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31.
32.
G. A. Zachariadis N. M. Tzollas M. Nikolaou E. Rosenberg 《Biomedical chromatography : BMC》2013,27(3):299-305
A headspace solid‐phase micro‐extraction (HS‐SPME) method was employed in order to study the effect of storage conditions of human urine samples spiked with tributyltin (TBT) using gas chromatography and mass spectrometry. To render the analyte more volatile, the derivatization (ethylation) was made in situ by sodium tetraethylborate (NaBEt4), which was added directly to dilute unpreserved urine samples and in buffers of similar acidity. The stability of TBT in human urine matrix was compared with the stability of TBT in buffer solutions of similar pH value. Critical parameters of storage conditions such as temperature and time, which affect the stability of TBT in this kind of matrix, were examined extensively. The tests showed that the stability of TBT remains practically satisfactory for a maximum of 2 days of storage either at +4 or 20°C. Greater variations were observed in the concentration of TBT in human urine samples at +4°C and lower ones at ?20°C over a month's storage. The freeze–thaw cycles have negative effect on the stability and should be kept to a minimum. The results from spiked urine samples are also discussed in comparison to those acquired from buffer solutions of equal TBT concentration. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
33.
Using an ionization gas dynamics code, we simulate a model of the wind-blown bubble around a 40 M⊙ star. We use this to compute the X-ray spectra from the bubble, which can be directly compared to observations. We outline our methods and techniques for these computations, and contrast them with previous calculations. Our simulated X-ray spectra compare reasonably well with observed spectra of Wolf–Rayet bubbles. They suggest that X-ray nebulae around massive stars may not be easily detectable, consistent with observations. 相似文献
34.
A. Haunold E. Rosenberg M. Grasserbauer 《International journal of environmental analytical chemistry》2013,93(1-4):157-172
Abstract Reliable and comprehensive sampling methods are required to obtain accurate data for VOC concentrations in air samples. The major drawback of the adsorption tube sampling method, widely employed in environmental studies, is the fact that C2 compounds are usually not trapped quantitatively. The focus of this work was thus to improve sampling based on adsorption tubes packed with Molsieve and Carbosieve. To improve the sampling efficiency for the C2 compounds, a cooling device, based on Peltier cooling was constructed, which could be operated at a temperature down to ?30°C. Experiments under laboratory and field conditions were carried out to study the influence of the sampling temperatuie on the recovery of ethane and ethene as the most volatile VOCs. The results clearly demonstrate the need for a cooled sampling device for the analysis of C2 compounds in air. Under the investigated conditions, the recoveries with ambient temperature sampling were only in the range of 38–46% for ethane and 33–59% for ethene respectively, in comparison to the cooled sampling device. These findings are only valid for the described conditions and can change significantly with temperature and concentration. A generalisation of the recovery is thus very difficult to give. The use of the sampling device for a field study is reported, where samples were collected simultaneously at three different altitudes in a diurnal profile on the slope of the Schulterberg mountain in Tyrol (Austria). 相似文献
35.
The understanding of the electronic effects of the diastereoselective addition of a nucleophile to a polar substituted aldehyde or ketone is not complete, with several theories competing to explain the data. For numerous hydride reductions of 3‐X‐2‐butanones (X = F, Cl, Br), the selectivity for the major syn isomer is significantly and consistently higher for X = Br than for X = F. This result is rationalized as a shift in mechanism from Cornforth (X = F) to Felkin–Anh (X = Br). The experimental data is well modeled by ab initio calculations for the addition to these ketones by BH3, but not by other nucleophiles such as LiH or LiAlH4. The energetic ordering of the BH3 transition states largely follows the trends for the ground state ketones. Here, consistent with electrostatic arguments, the anti orientation of the C―X and C?O bonds is always lower in energy than the syn arrangement. The gauche conformer is intermediate between these two, becoming gradually lower in energy as X increases in size. The hyperconjugative interaction invoked by the Felkin–Anh model provides only a modest stabilization of the relevant transition states as judged by NBO analysis. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
36.
