全文获取类型
收费全文 | 13520篇 |
免费 | 382篇 |
国内免费 | 46篇 |
专业分类
化学 | 10796篇 |
晶体学 | 73篇 |
力学 | 211篇 |
数学 | 1702篇 |
物理学 | 1166篇 |
出版年
2023年 | 108篇 |
2022年 | 449篇 |
2021年 | 510篇 |
2020年 | 289篇 |
2019年 | 333篇 |
2018年 | 254篇 |
2017年 | 215篇 |
2016年 | 437篇 |
2015年 | 442篇 |
2014年 | 426篇 |
2013年 | 834篇 |
2012年 | 866篇 |
2011年 | 982篇 |
2010年 | 592篇 |
2009年 | 580篇 |
2008年 | 828篇 |
2007年 | 814篇 |
2006年 | 690篇 |
2005年 | 627篇 |
2004年 | 528篇 |
2003年 | 447篇 |
2002年 | 440篇 |
2001年 | 163篇 |
2000年 | 137篇 |
1999年 | 110篇 |
1998年 | 113篇 |
1997年 | 99篇 |
1996年 | 129篇 |
1995年 | 87篇 |
1994年 | 85篇 |
1993年 | 79篇 |
1992年 | 63篇 |
1991年 | 78篇 |
1990年 | 54篇 |
1989年 | 74篇 |
1988年 | 62篇 |
1987年 | 51篇 |
1986年 | 52篇 |
1985年 | 64篇 |
1984年 | 83篇 |
1983年 | 43篇 |
1982年 | 66篇 |
1981年 | 60篇 |
1980年 | 55篇 |
1979年 | 46篇 |
1978年 | 54篇 |
1977年 | 39篇 |
1976年 | 32篇 |
1975年 | 25篇 |
1963年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
71.
The conduction mechanism in microcrystalline cellulose (MCC) tablets at varying relative humidity (RH) has been investigated by using the techniques of low frequency dielectric spectroscopy and transient current analysis at room temperature. The dependence on RH on the measured conductivity and charge carrier density indicates that a high-power-law-exponent percolation process of cations being conducted on water molecules occupying available 6-OH units on the cellulose chains is the dominating dc conduction mechanism at RH below 3 wt % of moisture content. The experimentally observed decrease in charge carrier mobility with increasing moisture content shows that protons and H3O+ ions that are being blocked at empty 6-OH sites also contribute to the charge transport process in cellulose at low moisture contents. 相似文献
72.
DellaGreca M Iesce MR Previtera L Temussi F Zarrelli A Mattia CA Puliti R 《The Journal of organic chemistry》2002,67(25):9011-9015
Androst-4-ene-3,17-dione (1) and 17alpha-methyltestosterone (2) are dimerized in the solid-state by UV radiation. These substances were selected by a search in the CSD among the steroid enones presenting in the crystalline state an intermolecular short contact between a hydrogen alpha to a carbonyl group and the oxygen of an enone system. Dimerization occurs by transfer of the hydrogen to the oxygen and connection between the two involved carbons. Androst-4-ene-3,17-dione (1) affords dimer 3 and trimer 4, both formed by connection of the C-16 of a molecule with the C-3 of a near one. Irradiation of 17alpha-methyltestosterone (2) gives the isomeric trienones 5 and 6. These compounds are reasonably formed by dehydration of unisolated intermediate products 7 and/or 8 obtained by coupling of two molecules through a linkage between the C-2 and the C-3' carbons. The formation mechanisms of the photoproducts are satisfactory explained on the basis of the molecular arrangement of the monomers in the crystal state. Modeling of the dimeric molecules was done using molecular mechanics calculations. A single-crystal X-ray of the dimer of androst-4-ene-3,17-dione confirms the structural interpretation of spectral data. The conformer found in the solid-state agrees well with the results of molecular mechanics calculations. 相似文献
73.
1,3-Dipolar cycloaddition of acrylamide with the cyclic nitrone derived from proline tert-butyl ester has been employed in the synthesis of bicyclic Gly-(s-cis)Pro isosteres suitably protected for the Fmoc-based solid phase peptide synthesis. (R)-1-Phenylethylamine was introduced as chiral auxiliary to resolve racemic intermediates and obtain enantiopure compounds. Using methacrylamide as dipolarophile, the analogous Ala-Pro mimetics have been prepared in racemic form, whereas the same strategy applied to methyl itaconate failed to give the corresponding Asp-Pro mimetic. 相似文献
74.
