全文获取类型
收费全文 | 3579篇 |
免费 | 164篇 |
国内免费 | 4篇 |
专业分类
化学 | 2555篇 |
晶体学 | 21篇 |
力学 | 55篇 |
数学 | 466篇 |
物理学 | 650篇 |
出版年
2023年 | 29篇 |
2022年 | 23篇 |
2021年 | 63篇 |
2020年 | 61篇 |
2019年 | 39篇 |
2018年 | 73篇 |
2017年 | 63篇 |
2016年 | 124篇 |
2015年 | 122篇 |
2014年 | 125篇 |
2013年 | 252篇 |
2012年 | 263篇 |
2011年 | 301篇 |
2010年 | 148篇 |
2009年 | 153篇 |
2008年 | 216篇 |
2007年 | 224篇 |
2006年 | 181篇 |
2005年 | 191篇 |
2004年 | 172篇 |
2003年 | 134篇 |
2002年 | 121篇 |
2001年 | 85篇 |
2000年 | 95篇 |
1999年 | 56篇 |
1998年 | 21篇 |
1997年 | 31篇 |
1996年 | 62篇 |
1995年 | 23篇 |
1994年 | 23篇 |
1993年 | 26篇 |
1992年 | 26篇 |
1991年 | 21篇 |
1990年 | 13篇 |
1989年 | 13篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 16篇 |
1985年 | 16篇 |
1984年 | 15篇 |
1983年 | 12篇 |
1982年 | 15篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 15篇 |
1978年 | 12篇 |
1977年 | 8篇 |
1976年 | 10篇 |
1974年 | 7篇 |
1973年 | 6篇 |
排序方式: 共有3747条查询结果,搜索用时 12 毫秒
71.
Baeyer-Villiger oxidation with potassium peroxomonosulfate supported on acidic silica gel 总被引:1,自引:0,他引:1
González-Núñez ME Mello R Olmos A Asensio G 《The Journal of organic chemistry》2005,70(26):10879-10882
[reaction: see text] Potassium peroxomonosulfate deposited onto silica SiO2 x KHSO5 efficiently reacts with ketones in dichloromethane at room temperature to give the corresponding esters or lactones in quantitative yields. This method avoids hydrolysis of the reaction products. The Baeyer-Villiger reaction is catalyzed by potassium hydrogensulfate present in the supported reagent. 相似文献
72.
Marulanda D Tasayco ML Cataldi M Arriaran V Polenova T 《The journal of physical chemistry. B》2005,109(38):18135-18145
De novo site-specific 13C and 15N backbone and sidechain resonance assignments are presented for uniformly enriched E. coli thioredoxin, established using two-dimensional homo- and heteronuclear solid-state magic angle spinning NMR correlation spectroscopy. Backbone dihedral angles and secondary structure were derived from the statistical analysis of the secondary chemical shifts, and are in good agreement with solution values for the intact full-length thioredoxin, with the exception of a small number of residues located at the termini of the individual secondary structure elements. A large number of cross-peaks observed in the DARR spectra with long mixing times correspond to the pairs of carbon atoms separated by 4-6 angstroms, suggesting that DARR could be efficiently employed for observation of medium- and long-range correlations. The 108 amino acid residue E. coli thioredoxin is the largest uniformly enriched protein assigned to this degree of completeness by solid-state NMR spectroscopy to date. It is anticipated that with a combination of two-dimensional correlation experiments and high magnetic fields, resonance assignments and secondary structure can be generally derived for other noncrystalline proteins. 相似文献
73.
Remedios González-Luque Manuela Merchán Piotr Borowski Björn O. Roos 《Theoretical chemistry accounts》1993,86(6):467-476
Summary Multiconfigurational electron correlation methods have been analyzed in order to theoretically compute the electron affinity (EA) of ozone. The near-degeneracy correlation effects, which are so important in O3 and O
3
–
, have been described using complete active space (CAS) SCF wave functions. Remaining dynamic correlation effects are computed using second-order perturbation theory (the CASPT2 method). The best calculated adiabatic value (including zero-point energy corrections), 2.19 eV, is about 0.09 eV larger than the experimental value. Comparative studies using size-consistent coupled pair functional approaches (CPF and ACPF) have also been performed. The harmonic frequencies in O
3
–
have been determined to be: 1=992, 2=572, and 3=879 cm–1, which gives a zero-point energy of 0.151 eV. 相似文献
74.