Dr. Julian Brunner Britta Maier Rose Rosenberg Sebastian Sturm Prof. Dr. Helmut Cölfen Dr. Elena V. Sturm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15242-15248
Applications in the fields of materials science and nanotechnology increasingly demand monodisperse nanoparticles in size and shape. Up to now, no general purification procedure exists to thoroughly narrow the size and shape distributions of nanoparticles. Here, we show by analytical ultracentrifugation (AUC) as an absolute and quantitative high-resolution method that multiple recrystallizations of nanocrystals to mesocrystals is a very efficient tool to generate nanocrystals with an excellent and so-far unsurpassed size-distribution (PDIc=1.0001) and shape. Similar to the crystallization of molecular building blocks, nonclassical recrystallization removes “colloidal” impurities (i.e., nanoparticles, which are different in shape and size from the majority) by assembling them into a mesocrystal. In the case of nanocrystals, this assembly can be size- and shape-selective, since mesocrystals show both long-range packing ordering and preferable crystallographic orientation of nanocrystals. Besides the generation of highly monodisperse nanoparticles, these findings provide highly relevant insights into the crystallization of mesocrystals. 相似文献
37.
38.
E. Trikas G. A. Zachariadis E. Rosenberg 《Analytical and bioanalytical chemistry》2014,406(14):3489-3496
Organic germanium compounds, especially Ge-132, more corrctly denoted as bis-beta-carboxyethyl germanium sesquioxide ([Ge(=O)CH2CH2CO2H]2O), are of continued interest as they are said to promote health and display anticancer activity. Although these beneficial effects have never been substantiated by comprehensive clinical studies, this drug can still be obtained through various sources and is usually marketed as a nutritional supplementation rather than an anticancer medication. As the quality standards under which this drug is produced are unknown, the need for an effective quality control of these products arises. To date, Ge-132 is considered generally as a safe compound for application in contrast to inorganic germanium which demonstrates severe renal toxicity. In this paper, a new approach to the determination of Ge-132, based on derivatization by ethyl chloroformate reagent (ECF), in the presence of ethanol and pyridine in the mixture, and subsequent analysis by gas chromatography coupled with microwave-induced plasma-atomic emission detection (GC-MIP-AED), is reported. Reaction conditions of the derivatization procedure were optimized with particular respect to the reagent (ECF) and catalyst (pyridine) concentrations. The proposed method is capable of distinguishing Ge-132 from inorganic germanium. The derivatization procedure was also tested with the use of methyl chloroformate (MCF) as alternative reagent, providing interesting additional information about the nature of the final product and the proposed reaction scheme. Among the two types of chloroformates, i.e., MCF and ECF, the latter proved to be more suitable for the proposed method, providing a calibration curve of superior sensitivity and linearity compared with the one obtained with MCF. The method was applied successfully in three real samples, two food supplements, and one commercially available fertilizer. The analysis of the Ge-132 derivative showed good linearity in the concentration of 1–250 mg L?1 (r 2?=?0.9986) and a satisfactory precision (RSD?=?6.8 %), which qualifies the proposed method for the speciation analysis of Ge in various matrices. 相似文献
39.
Clayton A. Whitmore Mariam I. Boules William J. Behof Justin R. Haynes Dmitry Koktysh Adam J. Rosenberg Mohammed N. Tantawy Wellington Pham 《Molecules (Basel, Switzerland)》2021,26(8)
Promethazine, an antihistamine drug used in the clinical treatment of nausea, has been demonstrated the ability to bind Abeta in a transgenic mouse model of Alzheimer’s disease. However, so far, all of the studies were performed in vitro using extracted tissues. In this work, we report the design and synthesis of a novel [11C]promethazine PET radioligand for future in vivo studies. The [11C]promethazine was isolated by RP-HPLC with radiochemical purity >95% and molar activity of 48 TBq/mmol. The specificity of the probe was demonstrated using human hippocampal tissues via autoradiography. 相似文献
40.
A new coaxial detection system for backscattered electrons in SEM is described. This coaxial detection system allows us to collect only the backscattered electrons that have lost a small percentage of the primary energy, emerging from the sample surface with a take-off angle defined by the objective lens. This new configuration reinforces the atomic-number contrast and suppresses effectively the topographic contrast. The simulation and experimental results confirm these expectations: this new type of SEM is very suitable for observing differences in atomic number. Moreover, by associating the obtained image with a conventional secondary electron image, we build a third (color) image that allows us to give finally at the same time, in a single image, both of the chemical and topographic information. 相似文献