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101.
Testosterone metabolism revisited: discovery of new metabolites 总被引:1,自引:0,他引:1
Oscar J. Pozo Josep Marcos Rosa Ventura Andreu Fabregat Jordi Segura 《Analytical and bioanalytical chemistry》2010,398(4):1759-1770
The metabolism of testosterone is revisited. Four previously unreported metabolites were detected in urine after hydrolysis
with KOH using a liquid chromatography–tandem mass spectrometry method and precursor ion scan mode. The metabolites were characterized
by a product ion scan obtained with accurate mass measurements. Androsta-4,6-dien-3,17-dione, androsta-1,4-dien-3,17-dione,
17-hydroxy-androsta-4,6-dien-3-one and 15-androsten-3,17-dione were proposed as feasible structures for these metabolites
on the basis of the mass spectrometry data. The proposed structures were confirmed by analysis of synthetic reference compounds.
Only 15-androsten-3,17-dione could not be confirmed, owing to the lack of a commercially available standard. That all four
compounds are testosterone metabolites was confirmed by the qualitative analysis of several urine samples collected before
and after administration of testosterone undecanoate. The metabolite androsta-1,4-dien-3,17-dione has a structure analogous
to that of the exogenous anabolic steroid boldenone. Specific transitions for boldenone and its metabolite 17β-hydroxy-5β-androst-1-en-3-one
were also monitored. Both compounds were also detected after KOH treatment, suggesting that this metabolic pathway is involved
in the endogenous detection of boldenone previously reported by several authors. 相似文献
102.
An efficient synthesis of 3-halo-7-oxygen-functionalized benzo[b]thiophenes bearing different substituents at C-2 has been developed from N,N-diethyl O-3-halophenylcarbamates. The key steps are an ortho-lithiation reaction, which gives rise to 3-halo-2-sulfanylphenol derivatives, and a electrophilic cyclization. The subsequent functionalization of the prepared halobenzothiophenes allows the access of a wide variety of 2,3,7-regioselectively functionalized benzo[b]thiophenes in good overall yields. 相似文献
103.
Hernando Quevedo 《General Relativity and Gravitation》2011,43(4):1141-1152
We present the Ernst potential and the line element of an exact solution of Einstein’s vacuum field equations that contains
as arbitrary parameters the total mass, the angular momentum, and the quadrupole moment of a rotating mass distribution. We
show that in the limiting case of slowly rotating and slightly deformed configuration, there exists a coordinate transformation
that relates the exact solution with the approximate Hartle solution. It is shown that this approximate solution can be smoothly
matched with an interior perfect fluid solution with physically reasonable properties. This opens the possibility of considering
the quadrupole moment as an additional physical degree of freedom that could be used to search for a realistic exact solution,
representing both the interior and exterior gravitational field generated by a self-gravitating axisymmetric distribution
of mass of perfect fluid in stationary rotation. 相似文献
104.
Krzysztof K. Zborowski Miquel Solà Jordi Poater Leonard M. Proniewicz 《Journal of Physical Organic Chemistry》2011,24(6):499-506
The aim of this project is to study the aromatic properties of various forms (neutral, cationic, and anionic) of selected hydroxypyrones (pyromeconic acid, maltol, and ethylmaltol) and their metalcomplexes with aluminum, gallium, and indium ions. Aromaticity of hydroxypyrone metalcomplexes is important because it can influence the stability of such complexes, which is crucial for their applications in medicinal and environmental chemistry. Results from ten different indices of aromaticity (HOMA, NICS(0), NICS(1), NICSscan, ASEiso, PDI, FLU, Iring, MCI, and KMCI) show that aromaticity in hydroxypyrones decreases in the order cations > neutral molecules > anions. Performed calculations situate the aromaticities of ligands in metalcomplexes close to their respective cations. This means that complexation causes a significant increase of the aromaticity of ligands, which stabilizes formed chelatocomplexes. On the other hand, we clearly show that rings that are involved in binding metal ions are not aromatic. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
105.
