全文获取类型
收费全文 | 7383篇 |
免费 | 324篇 |
国内免费 | 25篇 |
专业分类
化学 | 6121篇 |
晶体学 | 43篇 |
力学 | 79篇 |
数学 | 718篇 |
物理学 | 771篇 |
出版年
2023年 | 59篇 |
2022年 | 47篇 |
2021年 | 301篇 |
2020年 | 184篇 |
2019年 | 186篇 |
2018年 | 122篇 |
2017年 | 130篇 |
2016年 | 265篇 |
2015年 | 265篇 |
2014年 | 287篇 |
2013年 | 442篇 |
2012年 | 556篇 |
2011年 | 591篇 |
2010年 | 402篇 |
2009年 | 367篇 |
2008年 | 511篇 |
2007年 | 504篇 |
2006年 | 402篇 |
2005年 | 439篇 |
2004年 | 327篇 |
2003年 | 279篇 |
2002年 | 248篇 |
2001年 | 83篇 |
2000年 | 63篇 |
1999年 | 67篇 |
1998年 | 43篇 |
1997年 | 60篇 |
1996年 | 48篇 |
1995年 | 40篇 |
1994年 | 28篇 |
1993年 | 29篇 |
1992年 | 24篇 |
1991年 | 31篇 |
1990年 | 26篇 |
1989年 | 20篇 |
1988年 | 17篇 |
1987年 | 29篇 |
1986年 | 14篇 |
1985年 | 27篇 |
1984年 | 28篇 |
1983年 | 20篇 |
1982年 | 15篇 |
1981年 | 9篇 |
1980年 | 14篇 |
1979年 | 8篇 |
1978年 | 12篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1975年 | 9篇 |
1974年 | 6篇 |
排序方式: 共有7732条查询结果,搜索用时 406 毫秒
41.
Ana Bellomo 《Tetrahedron letters》2007,48(17):3047-3051
Diasterodivergent episulfides were chemoenzymatically derived from bromobenzene by sequential toluene dioxygenase dihydroxylation, followed by chemical epoxidation and thiolysis. The epoxide ring-opening by thiocyanate ion under literature conditions rendered the corresponding hydroxy thiocyanates and not the thiiranes as usually observed. Ring closing under carefully optimized conditions allowed the preparation of optically pure thiiranes that are key precursors for the preparation of thioconduritols and pseudodisaccharides. 相似文献
42.
Ana M. Piloto 《Tetrahedron》2006,62(51):11955-11962
The properties of three oxobenzo[f]benzopyrans as new fluorogenic photolabile protecting groups for the carboxylic function of amino acids were studied. Fluorescent amino acid conjugates were efficiently prepared and characterised. Photodeprotection of these compounds was carried out by irradiation at 300, 350 and 419 nm, the most suitable wavelength being 350 nm, on account of short irradiation times and good deprotection yields. 相似文献
43.
Om Prakash Ajay Kumar Richa Prakash Rosa M. Claramunt Ibon Alkorta José Elguero 《Tetrahedron》2005,61(27):6642-6651
Treatment of α,β-unsaturated carbonyl compounds, obtained by the reaction of DHA and aromatic (or heteroaromatic) aldehydes, with o-aminothiophenol results in the formation of 1,5-benzothiazepines and/or 1,4-benzothiazines depending upon the reaction conditions and structure of the aldehydes. The products were characterized by the combined use of multinuclear 1D and 2D NMR and GIAO/DFT calculations of 1H, 13C and 15N chemical shifts. The tautomerism of these compounds in solution was determined, they have an exocyclic CC double bond. 相似文献
44.
D. S. Gouveia R. Rosenhaim M. A. M. A. de Maurera S. J. G. Lima C. A. Paskocimas E. Longo A. G. Souza I. M. G. Santos 《Journal of Thermal Analysis and Calorimetry》2004,75(2):453-460
With the aim of obtaining materials with applications in pigments, CoxZn7-xSb2O12 spinels were synthesized using the Pechini method. This method consists in the formation of a polymeric net, where the metallic
cations are homogeneously distributed. In this work, two types of alcohol (ethyl glycol and ethylene glycol) were used for
the synthesis of a zinc antimoniate spinel, CoxZn7-xSb2O12 (x=0-7). The materials were characterized by termogravimetry (TG) and differential thermal analysis (DTA). TG results indicated
a decrease in total mass loss when cobalt was added to the solution substituting zinc, for samples prepared using the two
different alcohols. Decomposition temperatures, obtained by TG and DTA, presented a decreasing behavior as cobalt was added
to the material. In relation to the alcohols, all results indicated a better polymerization of the resin when ethylene glycol
was used, being the most indicated one for cation immobilization. X-ray diffraction did not show differences between the two
alcohols - both presented the spinel phase (Co, Zn)2.33Sb0.67O4. Samples with higher quantity of cobalt also presented ilmenite phase (Co, Zn)Sb2O6.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
45.
