全文获取类型
收费全文 | 158篇 |
免费 | 14篇 |
专业分类
化学 | 119篇 |
力学 | 3篇 |
数学 | 21篇 |
物理学 | 29篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 3篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 7篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 14篇 |
2014年 | 14篇 |
2013年 | 9篇 |
2012年 | 13篇 |
2011年 | 17篇 |
2010年 | 7篇 |
2009年 | 6篇 |
2008年 | 11篇 |
2007年 | 10篇 |
2006年 | 12篇 |
2005年 | 6篇 |
2004年 | 4篇 |
2003年 | 5篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1997年 | 1篇 |
1993年 | 1篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
排序方式: 共有172条查询结果,搜索用时 31 毫秒
61.
Gallyamov MO Tartsch B Mela P Börner H Matyjaszewski K Sheiko S Khokhlov A Möller M 《Physical chemistry chemical physics : PCCP》2007,9(3):346-352
Scanning force microscopy was applied to visualise the motion of single poly(butanoate-ethylmethacrylate)-graft-poly(n-butyl acrylate) molecules on silicon and SrTiO(3) substrates. Macromolecular mobility was induced by cyclic exposure of the wafers with the adsorbed brush-like macromolecules to water and alcohol vapours. Exposure to saturated alcohol vapour induced collapse of the adsorbed individual polymer chains while exposure to saturated water vapour promoted their extension. The characteristic times of both conformational changes were long enough that it was possible to visualise step-by-step the morphology transformation in situ by means of an environment-controlled scanning force microscope. Several successive collapse-decollapse cycles were recorded, and small diffusive shifts of the macromolecular position on the substrate were detected after each cycle. Manipulating and visualising single polymer molecules in situ and real time on a silicon substrate opens up new possibilities for the controlled structure formation in ultrathin polymer films. As shown on the sample of a faceted SrTiO(3) wafer, upon extension the brush-like molecules can crawl or extend along nanoscopic surface structures. Silicon can be structured both topographically and chemically at dimensions comparable to those of single polymer molecules with a variety of fabrication techniques ranging from well established conventional silicon micro- nano- machining to new tools constantly developed as dip-pen and nanoimprint lithography. 相似文献
62.
Thermal analysis of charge-transfer complex formed by nitrogen dioxide and substituted calix[4]arene
Amir A. Khabibullin Goulnaz D. Safina Marat A. Ziganshin Valery V. Gorbatchuk 《Journal of Thermal Analysis and Calorimetry》2012,110(3):1309-1313
Simultaneous thermal analysis with evolved gas analysis (STA-EGA) was used to study the ability of 1,3-alternate conformer of tert-butylcalix[4]arene with four n-propoxy substituents (1) to be applied for detection of nitrogen dioxide in reversible sensors. Solid calixarene 1 forms an intensively colored charge-transfer complex (CTC) with gaseous NO2/N2O4. Using the STA-EGA method, the nature and conditions of CTC bleaching were characterized, including the conditions of its reversible change of color from white to dark blue and back at CTC formation and decomposition. For this, the thermal stability of CTC and its regeneration products were studied. This, together with the ion thermograms for evolved gases, gives the information on the oxidation of 1 by nitrogen dioxide if present. 相似文献
63.
The bimolecular nucleophilic substitution reaction of CCl(4) and OH(-) in aqueous solution was investigated on the basis of a combined quantum mechanical and molecular mechanics method. A multilayered representation approach is employed to achieve high accuracy results at the CCSD(T) level of theory. The potential of mean force calculations at the DFT level and CCSD(T) level of theory yield reaction barrier heights of 22.7 and 27.9 kcal/mol, respectively. Both the solvation effects and the solvent-induced polarization effect have significant contributions to the reaction energetics, for example, the solvation effect raises the saddle point by 10.6 kcal/mol. The calculated rate constant coefficient is 8.6 × 10(-28) cm(3) molecule(-1) s(-1) at the standard state condition, which is about 17 orders magnitude smaller than that in the gas phase. Among the four chloromethanes (CH(3)Cl, CH(2)Cl(2), CHCl(3), and CCl(4)), CCl(4) has the lowest free energy activation barrier for the reaction with OH(-) in aqueous solution, confirming the trend that substitution of Cl by H in chloromethanes diminishes the reactivity. 相似文献
64.
Valentina K. Yu Tynyshtyk K. Iskakova Marat F. Faskhutdinov Kaldybay D. Praliyev Chengeer P. Lee 《Phosphorus, sulfur, and silicon and the related elements》2014,189(7-8):864-872
AbstractBased upon the analysis of 1H NMR data, along with molecular modeling, it was shown that the reduction of 3,7-dihetera(N,N-; N,O-; N,S-)bicyclo[3.3.1]nonan-9-ones by LiAlH4 led to a mixture of two stereoisomeric secondary alcohols with different orientations of the hydroxyl groups in one of the ring systems. Diaza derivatives in deuterochloroform exist in predominant chair-boat conformations. However, the replacement of nitrogen in one of the heterocycles by oxygen or sulfur led to stereoisomers one of which existed in chair-boat conformation and another in a chair–chair conformation. In all cases the boat conformation is stabilized by formation of an intramolecular hydrogen bond (IMHB) between a lone electron pair of the nitrogen atom and a proton on the pseudo axial hydroxyl group of the other ring. 相似文献
65.
