全文获取类型
收费全文 | 3991篇 |
免费 | 422篇 |
国内免费 | 94篇 |
专业分类
化学 | 2785篇 |
晶体学 | 44篇 |
力学 | 400篇 |
综合类 | 16篇 |
数学 | 452篇 |
物理学 | 810篇 |
出版年
2024年 | 8篇 |
2023年 | 50篇 |
2022年 | 152篇 |
2021年 | 158篇 |
2020年 | 190篇 |
2019年 | 154篇 |
2018年 | 99篇 |
2017年 | 138篇 |
2016年 | 191篇 |
2015年 | 141篇 |
2014年 | 168篇 |
2013年 | 369篇 |
2012年 | 268篇 |
2011年 | 216篇 |
2010年 | 146篇 |
2009年 | 175篇 |
2008年 | 177篇 |
2007年 | 208篇 |
2006年 | 174篇 |
2005年 | 142篇 |
2004年 | 128篇 |
2003年 | 125篇 |
2002年 | 161篇 |
2001年 | 88篇 |
2000年 | 113篇 |
1999年 | 80篇 |
1998年 | 67篇 |
1997年 | 46篇 |
1996年 | 39篇 |
1995年 | 41篇 |
1994年 | 43篇 |
1993年 | 31篇 |
1992年 | 26篇 |
1991年 | 21篇 |
1990年 | 18篇 |
1989年 | 16篇 |
1988年 | 19篇 |
1987年 | 24篇 |
1986年 | 22篇 |
1985年 | 26篇 |
1984年 | 20篇 |
1983年 | 4篇 |
1982年 | 9篇 |
1981年 | 5篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有4507条查询结果,搜索用时 15 毫秒
71.
Gy. Marosi R. Lágner Gy. Bertalan P. Anna A. Tohl 《Journal of Thermal Analysis and Calorimetry》1996,47(4):1155-1161
Nucleating and transcrystallization behaviour of additives in engineering PP composites and the effect of modified interfacial structure is the subject of this series of papers. The first part concentrates on polypropylene/liquid crystalline polyester blends. Increased crystallisation temperature and degree of crystallinity of polypropylene is characteristic to the blends containing different amount of LCP additive. Transcrystallization process governs the formation of crystalline structure in these systems in course of isothermal crystallisation at 132C. The nucleating effect of LCP gives rise to more uniform crystalline structure in the polypropylene phase.The financial support of the OTKA 014194 is acknowledged with gratitude. 相似文献
72.
在量子化学对SiH与H2O和H2S反应计算的基础上,运用统计热力学和Wigner校正的Eyring过渡态理论,计算了上述两反应在200~2000 K温度范围内的热力学函数、平衡常数、频率因子A和速率常数随温度的变化。计算结果表明,两反应在低温下具有热力学优势,而在高温下具有动力学优势。比较两反应的计算结果发现,在相同的温度下,SiH与H2O反应比SiH与H2S反应放热较多,但速率常数却较小。SiH与H2O反应和前文报道的SiH与HF反应的比较表明,SiH与H2O反应放热较少,而且在相同温度下,速率常数也较小。 相似文献
73.
Andrei A. Gakh Bobby G. Sumpter Donald W. Noid Richard A. Sachleben Bruce A. Moyer 《Journal of inclusion phenomena and macrocyclic chemistry》1997,27(3):201-213
A computational neural network method was used for the prediction of stability constants of simple crown ether complexes. The essence of the method lies in the ability of a computer neural network to recognize the structure-property relationships in these host-guest systems. Testing of the computational method has demonstrated that stability constants of alkali metal cation (Na+, K+, Cs+)-crown ether complexes in methanol at 25 °C can be predicted with an average error of ±0.3 log K units based on the chemical structure of the crown ethers alone. The computer model was then used for the preliminary analysis of trends in the stabilities of the above complexes. 相似文献
74.
Alan P Marchand Bishwajit GangulyCarolina I Malagón Huiguo LaiWilliam H Watson 《Tetrahedron》2003,59(10):1763-1771
Diels-Alder cyclodimerization of 1,2,3,4,5-pentachlorocyclopentadiene (1) affords 2a as the exclusive reaction product. Diels-Alder cycloaddition of 1 to norbornadiene also proceeds stereoselectively to produce a single [4+2] cycloadduct, 4c. The structures of 2a and 4c were established unequivocally via application of single crystal X-ray crystallographic techniques. The origins of the observed diastereofacial selectivity in each of these cycloaddition processes have been investigated by application of semiempirical (AM1 Hamiltonian) and ab initio (Hartree-Fock 3-21G*) calculations. The computational results thereby obtained, which are based upon consideration of the kinetically favored transition state for each of the two cycloaddition reactions studied, are consistent with experiment. These semiempirical and ab initio methods also have been used to investigate the mechanisms of the Diels-Alder reactions that have been used to prepare aldrin and isodrin (7 and 8, respectively). The results thereby obtained suggest that isodrin formation via Diels-Alder cycloaddition of cyclopentadiene to 1,2,3,4,7,7-hexachloronorbornadiene proceeds with kinetic control of product stereochemistry. 相似文献
75.
