全文获取类型
收费全文 | 26979篇 |
免费 | 1648篇 |
国内免费 | 4225篇 |
专业分类
化学 | 26585篇 |
晶体学 | 547篇 |
力学 | 168篇 |
综合类 | 147篇 |
数学 | 1067篇 |
物理学 | 4338篇 |
出版年
2024年 | 36篇 |
2023年 | 224篇 |
2022年 | 531篇 |
2021年 | 503篇 |
2020年 | 579篇 |
2019年 | 1521篇 |
2018年 | 685篇 |
2017年 | 1500篇 |
2016年 | 926篇 |
2015年 | 838篇 |
2014年 | 1069篇 |
2013年 | 2292篇 |
2012年 | 1644篇 |
2011年 | 1758篇 |
2010年 | 1245篇 |
2009年 | 1498篇 |
2008年 | 1686篇 |
2007年 | 1767篇 |
2006年 | 1645篇 |
2005年 | 1471篇 |
2004年 | 1473篇 |
2003年 | 1187篇 |
2002年 | 1003篇 |
2001年 | 834篇 |
2000年 | 816篇 |
1999年 | 601篇 |
1998年 | 560篇 |
1997年 | 472篇 |
1996年 | 387篇 |
1995年 | 399篇 |
1994年 | 281篇 |
1993年 | 258篇 |
1992年 | 254篇 |
1991年 | 180篇 |
1990年 | 113篇 |
1989年 | 100篇 |
1988年 | 80篇 |
1987年 | 48篇 |
1986年 | 45篇 |
1985年 | 50篇 |
1984年 | 37篇 |
1983年 | 20篇 |
1982年 | 41篇 |
1981年 | 42篇 |
1980年 | 23篇 |
1979年 | 45篇 |
1978年 | 19篇 |
1977年 | 18篇 |
1976年 | 15篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Oleg Ya Borbulevych Ronald D ClarkAngela Romero Li TanMikhail Yu Antipin Vladimir N NesterovBeatriz H Cardelino Craig E MooreMohan Sanghadasa Tatiana V Timofeeva 《Journal of Molecular Structure》2002,604(1):73-86
Molecular and crystal structure of a series of derivatives of N,N-dimethyl-4-nitroaniline has been studied by both X-ray diffraction method and high-level ab initio calculations. According to these data, the dimethylamino groups were found to have a trigonal-pyramidal configuration and are considerably turned with respect to the ring plane in all molecules having a substituent in the ortho-position; on the contrary, this group is planar in the meta-substituted molecules. Topological analysis of the electron density function for all molecules studied within the framework of Bader's ‘atoms in molecules’ (AIM) theory revealed that introduction of a substituent into the ortho- or meta-position of the ring results in increasing of the contribution of the resonance forms different from the quinoid one. Contribution of the latter form is predominant for the structure of N,N-dimethyl-4-nitroaniline (1). Topological analysis of the electron density distribution was used to explain a decreasing of the molecular hyperpolarisabilites of the ortho- and meta-substituted compounds as compared with those for 1. 相似文献
942.
Maria Bocheska Maria Hoffmann Urszula Lesiska Emilia Luks Wanda Radecka-Paryzek 《Tetrahedron》2005,61(52):12307-12313
New compounds: 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diisopropoxyphosphorylpropoxy)calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-methoxyethoxyphosphorylpropoxy)calix[4]arene (2) were synthesized and their ionophoric properties in ion-selective membrane electrodes were studied in comparison with already described by us 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diethoxyphophorylpropoxy)calix[4]arene (3). Complexes of 1 with calcium(II), lanthanum(III), europium(III) and gadolinium(III) nitrates were prepared in direct reaction of the ligand and appropriate metal salts. They were characterized by spectral data (IR, UV/Vis, luminescence, NMR, ESI-MS) and elemental analysis. The similarity in complexing behavior of the (dialkoxyphosphoryl)propoxy-calix[4]arenes toward calcium and some lanthanides was observed. 相似文献
943.
V. N. Britsun A. N. Esipenko V. V. Pirozhenko M. O. Lozinskii 《Chemistry of Heterocyclic Compounds》2005,41(10):1334-1338
We have established that the products of aminolysis of 2-aryl-5-R-5,6-dihydro-7H-[1,2,4]triazolo-[5,1-b][1,3]thiazin-7-ones
in boiling ethanol are 3-R-3-(5-aryl-4H-1,2,4-triazol-3-ylsulfanyl)-propanamides, and at 180°C–210°C (depending on the structure
of the substituent R): 3-phenyl-4,5-dihydro-1H-1,2,4-triazoline-5-thione and 3-arylacrylamides or 3-(3-aryl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)propanamides.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1587–1592, October, 2005. 相似文献
944.
The general synthesis and a novel intramolecular nucleophilic aromatic substitution (SNAr) reaction of 2-carboxamido-3-arylquinazolin-4-ones, a potentially useful scaffold in the field of medicinal chemistry, are described. The synthetic utility of the SNAr reaction as a tool for the synthesis of secondary aryl amines, including diaryl amines, is also demonstrated. 相似文献
945.
