全文获取类型
收费全文 | 13216篇 |
免费 | 433篇 |
国内免费 | 45篇 |
专业分类
化学 | 10585篇 |
晶体学 | 73篇 |
力学 | 210篇 |
数学 | 1671篇 |
物理学 | 1155篇 |
出版年
2023年 | 89篇 |
2022年 | 249篇 |
2021年 | 508篇 |
2020年 | 283篇 |
2019年 | 334篇 |
2018年 | 253篇 |
2017年 | 213篇 |
2016年 | 435篇 |
2015年 | 443篇 |
2014年 | 419篇 |
2013年 | 835篇 |
2012年 | 861篇 |
2011年 | 973篇 |
2010年 | 594篇 |
2009年 | 581篇 |
2008年 | 824篇 |
2007年 | 806篇 |
2006年 | 689篇 |
2005年 | 623篇 |
2004年 | 533篇 |
2003年 | 449篇 |
2002年 | 438篇 |
2001年 | 169篇 |
2000年 | 136篇 |
1999年 | 114篇 |
1998年 | 114篇 |
1997年 | 100篇 |
1996年 | 130篇 |
1995年 | 88篇 |
1994年 | 85篇 |
1993年 | 78篇 |
1992年 | 61篇 |
1991年 | 76篇 |
1990年 | 55篇 |
1989年 | 74篇 |
1988年 | 62篇 |
1987年 | 50篇 |
1986年 | 53篇 |
1985年 | 64篇 |
1984年 | 84篇 |
1983年 | 46篇 |
1982年 | 66篇 |
1981年 | 59篇 |
1980年 | 55篇 |
1979年 | 47篇 |
1978年 | 54篇 |
1977年 | 38篇 |
1976年 | 33篇 |
1975年 | 24篇 |
1963年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
201.
Gancitano P Ciriminna R Testa ML Fidalgo A Ilharco LM Pagliaro M 《Organic & biomolecular chemistry》2005,3(13):2389-2392
Valuable organic compounds such as alpha-hydroxy acids are easily synthesised with relevant selectivity enhancement using a sol-gel hydrophobized nanostructured silica matrix doped with the organocatalyst TEMPO: A materials science based synthetic route which cannot be achieved via classical homogeneous synthesis. 相似文献
202.
Koulouri S Malamidou-Xenikaki E Spyroudis S Tsanakopoulou M 《The Journal of organic chemistry》2005,70(22):8780-8784
[reaction: see text] Thermal decomposition of phenyliodonium ylide of 2-hydroxy-1,4-naphthoquinone (lawsone) in the presence of indole derivatives affords 3-acylated indoles existing in their enol forms, through a ring contraction and alpha,alpha'-dioxoketene formation reaction. The same reactants afford 3-(3-indolyl)-2-hydroxy-1,4-naphthoquinones in a copper-catalyzed reaction. Enamines, among other C-nucleophiles tested, give analogous results. 相似文献
203.
Paolesse R Nardis S Venanzi M Mastroianni M Russo M Fronczek FR Vicente MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1192-1197
5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry. 相似文献
204.
Maria Jurkiewicz-Herbich 《Journal of Electroanalytical Chemistry》1981,119(2):275-288
Differential capacity and interfacial tension measurements were carried out on mercury for acetone+nitromethane mixtures with KPF6 as a supporting electrolyte. On the basis of Gibbs adsorption equation and Guggenheim's model of the surface phase the composition of the surface layer was estimated for different acetone contents and different charges on the mercury electrode. The results obtained indicate that the positive acetone adsorption is marked at negative charges with maximum at σm=?0.07 C m?2, but is practically non-existent at zero and positive charges. 相似文献
205.
Jose L. Zurita Maria L. G. de Soria Miguel A. Postigo Miguel Katz 《Journal of solution chemistry》1987,16(2):163-170
Densities, viscosities, enthalpies, vapor-liquid equilibria, and surface tensions were determined at 25°C for the 2-propanol+dichloromethane system. From the experimental results excess volumes, viscosities, enthalpies, Gibbs energies, and excess surface tensions were calculated. An attempt has been made to explain the observed deviations from ideal behavior on the basis of intermolecular interactions. 相似文献
206.
