全文获取类型
收费全文 | 382篇 |
免费 | 24篇 |
专业分类
化学 | 367篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 3篇 |
物理学 | 31篇 |
出版年
2023年 | 3篇 |
2021年 | 7篇 |
2020年 | 3篇 |
2019年 | 6篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 10篇 |
2013年 | 16篇 |
2012年 | 39篇 |
2011年 | 36篇 |
2010年 | 14篇 |
2009年 | 9篇 |
2008年 | 39篇 |
2007年 | 22篇 |
2006年 | 39篇 |
2005年 | 29篇 |
2004年 | 24篇 |
2003年 | 13篇 |
2002年 | 11篇 |
2001年 | 3篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1988年 | 1篇 |
1987年 | 4篇 |
1985年 | 4篇 |
1984年 | 7篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1977年 | 4篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 1篇 |
1971年 | 2篇 |
排序方式: 共有406条查询结果,搜索用时 31 毫秒
21.
A combination of fluorobenziodoxole (FBX) and BF3 ? OEt2 in cyclopentyl methyl ether promotes regio‐ and stereoselective addition of benziodoxole and methoxy groups to alkynes. This difunctionalization reaction tolerates a variety of functionalized internal and terminal alkynes to afford trans‐β‐alkoxyvinylbenziodoxoles, which represent versatile precursors to stereochemically well‐defined multisubstituted vinyl ethers. The reaction is proposed to involve cleavage of the I?F bond of FBX by BF3, followed by electrophilic activation of the alkyne by the resulting cationic IIII species that triggers the nucleophilic addition of the ethereal oxygen. 相似文献
22.
Computed Relative Populations of D2(22)‐C84 Endohedrals with Encapsulated Monomeric and Dimeric Water 下载免费PDF全文
Prof. Zdeněk Slanina Prof. Filip Uhlík Prof. Shigeru Nagase Prof. Xing Lu Prof. Takeshi Akasaka Prof. Ludwik Adamowicz 《Chemphyschem》2016,17(8):1109-1111
Water monomer and dimer encapsulations into D2(22)‐C84 fullerene are evaluated. The encapsulation energy is computed at the M06‐2X/6‐31++G** level, and it is found that the monomer and dimer storage in C84 yields an energy gain of 10.7 and 17.4 kcal mol?1, respectively. Encapsulation equilibrium constants are computed by using partition functions based on the M06‐2X/6‐31G** and M06‐2X/6‐31++G** molecular data. Under high‐temperature/high‐pressure conditions, similar to that for the encapsulation of rare gases in fullerenes, the computed (H2O)2@C84‐to‐H2O@C84 ratio is close to 1:2. 相似文献
23.
T. Kato T. Akasaka K. Kobayashi S. Nagase K. Yamamoto H. Funasaka T. Takahashi 《Applied magnetic resonance》1996,11(2):293-300
We observed photochemical and thermal addition of disilirane to the LaC82-A isomer, which give new ESR active species. Both ESR spectra of the adducts in photo- and thermal reactions are well simulated by at least six octet components, and the isotropic La coupling constants and g-factors of the six octet components are determined. On the other hand, the reaction of the LaC82-B isomer with disilirane gives no ESR active species. This fact is also verified by mass spectroscopic measurements. The different reactivities with disilirane of the two isomers are not interpreted by a popular view that the two isomers have a different C82 cage structure, but we rather suggest that the origin of the isomers of metallofullerenes should be re-examined. 相似文献
24.
Nakano K Suemura N Yoneda K Kawata S Kaizaki S 《Dalton transactions (Cambridge, England : 2003)》2005,(4):740-743
Two series of pyrazolato bridged dinuclear NCS and NCBH3 diiron(II) complexes with various types of 3- or 4-substituted pyridines, [{Fe(NCS or NCBH3)(X-py)}2(mu-bpypz)2], were prepared and their variable-temperature magnetic susceptibilities were measured. There were found linear correlations of the spin-crossover temperatures Tc not only between the NCS and NCBH3 complexes with the corresponding substituted pyridines, but also between the Tc and the Hammett constants, supporting the electronic substituent effect of the coordinated pyridine rather than a steric effect. The ligand field and the interelectronic repulsion parameters together with the thermodynamic data and/or cooperativity factor were discussed in relation with their spin-crossover behavior. 相似文献
25.
Ikuma N Tsue H Tsue N Shimono S Uchida Y Masaki K Matsuoka N Tamura R 《Organic letters》2005,7(9):1797-1800
[reaction: see text] Enantiomerically enriched samples of chiral cyclic nitroxides with a 4-hydroxyphenyl group on the stereogenic center bearing the NO radical group undergo unprecedented spontaneous racemization and/or epimerization in aprotic solvents, which can be well accounted for by the multistep equilibrations involving planar quinoid intermediates. 相似文献
26.
Shinohara Y Kawasaki N Ueno S Kobayashi I Nakajima M Amemiya Y 《Physical review letters》2005,94(9):097801
Crystallization of n-hexadecane in emulsion droplets was studied using time-resolved two-dimensional small- and wide-angle x-ray scattering with differential scanning calorimetry (2D-SAXS-WAXS-in situ DSC) which provides information about both nano- and subnanoscale structural change. n-hexadecane in droplets reproducibly crystallized into the stable triclinic phase via a transient-rotator phase. This is in contrast with previous results that the rotator phase of n-hexadecane was observed only occasionally for bulk samples. Thus we confirmed the existence of rotator phase in n-hexadecane, which is important for the study of crystallization of soft materials. We suggest that the rotator phase at the interface of oil and water plays a precursor role for bulk crystallization. This study demonstrates that 2D-SAXS-WAXS-in situ DSC is a powerful tool for the study of a transient phase. 相似文献
27.
Nakamura E Yamanaka M Yoshikai N Mori S 《Angewandte Chemie (International ed. in English)》2001,40(10):1935-1938
28.
The AcOEt extract of Hypholoma fasciculare yielded four new congeners, fascicularones H ( 4 ), I ( 5 ), J ( 6 ), and K ( 7 ). All structures were unambiguously established by 1D and 2D NMR and MS data. In a lettuce seedling assay, compounds 4 – 7 showed radicle elongation. 相似文献
29.
30.
This paper mainly focuses on refrigerant mixtures with relatively simple critical behavior, and presents a practical and useful method for the critical point calculation for the mixtures using mixture models based on Helmholtz energy equations of state. The expression for critical point criterion suitable for this objective is derived first. Numerical manipulations to obtain a physically correct solution are described in detail. For four binary refrigerant mixtures of difluoromethane (R-32) + pentafluoroethane (R-125), R-125 + 1,1,1,2-tetrafluoroethane (R-134a), R-125 + 1,1,1-trifluoroethane (R-143a), and R-32 + propane (R-290), the critical temperatures and critical molar volumes are calculated applying the presented method. The calculation results are compared with experimental values, and the capabilities of the mixture models for the mixtures in the critical region are discussed. 相似文献