全文获取类型
收费全文 | 8381篇 |
免费 | 545篇 |
国内免费 | 363篇 |
专业分类
化学 | 5147篇 |
晶体学 | 62篇 |
力学 | 418篇 |
综合类 | 40篇 |
数学 | 1160篇 |
物理学 | 2462篇 |
出版年
2024年 | 23篇 |
2023年 | 96篇 |
2022年 | 282篇 |
2021年 | 276篇 |
2020年 | 294篇 |
2019年 | 245篇 |
2018年 | 208篇 |
2017年 | 198篇 |
2016年 | 326篇 |
2015年 | 330篇 |
2014年 | 309篇 |
2013年 | 529篇 |
2012年 | 536篇 |
2011年 | 652篇 |
2010年 | 384篇 |
2009年 | 379篇 |
2008年 | 492篇 |
2007年 | 472篇 |
2006年 | 431篇 |
2005年 | 361篇 |
2004年 | 301篇 |
2003年 | 254篇 |
2002年 | 237篇 |
2001年 | 162篇 |
2000年 | 100篇 |
1999年 | 120篇 |
1998年 | 74篇 |
1997年 | 76篇 |
1996年 | 102篇 |
1995年 | 77篇 |
1994年 | 84篇 |
1993年 | 77篇 |
1992年 | 58篇 |
1991年 | 46篇 |
1990年 | 53篇 |
1989年 | 44篇 |
1988年 | 31篇 |
1987年 | 40篇 |
1986年 | 26篇 |
1985年 | 38篇 |
1984年 | 48篇 |
1983年 | 25篇 |
1982年 | 43篇 |
1981年 | 24篇 |
1980年 | 30篇 |
1979年 | 47篇 |
1978年 | 39篇 |
1977年 | 27篇 |
1976年 | 34篇 |
1974年 | 21篇 |
排序方式: 共有9289条查询结果,搜索用时 0 毫秒
51.
A procedure for the Raman spectra calculation of vitreous and molten silicates was presented in this paper. It includes molecular dynamics MD simulation for the generation of equilibrium configurations, Wilson's GF matrix method for the calculations of eigenfrequencies and corresponding vectors, electro-optical parameters method (EOPM) for the Raman intensity calculations, and the bond polarizability model (BPM) for the determination of polarizability and polarizability derivative. One of the most important characteristics of this procedure is the achievement of the partial Raman spectra of five tetrahedral units, as well as the total spectral envelope. In this paper, the calculation was carried out for the vitreous and molten calcium silicates with different compositions and at various temperatures. It is worthwhile to note that the calculation is based on statistical configurations distribution in the space and so it is not needed to artificially adjust the full width at half maximum (FWHM) of spectra. It was also tested through the good agreement of the calculated spectra with the experimental, including some regularity of spectral properties. According to the calculation, the symmetrical stretching of whole tetrahedral units, to which the stretching of Si-O(nb) bond gives the main contribution to intensity, is proven to be the dominance in the high-frequency range (800-1200 cm(-1)) and the symmetrical bending of Si-O(b)-Si, to which the stretching of Si-O(b) bond exhibits the main contribution, is the dominance in the medium-frequency range (400-700 cm(-1)). As the first theoretical results, the Raman scattering coefficient of each Q(i) was found little change along with the variation of composition and temperature. 相似文献
52.
trans-7α-carbomethoxy-decal-1-one (2) yields a mixture of the two oxy-esters 6 and 7 on reacting with MeMgX. Ratios were measured for reactions performed in benzene (with X = I) and in THF (with X = Cl). The small variations of the ratios as compared to those obtained in analogous experiments performed with methyl (2-oxo-cyclohexyl)-propionate 4 and methyl 4-methyl-5-oxo-hexanoate 5 suggest that conformational mobility plays a fundamental role in determining the variations of stereospecificity with varying the reaction conditions. Competitive Grignard reactions among 2,4 and 5 show that their reactivities are in the order 4>2>5 ( = 1.7; =0.8) when reactions are performed in benzene with X I and 2>4>5 (= 0.56; =0.25) when reactions are performed in THF with X C1. The experimental data are interpreted in terms of anchimeric assistance given by the ester group to the reactions of the keto group in conformationally mobile δ-keto esters. The occurrence of this effect depends on the reaction conditions which can favour, or not, folded transition states. 相似文献
53.
