全文获取类型
收费全文 | 3480篇 |
免费 | 592篇 |
国内免费 | 226篇 |
专业分类
化学 | 634篇 |
晶体学 | 17篇 |
力学 | 174篇 |
综合类 | 41篇 |
数学 | 1093篇 |
物理学 | 2339篇 |
出版年
2024年 | 9篇 |
2023年 | 20篇 |
2022年 | 283篇 |
2021年 | 370篇 |
2020年 | 148篇 |
2019年 | 92篇 |
2018年 | 94篇 |
2017年 | 86篇 |
2016年 | 129篇 |
2015年 | 94篇 |
2014年 | 148篇 |
2013年 | 199篇 |
2012年 | 151篇 |
2011年 | 171篇 |
2010年 | 156篇 |
2009年 | 195篇 |
2008年 | 220篇 |
2007年 | 201篇 |
2006年 | 185篇 |
2005年 | 186篇 |
2004年 | 142篇 |
2003年 | 153篇 |
2002年 | 142篇 |
2001年 | 93篇 |
2000年 | 76篇 |
1999年 | 76篇 |
1998年 | 62篇 |
1997年 | 71篇 |
1996年 | 36篇 |
1995年 | 26篇 |
1994年 | 36篇 |
1993年 | 26篇 |
1992年 | 34篇 |
1991年 | 19篇 |
1990年 | 17篇 |
1989年 | 21篇 |
1988年 | 25篇 |
1987年 | 16篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 9篇 |
1982年 | 12篇 |
1981年 | 9篇 |
1980年 | 9篇 |
1979年 | 7篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1973年 | 3篇 |
1969年 | 4篇 |
排序方式: 共有4298条查询结果,搜索用时 31 毫秒
101.
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
102.
C. Y. Zhu R. M. Izatt J. S. Bradshaw N. K. Dalley 《Journal of inclusion phenomena and macrocyclic chemistry》1992,13(1):17-27
Equilibrium constant (K), enthalpy change (H), and entropy change (S) values have been determined calorimetrically at 25°C in 90%MeOH 10%H2O (v/v) for the interactions of pyridino-18-crown-6 (P18C6) and diketopyridino-18-crown-6 (K2P18C6) with perchlorate salts of ammonium, benzylammonium,-phenylethylammonium,-phenylethylammonium, and-(1-naphthyl)ethyl-ammonium cations. The crystal structure of the complex of P18C6 with benzylammonium perchlorate was determined by X-ray crystallography. The1H 1D and 2D NMR spectra of some of these complexes were used to elucidate their structural features in solution. The logK values for the interaction of the ammonium cations with P18C6 are larger than those with K2P18C6, probably due to the higher degree of structural flexibility of P18C6. Ligand K2P18C6 displays appreciable - interaction with the-(1-naphthyl)ethylammonium cation, but not with the-phenylethylammonium cation.- interaction between ligand and cationSupplementary Data relating to this article are deposited with the British Library as Supplementary Publication No SUP 00000 (22 pages) 相似文献
103.
J. L. Oscarson R. M. Izatt P. R. Brown Z. Pawlak S. E. Gillespie J. J. Christensen 《Journal of solution chemistry》1988,17(9):841-863
The aqueous reactions,
相似文献
104.
A conductance study concerning the interaction between ammonium ion and several crown ethers in acetonitrile solution has been carried out at different temperatures. The stability constants of the resulting 11 complexes at various temperatures were determined from the molar conductance-mole ratio data and found to vary in the order DC18C6>18C6>DB30C10>DB21C7>DB24C8>DB18C6>15C5>B15C5. The enthalpy and entropy of complexation were determined from the temperature dependence of the formation constants. The influence on the thermodynamic data of different parameters such as cavity size and dimensionality of crown ethers, nature of substituents in the polyether ring, conformations of the free and complexed ligands, solvent-ligand interaction and number of N–H bonds available for hydrogen bonding are discussed. 相似文献
105.
Sue E. Gillespie Xuemin Chen John L. Oscarson Reed M. Izatt 《Journal of solution chemistry》1998,27(2):183-194
Dilution enthalpies, measured using isothermal flow calorimetry, are reported for aqueous solutions of KOH and CsOH at 300°C and 11.0 MPa, 325°C and 14.8 MPa, and for aqueous solutions of NaOH, KOH, and CsOH at 350°C and 17.6 MPa. Previously collected dilution enthalpies for aqueous solutions of NaOH at 300°C and 9.3 MPa and at 325°C and 12.4 MPa were included when fitting the Pitzer parameters. The concentration range of the hydroxide solutions was 0.5–0.02 molal. Parameters for the Pitzer excess Gibbs ion-interaction equation were determined from the fits of the experimental heat data. Equilibrium constants, enthalpy changes, entropy changes, and heat capacity changes for alkali metal ion association with hydroxide ion were estimated from the heat data. For all systems, the enthalpy changes and entropy changes were positive and had accelerating increases with temperature. The resulting equilibrium constants show significant, but smaller, increases with temperature. 相似文献
106.
