全文获取类型
收费全文 | 5742篇 |
免费 | 239篇 |
国内免费 | 43篇 |
专业分类
化学 | 4050篇 |
晶体学 | 35篇 |
力学 | 136篇 |
数学 | 1067篇 |
物理学 | 736篇 |
出版年
2024年 | 10篇 |
2023年 | 44篇 |
2022年 | 132篇 |
2021年 | 162篇 |
2020年 | 105篇 |
2019年 | 128篇 |
2018年 | 106篇 |
2017年 | 82篇 |
2016年 | 194篇 |
2015年 | 175篇 |
2014年 | 203篇 |
2013年 | 348篇 |
2012年 | 398篇 |
2011年 | 442篇 |
2010年 | 285篇 |
2009年 | 288篇 |
2008年 | 355篇 |
2007年 | 371篇 |
2006年 | 341篇 |
2005年 | 329篇 |
2004年 | 241篇 |
2003年 | 178篇 |
2002年 | 181篇 |
2001年 | 83篇 |
2000年 | 66篇 |
1999年 | 55篇 |
1998年 | 42篇 |
1997年 | 46篇 |
1996年 | 71篇 |
1995年 | 40篇 |
1994年 | 38篇 |
1993年 | 37篇 |
1992年 | 45篇 |
1991年 | 33篇 |
1990年 | 20篇 |
1989年 | 29篇 |
1988年 | 23篇 |
1987年 | 21篇 |
1986年 | 25篇 |
1985年 | 37篇 |
1984年 | 31篇 |
1983年 | 22篇 |
1982年 | 29篇 |
1981年 | 17篇 |
1980年 | 20篇 |
1979年 | 16篇 |
1978年 | 13篇 |
1977年 | 7篇 |
1975年 | 8篇 |
1974年 | 7篇 |
排序方式: 共有6024条查询结果,搜索用时 31 毫秒
991.
Martín N Altable M Filippone S Martín-Domenech A Martínez-Alvarez R Suarez M Plonska-Brzezinska ME Lukoyanova O Echegoyen L 《The Journal of organic chemistry》2007,72(10):3840-3846
Isoxazolino[4,5:1,2][60]- and -[70]fullerenes undergo an efficient retro-cycloaddition reaction to pristine fullerene by thermal treatment in the presence of an excess of a dienophile and Cu(II) catalysis, which can be selectively used in the presence of malonate or pyrrolidine cycloadducts. Trapping experiments using N-phenylmaleimide as dipolarophile have shown that the reaction mechanism occurs by thermal removal of the nitrile oxide 1,3-dipole, in a process which is favored by the presence of Cu(II) as the catalyst. The ESI-MS study supports the observed retro-cycloaddition process for both C60 and C70 derivatives. In contrast to previous electrochemical retro-cycloaddition processes observed in fulleropyrrolidines, isoxazolinofullerenes were stable under oxidative conditions. 相似文献
992.
Enantiomerically pure alpha-substituted alpha-amino phenylacetonitriles have been readily prepared from 2-p-tolylsulfinylbenzaldimines following a two-step sequence: a moderately stereoselective hydrocyanation of the imines and a completely stereoselective quaternization of the resulting diastereoisomeric mixture of alpha-amino phenylacetonitriles with different alkylating or acylating reagents in the presence of KHMDS. Theoretical calculations support a stereoselectivity control exerted by the remote sulfinyl group, as long as it is responsible for the conformational preferences of the benzyllithium intermediates, which suffer the attack of the electrophiles to the less hindered diastereotopic face. 相似文献
993.
The pseudo-intramolecular Diels-Alder (DA) reaction between a 2-substituted furan (1) and a N-maleimide derivative (2) has been analyzed using DFT methods. Formation of two hydrogen bonds between the appendages on furan and maleimide derivatives favors thermodynamically the formation of a molecular complex (MC1) through an efficient molecular recognition process. The large enthalpy stabilization associated with the molecular recognition overcomes the unfavorable activation entropy associated with the bimolecular process. As a consequence, the subsequent DA reaction is clearly accelerated through a pseudo-intramolecular process. 相似文献
994.
