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141.
142.
The Cage Structure of IndanCHF3 is Based on the Cooperative Effects of CH⋅⋅⋅π and CH⋅⋅⋅F Weak Hydrogen Bonds
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Dr. Laura B. Favero Weixing Li Lorenzo Spada Dr. Luca Evangelisti Giorgio Visentin Prof. Dr. Walther Caminati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):15970-15973
The structural and energetic features of the C?H???π interaction and the internal dynamics of the CHF3 group change drastically in going from benzene?CHF3 to indan?CHF3, according to the analysis of the rotational spectrum of the latter complex generated in a supersonic expansion. 相似文献
143.
Pavol Brunovský Alexander Erdélyi Hans-Otto Walther 《Journal of Dynamics and Differential Equations》2004,16(2):393-432
A delay differential equation is presented which models how the behavior of traders influences the short time price movements of an asset. Sensitivity to price changes is measured by a parameter a. There is a single equilibrium solution, which is non-hyperbolic for all a>0. We prove that for a< 1 the equilibrium is asymptotically stable, and that for a>1 a 2-dimensional global center-unstable manifold connects the equilibrium to a periodic orbit. Its birth at a=1 is not of Hopf type and seems part of a Takens–Bogdanov scenario. 相似文献
144.
Ruhland TM Gröschel AH Walther A Müller AH 《Langmuir : the ACS journal of surfaces and colloids》2011,27(16):9807-9814
We describe the first study on the self-assembly behavior of Janus cylinders at liquid/liquid interfaces. The Janus cylinders are characterized by a phase separation along the major axis into two hemicylinders of different wettability. The pendant drop technique and microscopic imaging were used to characterize the adsorption behavior and self-assembly of Janus cylinders at perfluorinated oil/dioxane and perfluorinated oil/dimethyl sulfoxide interfaces. According to the evolution of the interfacial tension and a series of TEM images taken during the cylinder adsorption, we will specify the characteristics of early to late stages of the Janus cylinder adsorption at a liquid-liquid interface and discuss the effect of Janus cylinder length and their concentration. We also establish that the broken symmetry of the corona leads to significantly higher interfacial activity as compared to homogeneous core-shell cylinders. The adsorption is characterized by three different adsorption stages: first, free diffusion to the interface, followed by continuous adsorption of cylinders including ordering and domain formation and, finally, additional packing with a rearrangement of domains and formation of a loose multilayer system. 相似文献
145.
Jensen RL Arnbjerg J Birkedal H Ogilby PR 《Journal of the American Chemical Society》2011,133(18):7166-7173
Singlet molecular oxygen, O(2)(a(1)Δ(g)), is an intermediate in a variety of processes pertinent to the function of biological systems, including events that result in cell death. Many of these processes involve a reaction between singlet oxygen and a given protein. It is acknowledged that the behavior of a protein can change upon reaction with singlet oxygen, as a result of a structural alteration and/or a direct chemical modification of an active site. However, the converse, where one considers how the behavior of singlet oxygen can be altered by changes in protein structure, has received little attention. In this report, we use a variety of proteins to demonstrate how the rate constant for singlet oxygen removal by a protein responds to (a) protein denaturation, (b) macromolecular crowding of the protein, (c) ligand binding by the protein, and (d) polymerization of the protein. From one perspective, the data show that the kinetics of singlet oxygen removal can be used to monitor protein dynamics. Most importantly, however, the data indicate that protein structural changes that either reveal or cloak a given amino acid residue can have a measurable effect on the overall rate constant for singlet oxygen removal which, in turn, can have ramifications for singlet-oxygen-mediated intracellular events that perturb cell function. 相似文献
146.
