全文获取类型
收费全文 | 1247篇 |
免费 | 59篇 |
国内免费 | 6篇 |
专业分类
化学 | 809篇 |
晶体学 | 11篇 |
力学 | 37篇 |
数学 | 201篇 |
物理学 | 254篇 |
出版年
2023年 | 9篇 |
2022年 | 22篇 |
2021年 | 28篇 |
2020年 | 36篇 |
2019年 | 38篇 |
2018年 | 27篇 |
2017年 | 17篇 |
2016年 | 41篇 |
2015年 | 48篇 |
2014年 | 47篇 |
2013年 | 74篇 |
2012年 | 100篇 |
2011年 | 117篇 |
2010年 | 60篇 |
2009年 | 55篇 |
2008年 | 91篇 |
2007年 | 74篇 |
2006年 | 58篇 |
2005年 | 51篇 |
2004年 | 42篇 |
2003年 | 29篇 |
2002年 | 22篇 |
2001年 | 11篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 13篇 |
1997年 | 6篇 |
1995年 | 9篇 |
1994年 | 6篇 |
1993年 | 10篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 10篇 |
1984年 | 15篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 8篇 |
1976年 | 9篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1971年 | 4篇 |
1969年 | 5篇 |
排序方式: 共有1312条查询结果,搜索用时 15 毫秒
121.
Smaoui S Mellouli L Lebrihi A Coppel Y Fguira LF Mathieu F 《Natural product research》2011,25(8):806-814
Thirty litres of fermentation broth was extracted from the newly isolated Streptomyces sp. strain TN17 and various separation and purification steps led to the isolation of three pure bioactive compounds (1-3). Compound 1: cyclo (L-Leu-L-Arg), a diketopiperazine 'DKP' derivative; 2: di-(2-ethylhexyl) phthalate, a phthalate derivative; and 3: cyclo 1-[2-(cyclopentanecarbonyl-3-phenyl-propionyl]-pyrrolidine-2-carboxylic acid (1-carbamoyl-propyl)-amide, a cyclic tetrapeptide derivative. The chemical structure of these three active compounds was established on the basis of spectroscopic studies (MS and NMR) and by comparison with data from the literature. According to our biological studies, the pure compounds (1-3) possess antibacterial and antifungal activities. 相似文献
122.
The reaction of [(CO)PPh3)2Re(μ-H)2(μ-NCHPh)Ru(PPh3)2(PhCN)] (2) with HBF4-Me2O generates [(CO)PPh3)2Re(μ- H)2(μ,η1,η2HNCHPh)Ru(PPh3)2(PhCN)][BF4] (3). Monitoring the reaction by NMR spectroscopy shows the intermediate formation of [(CO)(PPh3)2 HRe(μ-H)2(μ-NCHPh)Ru(PPh3)2(PhCN)][BF4] (4). Attempted reduction of the imine ligand by a nucleophile (H− or CN−) failed, regenerating 2. Under dihydrogen at 50 atm, 3 is slowly transformed into [(CO)(PPh3)2HRe(μ-H)3Ru(PPh3)2(PhCN)][BF4] (5) with liberation of benzyl amine. 相似文献
123.
The use of a so-called trihedral and a T-shaped cross-flow pneumatic nebulizer with dual solution loading for inductively coupled plasma optical emission spectrometry has been studied. By these devices analyte clouds from two solutions can be mixed during the aerosol generation step. For both nebulizers the correction of matrix effects using internal standardization and standard addition calibration in an on-line way was investigated and compared to elemental determinations using a conventional cross-flow nebulizer and calibration with synthetic standard solutions without matrix matching. A significant improvement of accuracy, both for calibration with internal standardization and standard addition, was obtained in the case of four synthetic solutions containing each 40 mmol L− 1 Na, K, Rb and Ba as matrix elements and 300 μg L− 1 Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb as analytes. Calibration by standard addition in the case of dual solution loading has been shown to be very useful in the determination of elements at minor and trace levels in steel and alumina reference materials. The results of analysis for minor concentrations of Cr, Cu and Ni in steel as well as for Ca, Fe, Ga, Li, Mg, Mn, Na, Si and Zn in alumina powder certified reference materials subsequent to sample dissolution were found to be in good agreement with the certificates. Limits of detection were found to be only slightly above those for a conventional cross-flow nebulizer and a precision better than 3% was realized with both novel nebulizers. 相似文献
124.
125.
126.
