全文获取类型
收费全文 | 79369篇 |
免费 | 12033篇 |
国内免费 | 4678篇 |
专业分类
化学 | 76331篇 |
晶体学 | 988篇 |
力学 | 1650篇 |
综合类 | 113篇 |
数学 | 5394篇 |
物理学 | 11604篇 |
出版年
2023年 | 191篇 |
2022年 | 499篇 |
2021年 | 796篇 |
2020年 | 1302篇 |
2019年 | 2982篇 |
2018年 | 2798篇 |
2017年 | 3230篇 |
2016年 | 3753篇 |
2015年 | 5892篇 |
2014年 | 5770篇 |
2013年 | 8257篇 |
2012年 | 6435篇 |
2011年 | 6044篇 |
2010年 | 4936篇 |
2009年 | 4948篇 |
2008年 | 5209篇 |
2007年 | 4693篇 |
2006年 | 4287篇 |
2005年 | 4061篇 |
2004年 | 3461篇 |
2003年 | 3157篇 |
2002年 | 4293篇 |
2001年 | 1990篇 |
2000年 | 1837篇 |
1999年 | 996篇 |
1998年 | 391篇 |
1997年 | 298篇 |
1996年 | 292篇 |
1995年 | 287篇 |
1994年 | 191篇 |
1993年 | 185篇 |
1992年 | 171篇 |
1991年 | 119篇 |
1990年 | 92篇 |
1989年 | 79篇 |
1988年 | 90篇 |
1985年 | 115篇 |
1984年 | 137篇 |
1983年 | 122篇 |
1982年 | 171篇 |
1981年 | 126篇 |
1980年 | 119篇 |
1979年 | 120篇 |
1978年 | 126篇 |
1977年 | 159篇 |
1976年 | 137篇 |
1975年 | 135篇 |
1974年 | 169篇 |
1973年 | 139篇 |
1972年 | 86篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
981.
Kremser L Brückner A Heger A Grunert T Buchacher A Josic D Allmaier G Rizzi A 《Electrophoresis》2003,24(24):4282-4290
The isoforms distribution of the glycoprotein antithrombin III (ATIII) derived from human plasma was investigated by means of isoelectric focusing (IEF) in polyacrylamide gels with immobilized pH gradients (IPG) and two-dimensional gel electrophoresis (2-DE) as well as capillary electrophoretic methods. It turned out that the presence of high concentrations of chaotropics (urea, thiourea) and zwitterionic detergents (3-[(3-cholamidepropyl)dimethylammonio]-1-propanesulfonate (CHAPS)) was decisive for attaining good resolution of the protein isoforms. Resolution by IPG-IEF was obtained with excellent reproducibility and pI differences down to 0.01 pH units could be distinguished. ATIII-alpha and ATIII-beta-fractions preseparated by heparin affinity chromatography showed an analogous but shifted spot pattern consisting each of one major and three minor isoforms. The main isoforms of ATIII-alpha and ATIII-beta exhibit pI values of 5.18 and 5.32, respectively, both values determined in the presence of high concentrations of urea. The pI difference of 0.14 pH units correspond to the effect of two sialic acids absent in ATIII-beta. The formation and occurrence of ATIII dimers and trimers turned out to be dependent on the sample preparation. The results obtained by 2-DE were compared with those of capillary zone electrophoresis (CZE) and capillary IEF (CIEF). Quantitative analysis regarding the CZE separated isoforms of plasma derived ATIII yielded a content of about 70% ATIII-alpha main isoform and about 6.6% of ATIII-beta. The pI values of ATIII determined by CIEF with internal calibration were in fair agreement with the pI values of the main isoforms achieved with 2-DE. 相似文献
982.
The reaction between 4-tert-butylbenzyl bromide and potassium iodide was carried out in microemulsions based on different nonionic surfactants, and the reaction rates were compared with those obtained in two-phase systems with added phase-transfer agent, either a quaternary ammonium salt or a crown ether. The reactions were relatively fast in the microemulsions and extremely sluggish in the two-phase systems without additional phase-transfer agent. Addition of a phase-transfer agent did not accelerate the reaction when a hydrocarbon was used as organic solvent, neither in the two-phase system nor in the microemulsion. When a chlorinated hydrocarbon was used as solvent, phase-transfer catalysis became effective and the rate obtained in the two-phase system with an equimolar amount of phase-transfer agent added was higher than that obtained in the microemulsion. When a catalytic amount of phase-transfer agent was used, the rate in the two-phase system was about the same as the rate obtained in the microemulsion without the phase-transfer agent. The combined approach, that is, use of a microemulsion as the reaction medium and addition of a phase-transfer agent, gave the highest reaction rate. The quaternary ammonium salt (tetrabutylammonium hydrogen sulfate) was a more efficient catalyst in the microemulsion system than the crown ether ([18]crown-6). 相似文献
983.
