全文获取类型
收费全文 | 213篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 203篇 |
晶体学 | 7篇 |
数学 | 4篇 |
物理学 | 9篇 |
出版年
2023年 | 5篇 |
2022年 | 16篇 |
2021年 | 23篇 |
2020年 | 7篇 |
2019年 | 7篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 11篇 |
2015年 | 9篇 |
2014年 | 3篇 |
2013年 | 13篇 |
2012年 | 13篇 |
2011年 | 19篇 |
2010年 | 6篇 |
2009年 | 10篇 |
2008年 | 12篇 |
2007年 | 11篇 |
2006年 | 11篇 |
2005年 | 6篇 |
2004年 | 5篇 |
2003年 | 2篇 |
2002年 | 5篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1995年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1981年 | 2篇 |
排序方式: 共有223条查询结果,搜索用时 390 毫秒
41.
Godsi O Turner B Suwinska K Peskin U Eichen Y 《Journal of the American Chemical Society》2004,126(41):13519-13525
The enolpyridine, OH-ketoenamime, NH equilibrium in crystals of 1,3-bis(pyridin-2-yl)propan-2-one was studied using temperature-dependent single-crystal X-ray diffraction. The relative population of the different tautomers was found to be sensitive to the temperature in the range of 100-300 K, illustrating the small thermodynamic difference between these two tautomers. This energy resemblance is partially attributed to the molecular packing in the crystal, where the molecules are arranged in the form of dimers. Ab initio electronic energy calculations (HF/6-31G** and MP2/6-31G**) reveal the effect of dimerization in the crystal on the electronic energy levels. Several tautomeric states were identified in the dimer of 1,3-bis(pyridin-2-yl)propan-2-one. A model is proposed in which four of these dimer states are populated in the crystal at ambient temperatures. The crystallographic data were treated according to this four-state dimer model, suggesting that the free energy of the OH-NH dimers is higher than that of the OH-OH dimers by 120 +/- 10 cal mol(-1) and that the NH-NH dimers are yet higher in free energy by 50 +/- 10 cal mol(-1). 相似文献
42.
Dr. Szymon Sobczak Kinga Roszak Prof. Andrzej Katrusiak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(45):e202201235
The pressure-induced transformation of plane-square complex nickel(II) bis(N,N-diethyldithiocarbamate) between its soft dithiocarbamate (form I) and thioureide (form II) mesomeres is coupled to the interchange of anagostic Ni⋅⋅⋅H−C interactions from methylene to the methyl group, respectively. At 1.23 GPa, the clearly visible giant anomalous compressibility of the crystal reveals a potential-energy difference of 5.4 kJ mol−1 between the two complex forms. The structural and spectroscopic results, which are supported by quantum-mechanical calculations, connect this solid-state phase transition with the mesomeric transition, and this is accompanied by the conformational transformation of anagostic Ni⋅⋅⋅H−C rearrangement and formation of the charge-assisted S−⋅⋅⋅H−C bond under pressure. 相似文献
43.
Magdalena Kowalska ukasz Fijakowski Monika Kubacka Kinga Saat Grzegorz Grzek Jacek Nowaczyk Alicja Nowaczyk 《Molecules (Basel, Switzerland)》2021,26(12)
Tiagabine is an antiepileptic drug used for the treatment of partial seizures in humans. Recently, this drug has been found useful in several non-epileptic conditions, including anxiety, chronic pain and sleep disorders. Since tachycardia—an impairment of cardiac rhythm due to cardiac ion channel dysfunction—is one of the most commonly reported non-neurological adverse effects of this drug, in the present paper we have undertaken pharmacological and numerical studies to assess a potential cardiovascular risk associated with the use of tiagabine. A chemical interaction of tiagabine with a model of human voltage-gated ion channels (VGICs) is described using the molecular docking method. The obtained in silico results imply that the adverse effects reported so far in the clinical cardiological of tiagabine could not be directly attributed to its interactions with VGICs. This is also confirmed by the results from the isolated organ studies (i.e., calcium entry blocking properties test) and in vivo (electrocardiogram study) assays of the present research. It was found that tachycardia and other tiagabine-induced cardiac complications are not due to a direct effect of this drug on ventricular depolarization and repolarization. 相似文献
44.
