全文获取类型
收费全文 | 10411篇 |
免费 | 497篇 |
国内免费 | 24篇 |
专业分类
化学 | 8124篇 |
晶体学 | 67篇 |
力学 | 118篇 |
数学 | 1309篇 |
物理学 | 1314篇 |
出版年
2023年 | 93篇 |
2022年 | 184篇 |
2021年 | 336篇 |
2020年 | 276篇 |
2019年 | 231篇 |
2018年 | 213篇 |
2017年 | 215篇 |
2016年 | 404篇 |
2015年 | 385篇 |
2014年 | 396篇 |
2013年 | 708篇 |
2012年 | 809篇 |
2011年 | 903篇 |
2010年 | 537篇 |
2009年 | 466篇 |
2008年 | 699篇 |
2007年 | 696篇 |
2006年 | 562篇 |
2005年 | 559篇 |
2004年 | 439篇 |
2003年 | 367篇 |
2002年 | 305篇 |
2001年 | 183篇 |
2000年 | 145篇 |
1999年 | 97篇 |
1998年 | 69篇 |
1997年 | 59篇 |
1996年 | 78篇 |
1995年 | 57篇 |
1994年 | 46篇 |
1993年 | 44篇 |
1992年 | 53篇 |
1991年 | 34篇 |
1990年 | 19篇 |
1989年 | 13篇 |
1988年 | 17篇 |
1987年 | 19篇 |
1986年 | 19篇 |
1985年 | 25篇 |
1984年 | 30篇 |
1983年 | 20篇 |
1982年 | 25篇 |
1981年 | 13篇 |
1980年 | 11篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1973年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 78 毫秒
71.
Ana A. C. Pacheco Arnaldo F. da Silva Filho Kristoffer Kortsen Magnus W. D. Hanson-Heine Vincenzo Taresco Jonathan D. Hirst Muriel Lansalot Franck D'Agosto Steven M. Howdle 《Chemical science》2021,12(3):1016
Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerisation of methyl methacrylate (MMA) is performed in supercritical carbon dioxide (scCO2) with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. Kinetic studies of the polymerisation in scCO2 also confirm these data. By contrast, only poor control of MMA polymerisation is obtained in toluene solution, as would be expected for this CTA which is better suited for acrylates. In this regard, we select a range of CTAs and use them to determine the parameters that must be considered for good control in dispersion polymerisation in scCO2. A thorough investigation of the nucleation stage during the dispersion polymerisation reveals an unexpected “in situ two-stage” mechanism that strongly determines how the CTA works. Finally, using a novel computational solvation model, we identify a correlation between polymerisation control and degree of solubility of the CTAs. All of this ultimately gives rise to a simple, elegant and counterintuitive guideline to select the best CTA for RAFT dispersion polymerisation in scCO2.RAFT dispersion polymerisation of methyl methacrylate is performed in scCO2 with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. 相似文献
72.
Martí MP Pino J Boqué R Busto O Guasch J 《Analytical and bioanalytical chemistry》2005,382(2):440-443
The aromatic composition of sugar cane spirits and, in general, of alcoholic beverages, is mainly influenced by the ageing process in wood barrels. There are several factors that affect the quality of the final aged product, but the time of the storage in the barrel is perhaps the most important one. Ageing time must therefore be controlled in order to detect counterfeits; however, this parameter is very difficult to control and, at present, there is no analytical method available to determine it. We propose a quantitative method for determining the ageing time of sugar cane spirits in oak barrels by using an electronic nose based on coupling directly a headspace sampler to a mass spectrometer (HS-MS), and multivariate calibration. The method developed is simple and provides, in 5 min, the ageing time of spirits with an accuracy of about 1 month. 相似文献
73.