R. González-Ramírez H. Jiménez-Domínguez O. Solorza-Feria E. Ordóñez-Regil A. Cabral-Prieto S. Bulbulian 《Journal of Radioanalytical and Nuclear Chemistry》1993,174(2):291-298
Conditions for the electrodeposition of59Co and57Co on stainless steel foils have been studied. A set of electrolytic parameters has been determined to get a reasonably good electrodeposited sample. The57Co electrodeposited foil was then introduced in a quartz tube to be annealed in an argon flow. The final product was a 11 Ci Mössbauer source for college experiments which was succesfully tested by obtaining spectra of stainless steel and sodium nitroprusside. 相似文献
75.
A.?González-Pérez J.?M.?RusoEmail author G.?Prieto F.?Sarmiento 《Colloid and polymer science》2004,282(4):351-356
The interactions of sodium dodecyl sulphate with ovalbumin in aqueous solution at room temperature are described for a wide concentration range of both substances. A phase diagram covering a wide range of concentrations shows a total of five different morphologies. Dynamic light scattering of the samples from each morphology offered better understanding of the different structures (between three and four) present in the solution. The amount of ovalbumin present in the solution was confirmed with differential scanning spectroscopy, while the interactions between sodium dodecyl sulphate and ovalbumin were interpreted by zeta potential and electrical conductivity measurements. 相似文献
76.
We report molecular dynamics computer simulations of the surface tension and interfacial thickness of ionic liquid-vapor interfaces modeled with a soft core primitive model potential. We find that the surface tension shows an anomalous oscillatory behavior with interfacial area. This observation is discussed in terms of finite size effects introduced by the periodic boundary conditions employed in computer simulations. Otherwise we show that the thickness of the liquid-vapor interface increases with surface area as predicted by the capillary wave theory. Data on the surface tension of size-asymmetric ionic liquids are reported and compared with experimental data of molten salts. Our data suggest that the surface tensions of size-asymmetric ionic liquids do not follow a corresponding states law. 相似文献
77.
González-Bravo L Marrero-Delange D González-Guevara JL 《Journal of chromatography. A》2000,888(1-2):159-173
The method's accuracy of a compound quantitation by chromatography depends on the calibration procedure with a pure standard of the target analyte, if the latter is unavailable uncertainty is unavoidable. The group method is a different approach in GC quantitative analysis that shows a practicable way for avoiding this uncertainty and accurately quantify a mixture containing one or more unavailable components. This paper is concerned with the definition of the group method quantitative parameters, the application procedures for their calculation, the determination of the quantitative proportion of a group of unavailable components of a mixture and the partial or total quantitation of the latter. The paper also describes the steps for carrying out the so-called group-correlation method in the determination of the response factors of unavailable compounds, which belong to a homologous series. The GC experimental corroboration of the group method approach employing model mixtures of compounds is also presented. 相似文献
78.
González-Pérez A. Galán J. J. Rodríguez J. R. 《Journal of Thermal Analysis and Calorimetry》2003,72(2):741-749
The specific conductivities of dodecyldimethylbenzylammonium bromide (C12BBr) have been determined in aqueous butanol and
aqueous benzyl alcohol solutions in the temperature range of 5-40°C. From these data the temperature dependent critical micelle
concentration (cmc) was determined. The molar fraction of alcohol in the micelle was estimated using the theory suggested by Motomura et al. for surfactant binary mixtures. The thermal properties such as standard Gibbs free energy, enthalpy and entropy of solubilization
of alcohols in the micelles were estimated for the phase separation model. The change in heat capacity upon solubilization
of alcohol in the micelle has been estimated form the above properties.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
79.