A large‐scale synthetic route to a variety of phosphaformamidines and phosphaformamidinates, a type of derivative that was not accessible by the methods previously known for preparing phosphaamidines and phosphaamidinates, is reported. Thermally stable ethyl N‐arylformimidates 1 (ArN?CH(OEt), Ar=2,4,6‐(Me)3Ph or 2,6‐(iPr)2Ph) readily reacted with lithium dialkyl‐ and diarylphosphanides to afford the corresponding N‐aryl phosphaformamidines in 80 and 60 % yield, respectively, whereas with lithium (aryl)(silyl)phosphanide, the N‐aryl‐N‐silylphosphaformamidine (60 % yield) was obtained. Addition of primary lithium arylphosphanides to 1 followed by addition of a stoichiometric amount of nBuLi gave rise to the respective phosphaformamidinates (70–88 % yield). Methanolysis of the products afforded the N‐aryl‐N‐hydrogenophosphaformamidines (90–95 % yield). The solid‐state structure of one of the phosphaformamidinates is also presented. 相似文献
54.
Liposomes have been widely used as cellular and bioparticle mimics due to their lipid bilayer structure and relative ease of production and manipulation. Such biocolloids are frequently characterized by capillary electrophoresis (CE), which promises a wealth of information about such properties as surface charge, composition, and rigidity. The applicability of this information is somewhat limited, however, since it is interpreted with colloidal theories that do not account for the unique properties of biocolloids. In this work, the effects of deformability, mobile surface charges, intrinsic polarizability, and uneven surface charge distributions are incorporated into colloidal theories in order to better model the electrophoretic behaviors of liposomes. 相似文献
55.
Ilaria Serafini Livia Lombardi Claudia Fasolato Manuel Sergi Francesca Di Ottavio Fabio Sciubba 《Natural product research》2019,33(7):1040-1051
AbstractIn this paper, the application of a multi-analytical approach for the characterisation of synthetic and natural dyes in a historical textile is presented. The work is focused on a historical dress of a Sicilian noblewoman, dating from about 1865–1870. Firstly, SERS on fibre was performed, in order to individuate the classes of dyes employed. The SERS spectra suggested the presence of two main dyes: mauveine and orcein. In order to confirm these preliminary results, two different extraction protocols were applied. The extracts obtained were analysed by ESI-MS, MALDI-ToF and UHPCL-MS analyses, confirming the SERS results. In particular, the application of the ammonia mild extraction technique allowed to selectively extract the phenoxazonic dyes, separating them already in the extraction step from the synthetic ones. Thanks to this multi-analytical approach, this dress could be considered as one of the first examples of employment of synthetic dyes in association with natural ones. 相似文献
56.
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
57.
A very simple, selective and sensitive method was developed for the spectrophotometric determination of Mo in the presence of W. The method was based on the formation of color charge transfer complex, molybdotungstophosphate-3,3',5,5'-tetramethylbezidine anion, which was solubilized and stabilized in PVA medium. Following the recommended procedure, molybdenum could be determined in the linear range of 0.04-2.5 mug ml(-1) and the molar absorptivity was 1.47x10(4) l mol(-1) cm(-1) at 660 nm. The proposed method had been applied to the determination of trace molybdenum in tungsten ore with satisfactory results. 相似文献
58.
De Riccardis F Di Filippo M Garrisi D Izzo I Mancin F Pasquato L Scrimin P Tecilla P 《Chemical communications (Cambridge, England)》2002,(24):3066-3067
The Na+ transporting properties of the first member of a new class of artificial ionophores, based on a C2-symmetric polyhydroxylated steroid dimer, are described. 相似文献
59.
Activation energies for the recombination of point defects generated by the /n,/ reaction in Ba (CoEDTA)2·4H2O, t-(Co(en)2(NO2)2)Cl and (Co(en)2(NO2)2) (CoEDTA)·1H2O, have been evaluated using isothermal step annealing. The reselts were interpreted in terms of compound structures. It is possible to relate the recoil atom behaviour between single complexes and the double one. 相似文献
60.
Quassinoids from Picrasma crenata 总被引:1,自引:0,他引:1
From woods of Picrasma crenata, a new stereoisomer dihydronorneoquassin was obtained together with others well knowns dihydronorneoquassin, parain, alpha-neoquassin, beta-neoquassin and quassin. The structures were determined by spectroscopic data and chemical evidence. 相似文献