Basurto S García S Neo AG Torroba T Marcos CF Miguel D Barberá J Ros MB de la Fuente MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5362-5376
Several new liquid-crystalline indene and pseudoazulene systems are reported. These molecules give rise to either columnar hexagonal mesophases and/or columnar plastic phases. The unique nature of these compounds stems from their non-classical discotic structure. Although the molecules have rigid aromatic cores, they lack terminal tails and instead the polarizable atoms (S, halogens) or polar groups (CN, CO) act as unusual soft parts. On the basis of many structurally related materials, we conclude that for this type of compound molecular stacking in the solid state is a prerequisite for the appearance of a columnar mesophase, although other intermolecular interactions within the layers are also important in establishing liquid-crystalline order. The behavior reported for these mesomorphic molecules opens up new possibilities in the search for related molecular interactions that might be useful for the construction of supramolecular architectures with particular properties. 相似文献
74.
[reaction: see text] A simple and efficient stereoselective synthesis of aziridine-2-phosphonate 3, and -phosphine oxide 5 by diastereoselective addition of Grignard reagents to 2H-azirine phosphonate 1 and -phosphine oxide 4 is reported. Similarly, the addition of heterocyclic amines and benzenethiol to aziridines 1 and 4 yielded functionalized aziridines 10, 11, and 18. These aziridines are used as intermediates for the regioselective synthesis of beta-aminophosphine oxides 6 and beta-aminophosphonates 7, as well as alpha- aminophosphonates 8. Phenylsulfenyl-substituted alpha-aminophosphorus derivatives 15 and 19 are obtained directly from benzenethiol and 2H-azirine phosphonates 1 and -phosphine oxides 4. 相似文献
75.
M. Jesús Rodríguez M. Isabel Fernndez Ana M. Gonzlez‐Noya Marcelino Maneiro Rosa Pedrido Miguel Vzquez Bruno Donnadieu Manuel R. Bermejo 《无机化学与普通化学杂志》2005,631(11):2161-2166
M(HL)(H2O)n complexes have been obtained by the electrochemical reaction of Fe, Co, Ni, Cu, Zn and Cd anodes with the potentially pentadentate and trianionic asymmetrical Schiff base 3‐aza‐N‐{2‐[1‐aza‐2‐(5‐nitro‐2‐hydroxylphenyl)‐vinyl]phenyl}‐4‐(5‐nitro‐2‐hydroxyphenyl)but‐3‐enamide (H3L), containing a hard amido donor atom. The complexes have been characterized by elemental analysis, mass spectrometry, IR and 1H NMR spectroscopies, magnetic measurements and molar conductivities. Co(HL)(H2O) ( 2 ) has been found to rearrange in DMF solution into a crystallographically solved octahedral complex, CoL1(H2O)2 ( 7 ) [where H2L1 is the symmetrical Schiff base ligand N,N′‐(1,2‐phenylene)‐bis(5‐nitro‐3‐hydroxysalicylidenimine)]. A hydrolysis mechanism is discussed to explain this rearrangement. 相似文献
76.
F López Arbeloa J Ba?uelos Prieto V Martínez Martínez T Arbeloa López I López Arbeloa 《Chemphyschem》2004,5(11):1762-1771
Absorption and fluorescence (steady-state and time-correlated) techniques are used to study the photophysical characteristics of the pyrromethene 650 (PM650) dye. The presence of the cyano group at the 8 position considerably shifts the absorption and fluorescence bands to lower energies with respect to other related pyrromethene dyes; this is attributed to the strong electron-acceptor character of the cyano group, as is theoretically confirmed by quantum mechanical methods. The fluorescence properties of PM650 are intensively solvent-dependent. The fluorescence band is shifted to lower energies in polar/protic solutions, and the evolution of the corresponding wavelength with the solvent is analysed by a multicomponent linear regression. The fluorescence quantum yield and the lifetime strongly decrease in polar/protic solvents, which can be ascribed to an extra nonradiative deactivation, via an intramolecular charge-transfer state (ICT state), favoured in polar media. 相似文献
77.