Guido Audisio Maria Grassi Piero Traldi Sergio Daolio 《Journal of mass spectrometry : JMS》1985,20(5):327-330
The positive ion chemical ionization (CI (isobutane)), negative ion chemical ionization (NICI) electron attachment (CH4, He) and NICI (OH?) spectra of the title compounds have been studied in detail with the aid of deuterium-labelled derivatives. The obtained results show that under CI conditions the stereospecificity is retained. Interesting correlations with the condensed phase epimerization yields are emphasized. 相似文献
207.
Ab initio calculations have been carried out on the 1,3,5,7- and 1,2,4,7-tetraene configurations of the cyclooctatetraenyl radical at UHF, ROHF, MCSCF, ROCISD, QCISD, and CCSD(T) levels of theory with 6-311G(d,p) and cc-pVDZ basis sets. Although spin contamination is present, the ROCISD calculations support the energies obtained from less intensive, UHF-based coupled cluster calculations over the energies obtained from MCSCF analysis of the pi-electron orbitals. The 1,3,5,7-form is a local minimum at the coupled cluster levels, higher in energy than the resonance-stabilized 1,2,4,7-form by 10-13 kJ/mol, but bounded by a barrier of less than 0.5 kJ/mol. The isomerization surface connecting these two structures is described and results reported from integration of the vibrational Schr?dinger equation on that surface. Excited vibrational states at energies just above the isomerization barrier are dominated by the character of the 1,3,5,7-tetraenyl radical, which suggests that chemistry involving this intermediate at typical combustion temperatures may branch at this juncture. 相似文献
208.
In-depth kinetic and mechanistic studies on the reversible binding of NO to water-soluble iron(III) porphyrins as a function of pH revealed unexpected reaction kinetics for monohydroxo-ligated (P)Fe(III)(OH) species formed by deprotonation of coordinated water in diaqua-ligated (P)Fe(III)(H(2)O)(2). The observed significant decrease in the rate of NO binding to (P)Fe(OH) as compared to that of (P)Fe(H(2)O)(2) does not conform with expectations based on previous mechanistic work on NO-heme interactions, which would point to a diffusion-limited reaction for the five-coordinate Fe(III) center in (P)Fe(OH). The decrease in rate and an associatively activated mode of NO binding observed at high pH is ascribed to an increase in the activation barrier related to spin state and structural changes accompanying NO coordination to the high-spin (P)Fe(III)(OH) complex. The existence of such a barrier has previously been observed in the reactions of five-coordinate iron(II) hemes with CO and is evidenced for the first time for the process involving coordination of NO to the iron heme complex. The observed reactivity pattern, relevant in the context of studies on NO interactions with synthetic and biologically important hemes (in particular, hemoproteins), is reported here for an example of a simple water-soluble iron(III) porphyrin [meso-tetrakis(sulfonatomesityl)porphinato]-iron(III), (TMPS)Fe(III). 相似文献
209.
Utilization of ferric chelate complex of trans-1,2-cyclohexanediaminetetraacetic acid (CDTA) for the oxidative scrubbing of H2S and CH3SH in Kraft mill streams can be beneficial from the standpoints of iron protection against precipitation and oxygen-mediated regenerative oxidation of the ferrous chelate CDTA. The physical solubility of methyl mercaptan in CDTA–Fe(III) complex cannot be measured directly because of oxidation of the sulfur-bearing gaseous species with the ferric chelate. Therefore, this investigation was carried out to determine the gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous iron-free CDTA solutions and non-reacting ferrous chelate solutions (CDTA–Fe(II) complex), using the static headspace method with an estimated accuracy of about 2%. Experiments with aqueous solutions of chelate concentrations varying between 38 and 300 mol m−3 were carried out at temperatures between 298 and 333 K and atmospheric pressure. It was shown that the methyl mercaptan solubility decreases with increasing temperature for all systems but was not much influenced, in the studied conditions, by the chelate concentration especially at larger temperatures. 相似文献
210.
Improved quantification limits in chiral capillary electrochromatography by peak compression effects
The peak compression effect has been applied to improve quantification limits in chiral capillary electrochromatography (CEC). A stationary phase based on the chiral selector vancomycin (Chirobiotic V) was used for separations of the enantiomers of mianserin. By adding solvents with a low dielectric constant, e.g. 2-propanol or tetrahydrofuran, to the sample solution, peak compression could be induced. The plate numbers for the minor enantiomer increased from approximately 100,000 to 1.4-1.6 million plates/m, when the composition of the mobile phase was adjusted so that the analyte eluted within either one of two system zones originating from the sample solution. A 10-fold improvement in the quantification limit for the minor enantiomer was obtained compared to elution under non-focused conditions. 相似文献