全文获取类型
收费全文 | 325篇 |
免费 | 25篇 |
专业分类
化学 | 272篇 |
晶体学 | 4篇 |
力学 | 2篇 |
数学 | 38篇 |
物理学 | 34篇 |
出版年
2023年 | 8篇 |
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 7篇 |
2019年 | 8篇 |
2018年 | 10篇 |
2017年 | 9篇 |
2016年 | 22篇 |
2015年 | 18篇 |
2014年 | 12篇 |
2013年 | 33篇 |
2012年 | 24篇 |
2011年 | 38篇 |
2010年 | 15篇 |
2009年 | 13篇 |
2008年 | 20篇 |
2007年 | 20篇 |
2006年 | 21篇 |
2005年 | 14篇 |
2004年 | 13篇 |
2003年 | 9篇 |
2002年 | 4篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1979年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有350条查询结果,搜索用时 724 毫秒
1.
2.
Violeta D'Accurso Francisco A. Manzano Verónica B. Slezak 《Applied physics. B, Lasers and optics》1996,63(4):375-380
A detailed model for the optogalvanic effect in a neon hollow cathode discharge irradiated by a chopped CW dye laser is presented. A rate equation formalism is used to calculate the evolution of the first and second electronic configuration populations coupled by the laser and of the electric charges number density. Processes as ambipolar-like electrons loss, electronic collisional coupling of level populations and electron emission by the cathode due to VUV radiation from the 1s
2 resonant level are taken into account and further discussed.The transients and steady-state magnitude of the optogalvanic signal are calculated, compared with experimental data and related to population changes. We predict sign changes of the optogalvanic signal when the laser is tuned over transitions originating from the resonant level with respect to transitions involving the metastables states. The optogalvanic signal is shown to be basically determined by the laser-induced variations of the excited-state populations while changes in the electron temperature, due to laser energy transfer by collisions between electrons and excited atoms, play a negligible role. 相似文献
3.
Sánchez ME Turina AV García DA Nolan MV Perillo MA 《Colloids and surfaces. B, Biointerfaces》2004,34(2):77-86
In the present work, we studied the ability of thymol to affect the organization of model membranes and the activity of an intrinsic membrane protein, the GABA(A) receptor (GABA(A)-R). In this last aspect, we tried to elucidate if the action mechanism of this terpene at the molecular level, involves its binding to the receptor protein, changes in the organization of the receptor molecular environment, or both. The self-aggregation of thymol in water with a critical micellar concentration approximately = 4 microM and its ability to penetrate in monomolecular layers of soybean phosphatidylcholine (sPC) at the air-water interface, even at surface pressures above the equilibrium, lateral pressure of natural bilayers were demonstrated. Thymol affected the self-aggregation of Triton X-100 and the topology of sPC vesicles. It also increased the polarity of the membrane environment sensed by the electrochromic dye merocyanine. A dipolar moment of 1.341 Debye was calculated from its energy-minimized structure. Its effect on the binding of [3H]-flunitrazepam ([3H]-FNZ) to chick brain synaptosomal membranes changed qualitatively from a tendency to the inhibition to a clear activatory regime, up on changing the phase state of the terpene (from a monomeric to a self-aggregated state). Above its CMC, thymol increased the affinity of the binding of [3H]-FNZ (K(d-control)= 2.9, K(d-thymol)= 1.7 nM) without changing the receptor density (B(max-control)= 910, B(max-thymol)= 895 fmol/mg protein). The activatory effect of thymol on the binding of [ [3H]-FNZ was observed even in the presence of the allosteric activator gamma-aminobutyric acid (GABA) at a concentration of maximal activity, and was blocked by the GABA antagonist bicuculline. Changes in the dipolar arrangement and in the molecular packing of GABA(A)-R environment are discussed as possible mediators of the action mechanism of thymol. 相似文献
4.
Marjan Kočevar Bojan Verček Branko Stanovnik Miha Tišler 《Monatshefte für Chemie / Chemical Monthly》1982,113(6-7):731-744
Pyrazine- and pyridinecarboxamidoximes with an amino, potentially tautomeric hydroxy or mercapto group inortho position could be transformed in the appropriate condensed azines. In this manner, representatives of pyrazolo(3,4-b)pyrazine, isoxazolo(4,5-b)pyrazine and isothiazolo(5,4-b)pyridine ring system were synthesized and some transformations investigated.Presented in part at the 8th International Congress of Heterocyclic Chemistry, Graz, 1981. 相似文献
5.
Fernández LE Verón MG Varetti EL 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(1-2):405-411
Force fields and vibrational wavenumbers were calculated for the molecules SO2X2 (X=F, Cl, Br) using DFT techniques. The previously available experimental data and assignments for SO2F2 and SO2Cl2 were compared with the theoretical results and revised, and new low temperature infrared and Raman data were obtained for SO2Cl2. These data were subsequently used in the definition of scaled quantum mechanics force fields for such molecules. Adjusted wavenumbers were also predicted for the still unknown SO2Br2. A comparison is made with results published for the VO2X2- anions. 相似文献
6.
