全文获取类型
收费全文 | 47317篇 |
免费 | 4479篇 |
国内免费 | 4058篇 |
专业分类
化学 | 26223篇 |
晶体学 | 228篇 |
力学 | 2542篇 |
综合类 | 223篇 |
数学 | 2123篇 |
物理学 | 9692篇 |
综合类 | 14823篇 |
出版年
2024年 | 106篇 |
2023年 | 509篇 |
2022年 | 973篇 |
2021年 | 1126篇 |
2020年 | 1418篇 |
2019年 | 1276篇 |
2018年 | 1122篇 |
2017年 | 1405篇 |
2016年 | 1706篇 |
2015年 | 1811篇 |
2014年 | 2321篇 |
2013年 | 2956篇 |
2012年 | 2813篇 |
2011年 | 3107篇 |
2010年 | 2483篇 |
2009年 | 2719篇 |
2008年 | 2773篇 |
2007年 | 3042篇 |
2006年 | 2853篇 |
2005年 | 2510篇 |
2004年 | 2242篇 |
2003年 | 1928篇 |
2002年 | 1782篇 |
2001年 | 1354篇 |
2000年 | 1226篇 |
1999年 | 1062篇 |
1998年 | 920篇 |
1997年 | 873篇 |
1996年 | 752篇 |
1995年 | 710篇 |
1994年 | 665篇 |
1993年 | 529篇 |
1992年 | 498篇 |
1991年 | 440篇 |
1990年 | 359篇 |
1989年 | 354篇 |
1988年 | 301篇 |
1987年 | 189篇 |
1986年 | 137篇 |
1985年 | 98篇 |
1984年 | 76篇 |
1983年 | 35篇 |
1982年 | 76篇 |
1981年 | 40篇 |
1980年 | 43篇 |
1979年 | 27篇 |
1978年 | 21篇 |
1977年 | 12篇 |
1976年 | 28篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 234 毫秒
991.
The modeling of liquid–vapor equilibrium in ternary mixtures that include substances found in alcoholic distillation processes of wine and musts is analyzed. In particular, vapor–liquid equilibrium in ternary mixtures containing water + ethanol + cogener has been modeled using parameters obtained from binary mixture data only. The congeners are substances that although present in very low concentrations, of the order of part per million, 10−6 to 10−4 mg/L, are important enological parameters [1] and [2]. In this work two predictive models, the PSRK equation of state and the UNIFAC liquid phase model and two semipredictive activity coefficient models: NRTL and UNIQUAC have been used. The results given by these different models have been compared with literature data and conclusions about the accuracy of the models studied are drawn, recommending the best models for correlating and predicting the phase equilibrium in this type of mixtures. 相似文献
992.
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
993.
Complexes of the general formulae Mn(2-bpy)2(CCl3COO)2, Co(2-bpy)2(CCl3COO)2·H2O and Ni(2-bpy)2(CCl3COO)2·2H2O (where: 2-bpy=2,2'-bipyridine) have been prepared and characterized by VIS and IR spectroscopy, conductivity and magnetic measurements.
The thermal properties of complexes in the solid state were studied under non-isothermal conditions in air atmosphere. During
heating the complexes decompose via different intermediate products to the oxides Mn3O4, CoO and NiO. A coupled TG-MS system was used to detection the principal volatile products of thermal decomposition and fragmentation
processes of obtained compounds. The principal volatile products of thermal decomposition of complexes are: H2O+, CO2
+, Cl2
+ and other.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
994.
In this work, the authors use complete active space self-consistent field method to investigate the photoinduced charge-separated states and the electron transfer transition in complexes ethylene-tetracyanoethylene and tetramethylethylene-tetracyanoethylene. Geometries of isolated tetracyanoethylene, ethylene, and tetramethylethylene have been optimized. The ground state and the low-lying excited states of ethylene and tetracyanoethylene have been optimized. The state energies in the gas phase have been obtained and compared with the experimentally observed values. The torsion barrier of tetracyanoethylene has been investigated through the state energy calculation at different conformations. Attention has been particularly paid to the charge-separated states and the electron transfer transition of complexes. The stacked conformations of the donor-acceptor complexes have been chosen for the optimization of the ground and low-lying excited states. Equilibrium solvation has been considered by means of conductor-like screening model both in water and in dichloromethane. It has been found that the donor and tetracyanoethylene remain neutral in complexes in ground state (1)A(1) and in lowest triplet state (3)B(1), but charge separation appears in excited singlet state (1)B(1). Through the correction of nonequilibrium solvation energy based on the spherical cavity approximation, pi-->pi* electron transfer transition energies have been obtained. Compared with the experimental measurements in dichloromethane, the theoretical results in the same solvent are found higher by about 0.5 eV. 相似文献
995.
Two hydrophobic vinyl saccharide monomers based on D ‐glucose and D ‐fructose were polymerized by employing the reversible addition‐fragmentation transfer (RAFT) miniemulsion polymerization technique to prepare well‐designed glycopolymers. Three dithiobenzoate‐RAFT agents [S?C(Ph)S? R], 1‐phenylethyl dithiobenzoate (PED), 2‐phenylprop‐2‐yl dithiobenzoate (PPD), and 2‐cyanoprop‐2‐yl dithiobenzoate (CPD), were used to control the growth of polymer chains. The best results were obtained in the presence of the PPD‐RAFT agent and the formed polymers have polydispersity index's (PDI) lower than 1.15. Under adequate miniemulsion polymerization conditions, a glycopolymer with PDI of 1.1 and molecular weight of 5 × 104 g/mol has been successfully synthesized in a short reaction time of 100 min. Furthermore, some block copolymers containing saccharide segment with butyl or methyl methacrylate were prepared. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
996.