Florian Meirer Jordi Cabana Yijin Liu Apurva Mehta Joy C. Andrews Piero Pianetta 《Journal of synchrotron radiation》2011,18(5):773-781
The ability to probe morphology and phase distribution in complex systems at multiple length scales unravels the interplay of nano‐ and micrometer‐scale factors at the origin of macroscopic behavior. While different electron‐ and X‐ray‐based imaging techniques can be combined with spectroscopy at high resolutions, owing to experimental time limitations the resulting fields of view are too small to be representative of a composite sample. Here a new X‐ray imaging set‐up is proposed, combining full‐field transmission X‐ray microscopy (TXM) with X‐ray absorption near‐edge structure (XANES) spectroscopy to follow two‐dimensional and three‐dimensional morphological and chemical changes in large volumes at high resolution (tens of nanometers). TXM XANES imaging offers chemical speciation at the nanoscale in thick samples (>20 µm) with minimal preparation requirements. Further, its high throughput allows the analysis of large areas (up to millimeters) in minutes to a few hours. Proof of concept is provided using battery electrodes, although its versatility will lead to impact in a number of diverse research fields. 相似文献
106.
Laura Parejo Dr. Mahdi Chaari Sara Santiago Dr. Gonzalo Guirado Prof. Francesc Teixidor Dr. Rosario Núñez Dr. Jordi Hernando 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):270-280
Icosahedral metallacarboranes are θ-shaped anionic molecules in which two icosahedra share one vertex that is a metal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(C2B9H11)2]−, whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes [Co(C2B9H11)2]− very appealing to participate in electron-transfer processes. In this work, [Co(C2B9H11)2]− is tethered to a perylenediimide dye to produce the first examples of switchable luminescent molecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C2B9H11)2]− with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systems based on conjugates of perylendiimides with ferrocene. Remarkably, they can form gels by treatment with appropriate mixtures of organic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimide conjugates into 1D nanostructures. The interplay between dye π-stacking and metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangement in these materials, which for one of the compounds prepared allows preserving the luminescent behavior in the gel state. 相似文献
107.
108.
109.
We give a construction of a reflexive Banach space Xω1 with a transfinite basis of length ω1 and with no unconditional basic sequence. In addition every bounded operator from a subspace of Xω1 into the space Xω1 is a sum of a simple diagonal operator and a strictly singular one. To cite this article: S.A. Argyros et al., C. R. Acad. Sci. Paris, Ser. I 337 (2003). 相似文献
110.
P. Crespo I. Navarro A. Hernando P. Rodrí guez A. Garcí a Escorial J. M. Barandiar n O. Drbohlav A. R. Yavari 《Journal of magnetism and magnetic materials》1995,150(3):409-416
A ferromagnetic solid solution with a nominal atomic composition Fe70Cu30 and a body-centered structure has been obtained by high-energy ball milling. The decomposition of the system is monitored by X-ray diffraction (XRD), magnetic measurements and Mössbauer spectroscopy. According to XRD, for healing temperatures below 723 K there is only a bcc phase in the material, while for heating temperatures above 723 K a new phase, with a fcc structure, appears, suggesting that the solid solution has decomposed into bcc-Fe and fcc-Cu. However, the magnetic behavior observed during the decomposition process indicates that this evolution is more complex than the simple decomposition into the equilibrium phases. This behavior can be summarized in two points: (1) a decrease in the magnetization at 5 K, and (2) drastic changes in the coercive field with the thermal treatment, soft magnetic behavior for the material in the as-milled state, superparamagnetism for low heating temperatures and a hardening of the material heated to above 723 K, for which the values of the coercive field at room temperature are several times higher than those for the as-milled sample. The Mössbauer spectroscopy performed at room temperature shows that for the heat-treated samples the Fe atoms are in two different phases: a ferromagnetic phase, which evolves to bcc-Fe, and a paramagnetic phase. 相似文献