全文获取类型
收费全文 | 6389篇 |
免费 | 167篇 |
国内免费 | 25篇 |
专业分类
化学 | 4306篇 |
晶体学 | 65篇 |
力学 | 180篇 |
数学 | 753篇 |
物理学 | 1277篇 |
出版年
2021年 | 45篇 |
2020年 | 64篇 |
2019年 | 68篇 |
2018年 | 43篇 |
2017年 | 42篇 |
2016年 | 122篇 |
2015年 | 92篇 |
2014年 | 117篇 |
2013年 | 257篇 |
2012年 | 343篇 |
2011年 | 397篇 |
2010年 | 212篇 |
2009年 | 171篇 |
2008年 | 334篇 |
2007年 | 366篇 |
2006年 | 370篇 |
2005年 | 336篇 |
2004年 | 280篇 |
2003年 | 251篇 |
2002年 | 232篇 |
2001年 | 99篇 |
2000年 | 93篇 |
1999年 | 51篇 |
1998年 | 76篇 |
1997年 | 71篇 |
1996年 | 103篇 |
1995年 | 67篇 |
1994年 | 84篇 |
1993年 | 87篇 |
1992年 | 61篇 |
1991年 | 74篇 |
1990年 | 65篇 |
1989年 | 68篇 |
1988年 | 66篇 |
1987年 | 44篇 |
1986年 | 48篇 |
1985年 | 91篇 |
1984年 | 81篇 |
1983年 | 58篇 |
1982年 | 82篇 |
1981年 | 88篇 |
1980年 | 78篇 |
1979年 | 71篇 |
1978年 | 78篇 |
1977年 | 73篇 |
1976年 | 63篇 |
1975年 | 66篇 |
1974年 | 65篇 |
1973年 | 70篇 |
1972年 | 38篇 |
排序方式: 共有6581条查询结果,搜索用时 15 毫秒
91.
The successful separation of 2- and 3-methyl-substituted positional isomers of butanol, butyl acetate, and butanoic acid and its ethyl ester, is reported. These compounds are of interest in the study of wine flavour, however the separation of the 2- and 3-methyl isomers may present problems, and more so in the presence of the wine matrix components, when single capillary column gas chromatography (GC) is used. The strategy to achieve separation was based on the use of shape-selective cyclodextrin derivative (CDD) capillary columns (commonly referred to as chiral columns). These columns provide simultaneous resolution of the enantiomeric pairs of the 2-methyl isomers, and at the same time the ability to separate the 3-methyl isomer from the 2-methyl is achieved in all but the case of the ( S)-2- and 3-methylbutanol. The advantages of using shape-selective columns to perform this study is demonstrated, with coupling of two CDD columns giving improved separations of these compounds. Although these compounds are relatively volatile, cryogenic modulated comprehensive two-dimensional GC was shown to provide good pulsed peak profiles with chiral separation in the first dimension when a thicker film trapping column segment was employed. The components of interest were well separated from other wine matrix components. 相似文献
92.
Soltero-Higgin M Carlson EE Phillips JH Kiessling LL 《Journal of the American Chemical Society》2004,126(34):10532-10533
The flavoenzyme uridine 5'-diphosphate (UDP)-galactopyranose mutase (UGM) plays a key role in the cell wall biosynthesis of many pathogens, including Mycobacterium tuberculosis. Using a synthetic fluorescent ligand, we screened 16 000 compounds in a fluorescence polarization assay. Effective inhibitors of UGM were identified. 相似文献
93.
Gallium metal is effective in mediating the allylation of various carbonyl compounds and imines under solvent-free conditions, with the application of sonic energy, affording the corresponding homoallylic alcohols and amines. The imines themselves were also prepared under solventless conditions in high yield, thereby establishing a two-step solvent-free synthesis of homoallylic amines. In comparison, indium metal produced a mixture of the desired homoallylic secondary amine and the bis-allylated species via an iminium ion intermediate. 相似文献
94.
A solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) sampling and analysis method was developed for bis(diisopropylaminoethyl)disulfide (a degradation product of the nerve agent VX) in soil. A 30-min sampling time with a polydimethylsiloxane-coated fiber and high temperature alkaline hydrolysis allowed detection with 1.0 microg of VX spiked per g of agricultural soil. The method was successfully used in the field with portable GC-MS instrumentation. This method is relatively rapid (less than 1 h), avoids the use of complex preparation steps, and enhances analyst safety through limited use of solvents and decontamination of the soil before sampling. 相似文献
95.
Paul D. Beer Zheng Chen Philip A. Gale Jennifer A. Heath Rachel J. Knubley Mark I. Ogden Michael G. B. Drew 《Journal of inclusion phenomena and macrocyclic chemistry》1994,19(1-4):343-359
The synthesis, metal, ammonium and alkyl ammonium cation coordination chemistry and electrochemical recognition studies of new diester-and diamide-calix[4]arenediquinone receptors are described. In addition the synthesis and coordination properties of a novel diamide benzo-15-crown-5-calix[4]arene molecule is reported.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes. 相似文献
96.
Wright RJ Phillips AD Hino S Power PP 《Journal of the American Chemical Society》2005,127(13):4794-4799
The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons. 相似文献
97.
