全文获取类型
收费全文 | 7976篇 |
免费 | 531篇 |
国内免费 | 371篇 |
专业分类
化学 | 4912篇 |
晶体学 | 60篇 |
力学 | 356篇 |
综合类 | 40篇 |
数学 | 1164篇 |
物理学 | 2346篇 |
出版年
2023年 | 87篇 |
2022年 | 266篇 |
2021年 | 249篇 |
2020年 | 287篇 |
2019年 | 230篇 |
2018年 | 194篇 |
2017年 | 184篇 |
2016年 | 315篇 |
2015年 | 302篇 |
2014年 | 291篇 |
2013年 | 516篇 |
2012年 | 505篇 |
2011年 | 633篇 |
2010年 | 382篇 |
2009年 | 368篇 |
2008年 | 467篇 |
2007年 | 451篇 |
2006年 | 403篇 |
2005年 | 332篇 |
2004年 | 271篇 |
2003年 | 234篇 |
2002年 | 196篇 |
2001年 | 153篇 |
2000年 | 99篇 |
1999年 | 112篇 |
1998年 | 73篇 |
1997年 | 71篇 |
1996年 | 88篇 |
1995年 | 71篇 |
1994年 | 94篇 |
1993年 | 79篇 |
1992年 | 63篇 |
1991年 | 47篇 |
1990年 | 52篇 |
1989年 | 36篇 |
1988年 | 27篇 |
1987年 | 29篇 |
1986年 | 27篇 |
1985年 | 47篇 |
1984年 | 48篇 |
1983年 | 27篇 |
1982年 | 49篇 |
1981年 | 36篇 |
1980年 | 35篇 |
1979年 | 51篇 |
1978年 | 33篇 |
1976年 | 31篇 |
1975年 | 21篇 |
1974年 | 28篇 |
1973年 | 21篇 |
排序方式: 共有8878条查询结果,搜索用时 15 毫秒
51.
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
52.
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
53.
Aschi M Lucente G Mazza F Mollica A Morera E Nalli M Paglialunga Paradisi M 《Organic & biomolecular chemistry》2003,1(11):1980-1988
The conformational study of a new group of synthetic peptides containing 4-amino-1,2-dithiolane-4-carboxylic acid (Adt), a cysteine-related achiral residue, has been carried out through a joint application of computational and experimental methodologies. Molecular Dynamics simulations clearly suggest the tendency of this molecule to adopt a gamma-turn conformation in vacuum and help in analyzing the complex and crucial conformational behaviour of the dithiolane ring which appears to preferentially adopt a C(S)-like structure. Electronic structure calculations carried out in solution using the Density Functional Theory also indicate the preservation of the gamma-like folding in apolar solvents and the helix-like one in more polar solvents. A comparison with the achiral 1-aminocycloalkane-1-carboxylic acid (Ac5c) has been carried out using the same computational tools. NMR and IR data on dipeptide derivatives containing the Adt or Ac5c residue show that in chloroform solution all the models prefer a gamma-turn structure, centered at the cyclic residue, stabilized by an intramolecular H-bond, whereas in a more polar solvent, i.e. dimethyl sulfoxide, this folding is not maintained. The experimental conformational studies, extended to N-Boc protected tripeptides, clearly indicate the remarkable tendency of both the five-membered C(alpha)-tetrasubstituted cyclic amino acids Adt and Ac5c to induce the gamma-turn structure also in models able to adopt the beta-bend conformation. 相似文献
54.
Kuppuswamy Kalyanasundaram Enrico Borgarello Michael Grutzel 《Helvetica chimica acta》1981,64(1):362-366
Illumination of aqueous CdS dispersions loaded with Pt and RuO2 by visible light produces hydrogen and oxygen in stoichiometric proportion. No degradation of the photocatalyst is noted after 60 h of irradiation time. The RuO2 deposit on the particle surface greatly accelerates the transfer of holes from the semiconductor valence band to the aqueous solution thus inhibiting photocorrosion. 相似文献
55.