Walther J Gaertner M Cimalla P Burkhardt A Kirsten L Meissner S Koch E 《Analytical and bioanalytical chemistry》2011,400(9):2721-2743
Optical coherence tomography (OCT) is a noninvasive, high-resolution, interferometric imaging modality using near-infrared
light to acquire cross-sections and three-dimensional images of the subsurface microstructure of biological specimens. Because
of rapid improvement of the acquisition speed and axial resolution of OCT over recent years, OCT is becoming increasingly
attractive for applications in biomedical research. Therefore, OCT is no longer used solely for structural investigations
of biological samples but also for functional examination, making it potentially useful in bioanalytical science. The combination
of in vivo structural and functional findings makes it possible to obtain thorough knowledge on basic physiological and pathological
processes. Advanced applications, for example, optical biopsy in visceral cavities, have been enabled by combining OCT with
established imaging modalities. This report gives an outline of the state of the art and novel trends of innovative OCT approaches
in biomedical research in which the main focus is on applications in fundamental research and pre-clinical utilization. 相似文献
147.
A molecular dyad was synthesized in which a Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) photosensitizer and a phenothiazine redox partner are bridged by a sequence of tetramethoxybenzene, p-dimethoxybenzene, and p-xylene units. Hole transfer from the oxidized metal complex to the phenothiazine was triggered using a flash-quench technique and investigated by transient absorption spectroscopy. Optical spectroscopic and electrochemical experiments performed on a suitable reference molecule in addition to the above-mentioned dyad lead to the conclusion that hole transfer from Ru(bpy)(3)(3+) to phenothiazine proceeds through a sequence of hopping and tunneling steps: Initial hole hopping from Ru(bpy)(3)(3+) to the easily oxidizable tetramethoxybenzene unit is followed by tunneling through the barrier imposed by the p-dimethoxybenzene and p-xylene spacers. The overall charge transfer proceeds with a time constant of 41 ns, which compares favorably to a time constant of 1835 ns associated with equidistant hole tunneling between the same donor-acceptor couple bridged by three identical p-xylene units. The combined hopping/tunneling sequence thus leads to an acceleration of hole transfer by roughly a factor of 50 when compared to a pure tunneling mechanism. 相似文献
148.
149.
Feng G Evangelisti L Favero LB Grabow JU Xia Z Caminati W 《Physical chemistry chemical physics : PCCP》2011,13(31):14092-14096
We measured the molecular beam Fourier transform microwave spectra of six isotopologues of the 1?:?1 adduct of CH(3)CHClF with water. Water prefers to form an O-H···F rather than an O-H···Cl hydrogen bond. This is just the contrary of what was observed in the chlorofluoromethane-water adduct, where an O-H···Cl link was formed (W. Caminati, S. Melandri, A. Maris and P. Ottaviani, Angew. Chem., Int. Ed., 2006, 45, 2438). The water molecule is linked with an O-H···F bridge to the fluorine atom, with r(F···H(w)) = 2.14 ?, and with two C-H···O contacts to the alkyl hydrogens with r(C(1)-H(1)···O(w)) = 2.75 ? and r(C(2)-H(2)···O(w)) = 2.84 ?, respectively. Besides the rotational constants, the quadrupole coupling constants of the chlorine atom have been determined. In addition, information on the internal dynamics has been obtained. 相似文献
150.
Sadler JE Szumski DS Kierzkowska A Catarelli SR Stella K Nichols RJ Fonticelli MH Benitez G Blum B Salvarezza RC Schwarzacher W 《Physical chemistry chemical physics : PCCP》2011,13(40):17987-17993
A new in situ electrochemical method of functionalizing an oxide-free Ni surface is demonstrated using octanethiol. Initial adsorption results in a multilayer molecular film, which blocks both the hydrogen evolution reaction (HER) and re-oxidation of the Ni by ambient oxygen. However, excess octanethiol can be removed by rinsing with ethanol, leaving behind a monolayer that continues to protect against re-oxidation but gives rise to an unexpected enhancement in the HER, with a greater enhancement for longer film formation times. The presence of an octanethiol monolayer on the surface was confirmed by spectroscopic observation of the CH(2), CH(3) and thiolate groups using infra red spectroscopy, while X-ray photo-electron spectroscopy demonstrated the effectiveness of the thiol layer as a barrier to surface oxidation. The electrochemically prepared octanethiol film impedes oxidation of the Ni in air more effectively than a film formed by immersion in a solution of octanethiol in ethanol. 相似文献