Miguel Gd Pérez-Morales M Martín-Romero MT Muñoz E Richardson TH Camacho L 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3794-3801
The molecular organization of a mixed film, containing a water-soluble tetracationic porphyrin (TMPyP) and a p-tert-butyl calix[8]arene octacarboxylic acid derivative (C8A), at the air-water interface and on a solid support (LB film), has been investigated. Although the TMPyP aggregation was not detected at the air-water interface, TMPyP J-aggregates have been found in the LB films (Y-type). Unlike tetraanionic porphyrins, for example TSPP, the TMPyP J-aggregates are not induced by a zwitterion formation. The TMPyP J-aggregation is a result of a "double comb" configuration, where porphyrins from opposite layers are interwoven in a linear infinite J-aggregate. Our results confirm that TMPyP molecules tend to self-aggregate strongly, provided the electrostatic repulsions of their peripheral groups are cancelled by the anionic groups of the C8A matrix. 相似文献
995.
Urade VN Bollmann L Kowalski JD Tate MP Hillhouse HW 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4268-4278
The double-gyroid phase of nanoporous silica films has been shown to possess facile mass-transport properties and may be used as a mold to fabricate a variety of highly ordered inverse double-gyroid metal and semiconductor films. This phase exists only over a very small region of the binary phase diagram for most surfactants, and it has been very difficult to synthesize metal oxide films with this structure by evaporation-induced self-assembly (EISA). Here, we show the interplay of the key parameters needed to synthesize these structures reproducibly and show that the interfacial curvature may be systematically controlled. Grazing angle of incidence small-angle X-ray scattering (GISAXS) is used to determine the structure and orientation of nanostructured silica films formed by EISA from dilute silica/(poly(ethylene oxide)-b-poly(propylene oxide)-b-alkyl) surfactant solutions. Four different highly ordered film structures are observed by changing only the concentration of the surfactant, the relative humidity during dip-coating, and the aging time of the solution prior to coating. The highly ordered films progress from rhombohedral (Rm) to 2D rectangular (c2m) to double-gyroid (distorted Iad) to lamellar systematically as interfacial curvature decreases. Under all experimental conditions investigated, increasing the aging time of the coating solution was found to decrease the interfacial curvature. In particular, this parameter was critical to being able to synthesize highly ordered, pure-phase double-gyroid films. The key role of the aging time is shown via processing diagrams that map out the interplay between the aging time, composition, and relative humidity. 29Si nuclear magnetic resonance (NMR) spectroscopy and solution-phase small-angle X-ray scattering (SAXS) of the aged coating solutions presented in part I of this series are then used to interpret the effects of aging prior to dip-coating. Specifically, it was found that a predictive model based on volume fractions and the silica cluster stoichiometry obtained from 29Si NMR qualitatively explains the trends observed with composition and aging. However, apart from the effects of relative humidity, a quantitative comparison of the predicted phase with the experimental processing diagram suggests that less-condensed silica clusters are more effective at swelling the EO blocks at early aging times. This enhanced swelling decreases with aging time and results in lower-curvature nanostructures such as the double-gyroid. The decrease in swelling is attributed to the decreased thermodynamic driving force for the more-condensed silica clusters to mix with the EO block of the surfactant. 相似文献
996.
Keita B Kortz U Brudna Holzle LR Brown S Nadjo L 《Langmuir : the ACS journal of surfaces and colloids》2007,23(19):9531-9534
Original and simple procedures for glassy carbon electrode modification with polyoxometalates (POMs), phosphotungstate [H7P8W48O184]33-, and Co(II)-containing silicotungstates [Co6(H2O)30{Co9Cl2(OH)3(H2O)9(beta-SiW8O31)3}]5- and [{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29OH)2}2]22- give stable and very active surfaces for the hydrogen-evolution reaction (HER). For this purpose, the selected POMs fixed on Vulcan XC-72 were adsorbed on the electrode surface or were directly entrapped in polyvinylpyridine films on the electrode. Cyclic voltammetry and confocal microscopy results converge to indicate that the activation is related to the proton and electron reservoir-like behaviors of these molecular oxides and not to any electrode surface area increase. However, the Tafel parameters of the HER process, which are different from one POM to the next, are in the range of those of the best metallic electrodes. 相似文献
997.