García Ruano JL Fraile A González G Martín MR Clemente FR Gordillo R 《The Journal of organic chemistry》2003,68(17):6522-6534
The addition of diazomethane and diazoethane to (5S,SS)- and (5R,SS)-5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones (1a and 1b) and their 4-methylderivatives (2a and 2b) proceeded in almost quantitative yields and complete regioselectivity. The observed pi-facial selectivity is determined by the configurations at both C-5 and the sulfinyl group, the later being the most important. The syn adducts were almost exclusively obtained from 1a and 2a in apolar solvents but the pi-facial selectivity was strongly decreased in more polar solvents. On the other hand, the major adducts from 1b and 2b were the anti ones and such predominance was slightly increased with solvent polarity. The exo-selectivity was complete in all the cases except for the anti approach to compounds 2a (in polar solvents) and 2b. The role of the sulfinyl group in this behavior was inferred by comparison of these results with those obtained in reactions of diazoalkanes with 5-methoxyfuran-2(5H)-one (3). Steric interactions seem to be the main ones responsible for the observed exo selectivity of reactions with diazoethane, but electronic factors, which can be modulated by the solvent, are also significant in the pi-facial selectivity control. DFT computational methods are able to correctly predict the reactivity, regioselectivity, and pi-facial selectivity exhibited by 5-alkoxyfuranones as well as their changes with the solvent polarity. A C-H.O hydrogen bond, involving the oxygen atom of the 5-alkoxy group at dipolarophiles and the endo-hydrogen atom at dipoles, seems to play a key role in the electronic interactions influencing the stereochemical course of these reactions. 相似文献
78.
Uranium(VI and IV) and thorium(IV) give cathodic indentations in supporting electrolytes prepared from 0.1M perchloric acid, 0.5 M ammonium thiocyanate and 5·10-3M cupferron (solution A) or from 0.1 M succinic-succinate buffer pH 4, 0.1 M sodium chloride, 10-3M cupferron and 0.05% gelatine (solution B). The uranium indentation on the dE/dt = f(E) curve (Q=0.75 and 0.73) permits its detection at the 3·10-7M level. The thorium indentation (Q=0.78) permits its detection at the 4·10-7M level in solution B. Methods for the elimination of interfering ions for the uranium determination are described. In the determination of thorium, Ga(III), Fe(III), Ti(IV) and U(VI) interfere. 相似文献
79.
M. Galán López A. Martín Sánchez V. Gómez Escobar 《Journal of Radioanalytical and Nuclear Chemistry》2004,261(3):631-636
A procedure for the determination of 222Rn in environmental water samples using liquid scintillation counting (LSC) was applied. The extractive scintillator RADONSÒ and an ultra-low background 1220 QuantulusÔ were used. A minimum detectable activity of 0.1 Bq·l?1 in 20 ml was found with low-diffusion polyethylene vials and 200 minute measurement time. Quenching effects and possible interferences due to the existence of other radionuclides in the extraction process were studied. The procedure was controlled by gamma-ray spectrometry of the 222Rn daughters. Applications to environmental samples collected from spas, wells, and public springs in Extremadura (Spain) are presented. 相似文献
80.
Cuadros-Rodríguez L Almansa-López EM García-Campaña AM González-Casado A Egea-González FJ Garrido-Frenich A Martínez-Vidal JL 《Talanta》2005,66(4):1063-1072
The use of the recovery term has presented some confusion in Analytical Chemistry. Recent IUPAC recommendations propose to distinguish between two terms: recovery or recovery factor, ℜ, and apparent recovery, ℜ*. Apparent recovery includes recovery factor and a new recovery term proposed in this paper, named calibration recovery, ℜC, which depends of the type of systematic error due to the matrix effect (constant and/or proportional) and is related to the applied calibration methodology. This paper highlights the dependence of the calibration recovery on the sample analyte concentration and, for extension, of the apparent recovery, defines the recovery profile, and makes evident the need to determine a “fit for purpose” analyte concentration interval to comply with a regulated recovery requirements. An approach to estimate the calibration recovery and its associated uncertainty in relation to the above-mentioned dependence is presented. The usefulness of the proposed methodology has been shown in the quantification of a pesticide by GC-ECD for assessing dermal exposure. 相似文献