46.
The method of differences is used to establish that every 2-regular multigraph onv– 10,2 (mod 3) points occurs as the neighbourhood graph of an element in a twofold triple system of orderv, with two exceptions: C2C3and C3C3.Dedicated to Professor Hanfried Lenz on the occasion of his seventieth birthday 相似文献
47.
Silva L Coutinho A Fedorov A Prieto M 《Journal of photochemistry and photobiology. B, Biology》2003,72(1-3):17-26
Nystatin is a polyene antibiotic frequently applied in the treatment of topical fungal infections. In this work, a 7-nitrobenz-2-oxa-1,3-diazole (NBD) hexanoyl amide derivative of nystatin was synthesized and its detailed photophysical characterization is presented. The average conformation of the labelled antibiotic in tetrahydrofuran, ethanol and methanol was determined by intramolecular (tetraene to NBD) fluorescence resonance energy transfer measurements. At variance with the literature [Can. J. Chem. 63 (1985) 77-85], it was concluded that there is no need to invoke a solvent-dependent conformational equilibrium between extended and closed conformers of the antibiotic, because the mean tetraene-to-NBD separating distance was found to remain constant (approximately 18 A) in all the solvents studied. In addition, the large solvent dependence of the fluorescence anisotropy observed for the non-derivatized nystatin, was rationalized on the basis of the prolate ellipsoidal geometry of the molecule. It was concluded that the rod shaped and amphipathic antibiotic remains monomeric in different solvents within the concentration range studied (2-20 microM). 相似文献
48.
Pérez-Juste I Graña AM Carballeira L Mosquera RA 《The Journal of chemical physics》2004,121(21):10447-10455
Linear sulfur-carbon chains C(n)S (n=1-6) of astronomical interest were examined by means of several theoretical methods. The three smallest compounds of the series were chosen to evaluate the performance of several computational models, including Hartree-Fock theory, density functional theory with the Becke's three parameter exchange functional and the correlation functional of Lee, Yang, and Parr (B3LYP), and electron-correlated methods (second-order Moller-Plesset perturbation method (MP2), configuration interaction method including single and double excitations (CISD), and quadratic configuration interaction method including single and double excitations (QCISD) in combination with a large variety of basis sets. The systematic comparison between the experiment and theory indicates that the B3LYP/6-311G** method can be considered suitable for the study of the electronic structures of the C(n)S compounds. The electronic ground states of the C(n)S molecules alternate between 1Sigma and 3Sigma for odd and even values of n, respectively. The B3LYP/6-311G** wave functions for these electronic ground states were analyzed by means of the atoms in molecules (AIM) and natural bond orbital (NBO) methods. Both approaches suggest that the electronic structures for the singlet and triplet compounds must be considered separately. According to the NBO method, singlet compounds can be properly represented by acetylenic structures with alternating single and triple bonds (S[triple bond]C-C[triple bond]C...). However, triplet compounds are better described by means of double bond-double bond cumulenic structures (S=C=C=C=C...) as a consequence of the average between different alpha and beta electronic densities. AIM delocalization indexes and NBO interactions between localized orbitals also indicate that these structures are strongly pi delocalized. Finally, the different singlet and triplet structures proposed provide a consistent explanation for the geometries, dipole moments, and spin-density values of the C(n)S compounds studied. 相似文献
49.
Four new fluorescent macrocyclic ligands derived from biphenyl are described. The new compounds have been used in liquid-liquid extraction experiments and the influence of pH has been studied in those ligands containing carboxylic groups. The results obtained for the latter ligands have been compared with those observed in the presence of an external acid. 相似文献
50.
Ana A. C. Pacheco Arnaldo F. da Silva Filho Kristoffer Kortsen Magnus W. D. Hanson-Heine Vincenzo Taresco Jonathan D. Hirst Muriel Lansalot Franck D'Agosto Steven M. Howdle 《Chemical science》2021,12(3):1016
Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerisation of methyl methacrylate (MMA) is performed in supercritical carbon dioxide (scCO2) with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. Kinetic studies of the polymerisation in scCO2 also confirm these data. By contrast, only poor control of MMA polymerisation is obtained in toluene solution, as would be expected for this CTA which is better suited for acrylates. In this regard, we select a range of CTAs and use them to determine the parameters that must be considered for good control in dispersion polymerisation in scCO2. A thorough investigation of the nucleation stage during the dispersion polymerisation reveals an unexpected “in situ two-stage” mechanism that strongly determines how the CTA works. Finally, using a novel computational solvation model, we identify a correlation between polymerisation control and degree of solubility of the CTAs. All of this ultimately gives rise to a simple, elegant and counterintuitive guideline to select the best CTA for RAFT dispersion polymerisation in scCO2.RAFT dispersion polymerisation of methyl methacrylate is performed in scCO2 with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. 相似文献