全文获取类型
收费全文 | 859篇 |
免费 | 9篇 |
国内免费 | 2篇 |
专业分类
化学 | 724篇 |
晶体学 | 5篇 |
力学 | 14篇 |
数学 | 31篇 |
物理学 | 96篇 |
出版年
2021年 | 6篇 |
2020年 | 6篇 |
2018年 | 5篇 |
2016年 | 9篇 |
2015年 | 7篇 |
2014年 | 14篇 |
2013年 | 38篇 |
2012年 | 38篇 |
2011年 | 53篇 |
2010年 | 14篇 |
2009年 | 32篇 |
2008年 | 49篇 |
2007年 | 41篇 |
2006年 | 44篇 |
2005年 | 52篇 |
2004年 | 52篇 |
2003年 | 52篇 |
2002年 | 35篇 |
2001年 | 13篇 |
2000年 | 8篇 |
1999年 | 13篇 |
1998年 | 14篇 |
1997年 | 4篇 |
1996年 | 10篇 |
1995年 | 5篇 |
1994年 | 6篇 |
1993年 | 6篇 |
1992年 | 4篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 12篇 |
1986年 | 7篇 |
1985年 | 17篇 |
1984年 | 13篇 |
1982年 | 7篇 |
1981年 | 16篇 |
1980年 | 14篇 |
1979年 | 10篇 |
1978年 | 12篇 |
1977年 | 11篇 |
1976年 | 10篇 |
1975年 | 15篇 |
1974年 | 6篇 |
1973年 | 7篇 |
1972年 | 5篇 |
1969年 | 7篇 |
1967年 | 7篇 |
1966年 | 4篇 |
排序方式: 共有870条查询结果,搜索用时 218 毫秒
21.
N. A. Keiko Yu. A. Chuvashev T. A. Kuznetsova L. G. Stepanova L. I. Larina L. V. Sherstyannikova M. G. Voronkov 《Russian Chemical Bulletin》1998,47(7):1379-1381
Cyanosilylation of α-butylthioacrolein with trimethylsilyl cyanide occurs as 1,2-addition. Concurrent rapid dimerization of
α-butylthioacrolein occurred both in the presence and in the absence of H2PtCl6·6H2O as a catalyst to give 2,5-dibutylthio-2,3-dihydro-4H-pyran-2-carbaldehyde, whose cyanosilylation afforded the corresponding cyanohydrin. The latter is prone to retrodiene degradation
upon heating.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1418–1420, July, 1998. 相似文献
22.
In peptide synthesis, hydrazides are important intermediates for the azide coupling method. A hydrazide is converted to the corresponding azide in the presence of an acid and a nitrite. When acetic acid (or formic acid) is used as the acid, partial acetylation (or formylation) of the hydrazide occurs as a side reaction. Formylation of the hydrazide is much faster than acetylation. Removal of the formyl group on the hydrazide with hydrazine and hydroxylamine was studied. The rate of deformylation with hydrazine treatment is faster than that with hydroxylamine treatment. 相似文献
23.
The polymerization of isobutyl vinyl ether was studied in a heterogeneous system using iron (II) sulfate calcined in air at various temperatures as a catalyst. The maximum activity was shown by the catalyst calcined at 700°C, which effected the polymerization at room temperature in a few seconds, while the sulfate treated at 750°C was totally inactive. Poly(vinyl ethyl ether) was also obtained by the FeSO4 (700°C) catalyst at room temperature. This catalyst formed the crystalline polymer (melting temperature 135–138°C) when the reaction was performed in toluene as solvent at room temperature. Poisoning experiments with Hammett indicators were carried out with the FeSO4 (700°C) catalyst. The treatment with n-butylamine rendered it inactive in the reaction of isobutyl vinyl ether, while its catalytic activity was little affected by dicinnamalacetone. On the basis of the observed results, the nature of active sites of catalyst is discussed. 相似文献
24.