N. V. Gorbulenko T. M. Tkachuk T. V. Shokol V. V. Semeniuchenko A. V. Turov V. P. Khilya 《Chemistry of Heterocyclic Compounds》2007,43(5):569-575
The interaction has been studied of a series of substituted 3-hetaryl-7-hydroxychromones with amino acids and formaldehyde
(reactants ratio 1: 1: 2 respectively). In the case of glycine and Het = 3-isoxazolyl the product of aminomethylation at position
8 of the chromone was obtained, and with other Het (including Het = 4-phenyl-1,2,4-triazol-3-yl) 2-[6-alkyl-3-hetaryl-4-oxo-9,10-dihydro-4H,8H-chromeno[8,7-e][1,3]-oxazin-9-yl]acetic
acids were formed. With β-alanine and Het = 4-phenyl-1,2,4-triazol-3-yl the corresponding β-substituted propionic acid was
synthesized, but proline did not participate in the reaction, leading to bis(6-ethyl-3-hetaryl-7-hydroxychromon-8-yl)methane.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 683–689, May, 2007. 相似文献
946.
Elka Kraleva Alla Spojakina Rumiana Edreva-Kardjieva Kveta Jiratova Lacezar Petrov 《Reaction Kinetics and Catalysis Letters》2007,92(1):111-119
HDS catalysts were prepared by loading H3PMo12O40 or H4PMo11V1O40 polyoxometallates on TiO2 (0.5 and 1.0 mmol (Mo+V)). Activity of the catalysts was tested in the HDS of thiophene. The activity of catalysts of low
concentration was 2–3 times higher than the activity of those of high concentration. Temperature programmed reduction (TPR)
and IR spectroscopy were used to determine the properties of the catalyst. TPR measurements proved that vanadium promotes
and stabilizes HDS activity due to an increase in the Mo5+/Mo4+ ratio. 相似文献
947.
Christopher M. Timperley Krystal E. Casey Stuart Notman David J. Sellers Nancy E. Williams Nichola H. Williams Gareth R. Williams 《Journal of fluorine chemistry》2006,127(12):1554-1563
Eighteen new fluorogenic analogues of organophosphorus nerve agents were synthesised and characterised. They included analogues of tabun, sarin, cyclosarin, soman, VX, and Russian VX, with the 7-oxy-4-methylcoumarin or 7-oxy-4-(trifluoromethyl)coumarin leaving group. These analogues inhibited acetylcholinesterase (AChE) effectively in vitro and therefore have potential as tools for the identification of novel organophosphatases in biological systems. Analogues of VX and Russian VX with the 7-amino-4-methylcoumarin group, although poor AChE inhibitors, may have utility for screening enzyme libraries for phosphoramidases capable of cleaving P-N bonds. 相似文献
948.
Iván da Silva Cristina González-Silgo Juan Rodríguez-Carvajal Lourdes Mestres 《Journal of solid state chemistry》2005,178(5):1601-1608
The crystal structure of potassium, rubidium and caesium fluoroberyllates have been re-examined by neutron powder diffraction at room temperature and at 1.5 K. Previously, their structures, obtained from X-ray data, were described in the Pn21a space group. However, the results obtained from Rietveld refinements, using powder neutron diffraction, at both temperatures, indicated that all structures are orthorhombic with space group Pnma. The known phase transition at high temperature is probably related to the appearance of a hexagonal pseudo-symmetry instead of the elimination of the mirror plane between the above mentioned orthorhombic space groups. A possible phase transition, at very low temperature, was discarded considering the stereochemical criteria concerning the structural stability of A2BX4 compounds. This was confirmed by thermal analysis. On the other hand, a modulated background has been detected in all samples during the refinements. This is compatible with the presence of an amorphous phase, coexisting with the crystalline phase, or with a disordered component within the main crystalline phase. Instead of using a polynomial function, the background was modelled by Fourier filtering improving the fit for all patterns. The radial distribution function (RDF) was obtained from the analysis of the calculated background and compared with the RDF from the average crystal structure. The advantages of neutron with respect to X-ray diffraction were evidenced for this type of compound with β-K2SO4-type structure. 相似文献
949.
AES depth profiles on ceramic powders (untreated/hydrolyzed/oxidized/ (Al, Y)2O3 coated Si3N4, [BaO, SiO2] coated Al2O3) are feasible on thin, homogeneous layers or m sized agglomerations prepared on an Au foil. By means of the depth profiles one can qualitatively characterize the coating around the particles. Factor analysis of the depth profiles on the differently treated Si3N4 powders suggests the existence of an Si2N2O phase on the oxidized sample.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday 相似文献
950.
离子液体存在下脂肪醛的环化三聚反应 总被引:1,自引:0,他引:1
Aliphatic aldehydes such as ethanal,propanal,n-butanal,isobutyraldehyde,n-valeraldehyde,isovaleraldehyde,n-hexanal and n-octanal were converted into the corresponding 2,4,6-trialkyl-1,3,5-trioxanes through cyclotrimer-ization in the presence of the ferric chloride based ionic liquids at room temperature without solvent in high selec-tivity.The effects of different ionic liquids,acidity of ionic liquids and temperature on cyclotrimerization were alsostudied.The results showed that the ferric chloride based ionic liquids(apparent molar fraction of FeCl_3(x(FeCl_3)=0.62))were a kind of efficient catalysts for the cyclotrimerization of aliphatic aldehyde which could be separatedconveniently from the reaction mixture and recycled without loss of catalytic activity.The conversion of isobu-tyraldehyde and the selectivity to 2,4,6-triisopropyl-1,3,5-trioxane were 91.1% and 99.8% respectively under opti-mum reaction condition(isobutyraldehyde 25.0 g,[Et_3NH]Cl/FeCl_3(x(FeCl_3)=0.62)1.0 g,25 ℃for 1 h). 相似文献