全文获取类型
收费全文 | 1717篇 |
免费 | 49篇 |
国内免费 | 5篇 |
专业分类
化学 | 1318篇 |
晶体学 | 11篇 |
力学 | 32篇 |
数学 | 195篇 |
物理学 | 215篇 |
出版年
2023年 | 16篇 |
2022年 | 66篇 |
2021年 | 59篇 |
2020年 | 33篇 |
2019年 | 33篇 |
2018年 | 23篇 |
2017年 | 20篇 |
2016年 | 55篇 |
2015年 | 41篇 |
2014年 | 56篇 |
2013年 | 105篇 |
2012年 | 92篇 |
2011年 | 132篇 |
2010年 | 70篇 |
2009年 | 62篇 |
2008年 | 130篇 |
2007年 | 99篇 |
2006年 | 91篇 |
2005年 | 99篇 |
2004年 | 87篇 |
2003年 | 51篇 |
2002年 | 54篇 |
2001年 | 19篇 |
2000年 | 23篇 |
1999年 | 15篇 |
1998年 | 14篇 |
1997年 | 14篇 |
1996年 | 28篇 |
1995年 | 17篇 |
1994年 | 10篇 |
1993年 | 16篇 |
1992年 | 14篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 13篇 |
1986年 | 8篇 |
1985年 | 10篇 |
1984年 | 6篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1973年 | 3篇 |
排序方式: 共有1771条查询结果,搜索用时 0 毫秒
51.
The multicomponent Amine-Aldehyde-Dienophile reaction is optimized employing benzyl or 4-methoxybenzylamine. The interest of the transformation consist in the synthesis of polysubstituted cyclohex-2-enylamines. The study of the scope of this AAD process is carried out, as well as the diastereoselective version, employing commercially available chiral benzylic amines and a maleimide with the chiral information at the N-substituent. VCD spectroscopy is a very useful tool for the determination of the absolute configuration of the isolated enantiomerically enriched compounds. 相似文献
52.
Sabine Kopec Emilio Martínez-Núñez Juan Soto Daniel Peláez 《International journal of quantum chemistry》2019,119(21):e26008
We present a generalization of the transition state search using chemical dynamics simulations (TSSCDS) methodology (discussed in a previous study) which allows the topographical characterization of intermolecular potential energy surfaces (IPES) for non-covalently bound complexes (vdW-TSSCDS). Starting from a single random input geometry, we show that vdW-TSSCDS is able to globally and automatically locate stationary points of an IPES, even in limiting cases such as extremely flat regions or nontrivial topologies (eg, bifurcation points). The basic idea is the expression of the connectivity matrix in block structure, where diagonal blocks correspond to the isolated fragments and off-diagonal blocks provide the intermolecular connectivity. To this end, we introduce a new definition of bound or not, in a non-covalent sense, utilizing an extra set of van der Waals distances, which encompasses all kinds of non-covalent distances. To discuss the use of the vdW-TSSCDS method, we present a series of 2-body van der Waals systems, namely, Ar-Benzene (3D), N2-Benzene (6D) and H2O-Benzene (9D). Finally, we further illustrate its capabilities by presenting some applications for n-body problems (n > 2), (H2O)2-Benzene (12D) and (H2O)3-Benzene (21D), as well as to a reactive, fully-flexible, system (Benzene-NO2)+ (39D) in which the simultaneous breaking/formation of both covalent and non-covalent interactions takes place. 相似文献
53.
Martín Soto Dr. Raquel G. Soengas Prof. Artur M. S. Silva Prof. Vicente Gotor-Fernández Prof. Humberto Rodríguez-Solla 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(57):13104-13108
In this work, the first example of a radical stereodivergent reaction directed towards the stereoselective synthesis of both (R*,R*)- and (R*,S*)-2,2′-biflavanones promoted by samarium diiodide is reported. Control experiments showed that the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate a variety of 2,2′-biflavanones bearing different substitution patterns at the aromatic ring in good-to-quantitative yields, being both stereoisomers of the desired compounds obtained with total or high control of selectivity. A mechanism that explains both the generation of the corresponding 2,2′-biflavanones and the selectivity is also discussed. The structure and stereochemistry determination of each isomer was unequivocally elucidated by single-crystal X-ray diffraction experiments. 相似文献
54.
