducibility. A reaction between 3 and bpy affords [Ru(II)(baia)(bpy)](BF(4))(2) (6) (baia = bis(2-aminoethyl)(iminomethyl)amine), in which tren undergoes a selective dehydrogenation into baia. The crystal structures of 2-6 have been determined by X-ray diffraction, and their structural features are discussed in detail. Crystallographic data are as follows: 2, RuF(8)ON(6)C(20)B(2)H(34), monoclinic, space group P2(1)/c with a = 12.448(3) ?, b = 13.200(7) ?, c = 17.973(4) ?, beta = 104.28(2) degrees, V = 2862(2) ?(3), and Z = 4; 3, RuCl(4)O(0.5)N(4)C(6)H(20), monoclinic, space group P2(1)/a with a = 13.731(2) ?, b = 14.319(4) ?, c = 13.949(2) ?, beta = 90.77(1) degrees, V = 2742(1) ?(3), and Z = 8; 4, RuKCl(6)O(4)N(4)C(6)H(28), trigonal, space group R&thremacr; with a = 10.254(4), c = 35.03(1) ?, V = 3190(2) ?(3), and Z = 6; 5, RuCl(2)O(5.5)N(4)C(8)H(22), triclinic, space group P&onemacr; with a = 10.336(2) ?, b = 14.835(2) ?, c = 10.234(1) ?, alpha = 90.28(1) degrees, beta = 90.99(1) degrees, gamma = 92.07(1) degrees, V = 1567.9(4) ?(3), and Z = 4; 6, RuF(8)N(6)C(16)B(2)H(24), monoclinic, space group P2(1)/c, a = 10.779(2) ?, b = 14.416(3) ?, c = 14.190(2) ?, beta = 93.75(2) degrees, V = 2200.3(7) ?(3), and Z = 4. Compound 4 possesses a very unique layered structure made up of both anionic and cationic slabs, {[K(tren)](2)[Ru(III)Cl(6)]}(n)()(n)()(-) and {(H(5)O(2))(4)[Ru(III)Cl(6)]}(n)()(n)()(+) (n = infinity), in which both sheets {[K(tren)](2)}(n)()(2)(n)()(+) and {(H(5)O(2))(4)}(n)()(4)(n)()(+) offer cylindrical pores that are occupied with the [Ru(III)Cl(6)](3)(-) anions. The presence of a C=N double bond of baia in 6 is judged from the C-N distance of 1.28(2) ?. It is suggested that the structural restraint enhanced by the attachment of alkylene chelates at the nitrogen donors of amines results in either the mislocation or misdirection of the donors, leading to the elongation of the Ru-N(amine) distances and to the weakening of their trans influence. Such structural strain is also discussed as related to the spectroscopic and electrochemical properties of the cis-[Ru(II)L(4)(bpy)](2+) complexes (L(4) = (NH(3))(4), (ethylenediamine)(2), and cyclam). 相似文献
93.
Fukuzumi S Okamoto K Tokuda Y Gros CP Guilard R 《Journal of the American Chemical Society》2004,126(51):17059-17066
Dehydrogenation of 10-methyl-9,10-dihydroacridine (AcrH(2)) by dioxygen (O(2)) proceeds efficiently, accompanied by the two-electron and four-electron reduction of O(2) to produce H(2)O(2) and H(2)O, which are effectively catalyzed by monomeric cobalt porphyrins and cofacial dicobalt porphyrins in the presence of perchloric acid (HClO(4)) in acetonitrile (MeCN) and benzonitrile (PhCN), respectively. The cobalt porphyrin catalyzed two-electron reduction of O(2) also occurs efficiently by 9-alkyl-10-methyl-9,10-dihydroacridines (AcrHR; R = Me, Et, and CH(2)COOEt) to yield 9-alkyl-10-methylacridinium ion (AcrR+) and H(2)O(2). In the case of R = Bu(t) and CMe(2)COOMe, however, the catalytic two-electron and four-electron reduction of O(2) by AcrHR results in oxygenation of the alkyl group of AcrHR rather than dehydrogenation to yield 10-methylacridinium ion (AcrH+) and the oxygenated products of the alkyl groups, i.e., the corresponding hydroperoxides (ROOH) and the alcohol (ROH), respectively. The catalytic mechanisms of the dehydrogenation vs the oxygenation of AcrHR in the two-electron and four-electron reduction of O(2), catalyzed by monomeric cobalt porphyrins and cofacial dicobalt porphyrins, respectively, are discussed in relation to the C(9)-H or C(9)-C bond cleavage of AcrHR radical cations produced in the electron-transfer oxidation of AcrHR. 相似文献
94.
Yoshitsugu Kojima Takaaki Matsuoka Norio Sato Hideroh Takahashi 《Journal of polymer science. Part A, Polymer chemistry》1995,33(17):2935-2940
New conjugated oligomers were prepared by reacting phenylacetylene under high pressure of 0.11 to 0.92 GPa at 100–200°C for 0–5 h. The number-average molecular weight M?n, the weight-average molecular weight M?w, and the oligomer yield increased with pressure, tem-perature, and time. The average molecular weight of the oligomer showed the maximum value (M?n: 830, M?w: 2400) under 0.92 GPa, the maximum pressure, where phenylacetylene was oligomerized at a constant temperature. The structure of the oligomer was investigated from ESR, infrared, UV–VIS, field desorption mass (FDMS) spectra, and 13C NMR spec-trum. Analysis of the FDMS spectrum revealed that the molecular weight of the oligomer was multiple of the monomer. 13C NMR spectrum of the oligomer showed the absence of sp-carbon (? C?). We found that the oligomer had a cyclic structure. The cyclic oligomers of pentamer or more were new compounds. © 1995 John Wiley & Sons, Inc. 相似文献
95.