Gregory M. Anstead Kathryn E. Carlson Philip R. Kym Kwang-Jin Hwang John A. Katzenellenbogen 《Photochemistry and photobiology》1993,58(6):785-794
Abstract The absorption and emission characteristics of five hydroxytetrahydrochrysenes substituted with acceptor groups (nitro, cyano, methylketone, 1° amide and methyl ester) (THC-NO2, THC-CN, THC-COCH3, THC-CONH2 and THC-CO2CH3, respectively) were investigated in an extensive set of solvents. The order of absorption and fluorescence bathochromicity are: THC-NO2 > THC-COCH3 > THC-CN ≥ THC-CO2CH3 > THC-CONH2 and THC-NO2 >> THC-COCH3 > THC-CO2CH3 > THC-CN > THC-CONH2, respectively. The emission spectra of these compounds are sensitive to the solvent polarity (ET[30] scale) in the order: THC-NO2 > THC-COCH3 > THC-CO2CH3 > THC-CONH2 > THC-CN. The response of the emission maxima of these compounds to the solvent polarity and hydrogen-bond donor/acceptor properties (π*/α/β and acity/basity scales) was also determined. The emission energies of THC-NO2 were most sensitive to π*, β, acity, and basity of the solvent; those of the amide were least sensitive to the solvent π*, β, and basity. The ground- and excited-state dipole moments were determined by semiempirical molecular orbital calculations and the absorption/fluorescence solvent-shift method, respectively. THC-NO2 had the largest ground- and excitedstate moments. The ester and amide had the smallest ground- and excited-state moments, respectively. In general, unsatisfactory results were obtained for correlations of the emission and absorption energies, fluorescence solvatochromism and the ground- and excited-state dipole moments with the Hammett substituent constants of the five acceptor groups. Acceptable correlations were obtained for the absorption and emission energies and the fluorescence solvatochromism with the substituent constants if the cyano compound was excluded. 相似文献
98.
Raymond J. Abraham Lee Griffiths Philip Loftus 《Journal of computational chemistry》1982,3(3):407-416
Alternative methods of estimating atomic charges in haloalkanes are presented, derived from quantum mechanical and classical treatments. A scheme based on a breakdown of the transmission of charge by polar atoms into one-bond, two-bond, and three-bond additive contributions is given, in which the one-bond effect is proportional to the difference in the electronegativities of the bonded atoms, and the two- and three-bond effects functions of the atomic electronegativity and polarizability. Suitable developments of the basic scheme, including an iterative self-consistent process, give calculated dipole moments for a variety of haloalkanes in good agreement with the observed values. The atomic charges obtained by this scheme are compared with other estimates of these charges. They are similar to those derived from a simple LCAO –MO scheme but differ from those obtained by population analysis of more refined quantum mechanical calculations. 相似文献
99.
Tetraethylammonium perchlorate, compared to lithium perchlorate as background electrolyte for the reduction of pyridinium ion in pyridine, is effective over a wider potential range, but is more difficult to obtain in a pure state; slight amounts of impurities do not, however, affect the pyridinium wave. The pyridinium wave produced in 0.1 M Et4NClO4 may occur at a more negative potential than the main pyridinium wave in 0.1 M LiClO4, depending on the source of the pyridinium ion, but still appears to be due to a diffusion-controlled reduction, whose limiting current is linearly proportional to concentration; the prewave observed in LiCl04 background generally does not appear in Et4NClO4 background. Specific differences in the effect of Li(I), Na(I) and Et4N(I) background cation appear to be due to electrocapillary phenomena and perhaps to the extent of solvation of the ions. The constancy of current for solutions containing acetic acid with added acetate, pyridinium nitrate with added nitrate, and benzoic acid with added benzoate indicate that the pyridinium reduction is independent of anion concentration. 相似文献
100.
Kwok WM Zhao C Guan X Li YL Du Y Phillips DL 《The Journal of chemical physics》2004,120(19):9017-9032
A combined experimental and theoretical study of the ultraviolet photolysis of CH2I2 in water is reported. Ultraviolet photolysis of low concentrations of CH2I2 in water was experimentally observed to lead to almost complete conversion into CH2(OH)2 and 2HI products. Picosecond time-resolved resonance Raman spectroscopy experiments in mixed water/acetonitrile solvents (25%-75% water) showed that appreciable amounts of isodiiodomethane (CH2I-I) were formed within several picoseconds and the decay of the CH2I-I species became substantially shorter with increasing water concentration, suggesting that CH2I-I may be reacting with water. Ab initio calculations demonstrate the CH2I-I species is able to react readily with water via a water-catalyzed O--H-insertion and HI-elimination reaction followed by its CH2I(OH) product undergoing a further water-catalyzed HI-elimination reaction to make a H2C=O product. These HI-elimination reactions produce the two HI leaving groups observed experimentally and the H2C=O product further reacts with water to produce the other final CH2(OH)2 product observed in the photochemistry experiments. These results suggest that CH2I-I is the species that reacts with water to produce the CH2(OH)2 and 2HI products seen in the photochemistry experiments. The present study demonstrates that ultraviolet photolysis of CH2I2 at low concentration leads to efficient dehalogenation and release of multiple strong acid (HI) leaving groups. Some possible ramifications for the decomposition of polyhalomethanes and halomethanols in aqueous environments as well as the photochemistry of polyhalomethanes in the natural environment are briefly discussed. 相似文献