全文获取类型
收费全文 | 824篇 |
免费 | 69篇 |
国内免费 | 59篇 |
专业分类
化学 | 879篇 |
晶体学 | 9篇 |
力学 | 1篇 |
综合类 | 5篇 |
物理学 | 58篇 |
出版年
2023年 | 5篇 |
2022年 | 19篇 |
2021年 | 37篇 |
2020年 | 36篇 |
2019年 | 22篇 |
2018年 | 13篇 |
2017年 | 19篇 |
2016年 | 25篇 |
2015年 | 35篇 |
2014年 | 22篇 |
2013年 | 97篇 |
2012年 | 47篇 |
2011年 | 42篇 |
2010年 | 19篇 |
2009年 | 42篇 |
2008年 | 37篇 |
2007年 | 43篇 |
2006年 | 46篇 |
2005年 | 31篇 |
2004年 | 46篇 |
2003年 | 56篇 |
2002年 | 62篇 |
2001年 | 29篇 |
2000年 | 23篇 |
1999年 | 14篇 |
1998年 | 14篇 |
1997年 | 16篇 |
1996年 | 7篇 |
1995年 | 13篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有952条查询结果,搜索用时 21 毫秒
71.
72.
73.
将Se固溶复合到链状小硫分子S2~4中,利用超微孔碳(UMC)的空间限域效应,在UMC中成功构建了链状SemSn(2≤m+n≤4)小分子,并用作锂硫(Li-S)电池正极材料。与链状S2~4小分子相比,改性后的SemSn(2≤m+n≤4)小分子电导率更高,锂化能更低,放电锂化过程更容易。所制得的UMC/SemSn(2≤m+n≤4)复合正极材料的放电过程为一步固相转化反应,从而有效抑制了活性物质的穿梭流失。与UMC/S2~4复合正极材料相比,UMC/SemSn(2≤m+n≤4)复合正极材料的电荷传递阻抗更小,放电比容量更高。因此,UMC/SemSn-40(2≤m+n≤4,wSeS2∶wUMC=4∶6)复合正极材料在0.1C时循环100次后,比容量依然保持有844 mAh·g-1;在0.5C下长时间循环500次时,每次循环容量损失仅约为0.07%,表现出优异的循环稳定性。 相似文献
74.
Copper‐Catalyzed CH Bond Direct Chalcogenation of Aromatic Compounds Leading to Diaryl Sulfides,Selenides, and Diselenides by Using Elemental Sulfur and Selenium as Chalcogen Sources Under Oxidative Conditions 下载免费PDF全文
Prof. Fumitoshi Shibahara Takafumi Kanai Eiji Yamaguchi Akika Kamei Takayuki Yamauchi Prof. Toshiaki Murai 《化学:亚洲杂志》2014,9(1):237-244
The reactions of aromatic compounds and elemental chalcogens catalyzed by a copper salt with molecular oxygen as an oxidant were carried out. The reaction of 3‐substituted imidazo[1,5‐a]pyridines and elemental sulfur in the presence of CuTC (copper(I) thiophenecarboxylate) gave the corresponding bisimidazopyridyl sulfides in good to quantitative yields. The reaction proceeded even under aerobic oxidation conditions. The use of a polar solvent was crucial for the reaction, and DMSO (dimethyl sulfoxide) in particular stimulated the reaction. The reaction could be applied to common aromatic compounds, such as N‐methyl indole and dialkyl anilines. The reaction of indole proceeded at the nucleophilic C3 position rather than at the acidic C2 position. In addition, the reaction of dialkyl anilines proceeded with an ortho, para orientation. The reactions of imidazopyridines and elemental selenium under similar conditions gave the corresponding bisimidazopyridyl diselenides along with bisimidazopyridyl monoselenides. The resulting diselenides were readily converted to the corresponding monoselenides with unreacted imidazopyridines under the same conditions. The reaction could be applied to the copolymerization of bifunctional bisimidazopyridines and elemental sulfur to give oligomeric copolymers in quantitative yield. 相似文献
75.