Rapid determination of orotic acid in urine by a fast liquid chromatography/tandem mass spectrometric method 总被引:1,自引:0,他引:1
la Marca G Casetta B Zammarchi E 《Rapid communications in mass spectrometry : RCM》2003,17(8):788-793
Quantification of orotic acid (uracil-6-carboxylic acid) in urine is an important tool to diagnose some inherited diseases, such as urea cycle disorder (OTCD) and hereditary orotic aciduria. New rapid analytical methods are necessary to provide high-throughput orotic acid analyses. A new analytical method has been developed for the rapid analysis of orotic acid in urine by liquid chromatography coupled with ion spray tandem mass spectrometry (LC/MS/MS). After a sample dilution 1:20, the analysis was performed in the selected reaction monitoring mode in which orotic acid was detected through the transition m/z 155 to 111. The retention time was 3.9 min in a 4.5-min analysis. Daily calibration between 0.5-5.0 micromol/L of orotic acid, corresponding to 10-100 micromol/L in urine before the 1:20 dilution, offered consistent linearity and reproducibility. Interassay coefficient of variance (c.v.) was 4.97% at a mean concentration of 10.99 micromol/L. The sensitivity and specificity of tandem mass spectrometry permitted a high volume of analyses of orotic acid. The sample preparation is simple, inexpensive and not time demanding. 相似文献
56.
Enza Di Gregorio Luciano Lattuada Alessandro Maiocchi Silvio Aime Giuseppe Ferrauto Eliana Gianolio 《Chemical science》2021,12(4):1368
The set-up of reversible binding interactions between the hydrophobic region of macrocyclic GBCAs (Gadolinium Based Contrast Agents) and SO3−/OH containing pyrene derivatives provides new insights for pursuing relaxivity enhancements of this class of MRI contrast agents. The strong binding affinity allows attaining relaxation enhancements up to 50% at pyrene/GBCA ratios of 3 : 1. High resolution NMR spectra of the Yb-HPDO3A/pyrene system fully support the formation of a supramolecular adduct based on the set-up of hydrophobic interactions. The relaxation enhancement may be accounted for in terms of the increase of the molecular reorientation time (τR) and the number of second sphere water molecules. This effect is maintained in blood serum and in vivo, as shown by the enhancement of contrast in T1w-MR images obtained by simultaneous injection of GBCA and pyrene derivatives in mice.The set-up of reversible binding interactions between the hydrophobic region of macrocyclic gadolinium based contrast agents and SO3−/OH containing pyrene derivatives provides new insights for pursuing relaxivity enhancement of MRI contrast agents. 相似文献
57.
Changlun Chen Di Xu Xiaoli Tan Xiangke Wang 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(1):227-233
The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions.
The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In
this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations
on the Co(II) sorption on γ-Al2O3 in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al2O3 in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed
that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition
orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated
that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly
positive influence of HA at low pH on the Co(II) sorption on γ-Al2O3 was attributed to strong surface binding of HA on γ-Al2O3 and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO−)
x
Co2−x
. Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al2O3 in the presence of HA. 相似文献
58.
Ahlen S Ambrosio M Antolini R Auriemma G Baker R Baldini A Bam BB Barbarino GC Barish BC Battistoni G Bellotti R Bemporad C Bernandini P Bilokon H Bisi V Bloise C Bower C Bussino S Cafagna F Calicchio M Campana D Campana P Carboni M Cecchini S Cei F Chiarella V Cormack R Corona A Coutu S De Cataldo G Dekhissi H De Marzo C De Vincenzi M Di Credico A Diehl E Erriquez O Favuzzi C Ficenec D Forti C Fusco P Giacomelli G Giannini G Giglietto N Giubellino P Grassi M Green P Grillo A Guarino F 《Physical review letters》1994,72(5):608-612
59.
60.
S. Tosto A. Di Bartolomeo P. Di Lazzaro 《Applied Physics A: Materials Science & Processing》1996,63(4):385-389
This paper presents the surface microstructure of Ti and Ti6Al4V alloy irradiated with a high output energy XeCl ( = 308 nm) excimer laser. The treatments are carried out on both materials at two beam fluences and the effects of single- and multiple-pulse irradiation are compared. The results of the scanning electron microscopy and of the X-ray diffraction techniques suggest the possible influence of both time-behaviour and energy fluence of the laser pulse on the relative weight of the ablation rate and of the reaction product deposition rate at the sample surface. 相似文献