全文获取类型
收费全文 | 1252篇 |
免费 | 54篇 |
国内免费 | 15篇 |
专业分类
化学 | 947篇 |
晶体学 | 18篇 |
力学 | 29篇 |
综合类 | 3篇 |
数学 | 129篇 |
物理学 | 195篇 |
出版年
2023年 | 10篇 |
2022年 | 41篇 |
2021年 | 48篇 |
2020年 | 37篇 |
2019年 | 27篇 |
2018年 | 21篇 |
2017年 | 19篇 |
2016年 | 31篇 |
2015年 | 53篇 |
2014年 | 41篇 |
2013年 | 95篇 |
2012年 | 101篇 |
2011年 | 91篇 |
2010年 | 53篇 |
2009年 | 68篇 |
2008年 | 99篇 |
2007年 | 72篇 |
2006年 | 59篇 |
2005年 | 39篇 |
2004年 | 58篇 |
2003年 | 41篇 |
2002年 | 29篇 |
2001年 | 21篇 |
2000年 | 25篇 |
1999年 | 16篇 |
1998年 | 8篇 |
1997年 | 15篇 |
1996年 | 8篇 |
1995年 | 6篇 |
1994年 | 10篇 |
1993年 | 7篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1985年 | 8篇 |
1984年 | 1篇 |
1983年 | 5篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1975年 | 1篇 |
1948年 | 1篇 |
1938年 | 1篇 |
1934年 | 2篇 |
1925年 | 2篇 |
1924年 | 2篇 |
排序方式: 共有1321条查询结果,搜索用时 19 毫秒
11.
V. V. Kuznetsov A. Pal'ma A. é. Aliev M. Fernandes N. S. Prostakov A. V. Varlamov 《Chemistry of Heterocyclic Compounds》1993,29(6):671-675
The cydization of 1-allyl-1-arylaminocyclohexanes under conditions of acid catalysis afforded 1,2,3,4-tetrahydro-4-methylspiro [quinoline-2-cyclohexanes] methyl (methoxy)-substituted in the phenylene ring. Their mono- and dinitro derivatives were synthesized, and their structure was established. Propositions on the direction of the nitration reaction of these heterocyclic compounds were expressed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 784–788, June, 1993. 相似文献
12.
2'-azido-2'-deoxyribonucleoside 5'-diphosphates are mechanism-based inhibitors of Ribonucleotide Reductase. Considerable effort has been made to elucidate their mechanism of inhibition, which is still controversial and not fully understood. Previous studies have detected the formation of a radical intermediate when the inhibitors interact with the enzyme, and several authors have proposed possible structures for this radical. We have conducted a theoretical study of the possible reactions involved, which allowed us to identify the structure of the new radical among the several proposals. A new reactional path is also proposed that is the most kinetically favored to yield this radical and ultimately inactivate the enzyme. The energetic involved in this mechanism, both for radical formation and radical decay, as well as the calculated Hyperfine Coupling Constants for the radical intermediate, are in agreement with the correspondent experimental values. This mechanistic alternative is fully coherent with remaining experimental data. 相似文献
13.
Fernandes MX Kairys V Gilson MK 《Journal of chemical information and computer sciences》2004,44(6):1961-1970
Standard uses of ligand-receptor docking typically focus on the association of candidate ligands with a single targeted receptor, but actual applications increasingly require comparisons across multiple receptors. This study demonstrates that comparative docking to multiple receptors can help to select homology models for virtual compound screening and to discover ligands that bind to one set of receptors but not to another, potentially similar, set. A serial docking algorithm is furthermore described that reduces the computational costs of such calculations by testing compounds against a series of receptor structures and discarding a compound as soon as it fails to satisfy specified bind/no bind criteria for each receptor. The algorithm also realizes substantial efficiencies by taking advantage of the fact that a ligand typically binds in similar conformations to similar receptors. Thus, once detailed docking has been used to fit a ligand into the first of a series of similar receptors, much less extensive calculations can be used for the remaining structures. 相似文献
14.
A method for the direct determination of Pb in wines by simultaneous multi-element atomic absorption spectrometry (SIMAAS) using a transversely heated graphite atomizer, Zeeman-effect background corrector and internal standardization is proposed. Bismuth was used as an internal standard and Pd(NO3)2 plus Mg(NO3)2 as chemical modifier to stabilize both the analyte and the internal standard. The implementation of two pyrolysis steps avoided any build-up of carbonaceous residues on the graphite platform. All diluted samples (1 + 1 v/v) in 0.2% v/v HNO3 and reference solutions (5.0-50 microg l(-1) Pb in 0.2% v/v HNO3) were spiked with 25 microg l(-1) Bi. For a 20 microl aliquot dispensed into the graphite tube, a good correlation (r = 0.9997) was obtained between the ratio of the analyte signal to the internal standard signal and the analyte concentration of the reference solutions. The electrothermal behaviour of Pb and Bi in red, white and rosé wines were compared. In addition, absorbance variations due to changes in experimental conditions, such as atomizer temperature, integration time, injected sample volume, radiation beam intensity, graphite tube surface, dilution and sample composition, were minimized by using Bi as internal standard. Relative standard deviations of measurements based on integrated absorbance varied from 0.1 to 3.4% and from 0.5 to 7.3% (n = 12) with and without internal standard correction, respectively. Good recoveries (91-104%) for Pb spikes were obtained. The characteristic mass was 45 pg Pb and the limit of detection based on integrated absorbance was 0.9 microg l(-1) Pb. Internal standardization increased the lifetime of the tube by 25%. Direct determinations of Pb in wines with and without internal standardization approaches were in agreement at the 95% confidence level. The repeatability and the tube lifetime were improved when using Bi as internal standard. The improvement in accuracy using an internal standard was only observed when the analytical results were affected by errors. 相似文献
15.