Dr. Anna Kamecka Prof. Andrzej Kapturkiewicz M.Sc. Patryk Wójcik Prof. Kinga Suwińska Dr. Joanna Masternak 《欧洲无机化学杂志》2023,26(33):e202300438
The paper deals with the synthesis of a series of cationic [Pt(ppz)2(N^N)]2+ complexes containing deprotonated 1-phenyl-1H-pyrazole as cyclometallating (C^N) ligands and α-diimines (N^N) in the form of water-soluble salts with OTf− (trifluoromethanesulfonate) counter ions. These complexes were obtained from cis-[Pt(ppz)2Cl2] through chloride ligands substitution with α-diimines. The complexes were identified by means of NMR spectroscopy and their molecular structures were confirmed by X-ray crystallography. The photophysical properties of these complexes were studied in detail. These complexes showed strong luminescence in MeOH/EtOH 1 : 1 glasses at 77 K but were almost non-emitting in MeCN solutions at room temperature. Their emission properties were compared to analogues IrIII complexes. 相似文献
45.
Kinga Wzgarda-Raj Agnieszka J. Rybarczyk-Pirek Sawomir Wojtulewski Marcin Palusiak 《Acta Crystallographica. Section C, Structural Chemistry》2022,78(1):7-13
The structures of novel cocrystals of 4-nitropyridine N-oxide with benzenesulfonamide derivatives, namely, 4-nitrobenzenesulfonamide–4-nitropyridine N-oxide (1/1), C5H4N2O3·C6H6N2O4S, and 4-chlorobenzenesulfonamide–4-nitropyridine N-oxide (1/1), C6H6ClNO2S·C5H4N2O3, are stabilized by N—H…O hydrogen bonds, with the sulfonamide group acting as a proton donor. The O atoms of the N-oxide and nitro groups are acceptors in these interactions. The latter is a double acceptor of bifurcated hydrogen bonds. Previous studies on similar crystal structures indicated competition between these functional groups in the formation of hydrogen bonds, with the priority being for the N-oxide group. In contrast, the present X-ray studies indicate the existence of a hydrogen-bonding synthon including N—H…O(N-oxide) and N—H…O(nitro) bridges. We present here a more detailed analysis of the N-oxide–sulfonamide–nitro N—H…O ternary complex with quantum theory computations and the Quantum Theory of Atoms in Molecules (QTAIM) approach. Both interactions are present in the crystals, but the O atom of the N-oxide group is found to be a more effective proton acceptor in hydrogen bonds, with an interaction energy about twice that of the nitro-group O atoms. 相似文献
46.
Kinga Zr Roberto Ortiz Ebru Saatci Ronald Bardsley Tim Parr Elisabeth Csregi Mihaela Nistor 《Bioelectrochemistry (Amsterdam, Netherlands)》2009,76(1-2):93
An immunological capacitive biosensor for calpastatin was developed, optimized and applied for the analysis of meat extract samples. Anti-calpastatin antibody was immobilized on a gold electrode modified with a self-assembled monolayer of mercaptoundecanoic acid and Protein A from Staphylococcus aureus, and the obtained immunosensor was inserted as the working electrode in an electrochemical cell of a flow injection system. The dynamic range of the sensor was 20 to 160 ng/mL calpastatin. The electrode could be regenerated and re-used for more than 7 days with minimal reduction in sensitivity. For the analysis of real samples, the target analyte was extracted from the Longissimus dorsi muscle from beef carcasses directly after slaughtering. The extract was analyzed both with the developed immunosensor and microtiter plate ELISA, and a good correlation was obtained. However the immunosensor offers advantages of speed, simplicity, sensitivity and possibility for miniaturization over conventional assays for calpastatin quantification. 相似文献
47.