Fourier transform Raman spectra of eight mixtures of four organic solids, namely dicyandiamide, melamine, acetamide and urea were measured. Matrices formed from these spectra were first subjected to singular value decomposition to obtain the right singular vectors. The right singular vectors were then subjected to blind source separation using band-target entropy minimization (BTEM), thus no a priori information (i.e. involving the nature of the components present, their spectra, nor their concentrations) was included in the analysis. The recovered pure component spectra are of exceptionally high quality and are consistent with pure reference spectra. Various empirical and statistical tests, such as the Euclidean norm and target transform factor analysis, were employed to assess the quality of the recovered spectra. The present results indicate the applicability of combined Raman and BTEM analysis for solid mixtures. 相似文献
107.
G. I. Berezin G. A. Petukhova N. S. Polyakov M. L. Gubkina 《Russian Chemical Bulletin》1997,46(3):443-447
The state of water adsorbed on active carbons and canal soot was studied using the “chemical potential—entropy—temperature”
diagram. In the range of the relative pressures from 0.174 to 1, the state of adsorbed water is similar to the state of a
stretched liquid. The molar volume, heat of evaporation, and surface tension of stretched water were calculated at different
relative pressures. Near the spinodal, the molar volume of stretched water is 25% higher, and the surface tension is considerably
lower compared to water.
Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 464–468, March, 1997. 相似文献
108.
Louis Carlacci 《Journal of computer-aided molecular design》1998,12(2):195-213
[Met5]-Enkephalin has the sequence Tyr-Gly-Gly-Phe-Met. Only the extended conformation of the peptide has been observed by X-ray crystallography. Nuclear magnetic resonance spectroscopy supports the presence of a turn at Gly 3 and Phe 4 in dimethyl sulfoxide. In this study, the peptide conformational states and thermodynamic properties are understood in terms of ionization state and solvent environment. In the calculation, final conformations obtained from multiple independent Monte Carlo simulated annealing conformational searches are starting points for molecular dynamics simulations. In an aqueous environment given by the use of solvation free energy and the zwitterionic state, dominant structural motifs computed are G-P Type II bend, G-G Type II bend, and G-G Type I bend motifs, in order of increasing free energy. In the calculation of the peptide with neutral N- and C-termini and solvation free energy, the extended conformer dominates (by at least a factor of 2.5), and the conformation of another low free energy conformer superimposes well on the pharmacophoric groups of morphine. Neutralization of charge and solvation induce and stabilize the extended conformation, respectively. A mechanism of inter-conversion between the extended conformer and three bent conformers is supported by /-scatter plots, and by the conformer relative free energies. An estimate of the entropy change of receptor unbinding is 8.3 cal K-1 mol-1, which gives rise to a -2.5 kcal/mol entropy contribution to the free energy of unbinding at 25 °C. The conformational analysis methodology described here should be useful in studies on short peptides and flexible protein surface loops that have important biological implications. 相似文献
109.
Howell EE Shukla U Hicks SN Smiley RD Kuhn LA Zavodszky MI 《Journal of computer-aided molecular design》2001,15(11):1035-1052
R67 dihydrofolate reductase (DHFR) is a novel enzyme that confers resistance to the antibiotic trimethoprim. The crystal structure of R67 DHFR displays a toroidal structure with a central active-site pore. This homotetrameric protein exhibits 222 symmetry, with only a few residues from each chain contributing to the active site, so related sites must be used to bind both substrate (dihydrofolate) and cofactor (NADPH) in the productive R67 DHFR?NADPH?dihydrofolate complex. Whereas the site of folate binding has been partially resolved crystallographically, an interesting question remains: how can the highly symmetrical active site also bind and orient NADPH for catalysis? To model this ternary complex, we employed DOCK and SLIDE, two methods for docking flexible ligands into proteins using quite different algorithms. The bound pteridine ring of folate (Fol I) from the crystal structure of R67 DHFR was used as the basis for docking the nicotinamide-ribose-Pi (NMN) moiety of NADPH. NMN was positioned by both DOCK and SLIDE on the opposite side of the pore from Fol I, where it interacts with Fol I at the pore's center. Numerous residues serve dual roles in binding. For example, Gln 67 from both the B and D subunits has several contacts with the pteridine ring, while the same residue from the A and C subunits has several contacts with the nicotinamide ring. The residues involved in dual roles are generally amphipathic, allowing them to make both hydrophobic and hydrophilic contacts with the ligands. The result is a `hot spot' binding surface allowing the same residues to co-optimize the binding of two ligands, and orient them for catalysis. 相似文献
110.
Laurence E. Strong Carter Van Waes Kenneth H. Doolittle II 《Journal of solution chemistry》1982,11(4):237-258
The three monofluorobenzoic acids together with 2,4-difluoro and 2,6-difluorobenzoic acids in aqueous solution are the subject of precision conductance measurements. The experimental data are analyzed to give ionization constants and limiting conductances at temperatures from 0 to 100°C. Walden products for the acid anions are derived from the limiting conductances while the ionization consatants are fitted by statistical methods to the function pK
a
(m)=A+B/T+ C logT+DT. Only the 2,6- acid requires the fourth term of the function to fit the data to a precision of better than 0.03%. Mathematical analysis of the pK function gives the standard changes in enthalpy, entropy, and heat capacity. All the acids studied are more acidic than the parent, benzoic acid, as well as more acidic than the isoelectronic methylbenzoic acids. In general the increased acidity is tied to decreases in enthalpy while entropy changes on ionization differn little from those found for the parent acid. 相似文献
|