Anthony Linden Yuehui Zhou Heinz Heimgartner 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(5):482-487
In the selenium‐containing heterocyclic title compound {systematic name: N‐[5‐(morpholin‐4‐yl)‐3H‐1,2,4‐diselenazol‐3‐ylidene]benzamide}, C13H13N3O2Se2, the five‐membered 1,2,4‐diselenazole ring and the amide group form a planar unit, but the phenyl ring plane is twisted by 22.12 (19)° relative to this plane. The five consecutive N—C bond lengths are all of similar lengths [1.316 (6)–1.358 (6) Å], indicating substantial delocalization along these bonds. The Se...O distance of 2.302 (3) Å, combined with a longer than usual amide C=O bond of 2.252 (5) Å, suggest a significant interaction between the amide O atom and its adjacent Se atom. An analysis of related structures containing an Se—Se...X unit (X = Se, S, O) shows a strong correlation between the Se—Se bond length and the strength of the Se...X interaction. When X = O, the strength of the Se...O interaction also correlates with the carbonyl C=O bond length. Weak intermolecular Se...Se, Se...O, C—H...O, C—H...π and π–π interactions each serve to link the molecules into ribbons or chains, with the C—H...O motif being a double helix, while the combination of all interactions generates the overall three‐dimensional supramolecular framework. 相似文献
76.
The vibrational structure of the photoelectron spectra of selenium difluoride and selenium dichloride have been simulated using the computed Franck-Condon factors in the harmonic oscillator approximation. Spectral simulations have been carried out employing the coupled-cluster singles, doubles, and triples (CCSD(T)) and the Becke three-parameter Lee, Yang, and Parr (B3LYP) values for the ground electronic states of the neutral molecules and the cations selenium difluoride and selenium dichloride, respectively. The Duschinsky rotations among the normal modes of two ground electronic states of species involved in the transition are fully taken into account. The ionization energies obtained for selenium difluoride and selenium dichloride are in reasonable agreement with the experimentally determined values. The spectral simulations of vibrational structures including frequency changes and Duschinsky rotation upon the electronic excitation are in agreement with the experimental results. 相似文献
77.
We have studied antimony and selenium atomization processes including a chemical matrix modifier (palladium-containing activated
carbon) during their determination by electrothermal atomic absorption spectrometry. We have developed and fine-tuned an experimental
setup for determining the kinetic characteristics (activation energy and frequency factor) for element atomization processes
from measurements in the initial section of the analytical signal. We provide a rationale for the most likely mechanism for
the interactions that occur. The results of the kinetic studies of the atomization processes showed that the modifier we developed
was highly effective, as a result of formation of a thermally stable condensed system C-Pd-A (where A is the analyte).
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 530–534, July–August, 2006. 相似文献
78.
S. S. Yarovoi S. F. Solodovnikov Z. A. Solodovnikova Yu. V. Mironov V. E. Fedorov 《Journal of Structural Chemistry》2006,47(1):97-101
A cluster complex of the composition [Th(DMSO)8Cl][Re6Se7Cl7] has been obtained by interaction of ThCl4 solution in DMSO with a water solution of K3[Re6Se7Cl7] and KCl. The compound crystallizes in the rhombic space group Pbcm with unit cell parameters a = 12.262(2) Å, b = 19.653(6) Å, c = 23.603(6) Å, V = 5688(2) Å3, Z = 4, d calc = 3.282 g/cm3. The structure is built from centrosymmetric cluster anions [Re6Se7Cl7]3? and complex cations [Th(DMSO)8Cl]3+ possessing mirror-plane symmetry, half of the DMSO ligands being doubly disordered. 相似文献
79.
E. Lukevics P. Arsenyan S. Belyakov O. Pudova 《Chemistry of Heterocyclic Compounds》2002,38(7):763-777
The results of X-ray diffraction investigations of compounds containing selenophene and tellurophene fragments are reviewed and analyzed. The structural features of unsubstituted selenophene and tellurophene and their mono-, di-, tri-, and tetrasubstituted derivatives and also the structure of the complexes of selenophenes and tellurophenes with transition metals are discussed. 相似文献
80.
2,2′‐Dipyridyl‐3,3′‐dipyridyl,5,5′‐dipyridyl‐diselenides have been synthesized by a convenient method employing non‐cryogenic conditions. Various bromopyridines (2‐Bromopyridine, 2,5‐dibromopyridines and 2,3,5‐Tribromopyridines) undergo selective monobromine–magnesium exchange to yield the corresponding pyridyl magnesium chlorides at room temperature upon treatment with iPrMgCl. The resulting pyridyl magnesium chloride is quenched with elemental selenium, which upon further oxidation affords the above diselenides in good yields. The compounds prepared using this methodology have been characterized by elemental analysis, IR, NMR (1H, 13C, 77Se) and mass spectral analysis. The molecular structure of 2,2′,5,5′‐Tetrabromo‐3,3′‐dipyridyldiselenide has been established by single‐crystal X‐ray diffraction analysis. It exists as a dimeric form due to the non‐bonding interactions between the selenium of one pyridine moiety and the hydrogen of the other. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献