De la Fuente JR Jullian C Saitz C Neira V Poblete O Sobarzo-Sánchez E 《The Journal of organic chemistry》2005,70(22):8712-8716
[reaction: see text] Photoreduction of oxoisoaporphine dyes occurs via a stepwise mechanism of electron-proton-electron transfer that leads to the N-hydrogen oxoisoaporphine anion. When triethylamine, TEA, was used as the electron donor in anaerobic conditions, 1-diethylaminobutadiene, DEAB, was one of the oxidation products of TEA, among diethylamine and acetaldehyde. DEAB was identified by (1)H NMR and GC-MS experiments by comparison with the authentic 1-diethylaminobutadiene. This is the first report of a butadienyl derivative formed in the dye-sensitized photooxidation of TEA. In addition, isotopic exchange experiments with TEA-d(15) and D(2)O show that the hydrogens at carbon-2 and carbon-4 of the butadienyl moiety are exchangeable. The observed isotopic exchange pattern could be explained by the head-to-tail coupling of an N,N-diethylvinylamine intermediate that exchanges hydrogens at the C-beta via the enammonium ion. 相似文献
7.
Michelle Hernández-Arganis Rubén A. Toscano Mónica Moya-Cabrera Verónica García-Montalvo Raymundo Cea-Olivares Dr. 《无机化学与普通化学杂志》2004,630(11):1627-1631
The alkaline 1-phenyl-1H-1, 2, 3, 4-tetrazole-5-thiolate salts, M[C6H5N4CS] (M = Li ( 1 ), Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 )) were obtained and characterized by means of mass spectrometry (FAB+) and NMR (1H; 13C) spectroscopy. The structures of Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 ) compounds were determined by X-ray diffraction methods. The ligand shows a rich variety of coordination patterns with the alkaline cations. The formation of a four-membered ring MSCN in the compounds with heavier alkali cations (K, Rb and Cs) is shown. In all the cations the coordination number around it increases with the ionic radius. Compounds with Cs+ and Rb+ exhibited the formation of Cs-C and Rb-C interactions with the phenyl group. 相似文献
8.
Determination of acrylamide monomer in polyacrylamide degradation studies by high-performance liquid chromatography 总被引:1,自引:0,他引:1
Ver Vers LM 《Journal of chromatographic science》1999,37(12):486-494
A high-performance liquid chromatography method using C18 and ion-exchange columns in series is developed for the determination of acrylamide and acrylic acid monomers in polymeric samples. The C18 column acts as a guard column, trapping surfactants and impurities and retaining the nonionic species. The ion-exchange column then separates the monomers according to their respective ionic strengths. This method has been proven in the laboratory to work successfully for all types of acrylamide/acrylic acid polymers and matrices. Detection limits for both monomers can be achieved in the parts-per-billion range. The method is used to study the possible degradation of polyacrylamide to acrylamide monomer in the presence of glyphosate (a herbicide) and sunlight. Polyacrylamide is used as a spray drift reduction aid in combination with glyphosate. In normal applications, the polymer and herbicide are in contact with each other in the presence of sunlight. The results show that the polymer does not degrade to acrylamide in the presence of glyphosate or sunlight or any combination of the two. It is also observed that glyphosate influences the solubility of polyacrylamide, and care must be used when combining the two. 相似文献
9.
Mojca Dobnikar Marijan Kočevar Andrej Petrič Miha Tišler Bojan Verček 《Monatshefte für Chemie / Chemical Monthly》1989,120(3):269-272
Summary Syntheses of 1-methylimidazo[1,2-c]quinazolinium iodide (3) and 1-methylimidazo[2,1-f]pyrido[3,2-d]pyrimidinium iodide (4) are described. These tricyclic compounds react with nucleophiles derived from active methylene compounds to give the corresponding open-chain enamines.
Reaktionen von quaternisierten Imidazo-Chinazolinen und -Pyridopyrimidinen mit Verbindungen mit reaktiven Methylengruppen
Zusammenfassung Synthesen von 1-Methylimidazo[1,2-c]chinazoliniumjodid (3) und 1-Methylimidazo[2,1-f]pyrido[3,2-d]pyrimidiniumjodid (4) werden beschrieben. Diese tricyclischen Verbindungen reagieren mit einigen Carbanionen aus Verbindungen mit reaktiven Methylengruppen, wobei die offenkettigen Enamine entstehen.相似文献
10.
Estela M. Alvarez Patricia H. Risso Carlos A. Gatti Martín S. Armesto Mariano Burgos Verónica M. Relling 《Colloid and polymer science》2006,284(9):1016-1023
Colloidal casein aggregates (CCA) prepared from soluble whole bovine caseinates in the presence of Ca2+ and phosphate (Pi) ions by addition of different citrate (Cit) concentrations showed different mineral and proteic composition. Citrate concentration conditions the Ca and Pi concentrations incorporated into CCA, probably due to the complexing effect of this anion on calcium. A significant change in the incorporated Ca/Pi ratio at 8 mM citrate could very likely be associated to changes in CCA net charge. The incorporation of individual caseins to the colloidal particles obtained, as well as their average size and size distribution, depended also on the Cit concentration used [Cit]P. αS- and β-caseins assembled in the CCA structure sharply decreased at a [Cit]P higher than 15 mM, i.e., at a low Ca2+ concentration in the aggregates, showing that the presence of this cation is necessary for the incorporation of these caseins. An inverse relationship between the aggregation step rate in CCA enzymic coagulation and their average size was observed. The aggregation rate vs the average size curve obtained at [Cit]P 8 mM clearly differed from the curves obtained at 10 and 12 mM, respectively, a fact probably related to a change in the CCA net charge. This behavior showed the effect of citrate concentration on CCA functional properties. 相似文献