Dr. Aurélien Tap Camille Lecourt Sabrina Dhambri Mathieu Arnould Dr. Gilles Galvani Dr. Olivier Nguyen Van Buu Dr. Morgan Jouanneau Dr. Jean‐Pierre Férézou Prof. Janick Ardisson Dr. Marie‐Isabelle Lannou Dr. Geoffroy Sorin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4938-4944
The development of an intramolecular rhodium(I)‐catalyzed Pauson–Khand reaction of alkoxyallene‐ynes with a proximal alkoxy group is reported. This reaction, in the presence of a [Rh(cycloocta‐1,5‐diene)Cl]2/propane‐1,3‐diylbis(diphenylphosphane) system under a CO atmosphere, constitutes a powerful tool for selectively accessing carbo‐ and heterobicyclo[5.3.0] frameworks featuring an enol ether moiety. Through this procedure, a straightforward access to guaiane skeletons with a tertiary hydroxy group at the C10 position was achieved. 相似文献
127.
Dr. Shuai Wang Lucie Dupin Mathieu Noël Cindy J. Carroux Dr. Louis Renaud Dr. Thomas Géhin Albert Meyer Dr. Eliane Souteyrand Dr. Jean‐Jacques Vasseur Dr. Gérard Vergoten Dr. Yann Chevolot Dr. François Morvan Dr. Sébastien Vidal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(33):11785-11794
Anti‐infectious strategies against pathogen infections can be achieved through antiadhesive strategies by using multivalent ligands of bacterial virulence factors. LecA and LecB are lectins of Pseudomonas aeruginosa implicated in biofilm formation. A series of 27 LecA‐targeting glycoclusters have been synthesized. Nine aromatic galactose aglycons were investigated with three different linker arms that connect the central mannopyranoside core. A low‐nanomolar (Kd=19 nm , microarray) ligand with a tyrosine‐based linker arm could be identified in a structure–activity relationship study. Molecular modeling of the glycoclusters bound to the lectin tetramer was also used to rationalize the binding properties observed. 相似文献
128.
Dubois M Becher F Herbet A Ezan E 《Rapid communications in mass spectrometry : RCM》2007,21(3):352-358
In order to increase the sensitivity of liquid chromatography/mass spectrometry (LC/MS) assays of recombinant proteins for pharmacokinetics studies, we have developed an immuno-mass spectrometry assay for EPI-hNE4, a 6237 Da protein currently developed for respiratory distress syndromes. After immunocapture of the analyte in human plasma with magnetic beads coated with anti-EPI-hNE4 antibodies, the intact protein was eluted and separated in reversed-phase LC and then analysed by tandem mass spectrometry (MS/MS) in selected reaction monitoring (SRM) mode. The problem of analytical interference due to endogenous binding antibodies was addressed by successive steps of acidification and neutralisation before immunocapture. Furthermore, potential variations in the recovery of analyte during sample extraction were compensated for by addition of an internal standard recognised by the antibodies. The precision of the assay remained therefore below 15%. A significant increase in assay sensitivity was achieved since the extraction step allowed sample concentration and removal of matrix components interfering with the electrospray ionisation process. Using 0.4 mL of plasma, a limit of quantification at 0.5 ng/mL (80 pM) was reached, which represents a 10-fold improvement in sensitivity over our previous work using sample precipitation. This technique was able to monitor EPI-hNE4 kinetics in the plasma of human subjects for 36 h after an intravenous administration of 0.125 mg/kg. 相似文献
129.
The authors analyze the long-time self-diffusion of charge-stabilized colloidal macroions in nondilute suspensions using a mode-coupling scheme developed for multicomponent suspensions of interacting Brownian spheres. In this scheme, all ionic species, including counterions and electrolyte ions, are treated on an equal footing as charged hard spheres undergoing overdamped Brownian motion. Hydrodynamic interactions between all ions are accounted for on the far-field level. We show that the influence on the colloidal long-time self-diffusion coefficient arising from the relaxation of the microionic atmosphere surrounding the colloids, the so-called electrolyte friction effect, is usually insignificant in comparison with the friction contributions arising from direct and hydrodynamic interactions between the colloidal particles. This finding is true even for small colloid concentrations unless the mobility difference between colloidal particles and microions is not large. Furthermore, we observe an interesting nonmonotonic density dependence of the colloidal long-time self-diffusion coefficient in suspensions with low amount of added salt. We show that this unusual density dependence is due to colloid-colloid hydrodynamic interactions. 相似文献
130.
Fatima Hassine Said Gmouh Mathieu Pucheault Michel Vaultier 《Monatshefte für Chemie / Chemical Monthly》2007,57(12):1167-1174
In this work was presented an application of the use of task specific onium salts (TSOSs) as soluble supports in Grieco’s multicomponent synthesis of tetrahydroquinolines. These soluble supports are of wide applicability and combine advantages
of solid phase synthesis without its limitations with those of solution phase chemistry. After a simple washing step, products
were cleaved from the supports and obtained in pure form and good yields. 相似文献