全文获取类型
收费全文 | 1921篇 |
免费 | 52篇 |
国内免费 | 3篇 |
专业分类
化学 | 1450篇 |
晶体学 | 32篇 |
力学 | 29篇 |
数学 | 79篇 |
物理学 | 386篇 |
出版年
2022年 | 12篇 |
2021年 | 26篇 |
2020年 | 23篇 |
2019年 | 32篇 |
2018年 | 16篇 |
2017年 | 16篇 |
2016年 | 26篇 |
2015年 | 33篇 |
2014年 | 30篇 |
2013年 | 93篇 |
2012年 | 88篇 |
2011年 | 92篇 |
2010年 | 74篇 |
2009年 | 61篇 |
2008年 | 118篇 |
2007年 | 119篇 |
2006年 | 93篇 |
2005年 | 119篇 |
2004年 | 86篇 |
2003年 | 81篇 |
2002年 | 67篇 |
2001年 | 51篇 |
2000年 | 43篇 |
1999年 | 31篇 |
1998年 | 32篇 |
1997年 | 17篇 |
1996年 | 25篇 |
1995年 | 21篇 |
1994年 | 17篇 |
1993年 | 27篇 |
1992年 | 29篇 |
1991年 | 25篇 |
1990年 | 17篇 |
1989年 | 28篇 |
1988年 | 13篇 |
1987年 | 10篇 |
1986年 | 20篇 |
1985年 | 22篇 |
1984年 | 23篇 |
1983年 | 21篇 |
1982年 | 22篇 |
1981年 | 21篇 |
1980年 | 16篇 |
1979年 | 24篇 |
1978年 | 15篇 |
1977年 | 19篇 |
1976年 | 19篇 |
1975年 | 11篇 |
1974年 | 18篇 |
1973年 | 11篇 |
排序方式: 共有1976条查询结果,搜索用时 15 毫秒
71.
The electronic structure of azulene molecule has been studied. We have obtained the optimized structures of ground and singlet excited states by using the complete active space self-consistent-field (CASSCF) method, and calculated vertical and 0-0 transition energies between the ground and excited states with second-order M?ller-Plesset perturbation theory (CASPT2). The CASPT2 calculations indicate that the bond-equalized C(2v) structure is more stable than the bond-alternating C(s) structure in the ground state. For a physical understanding of electronic structure change from C(2v) to C(s), we have performed the CASSCF calculations of Duschinsky matrix describing mixing of the b(2) vibrational mode between the ground (1A(1)) and the first excited (1B(2)) states based on the Kekule-crossing model. The CASPT2 0-0 transition energies are in fairly good agreement with experimental results within 0.1-0.3 eV. The CASSCF oscillator strengths between the ground and excited states are calculated and compared with experimental data. Furthermore, we have calculated the CASPT2 dipole moments of ground and excited states, which show good agreement with experimental values. 相似文献
72.
Ozeki H Nomoto A Ogawa K Kobuke Y Murakami M Hosoda K Ohtani M Nakashima S Miyasaka H Okada T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6393-6401
We synthesized special-pair/electron-acceptor systems consisting of a complementary slipped cofacial dimer of imidazolyl-substituted zinc porphyrin, bearing pyromellitdiimide as the electron acceptor. In the case of the dimer, the first and second oxidation potentials were split into a total of four peaks in the differential pulse voltammetry measurement. Furthermore, the shift values of the first oxidation potentials obtained by changing the solvent polarity for the dimer were almost half of those observed for the monomer. These results indicate that the radical cation is delocalized over the whole pi system of the dimer. Time-resolved transient absorption measurements revealed that, relative to the corresponding monomer, the dimer accelerated the charge separation rate, but decelerated the charge recombination rate. The smaller reorganization energy of the slipped cofacial dimer relative to that of the monomeric system demonstrates the significance of the special-pair arrangement for efficient charge separation in photosynthesis. 相似文献
73.
Tanaka T Murakami K Kanda A Patra D Yamamoto S Satoh N Kim SW Rahman SM Ohno H Iwata C 《The Journal of organic chemistry》2001,66(21):7107-7112
A total synthesis of (+/-)-stemodinone, a tetracyclic stemodane diterpene, from the known tricyclic methyl olefin 11 is described. The key steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed by the Pd(0)-catalyzed lactone-migration reaction reported by us. 相似文献
74.
Kenneth E. Laintz Shuichi Iso Yoshiro Meguro Zenko Yoshida 《Journal of separation science》1994,17(8):603-606
The chromatographic behaviors of lanthanide chelates of acetylacetone (ACAC), trifluoroacetylacetone (TFA), thenoyltrifluoroacetone (TTA), dipivaloylmethane (THD), 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione (FOD), and the thenoyltrifluoroacetonepyridine (TTA·Py) adduct were investigated using packed column supercritical fluid chromatography. Mobile phases consisting of neat and alcohol modified CO2 were used with a phenyl packed stationary phase. Lanthanide complexes of ACAC, THD, and FOD were shown to have better chromatographic performance compared to the corresponding chelates with TFA, TTA, and TTA·Py. In particular, TTA complexes such as Eu(TTA)3 showed characteristic thermal decomposition in the mobile phase at elevated temperature. In addition, retention behavior was found to be a temperature dependent function of volatility and solubility for all chelates studied. 相似文献
75.