Marta M.?Conceio V. J.?Fernandes Jr. F. S. M.?Sinfrnio J. C. O.?Santos M. C. D.?Silva V. M.?Fonseca A. G.?Souza 《Journal of Thermal Analysis and Calorimetry》2005,79(2):263-266
Summary Sulfonylureas are widely used for the treatment of non-insulin dependent diabetes mellitus. Glibenclamide belongs to the group of substituted arylsulfonylureas. Many representative of this group shows polymorphism. The purpose of this work was to investigate the thermal behaviour and compatibility between glibenclamide and some excipients using thermoanalytical techniques (TG-DTG/DSC). The thermal and isothermal kinetics data showed incompatibility between glibenclamide and magnesium stearate. 相似文献
16.
Garcia Jarem R. Peres Laura O. Fernandes Mauro R. Gruber Jonas Nart Francisco C. 《Journal of Solid State Electrochemistry》2004,8(2):122-126
In this communication we describe the electrochemical synthesis of poly(2,5-dicyano-p-phenylenevinylene) (DCNPPV) polymer films on indium tin oxide substrates. We investigate the purity, morphology, absorption and emission properties of the film. The purity was checked by infrared spectroscopy. The film formed presented spectroscopic purity equivalent to the chemically prepared PPV that was dialyzed for one week. Scanning electron microscopy of the surface revealed a grain-like morphology. The absorption and emission spectra showed absorption and emission bands at 420 nm and 575 nm, respectively, with the absorption onset at 422 nm, which corresponds to an energy gap of 2.25 eV. The electrochemical determination of the energy gap gives 2.05 eV, thus quite close to the optical energy gap at the onset of absorption. The EA and IP were determined by electrochemical measurements and are 3.46 eV and 5.51 eV, respectively.
相似文献
Francisco C. NartEmail: |
17.
The first example of an organic reduction with boranes catalyzed by a high valent oxo-complex is reported. The systems catecholborane/MoO2Cl2(H2O)2 (5 mol %) and BH3·THF/MoO2Cl2 (5 mol %) proved to be very efficient for the reduction of sulfoxides to the corresponding sulfides in excellent yields. 相似文献
18.
Elizabeth Nunes Fernandes Mariele Nair de Campos Moura Jos Luis F. Costa Lima Boaventura F. Reis 《Microchemical Journal》2004,77(2):107-112
An automatic flow procedure for the determination of glycerol in wines by employing a flow system based on multicommutation and enzymatic reaction is described. Glycerol dehydrogenase was immobilized on aminopropyl glass beads and packed into a column that was coupled to the flow system. The NADH produced by the enzymatic reaction was monitored by spectrophotometry at 340 nm and its radiation absorption presented a relationship with glycerol concentration. The system manifold comprised a set of three-way solenoid valves controlled by a microcomputer, which was furnished with electronic interfaces and runs a software that was designed to carry out on-line sample dilution, reagent addition, and data acquisition. The procedure allows the determination of glycerol in wine samples without any prior pretreatment. The procedure presented as profitable features a linear response range between 2.0 and 10.0 g l−1 glycerol (R=0.998), a detection limit of 0.006 g l−1 glycerol, a relative standard deviation of 1.8% (n=14) for a typical wine sample presenting 5.3 g l−1 glycerol, a sampling throughput of 33 determinations per hour, and a NAD+ consumption of 0.8 mg per determination. The results were compared with those obtained using a reference method and no significant difference at 90% confidence level was observed. 相似文献
19.
L. Fernandes C. Pagano Gonçalves da Silva 《Journal of Radioanalytical and Nuclear Chemistry》1993,172(2):313-318
The radiopharmaceutical201TlCl(thallium-201 chloride) is used in nuclear medicine for myocardial visualization. The solution of201TlCl was prepared using201Tl obtained by irradiating a natural mercury target with protons from the CV-28 cyclotron installed at IPEN-CNEN/SP. This solution was subjected to different quality control processes required for its use in medicine. Some of these controls concerned the determination of the radionuclidic impurities:200Tl,202Tl and203Hg; the chemical identification of201Tl+; the hydrazine concentration, mercury contamination and the presence of phosphate. Furthermore. the biological distribution in Wistar rats and tests for sterility, pyrogenicity and toxicity were carried out. It was verified that the solution obtained was in the form of thallous chloride. This radiopharmaceutical gave good heart images in animals but due to the high levels of200Tl and202Tl its use in humans is not possible unless enriched202Hg is used as target in the irradiation. 相似文献
20.
Fernandes SA Nachtigall FF Lazzarotto M Fujiwara FY Marsaioli AJ 《Magnetic resonance in chemistry : MRC》2005,43(5):398-404
'Non-covalent synthesis' of novel chiral hosts (calix[6]arene-chiral amine complexes) and its application to enantiomeric discrimination was investigated by (1)H NMR spectroscopy. The topology of a ternary complex was proposed for the calix[6]arene-amine-sulfoxide to rationalize the chiral recognition. 相似文献