96.
M S Lie Ken Jie 《Journal of chromatography. A》1975,109(1):81-87
Five trimethylene-interrupted methyl octadecadiynoates, C18 delta-2a,-7a; delta-3a,-8a; delta-4a,-9a; delta-5a,-10a and delta-6a,-11a, and the corresponding cis,cis-octadecadienoates were synthesized, and their gas-liquid chromatographic properties were studied on Apiezon L, diethylene glycol succinate polyester and Silac 10C stationary phases. The equivalent chain lengths of these esters have been determined, and the separation of mixtures and the prediction of gas chromatographic behaviour of these isomers are discussed. 相似文献
97.
Matsuoka T Tokumori D Kotsuki H Ishida M Matsushita M Kimura S Itoh T Checcucci G 《Photochemistry and photobiology》2000,72(5):709-713
In the ciliated protozoan Blepharisma, step-up photophobic response is believed to be mediated by a novel type of photosensory pigment known as "blepharismins" (BL) that are contained in the pigment granules located just beneath the plasma membrane. We examined the ultrastructure of the pigment granules by freeze-fracture and thin-section electron microscopy and proposed a schematic diagram showing the granules' three-dimensional inner membranous structure. Some of the BL are suggested to be associated with 200 kDa membrane protein. High-pressure liquid chromatography analysis of pigment species associated with 200 kDa protein obtained from blue forms of Blepharisma (oxyblepharisma) revealed that the 200 kDa protein was associated with five types of oxyblepharismin. The fluorescence intensity was increased when the pigments were dissociated from the 200 kDa protein. The result supports the hypothesis that the pigment-200 kDa complex is able to transduce light energy into signals mediating the photobehavior of Blepharisma. 相似文献
98.
We estimated the energy barriers of proton transfers in the systems of (CF3SO3/H/SO3CF3)− and (CF3SO3/H/H2O/SO3CF3)− as models of a water-swollen Nafion membrane by an ab initio density functional quantum calculation method with consideration of the hydration effect. As a result, the proton transfer between the SO sites, which is accompanied by one water molecule, was found to be one of the proton-transfer mechanisms in the water-swollen Nafion membrane; that is, the surface diffusion mechanism was found to be important for the proton transfer in that membrane. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1905–1914, 2004 相似文献
99.
Fukuzumi S Okamoto K Yoshida Y Imahori H Araki Y Ito O 《Journal of the American Chemical Society》2003,125(4):1007-1013
A ferrocene-quinone dyad (Fc-Q) with a rigid amide spacer and Fc-(Me)Q dyad, in which the amide proton acting as a hydrogen-bonding acceptor is replaced by the methyl group, are employed to examine the effects of hydrogen bonding on both the thermal and the photoinduced electron-transfer reactions. The hydrogen bonding of the semiquinone radical anion with the amide proton in Fc-Q(.-) produced by the electron-transfer reduction of Fc-Q is indicated by the significant positive shift of the one-electron reduction potential of Fc-Q. The hyperfine coupling constants of Fc-Q(.-) also indicate the existence of hydrogen bonding, agreeing with those predicted by the density functional calculation. The hydrogen-bonding dynamics in the photoinduced electron transfer from the ferrocene (Fc) to the quinone moiety (Q) in Fc-Q have been successfully detected in the femtosecond laser flash photolysis experiments. Thermal intramolecular electron transfer from Fc to Q in Fc-Q and Fc-(Me)Q also occurs efficiently in the presence of metal ions in acetonitrile at 298 K. The hydrogen bond formed between the semiquinone radical anion and the amide proton in Fc-Q results in remarkable acceleration of the rate of metal ion-promoted electron transfer as compared to the rate of Fc-(Me)Q in which hydrogen bonding is prohibited. The metal ion-promoted electron-transfer rates are well correlated with the binding energies of superoxide ion-metal ion complexes, which are derived from the g(zz) values of the ESR spectra. 相似文献
100.
Kosaka T Yoneyama-Takazawa T Kubota K Matsuoka T Sato I Sasaki T Tanaka Y 《Journal of mass spectrometry : JMS》2003,38(12):1281-1287
We have developed a method for protein identification with peptide mass fingerprinting and sequence tagging using nano liquid chromatography (LC)/Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). To achieve greater sensitivity, a nanoelectrospray (nano-ES) needle packed with reversed-phase medium was used and connected to the nano-ES ion source of the FTICR mass spectrometer. To obtain peptide sequence tag information, infrared multiphoton dissociation (IRMPD) was carried out in nano-LC/FTICR-MS analysis. The analysis involves alternating nano-ES/FTICR-MS and nano-ES/IRMPD-FTICR-MS scans during a single LC run, which provides sets of parent and fragment ion masses of the proteolytic digest. The utility of this alternating-scan nano-LC/IRMPD-FTICR-MS approach was evaluated by using bovine serum albumin as a standard protein. We applied this approach to the protein identification of rat liver diacetyl-reducing enzyme. It was demonstrated that this enzyme was correctly identified as 3-alpha-hydroxysteroid dehydrogenase by the alternating-scan nano-LC/IRMPD-FTICR-MS approach with accurate peptide mass fingerprinting and peptide sequence tagging. 相似文献