Coderch L Méndez S Martí M Pons R Parra JL 《Colloids and surfaces. B, Biointerfaces》2007,60(1):89-94
Small angle X-ray scattering (SAXS) was applied to a new lipid model arrangement, which was achieved by concentrating or diluting internal wool lipid liposome suspensions in varying water concentrations. The influence of the water content in the lamellar structure of the internal wool lipids is compared with the lamellar structure of phosphatidylcholine bilayers present in the membranes of the living cells. The high increase in the lamellar distances with the water content indicates that large amounts of water can be retained in the lipid wool membrane in contrast to the case of phosphatidylcholine liposomes. A transition temperature between 40 and 50 degrees C tends to eliminate the ordered lamellar structure when more than 60% of water is present in the bilayer structure. This could account for the increase in the permeability of the wool fibres when these are soaked in water at temperatures exceeding 40 degrees C. 相似文献
998.
Four new and seven known diterpenes have been isolated from the dichloromethane extract of the aerial parts of Calceolaria polifolia. The structures of the new compounds were established by spectroscopic evidence. 相似文献
999.
Julia Martín Carmen Mejías Juan Luis Santos Irene Aparicio Esteban Alonso 《Molecules (Basel, Switzerland)》2021,26(19)
This work evaluated the availability and sorption behaviour of four pharmaceuticals and eight of their metabolites in sewage sludge and sludge-amended soil. Digested sludge and compost were evaluated. The highest levels found in digested sludge corresponded to caffeine (up to 115 ng g−1 dm), ibuprofen (45 ng g−1 dm) and carbamazepine (9.3 ng g−1 dm). The concentrations measured in compost were even lower than in digested sludge. No compound was detected in sludge-amended soils. This fact could be due to the dilution effect after sludge application to soil. Different adsorption capacities in sludge–soil mixtures were measured for the studied compounds at the same spike concentration. In general, except for paraxanthine and 3-hydroxycarbamazepine, the metabolite concentrations measured in the mixtures were almost two-fold lower than those of their parent compounds, which can be explained by their mobility and lixiviation tendency. The log Kd ranged from −1.55 to 1.71 in sludge samples and from −0.29 to 1.18 in soil–sludge mixtures. The log Kd values calculated for compost were higher than those calculated for digested sludge. The obtained results implied that the higher organic carbon content of compost could influence soil contamination when it is applied to soil. 相似文献
1000.
Osvaldo Cox Jos A. Dumas Luis A. Rivera Carmelo García Antonio E. Alegria 《Journal of heterocyclic chemistry》1999,36(4):943-947
The electrochemical reduction of the chloride or perchlorate salts of benzazolo[3,2-a]quinolinium ion and several of its analogues is reported. The compounds studied are the perchlorate salt of 3-nitrobenzothiazolo-and 3-nitro-9-methoxybenzothiazolo[3,2-a]quinolinium, and the chloride salts of 7-ethyl-, 3-nitro-7-methyl-, 3-nitro-7-ethyl-, 3-nitro-7-isopropyl-, 3-nitro-7-butyl- and 3-nitro-7-benzylbenzimidazolo[3,2-a]-quinolinium, respectively. Cyclic voltammetry of the corresponding 3-nitrobenzothiazolo[3,2-a]quinolinium derivatives in N,N-dimethylformamide shows an irreversible peak potential at -0.6 and a quasi-reversible peak at -(1.2–1.3) volts, respectively, relative to the standard calomel electrode. In contrast, the corresponding 3-nitrobenzimidazolo[3,2-a]quinolinium derivatives show, in general, reversible peaks at near -0.8 and -(1.2–1.4) volts, respectively. Upon electrolytic reduction, only the nitro-substituted derivatives produced observable electron paramagnetic resonance electron spin resonance spectra. This observation is explained in terms of the stabilization of the radicals produced by the nitro group. Theoretical MM+/AM1/UHF calculations support the idea that the larger nitrogen splitting is caused by N-12 and the minor splittings by N-7 in the benzimidazolo[3,2-a]quinolinium ion series. 相似文献