全文获取类型
收费全文 | 680篇 |
免费 | 42篇 |
国内免费 | 5篇 |
专业分类
化学 | 394篇 |
晶体学 | 6篇 |
力学 | 23篇 |
数学 | 132篇 |
物理学 | 172篇 |
出版年
2023年 | 7篇 |
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 10篇 |
2019年 | 15篇 |
2018年 | 9篇 |
2017年 | 14篇 |
2016年 | 27篇 |
2015年 | 26篇 |
2014年 | 33篇 |
2013年 | 40篇 |
2012年 | 42篇 |
2011年 | 46篇 |
2010年 | 22篇 |
2009年 | 33篇 |
2008年 | 35篇 |
2007年 | 30篇 |
2006年 | 35篇 |
2005年 | 29篇 |
2004年 | 24篇 |
2003年 | 26篇 |
2002年 | 29篇 |
2001年 | 17篇 |
2000年 | 19篇 |
1999年 | 2篇 |
1998年 | 16篇 |
1997年 | 7篇 |
1996年 | 5篇 |
1995年 | 8篇 |
1994年 | 8篇 |
1993年 | 12篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 7篇 |
1984年 | 13篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1967年 | 1篇 |
1963年 | 1篇 |
1943年 | 2篇 |
排序方式: 共有727条查询结果,搜索用时 153 毫秒
11.
We establish here the convergence (thereby proving the existence) of a semi-discrete scheme for the quasilinear hyperbolic equation where x ∈ Rn, t ∈ [0,T], and ? ∈ L∞ (Rn). It is well known that the above problem does not necessarily have global classical solutions and the usual concepts of weak solution. do not lead to a unique solution The existence of a unique solution to the above problem in a suitable sense was established in [3], where a parabolic problem obtained by introducing the term ??Δu was studied and then the behavior as ? → 0 was discussed. A difference scheme approach to a problem of the above type where ?i does not depend on x and t and Ψ does not depend on u was also studied in [2]. The aim of this paper is to present a proof for the case when ? depends on x, Ψ depends on u, and the technical complications in this case are nontrivial. The discussions in this paper my be considered as continuation of the ideas in the above papers. 相似文献
12.
Humblot V Lorenzo MO Baddeley CJ Haq S Raval R 《Journal of the American Chemical Society》2004,126(20):6460-6469
A detailed comparison of tartaric acid (HOOC-CHOH-CHOH-COOH) and succinic acid (HOOC-CH(2)-CH(2)-COOH) molecules on a Cu(110) surface is presented with a view to elucidate how the two-dimensional chirality exhibited by such robust, chemisorbed systems is affected when both OH groups of the former molecule are replaced with H groups, a stereochemical change that leaves the metal-bonding functionalities of the molecule untouched but destroys both chiral centers. It is found that this change does not significantly affect the thermodynamically preferred chemical forms that are adopted, namely the doubly deprotonated bicarboxylate at low coverages (theta = (1)/(6) ML) and the singly deprotonated monocarboxylate at higher coverage. However, the kinetics of phase formation are significantly affected so that the conditions required for self-assembling pertinent two-dimensional chiral phases alter substantially. For both molecules, two-dimensional assembly is found to depend strongly on the nature of the local adsorption motif created, with each motif essentially acting as a "synthon" for the supramolecular assembly. In this respect, it seems that molecule-metal bonding interactions define the general self-assembly structure. The presence/absence of the OH groups, instead, cause a subtler, second-order effect on the finer details of the self-assembled structure. Finally, the creation of chirality in the achiral succinate system is shown to arise from adsorption-induced asymmetrization, inducing point chirality via molecular distortion and/or metal reconstruction of the local adsorption unit. This chiral adsorption unit is then responsible for creating chiral supramolecular through-space and through-metal interactions that propagate a chiral organization. However, the achirality of the succinate ensures that nucleation points of either chirality are equally created, producing a racemic conglomerate of coexisting mirror domains. It is in this aspect that the uniquely aligned OH groups of the rigid bitartrate system wield the greatest effect, by favoring one distortion/reconstruction for the (R,R)-bitartrate and its mirror image distortion/reconstruction for the (S,S)-enantiomer, creating surfaces that are globally chiral on the macroscopic scale. So overall, the OH groups do not dictate the general nature of the assembly but are critical as chiral propagators, breaking the degeneracy and thus promoting asymmetry to chirality. 相似文献
13.
The design and construction of a simple device for measuring ionic concentrations (or pH) with ion-selective electrodes are described. The automated system includes a special electronic circuit with an operational amplifier, a signal conditioner and a personalcomputer. A digital multimeter can be used if automation is not required. The results obtained in tests with iodide-, chloride- and nitrate-selective electrodes and glass electrodes show very good agreement with those obtained with sophisticated commercial apparatus. 相似文献
14.
The surface pressure (Π) vs surface concentration (Γs) curves of the hydrogen-bonded polymer blend poly(vinylacetate)+ poly(4-hydro-xystyrene) (PVAc+P4HS) have been measured at
25 °C onto a water subphase at pH=2.0. While PVAc forms extended monolayers, and the free surface of water is found to be
a good solvent for it, P4HS forms compressed monolayers, and the surface is a near Θ-type solvent for it. PVAc and P4HS form
miscible non-ideal monolayers until near the collapse pressure through the whole concentration range. The composition dependence
of the Π–Γs curves is rather complex. Contrary to what might be expected, the addition of PVAc to the blend does not reduce the rigidity
of the monolayer until its weight fraction is larger than 0.5. The compressibility data of the P4HS-rich monolayers suggest
the existence of a second maximum at high surface coverages, a result already observed in some polysiloxanes.
Received: 11 March 1998 Accepted: 7 May 1998 相似文献
15.
