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111.
Mark S. Oliver Kay Y. Blohowiak Reinhold H. Dauskardt 《Journal of Sol-Gel Science and Technology》2010,55(3):360-368
The mechanical reliability of hybrid films depends critically on their fracture properties which are controlled largely by
the film composition and molecular structure. We have investigated the adhesive and cohesive fracture properties of hybrid
films processed from 3-glycidoxypropyltrimethoxysilane (GPTMS) and tetra n-propoxyzirconium (TPOZ), for which the roles of molecular structure and composition have not been well established. The influences
of film Zr/GPTMS ratio, silane crosslinking, and substrate composition on fracture resistance were quantified in terms of
the critical strain energy release rate, GC Film fracture energy was found to increase, then decrease with increasing Zr/GPTMS ratio. Removal of the epoxy rings of GPTMS
from the film was found to drastically decrease the cohesive fracture energy of the film as well as the adhesive fracture
energy of the film/epoxy interface. Finally, films deposited on silicon had much higher fracture energies compared to those
deposited onto aluminum and titanium from identical sols. FTIR, XPS, and AFM were used to characterize the film structure
and fracture surfaces. The molecular-scale mechanisms responsible for the observed trends are discussed. These results provide
new insights into the interaction between the substrate chemistry, molecular structure, and mechanical reliability of hybrid
sol-gel films. 相似文献
112.
Sébastien Rochat Jie Gao Xuhong Qian Prof. Friederike Zaubitzer Kay Severin Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(1):104-113
A simple but powerful method for the sensing of peptides in aqueous solution has been developed. The transition‐metal complexes [PdCl2(en)], [{RhCl2Cp*}2], and [{RuCl2(p‐cymene)}2] were combined with six different fluorescent dyes to build a cross‐reactive sensor array. The fluorescence response of the individual sensor units was based on competitive complexation reactions between the peptide analytes and the fluorescent dyes. The collective response of the sensor array in a time‐resolved fashion was used as an input for multivariate analyses. A sensor array comprised of only six metal–dye combinations was able to differentiate ten different dipeptides in buffered aqueous solution at a concentration of 50 μM . Furthermore, the cross‐reactive sensor could be used to obtain information about the identity and the quantity of the pharmacologically interesting dipeptides carnosine and homocarnosine in a complex biological matrix, such as deproteinized human blood serum. The sensor array was also able to sense longer peptides, which was demonstrated by differentiating mixtures of the nonapeptide bradykinin and the decapeptide kallidin. 相似文献
113.
114.
We show that the weak signal that remains after (13)C-detected experiments (the (13)C "afterglow") can still be measured with high sensitivity by proton detection. This is illustrated by the incorporation of two experiments, 2D (HA)CACO and 3D (HA)CA(CO)NNH, into a single pulse sequence that makes use of two receivers in parallel. In cases where the sensitivity is not limiting, such as applications to small proteins, the inclusion of the projection-reconstruction method permits the recording of both spectra in only 15 min. High-quality data sets for the 143 residue nuclease A inhibitor (2 °C, correlation time 17.5 ns) were obtained in 3 h, illustrating the utility of the method even in studies of moderately sized proteins. 相似文献
115.
Mohamed E. El‐Khouly Dr. Ki‐Jong Han Dr. Kwang‐Yol Kay Prof. Dr. Shunichi Fukuzumi Prof. Dr. 《Chemphyschem》2010,11(8):1726-1734
Spectroscopic, redox, computational, and electron transfer reactions of the covalently linked zinc porphyrin–triphenylamine–fulleropyrrolidine system are investigated in solvents of varying polarity. An appreciable interaction between triphenylamine and the porphyrin π system is revealed by steady‐state absorption and emission, redox, and computational studies. Free‐energy calculations suggest that the light‐induced processes via the singlet‐excited porphyrin are exothermic in benzonitrile, dichlorobenzene, toluene, and benzene. The occurrence of fast and efficient charge‐separation processes (≈1012 s?1) via the singlet‐excited porphyrin is confirmed by femtosecond transient absorption measurements in solvents with dielectric constants ranging from 25.2 (benzonitrile) to 2.2 (benzene). The rates of the charge separation processes are much less solvent‐dependent, which suggests that the charge‐separation processes occur at the top region of the Marcus parabola. The lifetimes of the singlet radical‐ion pair (70–3000 ps at room temperature) decrease substantially in more polar solvents, which suggests that the charge‐recombination process is occurring in the Marcus inverted region. Interestingly, by utilizing the nanosecond transient absorption spectral technique we can obtain clear evidence about the existence of triplet radical‐ion pairs with relatively long lifetimes of 0.71 μs (in benzonitrile) and 2.2 μs (in o‐dichlorobenzene), but not in toluene and benzene due to energetic considerations. From the point of view of mechanistic information, the synthesized zinc porphyrin–triphenylamine–fulleropyrrolidine system has the advantage that both the lifetimes of the singlet and triplet radical‐ion pair can be determined. 相似文献
116.