66.
67.
Mourran A Tartsch B Gallyamov M Magonov S Lambreva D Ostrovskii BI Dolbnya IP de Jeu WH Moeller M 《Langmuir : the ACS journal of surfaces and colloids》2005,21(6):2308-2316
Scanning force microscopy on monomolecular films of eicosylperfluorotetradecane, F(CF(2))(14)(CH(2))(20)H, on mica, silicon oxide, or water revealed spontaneous organization to well-defined nanoscopic ribbon and spiral or toroidal superstructures. Whether ribbons or nanospirals were formed depended on the solvent from which the molecular monofilm was cast. Ribbons were observed when a hydrocarbon or a perfluorocarbon solvent was used, e.g., decalin or perfluorodecalin. When the compound, however, was deposited from nonselective hexafluoroxylene, the molecules assembled into spirals of defined size. The spirals/toroids transformed to ribbons when exposed either to decalin or perfluorodecalin vapor, and the ribbons transformed to toroids when exposed to hexafluoroxylene vapor. These changes could be observed in situ. Scanning force microscopy yielded an identical height and width for the bands forming the spirals and for the parallel flat ribbons. X-ray reflectivity yielded a height of 3.61 +/- 0.05 nm, again identical for both morphologies. Yet, the length of the extended F(CF(2))(14)(CH(2))(20)H molecule, i.e., 4.65 nm, exceeds the layer thickness obtained from X-ray reflectometry. It is, however, consistent with an arrangement where the fluorinated chains are oriented normal to the surface layer and where the alkyl segments are tilted with a 122 degrees angle between the two segments. Within the plane defined by the tilt, this angle allows a dense packing of the alkyl segments compensating for the larger cross-section of the fluorocarbon segment. The tilt plane defines an "easy" direction along which the monolayer structure can preserve order. In the plane perpendicular to this axis, long-range ordered dense packing of the alkyl chains is not possible. Incommensurable packing can in principle explain the finite and regular width of the ribbons and the stepwise turn in the spirals. 相似文献
68.
N. V. Konenkov A. N. Korolkov Marat Machmudov 《Journal of the American Society for Mass Spectrometry》2005,16(5):800-800
Modulation of the voltages applied to a quadrupole mass filter (QMF), either RF or RF and DC, leads to splitting of the stability region into islands of stability. The ion optical properties, such as transmission, resolving power and peak tails of the first upper stability islands have been investigated by numerical simulation of ion trajectories. The dependence of the location of this island on the amplitude of the modulation and the parameter ν=ω/Ω=Q/P where ω is modulation frequency, Ω is main angular radio frequency, and Q and P are integers, is calculated in detail. Different methods of adjusting the QMF resolution are examined. It is found that operation at the upper and lower tips of the stability islands created by amplitude modulation of the RF voltage is preferred, because of the technical simplicity of this method and a reduction of the required separation time. Amplitude modulation improves the performance of a QMF constructed with round rods, in comparison to perfect quadrupole fields. For example, with amplitude modulation of the RF, to reach a resolution of R0.1=1200 requires only about 75 RF cycles of ion motion in a quadrupole field created by round rods. 相似文献
69.
Metastable tert-butylcalix[6]arene with unusually large tunable free volume for non-threshold enclathration of volatiles 总被引:1,自引:0,他引:1
Yakimov AV Ziganshin MA Gubaidullin AT Gorbatchuk VV 《Organic & biomolecular chemistry》2008,6(6):982-985
A metastable material with tunable free volume of molecular size, vapor sorption properties of a porous sorbent and variable thermal stability was prepared from tert-butylcalix[6]arene. 相似文献
70.
Lipton AS Heck RW Staeheli GR Valiev M De Jong WA Ellis PD 《Journal of the American Chemical Society》2008,130(19):6224-6230
We present here a (67)Zn solid-state NMR investigation of Zn(2+) substituted rubredoxin. The sample has been prepared as both a dry powder and a frozen solution to determine the effects of static disorder on the NMR line shape. Low-temperature experiments have been performed at multiple fields to determine the relative contributions to the NMR line shape from the electric field gradient and the anisotropic shielding tensors. Finally we present the theoretical interpretation of the experimental results utilizing a combined quantum mechanical molecular mechanics (QM/MM) approach. Theory predicts a sizable contribution from anisotropic shielding as compared with previously examined model systems. This is in good agreement with the experimental data. 相似文献