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121.
Determination of polydimethylsiloxane-air partition coefficients using headspace sorptive extraction
Polydimethylsiloxane-air partition coefficients (K(PDMS-A)) were determined using direct headspace analysis and headspace sorptive extraction (HSSE) with polydimethylsiloxane-coated (PDMS) stir bars. The partition coefficients were investigated for three compounds, p-dichlorobenzene (PDCB), naphthalene and camphor, all of which sublimate at room temperature and find use as moth repellents. In order to determine the K(PDMS-A) values of these compounds, the air concentration and the concentration present on PDMS, both at equilibrium, were measured. The results indicate that PDMS-air partition coefficients are proportional to octanol-air partition coefficients. Thus, the latter could be used to estimate the extraction efficiency of PDMS for these compounds in air. Alternatively, octanol-air partition coefficients for organic compounds could be estimated from the PDMS-air partition coefficient values. As expected, the PDMS-air (or octanol-air) partition coefficient increased with decreasing temperature. Importantly, the partition coefficients determined at saturated vapor pressures were lower than the values determined at lower analyte concentrations, with the differences being greater for compounds with larger partition coefficients. Consequently, caution should be exercised when applying K(PDMS-A) values determined at high analyte concentrations to measurements at lower concentrations, especially when the partition coefficients are large. 相似文献
122.
Zrig S Koeckelberghs G Verbiest T Andrioletti B Rose E Persoons A Asselberghs I Clays K 《The Journal of organic chemistry》2007,72(15):5855-5858
The synthesis of a new series of Lambda-type, D-Pi-A regioregular oligothiophenes is described. The simultaneous presence of the chiral centers and the Lambda-type structure disfavored the formation of centro-symmetrical dimeric assemblies. Hence, enhanced first hyperpolarizabilities betaHRS were measured in comparison with those of the corresponding monomers. 相似文献
123.
Numerical computation of stability and detection of Hopf bifurcations of steady state solutions of delay differential equations 总被引:3,自引:0,他引:3
The characteristic equation of a system of delay differential equations (DDEs) is a nonlinear equation with infinitely many
zeros. The stability of a steady state solution of such a DDE system is determined by the number of zeros of this equation
with positive real part. We present a numerical algorithm to compute the rightmost, i.e., stability determining, zeros of
the characteristic equation. The algorithm is based on the application of subspace iteration on the time integration operator
of the system or its variational equations. The computed zeros provide insight into the system’s behaviour, can be used for
robust bifurcation detection and for efficient indirect calculation of bifurcation points.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
124.
125.
Mathias Kersemans Wim Van Paepegem Koen Van Den Abeele Lincy Pyl Filip Zastavnik Hugo Sol Joris Degrieck 《Ultrasonics》2014
The ultrasonic polar scan (UPS), either in transmission, reflection or backscatter mode, is a promising non-destructive testing technique for the characterization of composites, providing information about the mechanical anisotropy, the viscoelastic damping, the surface roughness, and more. At present, the technique is merely being used for qualitative purposes. The limited quantitative exploration and use of the technique can be primarily ascribed to limitations of current theoretical models as well as the difficulty to perform accurate, and more importantly, reproducible UPS experiments. Over the last years, we have identified several potential pitfalls in the experimental implementation of the technique which severely deteriorate the accurateness and reproducibility of a UPS. In this paper, we make an inventory of the most important difficulties, illustrate each of them by a real experiment and present a feasible mediation, either numerical or experimental in nature. Once the experimental set-up is fine-tuned to overcome these pitfalls, it is expected that the recording of high-level UPS experiments, in combination with numerical computations, will facilitate the technique to become a fully quantitative non-destructive characterization method. 相似文献
126.
Metabolism of methylstenbolone studied with human liver microsomes and the uPA+/+‐SCID chimeric mouse model 下载免费PDF全文
Lore Geldof Leen Lootens Michael Polet Daniel Eichner Thane Campbell Vinod Nair Francesco Botrè Philip Meuleman Geert Leroux‐Roels Koen Deventer Peter Van Eenoo 《Biomedical chromatography : BMC》2014,28(7):974-985
Anti‐doping laboratories need to be aware of evolutions on the steroid market and elucidate steroid metabolism to identify markers of misuse. Owing to ethical considerations, in vivo and in vitro models are preferred to human excretion for nonpharmaceutical grade substances. In this study the chimeric mouse model and human liver microsomes (HLM) were used to elucidate the phase I metabolism of a new steroid product containing, according to the label, methylstenbolone. Analysis revealed the presence of both methylstenbolone and methasterone, a structurally closely related steroid. Via HPLC fraction collection, methylstenbolone was isolated and studied with both models. Using HLM, 10 mono‐hydroxylated derivatives (U1–U10) and a still unidentified derivative of methylstenbolone (U13) were detected. In chimeric mouse urine only di‐hydroxylated metabolites (U11–U12) were identified. Although closely related, neither methasterone nor its metabolites were detected after administration of isolated methylstenbolone. Administration of the steroid product resulted mainly in the detection of methasterone metabolites, which were similar to those already described in the literature. Methylstenbolone metabolites previously described were not detected. A GC‐MS/MS multiple reaction monitoring method was developed to detect methylstenbolone misuse. In one out of three samples, previously tested positive for methasterone, methylstenbolone and U13 were additionally detected, indicating the applicability of the method. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
127.