Hasegawa E Takizawa S Iwaya K Kurokawa M Chiba N Yamamichi K 《Chemical communications (Cambridge, England)》2002,(17):1966-1967
Photoinduced electron transfer reaction of 2-bromomethyl-2-(3-butenyl)benzocyclic-1-alkanones with amines afforded 5-exo radical cyclization products while electron transfer reaction with samarium diiodide produced cyclopropanols. 相似文献
25.
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
26.
A procedure of analysis for small-angle X-ray scattering (SAXS) data has been established to obtain density fluctuation of supercritical fluids near the critical point. It is indispensable for the certain analysis to utilize both of high-quality SAXS data measured under stable thermodynamic condition and accurate P–ρ–T data in supercritical region. As a standard example, SAXS measurements have been performed for supercritical CO2, which is a suitable sample satisfying the condition for both experiment and analysis. The measurements were carried out along four isothermal conditions at reduced temperature of Tr = T/Tc = 1.020, 1.022, 1.043 and 1.064. Comparing the experimental density fluctuation with calculated one from the most reliable equation of state, the differences are within 8% at most. 相似文献
27.
We apply the singular value decomposition to compress the degrees of freedom of T3 amplitude for the CCSDT-1 method (compressed CCSDT-1). This method enables us to make the number of the T3 amplitudes less than that of the T2 amplitudes, making CCSDT-1 calculations much less expensive without losing accuracy. We perform test calculations on some atoms and molecules to investigate the applicability of this method. Computational results for the electronic energies as well as timings of these calculations are presented. 相似文献
28.
The potential of internal rotation about the
bond for vinyl methyl sulfide is applied with some modifications to rotation about the analogous bonds in the divinyl sulfide molecule. The potential energy map of divinyl sulfide is discussed with regard to the excited torsional vibrational states. Three stable conformers with approximately identical energies were established. For a complete picture of the rotational isomerism it is also necessary to take account of the torsional vibrational stationary states with large amplitude.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1531–1535, July, 1991. 相似文献
29.
Shigeyama M Ohgaya O Takeuchi H Hino T Kawashima Y 《Chemical & pharmaceutical bulletin》2001,49(2):129-133
We intended to develop a desired ointment base suitable for treatment of bedsores including the proliferation of granulation and epidermis. The main bedsore bacteria detected in our hospital were S. aureus in gram-positive coccus and P. aeruginosa in gram-negative bacillus. As the macrogol ointment (MO) was found to have bactericidal effects on these bacteria, MO was adopted as the base for the objective ointment. To improve the properties of the ointment base such as regulating the humidity of the exudation and controlling the release of antibiotics formulated in the ointment, co-formulating effects of various additives to MO were evaluated. The sustained release function of the ointment base was obtained by adding hydrophilic petrolatum (HP) to MO. However, the resultant ointment was found to have a poor humidity regulating property. On the other hand, MO containing 5% of hydroxypropyl cellulose (HPC) showed both the humidity regulating and the controlled drug releasing properties. It was considered that HPC particles dispersed in the ointment could be swelled by absorbing water to form a gel network. The curd tension meter tests for the ointments prepared with the various polymers showed that the MO-HPC base, which showed the highest sustained drug releasing property, was found to have the highest hardness. This result means that HPC formulated into the base forms the most rigid gel structure to resist the erosion of the ointment and to control the drug release. 相似文献
30.
Tetsuji Kametani Kazuo Kigasawa Mineharu Hiiragi Haruhide Ishimaru Seiji Haga Keiko Shirayama 《Journal of heterocyclic chemistry》1978,15(3):369-375
2-[4-(1-Oxo-2-isoindolinyl)phenyl]propanoic acid ( 1 ) having a potent analgesic and anti-inflammatory activity could be obtained by three methods, which were found to provide extremely useful ways for the synthesis of 1 from the industrial point of view. (E)- and (Z)-Isomers of 2-butenoic acid and oxiranecarboxylic acid derivatives as the intermedaites in the synthesis of 1 were separated and characterized. Furthermore, the optical resolution of (±)-2-[4-(1-oxo-2-isoindolinyl)phenyl]propanoic acid was successfully achieved using cinchonidine as a resolution reagent. 相似文献