Salgado-Petinal C Lamas JP Garcia-Jares C Llompart M Cela R 《Analytical and bioanalytical chemistry》2005,382(6):1351-1359
In this paper a solid-phase microextraction–gas chromatography–mass spectrometry (SPME–GC–MS) method is proposed for a rapid analysis of some frequently prescribed selective serotonin re-uptake inhibitors (SSRI)—venlafaxine, fluvoxamine, mirtazapine, fluoxetine, citalopram, and sertraline—in urine samples. The SPME-based method enables simultaneous determination of the target SSRI after simple in-situ derivatization of some of the target compounds. Calibration curves in water and in urine were validated and statistically compared. This revealed the absence of matrix effect and, in consequence, the possibility of quantifying SSRI in urine samples by external water calibration. Intra-day and inter-day precision was satisfactory for all the target compounds (relative standard deviation, RSD, <14%) and the detection limits achieved were <0.4 ng mL–1 urine. The time required for the SPME step and for GC analysis (30 min each) enables high throughput. The method was applied to real urine samples from different patients being treated with some of these pharmaceuticals. Some SSRI metabolites were also detected and tentatively identified. 相似文献
997.
Time-dependent density-functional theory(TDDFT)has been applied to calculate the electronic structure and second-order nonlinear optical(NLO) properties of some organic molecules.The two-dimensional(2-D)charge transfer charateristics of calculated molecules were studied and compared with corresponding experimental results.All the theoretical results agree well with the measurement.For 2-D molecule with two-fold symmetry,the dominant charge transfer is off-diagonal,while for three-fold symmetry 2-D molecule,the dominant charge transfer is not only between branches and central group but also among branches. 相似文献
998.
The standard potentialss
E
o of M/M+ (M=Li, Na, K, Rb, and Cs) electrodes in aqueous urea solutions containing 12, 20, 30 and 37% by weight of urea have been determined at 25°C from emf measurements on the cell M(Hg)/MCl (m), solvent/AgCl–Ag, from the activities of metals in amalgams by use of a similar type of cell in water, and from the values ofs
E
o of the Ag/AgCl electrode determined earlier. The standard free energies of transfer of MCl, G
t
o
(MCl), from water to the mixed solvents, computed by use of these values and those for the Ag–AgCl electrode, rise sharply from Li+ to Na+ but fall from Na+ to K+ and rather sharply from K+ to Cs+ with a maximum at Na+ in all the solvent compositions. This has been attributed to the superimposition of soft-soft interactions on the electrostatic interactions between the ions and the negative charge centers of the possible hydrogen-bonded solvent complexes in the mixed solvents. Comparison of G
t
o
(i) values for individual ions, obtained by a simultaneous extrapolation procedure, with those in aqueous mixtures of methanol,t-butanol, and dimethyl sulfoxide leads to the conclusion that the solvation of these ions in all these solvents is chiefly dictated by the acid-base type of ion-solvent interactions. 相似文献
999.
《Electroanalysis》2006,18(7):649-654
For the first time, the voltammetry of an ensemble of immobilized benzonitrile microdroplets containing 5,10,15,20‐tetraphenyl‐21H,23H‐porphine iron (III) chloride, TPPFeCl immobilized at platinum electrodes immersed in various aqueous electrolytes has been explored. The reduction of TPPFeCl was observed with the voltammetric response seen to be highly dependent on the nature of ions in the surrounding aqueous phase. Unlike voltammetry in purely homogeneous solution the nature of the aqueous electrolyte can influence the voltammetry in the droplet phase. The electrochemical reduction of TPPFeCl contained within tetrabutylammonium chloride (TBACl) supported benzonitrile (PhCN) microdroplets immersed into an aqueous solution of TBACl was first studied. During TPPFeCl reduction the resulting [TPPFeCl]? species is stabilized due to the excess of chloride anions inside the oil droplet. Voltammograms of homogeneous solutions of PhCN supported with TBACl show similar chemically reversible process which is also attributed to the stable [TPPFeCl]? species. This anion stabilization was not observed when the oil droplets were supported with tetrabutylammonium perchlorate (TBAP) or when the PhCN solution bathing the microdroplet ensemble was supported with TBAP resulting in a chemically irreversible process. The voltammetry of unsupported droplets immobilized on a platinum electrode immersed in different aqueous electrolytes was also explored and the fate of the [TPPFeCl]? species formed considered during the reduction sweep. Similarities and difference to voltammetry in purely homogeneous media are noted and the use of droplet voltammetry provides complimentary information. 相似文献
1000.
Summary The dependence of the chloride distribution coefficient on the co-ion of solutions of different alkali fluorides, MF, up to 11M is tested on the strongly basic anion-exchange resin AG1-X10. Under the same experimental conditions the distribution coefficient decreases in the following order for M+: Na+>K+>Rb+>Cs+. This can be explained by the different co-ion-chloride interactions. The consequence of this interaction for a chromatographic separation of chloride is shown with 5M KF and CsF solutions, used as eluants. Depending on the fluoride concentration, the distribution coefficient passes through a minimum value to increase again at higher electrolyte concentration. The non-exchange electrolyte in the resin phase is responsible for this effect. In addition, the bromide and the iodide distribution coefficients up to 10M KF solutions are determined. One results is that the selectivity coefficient between halide ions increases at higher electrolyte concentrations. 相似文献