Soto NO Horstkotte B March JG López de Alba PL López Martínez L Cerdá Martín V 《Analytica chimica acta》2008,611(2):182-186
A multisyringe flow injection analysis system was used for the determination of hypochlorite in cleaning agents, by measurement of the native absorbance of hypochlorite at 292 nm. The methodology was based on the selective decomposition of hypochlorite by a cobalt oxide catalyst giving chloride and oxygen. The difference of the absorbance of the sample before and after its pass through a cobalt oxide column was selected as analytical signal. As no further reagent was required this work can be considered as a contribution to environmental friendly analytical chemistry. The entire analytical procedure, including in-line sample dilution in three steps was automated by first, dilution in a stirred miniature vessel, second by dispersion and third by in-line addition of water using multisyringe flow injection technique. The dynamic concentration range was 0.04-0.78 g L−1 (relative standard deviation lower than 3%), where the extension of the hypochlorite decomposition was of 90 ± 4%. The proposed method was successfully applied to the analysis of commercial cleaning products. The accuracy of the method was established by iodometric titration. 相似文献
55.
A rapid method of capillary zone electrophoresis is described to determine the oxidized (GSSG) and reduced (GSH) form of glutathione in plant tissue. In order to separate both analytes in a fused-silica capillary, the pH and composition of the electrolyte solution were optimized. The electrolyte composition was 100 mmol/L, borate 25 mmol/L Tris, and 0.2% w/v metaphosphoric acid (MPA), pH 8.2. Some instrumental conditions used to run the samples were hydrostatic injection for 30 s, 30 kV applied voltage, and UV detection (185 nm) at 25 degrees C. Linearity and useful range obtained for the calibration curves were optimum, with correlation coefficients about 0.999 in the 0-120 micromol/L range. The migration time was highly reproducible, less than 5 min being afforded to run a sample. Electrolyte buffer and samples required a careful pH control for optimal separation of both analytes. This aspect constitutes a critical analytical step when acids are used in the procedure for sample preparation. Simultaneous analysis of GSH and GSSG may provide a useful tool for comparative studies of plants in order to select those species with a potential capacity for detoxification from toxic elements or those appearing promising from phytoremediation for these elements. 相似文献
56.
57.
The affinity of geldanamycin (GA) for binding to heat shock protein 90 (HSP90) is 50- to 100-fold weaker than is the affinity of the structurally distinct natural product radicicol. X-ray crystallography shows that although radicicol maintains its free conformation when bound to HSP90, the conformation of GA is dramatically altered from an extended conformation with a trans amide bond to a kinked shape in which the amide group in the ansa ring has the cis configuration. We have performed ab initio quantum chemical calculations to demonstrate that the trans-cis isomeriztion of GA in solution is both kinetically and thermodynamically unfavorable. Thus, we propose that HSP90 catalyzes the isomerization of GA. We identify Ser113, a conserved residue outside the ATP binding pocket, as essential for the isomerization of GA. In support of this model, we show that radicicol binds equally well to both wild-type HSP90 and the Ser113 mutant, whereas the binding of GA to the Ser113 mutant is decreased significantly from its binding to wild-type HSP90. Based on this finding, a mechanism of keto-enol tautomerization of GA catalyzed by HSP90 is proposed. The added requirement of isomerization prior to tight binding may explain the enhanced binding affinity of GA for HSP90 in a cell extract versus in a purified form. 相似文献
58.
Monica Bartolomei Maurizio Cignitti Marina Cotta Ramusino Gianfranco La Manna 《Journal of Molecular Structure》1995,330(1-3):431-435
7,8-dihydroquinoline-4,5 (1H,6H)-dione (1) and 7,8-dihydroquinoline-2,5-(1H,6H)-dione (2) in their tautomeric oxo and hydroxy forms have been studied by ab initio Hartree-Fock calculations; tautomerization energies predict a more stable hydroxy structure having an intramolecular hydrogen bond for compound 1, whereas the oxo form is slightly-preferred for compound 2. Fourier Transform-Infra Red (FT-IR) spectra in CHCl3 solution indicate that the predicted most stable tautomers in the vapour phase remain as such. 相似文献
59.
Hematite with different particle sizes was obtained through isothermal annealing and mechanochemical ball-milling methods. The hematite phase is very stable under air atmosphere. The thermal stabilities of hematite under argon atmosphere were characterized by thermal analysis studies up to 800 °C using a simultaneous DSC–TG technique. The lattice parameters a and c of hematite with different particle sizes were extracted from the Rietveld structural refinement of powder X-ray diffraction patterns. Decomposition of hematite into a lower oxidation state in inert argon atmosphere was studied by the TG experiments for the first time and the enthalpy associated with the decomposition reaction was determined from the DSC studies. Particle size has a strong effect on the thermal behavior of hematite samples. Ball-milled hematite samples with smaller particle size showed that the phase transformation was extended to higher temperature range with larger enthalpy. Hematite with larger average particle size showed higher stability under argon atmosphere. 相似文献
60.