Kepczyński M Nawalany K Jachimska B Romek M Nowakowska M 《Colloids and surfaces. B, Biointerfaces》2006,49(1):22-30
A system of poly(ethylene glycol) bound tetraarylporphyrin entrapped in liposomal membranes was investigated. The interactions between the 5-(4-hydroxymethylphenyl)-10,15,20-tritolylporphyrin (Po) covalently attached to the poly(ethylene glycol) chain (PEG-Po), and phosphatidylcholine liposomes in the aqueous solution were studied. The adsorption of the investigated polymer to lipid vesicles was confirmed by measurements of dynamic light scattering and zeta potential. Experimental results demonstrate that the diameter of liposomes increased and the absolute value of the zeta potential decreased after addition of PEG-Po. The binding constants (K(b)) of Po chromophores to liposome in pH range from 5.2 to 9.0 were determined using fluorescence spectroscopy. The degree of binding was found to be pH-independent and the average value was 24.6 +/- 0.9 mg ml(-1). The acid-base properties of the porphyrin chromophores and their aggregation in an aqueous solution were also studied. pK values associated with imine-N protonation of the porphyrin core were found to be 2.59 and 0.68 at the ionic strength of 0.1 M. The equilibrium constant for dimerization, K(D), was found to be 5 x 10(3) M(-1). 相似文献
48.
Haubner K Tarábek J Ziegs F Lukeš V Jaehne E Dunsch L 《The journal of physical chemistry. A》2010,114(43):11545-11551
The influence of the molecular structure on the stabilization of charged states was studied in detail by in situ ESR UV-vis NIR spectroelectrochemistry at a novel α,ω-dicyano substituted β,β'-dibutylquaterthiophene (DCNDBQT) and the electrochemically generated cation and anion radicals have been proved for the first time. The voltammetry of DCNDBQT results in two separate oxidation steps with the reversible first one. The experimental absorption maxima at 646 and 1052 nm together with the calculated ones (by DFT method) as well as an ESR signal at the first anodic step prove the presence of a radical cation. Three additional optical bands (554, 906, and 1294 nm for CT-transition) can be attributed to the formation of cation radical dimer. The dicationic structure formed in the second oxidation step is not stable. The stabilization proceeds via a dimer formation in two chemical follow-up reactions. The existence of the dimeric structures was proved by ex situ MALDI TOF mass spectrometry. As the substitution by cyano groups opens the route to cathodic reductions, DCNDBQT shows a single quasi-reversible reduction step. Here, the in situ ESR UV-vis NIR spectroelectrochemical measurements and theoretical calculations let us confirm the electrochemical generation of an anion radical. As we found a low number of anion radicals by quantitative ESR spectroelectrochemistry and an appearance of additional bands in the UV-vis NIR absorption spectra, the formation of dimeric structures must be considered and was corroborated by mass spectrometry. The role of dimerization in the reaction mechanism of the DCNDBQT oxidation and reduction are discussed in general. The experimental results were interpreted using the quantum chemical calculations based on density functional theory. 相似文献
49.
Stanisław Boryczka Kinga Suwińska Georges Le Guillanton Quang Tho Do Driss Elothmani 《Journal of chemical crystallography》1998,28(7):555-560
The title compound (C14H11NO2) is monoclinic with a = 13.579(2), b = 5.297(1), c = 16.455(2) Å, = 98.11(2)°, Z = 4, and space group P21/n. The significant structural features lie in the two carbonyl groups of the glyoxamide which are oriented antiperiplanar to each other [–163.6(3)°]. The central bond C(1)–C(2) is 1.545(4) Å. The observed conformation is stabilized by intramolecular hydrogen bonds. 相似文献
50.
Andrzej Ziba Andrzej Malankiewicz Kinga Suwiska 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):o32-o33
The title compound, C6H7NS, is planar, with endo‐C—N—C bond angles of 118.7 (2) and 118.8 (2)°, and C—S bond lengths of 1.697 (2) and 1.692 (2) Å for the two symmetrically independent molecules. 1‐Methylpyridinium‐4‐thiolate is the major contributor to the molecular structure in the solid state. 相似文献