Specific programming of automated HPLC systems allows total on-line qualification, validation and stability monitoring using the concept of deferred standards. Setting up such a process for routine analyses in an automated HPLC system requires specific autosampler programming as well as specific monitoring software. With an autosampler, a double injection procedure is programmed, the first introducing the sample, and the second, a few minutes deferred, the deferred control standard. Two additional compounds are therefore added to the sample before and during the chromatographic process: the intemal standard for sample quantification and the deferred standard for system control. Specific methodologies are described of how to obtain classical quantitative analysis information as well as system qualification validation stability information. Experiments were performed to develop specified methodologies to monitor the quality of quantitative analysis during the life of the column by using the deferred standard concept to probe the effects of column ageing on separation characteristics. 相似文献
75.
Maria Rosaria Acocella 《Tetrahedron letters》2005,46(36):6141-6144
The vinylogous aldol reaction of O-silyl dienolates deriving from 2,2-dimethyl-[1,3]-dioxin-4-ones proceeds in moderate to excellent yields in the presence of catalytic amounts of PhCOOH under solvent-free conditions. Modest to good yields can be obtained by using silica gel or 3 Å molecular sieves as heterogeneous catalysts. 相似文献
76.
The method is based on reduction of total iodine (10?7?10?5 M), to iodide with sulphite in acidic solution. The excess of sulphur dioxide is removed by bubbling with nitrogen, and the resulting solution is titrated spectrophotometrically with a standard solution of iodate, the absorbance being measured at 230 nm. Some Italian table salts, iodized or common, were analyzed for their iodide and total iodine content. 相似文献
77.
Massimo Lucarini Fabio Sciubba Donatella Capitani Maria Enrica Di Cocco Laura D’Evoli Alessandra Durazzo 《Natural product research》2020,34(1):53-62
AbstractThe study focuses on the understanding, at molecular level, the mechanism of interaction between protein and flavonoids. Collagen and catechin interactions were investigated by NMR in solution and solid state. The effect of catechin on the stability of collagen to oxidation was also explored. Collagen was treated with two concentrations of catechin solutions. Oxidation was carried out by incubation of collagen solution with three oxidation systems: Fe(II)/H2O2, Cu(II)/H2O2, and NaOCl/H2O2. The effects of oxidation systems were evaluated by high resolution 1?D and 2?D proton spectroscopy and solid state NMR (13C CP MAS) experiments. Interactions between collagen and catechin preferentially occur between catechin B ring and the amino acids Pro and Hyp of collagen. Results showed that both iron and copper oxidation systems were able to interact with collagen by site specific attack. Moreover, catechin protects collagen proline from oxidation by metal/H2O2 systems, preventing copper and iron approach to collagene molecule;this behaviour was more evident for the copper/H2O2 system. 相似文献
78.
Maxim A. Mironov Maria N. Ivantsova Maria I. Tokareva Vladimir S. Mokrushin 《Tetrahedron letters》2005,46(23):3957-3960
An accelerating effect of nucleophilic additives was revealed for the Passerini multi-component reaction. The influence of aqueous solutions on the reaction rate was studied in detail and the direct involvement of water in the bond-making step was attributed as the basis of an accelerating effect. Other nucleophiles were tested as alternatives to water; as a result N-hydroxysuccinimide is proposed as an accelerant of the Passerini reaction. 相似文献
79.
Production of antitumoral retamycin during fed-batch fermentations of Streptomyces olindensis 总被引:1,自引:0,他引:1
Fed-batch runs were performed in order to correlate the production of retamycin, an anthracycline antibiotic produced by Streptomyces olindensis in submerged cultures, with the specific growth rate. Maximum retamycin production was achieved with an exponential feed rate, controlling the specific growth rate at a low value (0.03 h-1, about 10% of the maximum specific growth rate). Control of the specific growth rate at higher values (0.10 and 0.17 h-1) caused a decrease in antibiotic production. Morphology, assessed by image analysis, was shown to be highly relevant in this process. Cell growth mainly in the form of clumps (90% clumps and 10% free filaments) led to better results than growth as clumps (75%) and free filaments (25%). 相似文献
80.
Maria Fernanda Silva Estela Soledad Cerutti Luis D. Martinez 《Mikrochimica acta》2006,155(3-4):349-364
The purpose of this article is to review and evaluate cloud point extraction of metals and its coupling to different contemporary
instrumental methods of analysis. This review covers a selection of the literature published on this topic over the period
mainly between 1997 and September 2005 (consisting of 50 publications). The current state of the art for CPE concerning metals
and metal chelates is presented with special emphasis on the hyphenation of this interesting extraction/preconcentration approach
mediated by surfactants to spectrophotometry, atomic spectroscopy and separation techniques. We present contemporary CPE developments
concerning metal speciation and determination and their application to different environmental, clinical, geological and food
samples. Strategies for method development as well as future perspectives are also covered. 相似文献