Hesam Makki Koen N. S. Adema Elias A. J. F. Peters Jozua Laven Leendert G. J. van der Ven Rolf A. T. M. van Benthem Gijsbertus de With 《Journal of Polymer Science.Polymer Physics》2016,54(6):659-671
In this article we studied the evolution of thermomechanical properties of a polyester‐urethane coating during degradation under different degradation conditions, i.e., aerobic and anaerobic conditions with and without dry/wet cycling during degradation. Dynamic mechanical and thermal analyses show that under aerobic conditions the coatings become stiffer and more brittle in the glassy state. This stiffening is probably due to the increase in the amount of hydrogen bonding and the formation of oxidized groups which increase the polarity of the material and enhance the interactions of the polymer segments. However, oxidation reactions result in a considerable decrease in cross‐link density and stiffness in the rubbery state. Both changes, in the glassy and rubbery states, give rise to development of internal stresses. These stresses increase as the degradation process proceeds. Nevertheless, for samples exposed to anaerobic conditions, the stiffness remains constant in the glassy state and the cross‐link density slightly increases as a result of degradation. This reconfirms the dominance of the effect of oxidation reactions on the mechanical failure of the coatings. Oxygen permeation measurements show a more‐or‐less time‐independent diffusion coefficient and a gradual decrease in solubility of oxygen as a function of exposure time. This results in a slight decrease in oxygen permeation (mainly in the early stage of the degradation) as degradation proceeds. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 659–671 相似文献
128.
Wout De Nolf Jakub Jaroszewicz Roberto Terzano Ole Christian Lind Brit Salbu Bart Vekemans Koen Janssens Gerald Falkenberg 《Spectrochimica Acta Part B: Atomic Spectroscopy》2009,64(8):775
The performance of a combined microbeam X-ray fluorescence/X-ray powder diffraction (XRF/XRPD) measurement station at Hamburger Synchrotronstrahlungslabor (HASYLAB) Beamline L is discussed in comparison to that at European Synchrotron Radiation Facility (ESRF) ID18F/ID22. The angular resolution in the X-ray diffractograms is documented when different combinations of X-ray source, optics and X-ray diffraction detectors are employed. Typical angular resolution values in the range 0.3–0.5° are obtained at the bending magnet source when a ‘pink’ beam form of excitation is employed. A similar setup at European Synchrotron Radiation Facility beamlines ID18F and ID22 allows to reach angular resolution values of 0.1–0.15°. In order to document the possibilities and limitations for speciation of metals in environmental materials by means of Hamburger Synchrotronstrahlungslabor Beamline L X-ray fluorescence/X-ray powder diffraction setup, two case studies are discussed, one involved in the identification of the crystal phases in which heavy metals such as chromium, iron, barium and lead are present in polluted soils of an industrial site (Val Basento, Italy) and another involved in the speciation of uranium in depleted uranium particles (Ceja Mountains, Kosovo). In the former case, the angular resolution is sufficient to allow identification of most crystalline phases present while in the latter case, it is necessary to dispose of an angular resolution of ca. 0.2° to distinguish between different forms of oxidized uranium. 相似文献
129.
130.
S. Bugani F. Modugno J. J. Łucejko G. Giachi S. Cagno P. Cloetens K. Janssens L. Morselli 《Analytical and bioanalytical chemistry》2009,395(7):1977-1985
In favourable conditions of low temperature and low oxygen concentration, archaeological waterlogged wooden artefacts, such
as shipwrecks, can survive with a good state of preservation. Nevertheless, anaerobic bacteria can considerably degrade waterlogged
wooden objects with a significant loss in polysaccharidic components. Due to these decay processes, wood porosity and water
content increase under ageing. In such conditions, the conservation treatments of archaeological wooden artefacts often involve
the replacement of water with substances which fill the cavities and help to prevent collapse and stress during drying. The
treatments are very often expensive and technically difficult, and their effectiveness very much depends on the chemical and
physical characteristics of the substances used for impregnation. Also important are the degree of cavity-filling, penetration
depth and distribution in the structure of the wood. In this study, the distribution in wood cavities of some mixtures based
on polyethylene glycols and colophony, used for the conservation of waterlogged archaeological wood, was investigated using
synchrotron radiation X-ray computed microtomography (SR-μCT). This non-destructive imaging technique was useful for the study
of the degraded waterlogged wood and enabled us to visualise the morphology of the wood and the distribution of the materials
used in the wood treatments. The study has shown how deposition is strictly related to the dimension of the wooden cavities.
The work is currently proceeding with the comparison of synchrotron observations with the data of the solutions viscosity
and with those of the properties imparted to the wood by the treatments. 相似文献