Summary The synthesis, characteristics, properties and reactions with metallic ions of the furfural-, thiophenal-, pyrrolal-, cinnamal-, acetal-, and propional-derivatives of 2-thiohydantoin have been studied. The reagents exhibit twopK values in aqueous solution, and sensitive colour reactions with Pd(II), Cu(I) and (II), Ag(I) and Hg(II). A comparison has been made of the reactivity of all the 2-thiohydantoin derivatives we have studied to date and conclusions have been drawn regarding the influence of the aromatic ring connected to 2-thiohydantoin.
Derivative des 2-Thiohydantoins als spektrophotometrische Reagenzien. III
Zusammenfassung Die Synthese, die Kennzahlen, die Eigenschaften der Furfural-, Thiophenal-, Pyrrolal-, Acetal-, Propional- sowie des Zimtsäurealdehyd-Derivates des 2-Thiohydantoins und deren Reaktionen mit Metallionen wurden untersucht. In wäßriger Lösung kommen diesen Reagenzien zwei pK-Werte zu. Sie geben empfindliche Farbreaktionen mit Pd(II), Cu(I) und (II), Ag(I) und Hg(II). Die Reaktivität der genannten Derivative wurde untersucht und der Einfluß des mit 2-Thiohydantoin verbundenen aromatischen Ringes daraus ermittelt.相似文献
80.
Vicente J González-Herrero P Pérez-Cadenas M Jones PG Bautista D 《Inorganic chemistry》2005,44(20):7200-7213
Platinum(II) complexes with (fluoren-9-ylidene)methanedithiolato and its 2,7-di-tert-butyl- and 2,7-dimethoxy-substituted analogues were obtained by reacting different chloroplatinum(II) precursors with the piperidinium dithioates (pipH)[(2,7-R2C12H6)CHCS2] [R = H (1a), t-Bu (1b), or OMe (1c)] in the presence of piperidine. The anionic complexes Q2[Pt{S(2)C=C(C12H6R(2)-2,7)}2] [R = H, (Pr(4)N)(2)2a; R = t-Bu, (Pr4N)(2)2b, (Et4N)(2)2b; R = OMe, (Pr4N)(2)2c] were prepared from PtCl(2), piperidine, the corresponding QCl salt, and 1a-c in molar ratio 1:2:2:2. In the absence of QCl, the complexes (pipH)(2)2b and [Pt(pip)(4)]2b were isolated depending on the PtCl(2):pip molar ratio. The neutral complexes [Pt{S2C=C(C12H6R(2)-2,7)L(2)] [L = PPh(3), R = H (3a), t-Bu (3b), OMe (3c); L = PEt(3), R = H (4a), t-Bu (4b), OMe (4c); L(2) = dbbpy, R = H (5a), t-Bu (5b), OMe (5c) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl)] were similarly prepared from the corresponding precursors [PtCl2L2] and 1a-c in the presence of piperidine. Oxidation of Q(2)2b with [FeCp2]PF6 afforded the mixed Pt(II)-Pt(IV) complex Q2[Pt2{S2C=C[C12H6(t-Bu)(2)-2,7]}4] (Q(2)6, Q = Et4N+, Pr4N+). The protonation of (Pr4N)(2)2b with 2 equiv of triflic acid gave the neutral dithioato complex [Pt2{S2CCH[C12H6(t-Bu)(2)-2,7]}4] (7). The same reaction in 1:1 molar ratio gave the mixed dithiolato/dithioato complex Pr4N[Pt{S2C=C[C12H6(t-Bu)(2)-2,7]}{S2CCH[C12H6(t-Bu)(2)-2,7]}] (Pr(4)N8) while the corresponding DMANH+ salt was obtained by treating 7 with 2 equiv of 1,8-bis(dimethylamino)naphthalene (DMAN). The crystal structures of 3b and 5c.CH2Cl2 have been solved by X-ray crystallography. All the platinum complexes are photoluminescent at 77 K in CH2Cl2 or KBr matrix, except for Q(2)6. Compounds 5a-c and Q8 show room-temperature luminescence in fluid solution. The electronic absorption and emission spectra of the dithiolato complexes reveal charge-transfer absorption and emission energies which are significantly lower than those of analogous platinum complexes with previously described 1,1-ethylenedithiolato ligands and in most cases compare well to those of 1,2-dithiolene complexes. 相似文献