Shuichi Naito Shigeru Aida Toshiki Kasahara Toshihiro Miyao 《Research on Chemical Intermediates》2006,32(3-4):279-290
In situ infrared spectroscopy was applied to elucidate the reaction mechanism of CO hydrogenation over Pd/CeO2. Instead of direct dissociation of CO, a new reaction pathway is proposed for methane formation, involving geminal dicarbonyl intermediates and (HCO)2(a) intermediates, which may be located on the surface of Pd covered with thin layers of reduced ceria (SMSI effect). Transformation of methane formation sites into methanol formation ones by the oxidation with water vapor formed during the CO?H2 reaction is proposed, which may be located on the Pd (111) planes adjacent to ceria support. 相似文献
76.
Six new furostanol-type steroid saponins called trigoneosides Xa, Xb, XIb, XIIa, XIIb, and XIIIa were isolated from the seeds of Egyptian Trigonella foenum-graecum L. (Leguminosae) together with six known furostanol-type steroid saponins: trigoneosides Ia, Ib, and Va, glycoside D, trigonelloside C, and compound C. The structures of trigoneosides Xa, Xb, Xlb, XIIa, Xllb, and XIIIa were determined on the basis of chemical and physicochemical evidence as 26-O-beta-D-glucopyranosyl-(25S)-5alpha-furostane-2alpha+ ++,3beta,22xi,26-tetraol 3-O-alpha-L-rhamnopyranosyl(1-->2)-,beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-5alpha-furostane-2 alpha,beta,22xi,26tetraol 3-O-alpha-L-rhamnopyranosyl(l -->2)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-5alpha-furostane2alpha++ +,beta,22xi,26-tetraol 3-O-beta-D-xylopyranosyl(l -->4)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25S)-furost-4-ene-3beta,22xi,26- triol 3-O-Ca-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-furost-4-ene-3beta,22xi+ ++,26-triol 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranoside, and 26-O-beta-D-glucopyranosyl(25S)-furost-5-ene-3beta,22xi,26-t riol 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl (1-->3)-beta-D-glucopyranosyl(1--4)]-beta-D-glucopyranoside, respectively. 相似文献
77.
The extraction of copper(II) from strongly acidic solution (0.01-8M hydrochloric acid) with ammonium 1-pyrrolidinecarbodithioate in isobutyl methyl ketone has been investigated. The shaking time needed for quantitative extraction decreases as the acidity is increased. The effect of the mutual solubility of the organic solvent and the aqueous phase is significant when the acidity of the aqueous phase is increased. The acidity of the aqueous phase mainly affects the kinetic stability of the chelate during the shaking period, rather than the decomposition of the chelating agent. The kinetic stability of the chelate apparently depends on the mole ratio of reagent to copper, the half-lives for the chelate extracted from 4M hydrochloric acid being 29.0, 40.0 and 85.0 min for reagent: metal mole ratios of 10, 100 and 1000, respectively. 相似文献
78.
Tetsuji Yano Makoto Ebizuka Hiroyuki Yamamoto Shuichi Shibata Masayuki Yamane 《Journal of Sol-Gel Science and Technology》2000,19(1-3):845-849
Na2O-B2O3-SiO2 (NBS) gels containing a large amount of CdS quantum-dots (10 wt%) were densified using the hot press (HP) sintering method. By HP treatment, full-densification temperature could be lowered by about 40°C than that of the normal non-pressing (NP) heat treatment. Exciton absorption of CdS quantum-dots in HP-sample showed a large blue shift compared with that in the NP sample, and the size-distribution of CdS dots remained very sharp, with a mean particle diameter d = 3.66 nm and a standard deviation of = 0.72. HP pressure had a large effect on the reduction of sintering temperature and time, resulting in the suppression of the aggregation and growth of CdS quantum-dots in NBS glasses. 相似文献
79.
Minemura Y Ito S Miyao T Naito S Tomishige K Kunimori K 《Chemical communications (Cambridge, England)》2005,(11):1429-1431
In preferential CO oxidation in H2-rich gas, K-Pt/Al2O3(K/Pt = 10) was very effective in decreasing CO concentration below 10 ppm in the 375-410 K range, and the turnover frequency of the K-Pt/Al2O3 was 20 times as high as that of Pt/Al2O3 at 353 K; furthermore, the activity of CO oxidation was promoted drastically by the presence of H2. 相似文献
80.
Hironobu Tahara Yudai Tanaka Shoko Yamamoto Shigeki Yonemori Bun Chan Hiroto Murakami Takamasa Sagara 《Chemical science》2021,12(13):4872
Redox-active ionic liquids (RAILs) are gaining attention as a material that can create a wide range of functions. We herein propose a charge-transfer (CT) RAIL by mixing two RAILs, specifically a carbazole-based ionic liquid ([CzC4ImC1][TFSI]) as a donor and a viologen-based ionic liquid ([C4VC7][TFSI]2) as an acceptor. We investigated the effect of CT interaction on the physicochemical properties of the CT ionic liquid (CT-IL) using the results of temperature-dependent measurements of UV-vis absorption, viscosity, and ionic conductivity as well as cyclic voltammograms. We employed the Walden analysis and the Grunberg–Nissan model to elucidate the effect of the CT interaction on the viscosity and ionic conductivity. The CT interaction reduces the viscosity by reducing the electrostatic attraction between the dicationic viologen and TFSI anion. It also reduces the ionic conductivity by the CT association of the dicationic viologen and carbazole. The electrochemically reversible responses of the viologens in [C4VC7][TFSI]2 and CT-IL are consistent with the Nernstian and the interacting two-redox site models. Notably, the transport and electrochemical properties are modulated by CT interaction, leading to unique features that are not present in individual component ILs. The inclusion of CT interaction in RAILs thus provides a powerful means to expand the scope of functionalized ionic liquids.A redox-active ionic liquid (RAIL) consisting of a carbazole and viologen shows charge transfer (CT) interaction. The physicochemical properties are modulated by the CT interaction by comparison with the individual RAILs. 相似文献