Martin Hoefling Francesco Iori Dr. Stefano Corni Dr. Kay‐Eberhard Gottschalk Dr. 《Chemphyschem》2010,11(8):1763-1767
The interactions of amino acids with inorganic surfaces are of interest for biologists and biotechnologists alike. However, the structural determinants of peptide–surface interactions have remained elusive, but are important for a structural understanding of the interactions of biomolecules with gold surfaces. Molecular dynamics simulations are a tool to analyze structures of amino acids on surfaces. However, such an approach is challenging due to lacking parameterization for many surfaces and the polarizability of metal surfaces. Herein, we report DFT calculations of amino acid fragments in vacuo and molecular dynamics simulations of the interaction of all amino acids with a gold(111) surface in explicit solvent, using the recently introduced polarizable gold force field GolP. We describe preferred orientations of the amino acids on the metal surface. We find that all amino acids preferably interact with the gold surface at least partially with their backbone, underlining an unfolding propensity of gold surfaces. 相似文献
117.
Thuro Arnold Kay Großmann Nils Baumann 《Analytical and bioanalytical chemistry》2010,396(5):1641-1653
Biofilms may immobilize toxic heavy metals in the environment and thereby influence their migration behaviour. The mechanisms
of these processes are currently not understood, because the complexity of such biofilms creates many discrete geochemical
microenvironments which may differ from the surrounding bulk solution in their bacterial diversity, their prevailing geochemical
properties, e.g. pH and dissolved oxygen concentration, the presence of organic molecules, e.g. metabolites, and many more,
all of which may affect metal speciation. To obtain such information, which is necessary for performance assessment studies
or the development of new cost-effective strategies for cleaning waste waters, it is very important to develop new non-invasive
methods applicable to study the interactions of metals within biofilm systems. Laser fluorescence techniques have some superior
features, above all very high sensitivity for fluorescent heavy metals. An approach combining confocal laser scanning microscopy
and laser-induced fluorescence spectroscopy for study of the interactions of biofilms with uranium is presented. It was found
that coupling these techniques furnishes a promising tool for in-situ non-invasive study of fluorescent heavy metals within
biofilm systems. Information on uranium speciation and uranium redox states can be obtained. 相似文献
118.
119.
We identify conditions under which correlations resulting from quantum measurements performed on macroscopic systems (systems composed of a number of particles of the order of the Avogadro number) can be described by local realism. We argue that the emergence of local realism at the macroscopic level is caused by an interplay between the monogamous nature of quantum correlations and the fact that macroscopic measurements do not reveal properties of individual particles. 相似文献
120.
Jewart CM Chen T Lindner E Fiebrandt J Rothhardt M Schuster K Kobelke J Bartelt H Chen KP 《Optics letters》2011,36(23):4491-4493
This Letter presents simulation and experimental results that explore bending insensitivity of fiber Bragg gratings in suspended-core optical fibers. The implementation of thin silica bridge in the fibers enhances index contrast of the fiber core and reduces bending-induced strain transfer to the fiber core. This fiber design lead to a reduction of over 7 times in strain-induced fiber Bragg grating resonant peak shifts in the suspended-core fiber compared with that in standard telecommunication fiber, and an 0.14 dB bending loss at a bending radius of 6.35 mm. 相似文献