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71.
Back Cover: Supramolecular Wiring of Benzo‐1,3‐chalcogenazoles through Programmed Chalcogen Bonding Interactions (Chem. Eur. J. 16/2016) 下载免费PDF全文
72.
Supramolecular Wiring of Benzo‐1,3‐chalcogenazoles through Programmed Chalcogen Bonding Interactions 下载免费PDF全文
Dr. Adrian Kremer Dr. Andrea Fermi Nicolas Biot Prof. Johan Wouters Prof. Dr. Davide Bonifazi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5665-5675
The high‐yielding synthesis of 2‐substituted benzo‐1,3‐tellurazoles and benzo‐1,3‐selenazoles through a dehydrative cyclization reaction has been reported, giving access to a large variety of benzo‐1,3‐chalcogenazoles. Exceptionally, these aromatic heterocycles proved to be very stable and thus very handy to form controlled solid‐state organizations in which wire‐like polymeric structures are formed through secondary N???Y bonding interactions (SBIs) engaging the chalcogen (Y=Se or Te) and nitrogen atoms. In particular, it has been shown that the recognition properties of the chalcogen centre at the solid state could be programmed by selectively barring one of its σ‐holes through a combination of electronic and steric effects exerted by the substituent at the 2‐position. As predicted by the electrostatic potential surfaces calculated by quantum chemical modelling, the pyridyl groups revealed to be the stronger chalcogen bonding acceptors, and thus the best ligand candidate for programming the molecular organization at the solid state. In contrast, the thiophenyl group is an unsuitable substituent for establishing SBIs in this molecular system as it gives rise to chalcogen–chalcogen repulsion. The weaker chalcogen donor properties of the Se analogues trigger the formation of feeble N???Se contacts, which are manifested in similar solid‐state polymers featuring longer nitrogen–chalcogen distances. 相似文献
73.
The use of 1,2‐diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) dianions [1,2‐(1,2‐C2B10H10)Se2]2? prepared in situ as the dilithium salt may lead to irreproducible results. This is shown by the straightforward synthesis of silanes using the purified and isolated dianions, in contrast with previous less successful attempts. Thus, the reactions of the dianions with dichlorosilanes afford the five‐membered diselenasila cycles containing the SiMe2 or the SiPh2 units, and with 1,2‐dichloro‐tetramethyldisilane the six‐membered cycle containing the Si2Me4 unit. The latter was studied by X‐ray diffraction, and all products were characterized by multinuclear magnetic resonance (1H, 13C, 29Si, 77Se NMR) in solution. Novel isotope effects were detected in 13C and 77Se NMR spectra. Exchange reactions of the five‐ and six‐membered diselanasila cycles with chlorosilanes were studied. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
74.
Basudeb Saha Sumana Gangopadhyay Mahammad Ali Pradyot Banerjee 《Journal of Chemical Sciences》1995,107(4):393-402
The kinetics of the reduction of [NiIII(L1)]2+ (where HL1 = 15-amino-3-methyl-4,7,10,13-tetraazapentadec-3-en-2-one oxime) by sulphur(IV) and selenium (IV) over the regions pH 2.50–8.02
and 2.01–4.00 respectively have been investigated at 30°C. Attempts were made to evaluate the reactivity of all the reacting
species, of sulphur(IV) and selenium(IV) by considering suitable pH ranges. The oxidation of SC2·H2O and HSO
3
−
is proposed to proceed through the formation of a hydrogen-bonded adduct. The reaction with SO
3
2−
seems to follow a direct outer-sphere route which is well supported by Marcus crossrelation calculation. The oxidation of
HSeO
l3
−
is ≈ 103 times slower than that of H2SeO3. The kinetic data indicate that the oxidation of sulphur(IV) by [NiIIIL1)]2+ is much more favourable as compared to the corresponding oxidation of selenium(IV). 相似文献
75.
76.
77.
Jacob C Giles GI Giles NM Sies H 《Angewandte Chemie (International ed. in English)》2003,42(39):4742-4758
Sulfur and selenium occur in proteins as constituents of the amino acids cysteine, methionine, selenocysteine, and selenomethionine. Recent research underscores that these amino acids are truly exceptional. Their redox activity under physiological conditions allows an amazing variety of posttranslational protein modifications, metal free redox pathways, and unusual chalcogen redox states that increasingly attract the attention of biological chemists. Unlike any other amino acid, the "redox chameleon" cysteine can participate in several distinct redox pathways, including exchange and radical reactions, as well as atom-, electron-, and hydride-transfer reactions. It occurs in various oxidation states in the human body, each of which exhibits distinctive chemical properties (e.g. redox activity, metal binding) and biological activity. The position of selenium in the periodic table between the metals and the nonmetals makes selenoproteins ideal catalysts for many biological redox transformations. It is therefore apparent that the chalcogen amino acids cysteine, methionine, selenocysteine, and selenomethionine exhibit a unique biological chemistry that is the source of exciting research opportunities. 相似文献
78.
富硒保健食品硒含量标准的探讨 总被引:13,自引:0,他引:13
介绍了开发富硒保健食品的意义,和提出了天然富硒食品硒含量的标准。 相似文献
79.
微量元素硒和糖耐量异常 总被引:5,自引:2,他引:3
非胰岛素依赖型糖尿病(NIDDM)已成为现代社会的主要疾病之一,尤其各种并发平给机体带来的致命后果使倍受重视。而预防的关键是,在耐量异常阶段发现并治疗,效果更佳。已发现在糖耐量异常(ICT)时存在各种抗氧化缺陷,因此,硒(Se)的抗氧化作用对IGT可能有一定的疗效。 相似文献
80.