Giovanni Zocchi 《Chemphyschem》2006,7(3):555-560
One common strategy for the detection of biomolecules is labeling either the target itself or an antibody that binds to it. Herein, a different approach, based on detecting the conformational change of a probe molecule induced by binding of the target is discussed. That is, what is being detected is not the presence of the target or the probe, but the conformational change of the probe. Recently, a single-molecule sensor has been developed that exploits this mechanism to detect hybridization of a single DNA oligomer to a DNA probe, as well as specific binding of a single protein to a DNA probe. Biomolecular recognition often involves large conformational changes of the molecules involved, and therefore this strategy may be applicable to other assays. 相似文献
76.
I.?S.?TerekhovaEmail author a?A.?Yu.?Manakov V.?V.?Feklistov Yu.?A.?Dyadin V.?YU.?Komarov D.?Yu.?Naumov 《Journal of inclusion phenomena and macrocyclic chemistry》2005,52(3-4):207-211
X-ray powder diffraction studies were performed of the polyhydrates, formed at positive temperature in swelled grains of carboxylic cation-exchange resins in the form of tetraisoamylammonium (cross-linked tetraisoamylammonium polyacrylates, differing in the degree of cross-linking: 1, 2 and 3%). It was shown that the polyhydrates exist as the crystalline phase under specific conditions, determined earlier by DTA technique. Diffraction patterns of the samples, recorded at the temperature +3 ± 1 °C, indicate that the polyhydrates crystallize in hexagonal symmetry, the unit cell parameters are close to a=12.25 Å, c=12.72 Å and do not depend significantly upon the degree of cross-linking. The suppositions were made concerning the size of hydrate crystallites, formed in the swelled grains of the studied resins.This revised version was published online in July 2005 with a corrected issue number. 相似文献
77.
Luigi R. Nassimbeni Sevi Papanicolaou Madeleine H. Moore 《Journal of inclusion phenomena and macrocyclic chemistry》1986,4(1):31-42
The structures of Ni(NCS)2(4-PhPy)4·4DMSO and Ni(NCS)2(3-MePy)4·CHCl3 have been elucidated. Movement of guest molecules through channels in the host structure was simulated by potential energy calculations. Ni(NCS)2(3,5-diMePy)4 does not form inclusion compounds. An intra-molecular potential energy study shows that theortho-hydrogens on the 3,5-dimethylpyridine ligands control the conformation of the molecule. The same result is obtained with the 4-methylpyridine ligand, which suggests that the extent of rotation of substituted pyridines about the Ni–N bounds is not a factor governing clathrate formation.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82030 (43 pages). 相似文献
78.
A new layered aluminophosphate, denoted AlPO-CJ12, has been synthesized in the system Al(OPri)3-H3PO4-tetramethylethylenediamine-triethyleneglycol and its structure solved by single-crystal X-ray diffraction analysis. It is further characterized by X-ray powder diffraction, ICP, TG, DTA, and elemental analyses. The compound has an empirical formula of [Al3P4O16][(CH3)2NHCH2CH2NH(CH3)2][H3O], and crystallizes in the triclinic space group P-1 (No. 2) with a=8.9907(6) Å b=9.8359(6) Å, c=14.5566(8) Å, α=75.872(3)°, β=88.616(3)°, γ=63.404(3)°, Z=2, R1=0.0451, and wR2=0.1094. The alternation of tetrahedral AlO4 and PO3 (=O) units forms a sheet structure with a 4×6×8 network. The inorganic layers stacked in an AAAA sequence are held together by the protonated organic amine and water molecules. The co-templating role of the water molecules is studied by the calculation of the nonbonding host-guest interaction energies through a computational simulation. 相似文献
79.
Photochemical reactions of benzyl, heteroaromaticmethyl and allylcobaloximes with aryldisulfonyl chlorides yield symmetrical disulfones. Allyl cobaloximes yield allyldisulfones as the major product whereas bibenzyl is the major product in benzylcobaloximes. A time dependent 1H NMR studies show that bibenzyl is formed from O-benzyldimethylglyoxime - a predominant product in the initial stage of the reaction. 相似文献
80.
The reaction between 5-amino-4-imino-1(2)-substituted-1(2)H-4,5-dihydropyrazolo[3,4-d]pyrimidines and several commercially available reactants afforded new heterocycles with a conserved pyrazolo[3,4-d]pyrimidine nucleus. The key intermediates employed proved to be suitable compounds by virtue of their two vicinal amino and imino groups that were used to obtain five, six and seven-membered rings. 相似文献