E. Burestedt J. Emnéus L. Gorton G. Marko-Varga E. Domínguez F. Ortega A. Narváez H. Irth M. Lutz D. Puig D. Barceló 《Chromatographia》1995,41(3-4):207-215
Summary A fully integrated screening system for phenolic compounds was developed incorporating on-line solid phase extraction, fractionation and biosensor detection. Two different types of biosensors, solid graphite and carbon paste electrodes incorporating the enzyme tyrosinase, were compared and used in the screening system. Interfacing of the solid phase extraction and fractionation with the biosensor detection was given special attention since the biosensors were not compatible with the organic modifier used for desorption of phenols from the solid phase extraction step. The system was validated with conventional analytical techniques. Surface water samples from the Ebro river were spiked with 1,10, and 25g L–1 of catechol, phenol,p-cresol, respectively. Three out of seven samples were spiked and the correct samples were identified, containing phenols equivalent to the spiked concentrations. 相似文献
16.
Angel Alberola Celia Andrs Alfonso Gonzlez Ortega Rafael Pedrosa Martina Vicente 《Journal of heterocyclic chemistry》1987,24(3):709-713
Unsymmetrically substituted β-aminoenones react with malononitrile, cyanomethylphenylsulfone, benzoyl-acetonitrile and ethyl cyanoacetate, in very mild conditions, to yield regiospecifically 3-functionalized 2(1H)-pyridones in high yields. 相似文献
17.
The complete assignment of the proton chemical shifts of coumarin ( 1 ), all monomethoxy derivatives and the six possible dimethoxyl substituted compounds at the aromatic ring was achieved at 60 MHz in a quantitative study utilizing Pr(fod)3 as the shift reagent. It was found that in addition to the complexation at the lactone carbonyl a second interaction of the lanthanide shift reagent occurs when two methoxyl groups are found in an ortho distribution. The results are discussed in comparison to data published for flavones in the presence of Pr(fod)3 shift reagent. 相似文献
18.
Velázquez MM Ortega F Monroy F Rubio RG Pegiadou S Pérez L Infante MR 《Journal of colloid and interface science》2005,283(1):144-152
We report the formation of Langmuir monolayers of pure zwitterionic hexadecyl 1-N-L-tryptophan glycerol ether (C(16)-TGE) surfactant and mixed monolayers of cationic-zwitterionic surfactant obtained modifying the pH of the subphase. The pressure-area and surface potential-area isotherms and fluorescence microscopy measurements have been used to characterize the surface phase transitions in the monolayers. These transitions appeared at larger areas as the pH decreased from 6.0 to 2.0 and almost disappeared as the pH decreased further. The analysis of the surface potential and the infrared reflection-absorption spectroscopy data suggests that the phase transition is associated with a change of orientation of both the hydrocarbon chain and the aromatic group of the surfactant with respect to the air-water surface. The surface rheology of the monolayers was studied by quasielastic light scattering and by the oscillatory barrier technique. The results indicate that there is at least one relaxation process in the monolayer. 相似文献
19.
Kotel'nikov A. I. Ortega J. M. Medvedev E. S. Psikha B. L. Garcia D. Mathis P. 《Russian Journal of Electrochemistry》2002,38(1):77-87
The electron transfer from the heme of cytochrome c to the bacteriochlorophill dimer in reaction centers of photosynthetic purple bacteria Rps. sulfoviridis is studied by laser flash photolysis at 40–296 K in conditions where one, two, or three cytochrome hemes are chemically reduced. In the model used for the electron transfer kinetics, the protein relaxation is described with a temperature-independent oscillatory coordinate and a temperature-dependent diffusion coordinate, with the protein dielectric relaxation times widely distributed along the diffusion coordinate. It is found that all the protein complexes can be divided into proteins with fast (k
et = 107 to 10–4 s–1) and slow (k
et 100 s–1) electron transfer. These populations presumably differ by the protonation state of the functional group. The contribution of the oscillatory and diffusion coordinates alters, which severely affects k
et. Parameters V
ab, G, , 0, and for these reactions are determined. 相似文献
20.
J. Morales L. Hernan L. V. Flores A. Ortega 《Journal of Thermal Analysis and Calorimetry》1982,24(1):23-34
Differential thermal analysis and differential scanning calorimetry techniques have been used to study the kinetics of phase transitions. The aragonite/calcite transformation was chosen as test reaction.Marked discrepancies were observed between the DTA kinetic results and those obtained from isothermal kinetic measurements. This disagreement is associated with the difficulty of determining accurately the reaction rate of the process from a DTA curve.In contrast, in DSC measurements, where the reaction rate is given by the height of the peak from the base-line, it is possible to get a satisfactory fit of the data, and the kinetic results obtained with this technique are in good agreement with the isothermal ones.
Zusammenfassung Die Differentialthermoanalyse und DSC wurden zur Untersuchung der Kinetik von Phasenübergängen eingesetzt. Die Umwandlung Aragonit/Calcit wurde als Testreaktion gewählt.Bedeutende Diskrepanzen wurden zwischen den kinetischen Ergebnissen der DTA und den durch isotherme kinetische Messungen erhaltenen Ergebnissen beobachtet. Diese Abweichungen sind damit verbunden, daß es schwierig ist, die Reaktionsgeschwindigkeit des Vorgangs aus einer DTA-Kurve genau zu ermitteln.Bei DSC-Messungen,wo die Reaktionsgeschwindigkeit durch die Höhe des Peaks von der Grundlinie gegeben ist, kann eine befriedigende Anpassung der Daten erhalten werden, und die durch diese Technik erhaltenen kinetischen Ergebnisse sind in guter Übereinstimmung mit den isothermen Ergebnissen.
. /. , . -. , , , , , .相似文献