《Electroanalysis》2004,16(10):827-831
An amperometric detector for hydrophobic ions based on a plasticized poly(vinyl) chloride (PVC) membrane incorporated in a flow‐injection system was developed. A four‐electrode potentiostat with ohmic drop compensation was used, while a flow‐through cell incorporated the four electrodes and the membrane, which contained tetrabutylammonium tetraphenylborate. When the influence of the applied potential and of the flow‐injection variables on the determination of tetrabutylammonium was studied, a linear relationship was observed between current peak height and ion concentration over a range of 5×10?6–6×10?5 M tetrabutylammonium. Good repeatability and between‐day reproducibility and high sample frequency were obtained. The effect of other ions was studied. Two different amperometric methods, indirect and direct, were also developed for the determination of dodecylsulfate in the concentration range 3×10?5–9×10?4 M. 相似文献
984.
Elena Khomko Leonid Mashlyakovskiy Claudio Tonelli 《Journal of polymer science. Part A, Polymer chemistry》2004,42(21):5354-5371
The effect of catalyst dibutyltin dilaurate (DBTDL) on the kinetics of urethane formation reactions of α,ω‐bis(hydroxy)‐terminated fluoropolyethers Fomblin® Z‐DOL TXs (FPEs) of various molecular weights and poly(oxyethylene) glycol PEG‐400 with isophorone diisocyanate (IPDI) in hexafluoroxylene (HFX) and tetrahydrofuran (THF) at 40 °C and NCO:OH = 2:1 have been studied in a broad range of catalyst (0.10–9.00) ×10?4 M and total reagents (10.0–60.1 wt %) concentrations. The rate of tin‐catalyzed second‐order reactions (with respect to diol and diisocyanate) was found to be proportional to the square root of catalyst concentration [DBTDL]0.5 both in low polar (HFX) and polar (THF) solvents. Effect of catalyst saturation was revealed for all the reaction systems at higher DBTDL concentrations as well as the appearance of the limiting catalyst concentrations Clim below which the rates of reaction were close to zero. Based on these findings new effective rate coefficients have been derived k = kcat/(C ? C) that are independent of the total reagent concentration in the range of 10.0–60.1 wt % ([OH] = 0.10–0.91 equiv/L). This new approach highlights that the rate of the tin‐catalyzed urethane formation reactions of α,ω‐bis(hydroxy)‐terminated fluoropolyethers Z‐DOL TXs with IPDI in HFX at 40 °C and NCO:OH = 2:1 increases significantly with increasing MW of FPE from 776 up to 3405. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5354–5371, 2004 相似文献
985.
Elisabete Curti Douglas de Britto Srgio Paulo Campana‐Filho 《Macromolecular bioscience》2003,3(10):571-576
N,N,N‐trimethylchitosan (TMC) was prepared by reacting purified chitosan with iodomethane, in the presence of sodium hydroxide, water and sodium iodide, at room temperature. The reaction medium was N‐methyl‐2‐pyrrolidone. Different samples of TMC were obtained by adding to the reaction medium a fixed volume (5.5 mL) of aqueous NaOH solutions at different concentrations (15, 20, 30 and 40 wt.‐%) and carrying out the reactions for 9 or 24 h. The features observed in the 1H and 13C NMR spectra of these chitosan derivatives, in respect of the chemical shift, number and relative intensity of the signals, depended strongly on the excess of NaOH and H3CI added to the reaction medium, but when the lowest excess was employed, the characteristics of the derivative were not affected by the reaction time to the same extent. The average degree of quaternization of these N‐methylated derivatives of chitosan ranged from 10.5% to 44.8%, according to the reaction conditions. Increasing the excess of NaOH, in reactions carried out for 9 h, resulted in TMC samples with progressively higher content of trimethylated sites however, the reaction yields were correspondingly lower and O‐alkylation was favored in these cases.
986.
Cabaleiro-Lago EM Rodríguez-Otero J García-López RM Peña-Gallego A Hermida-Ramón JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):5966-5974
A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth. 相似文献
987.
A stereoselective total synthesis of (S)-Virol C and (S)-1-dehydroxyvirol A has been developed, based upon the selective and sequential substitution of the two trimethylsilyl groups of readily available 1,4-bis(trimethylsilyl)-1,3-butadiyne. 相似文献
988.
989.