全文获取类型
收费全文 | 520篇 |
免费 | 13篇 |
专业分类
化学 | 314篇 |
晶体学 | 8篇 |
力学 | 21篇 |
数学 | 66篇 |
物理学 | 124篇 |
出版年
2024年 | 1篇 |
2023年 | 6篇 |
2022年 | 14篇 |
2021年 | 18篇 |
2020年 | 24篇 |
2019年 | 11篇 |
2018年 | 20篇 |
2017年 | 12篇 |
2016年 | 24篇 |
2015年 | 31篇 |
2014年 | 31篇 |
2013年 | 27篇 |
2012年 | 50篇 |
2011年 | 47篇 |
2010年 | 25篇 |
2009年 | 18篇 |
2008年 | 30篇 |
2007年 | 29篇 |
2006年 | 25篇 |
2005年 | 22篇 |
2004年 | 14篇 |
2003年 | 17篇 |
2002年 | 10篇 |
2001年 | 2篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1992年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
排序方式: 共有533条查询结果,搜索用时 15 毫秒
61.
Egbert Müller Judith Vajda Djuro Josic Tim Schröder Romain Dabre Tim Frey 《Journal of separation science》2013,36(8):1327-1334
An essential part of the modulation of protein‐binding capacity in hydrophobic interaction chromatography is the buffer‐salt system. Besides using “single” electrolytes, multicomponent electrolyte mixtures may be used as an additional tool. Both the protein solubility and the binding capacity depend on the position of a salt in the so‐called Hofmeister series. Specific interactions are observed for an individual protein‐salt combination. For salt mixtures, selectivity, recovery, and binding capacity do not behave like for the single salts that are positioned in between the two mixed components in the Hofmeister series, as the continuous correlation would suggest. Thus, finding strategies for mixed salts could potentially lead to improved capacities in hydrophobic interaction chromatography. Mixtures of ammonium sulfate, sodium citrate, sodium sulfate, sodium chloride, sodium acetate, and glycine were used to investigate the binding capacities for lysozyme and a monoclonal antibody on various hydrophobic resins. Resin capacity for two investigated proteins increases when mixtures consisting of a chaotropic and a kosmotropic salt are applied. It seems to be related to the rather basic isoelectric points of the proteins. 相似文献
62.
Dabre R Azad N Schwämmle A Lämmerhofer M Lindner W 《Journal of separation science》2011,34(7):761-772
Several methods for the separation of vitamins on HPLC columns were already validated in the last 20 years. However, most of the techniques focus on separating either fat- or water-soluble vitamins and only few methods are intended to separate lipophilic and hydrophilic vitamins simultaneously. A mixed-mode reversed-phase weak anion exchange (RP-WAX) stationary phase was developed in our laboratory in order to address such mixture of analytes with different chemical characteristics, which are difficult to separate on standard columns. The high versatility in usage of the RP-WAX chromatographic material allowed a baseline separation of ten vitamins within a single run, seven water-soluble and three fat-soluble, using three different chromatographic modes: some positively charged vitamins are eluted in ion exclusion and ion repulsion modes whereas the negatively charged molecules are eluted in the ion exchange mechanism. The non-charged molecules are eluted in a classical reversed-phase mode, regarding their polarities. The method was validated for the vitamin analysis in tablets, evaluating selectivity, robustness, linearity, accuracy, and precision. The validated method was finally employed for the analysis of the vitamin content of some commercially available supplement tablets. 相似文献
63.
Romain Valentin Karine Molvinger Françoise Quignard Francesco Di Renzo 《Macromolecular Symposia》2005,222(1):93-102
Nitrogen adsorption at 77 K has been applied to the study of the texture of alginate aerogel microspheres obtained by CO2 supercritical drying of alcogels. The limited volume shrinkage suggests that the aerogels preserve the texture of the hydrogels. Alginate aerogels presents a N2 adsorption at small pressure higher than reference non-porous silica, to be attributed to the polarity of the surface or to a small microporous volume. The aggregated nanobead strings of the guluronic-rich gels accounts for a significant mesoporosity. The N2 adsorption results correspond to electron microscopy observations for features smaller than 50 nm. 相似文献
64.
Romain Siegrist Corinne Baumgartner Paul Seiler Franois Diederich 《Helvetica chimica acta》2005,88(8):2250-2261
We report a short synthetic route that provides optically active 2‐substituted hexahydro‐1H‐pyrrolizin‐3‐ones in four steps from commercially available Boc (tert‐but(oxy)carbonyl))‐protected proline. Diastereoisomers (−)‐ 11 and (−)‐ 12 were assembled from the proline‐derived aldehyde (−)‐ 8 and ylide 9 via a Wittig reaction and subsequent catalytic hydrogenation (Scheme 3). Cleavage of the Boc protecting group under acidic conditions, followed by intramolecular cyclization, afforded the desired hexahydro‐1H‐pyrrolizinones (−)‐ 1 and (+)‐ 13 . Applying the same protocol to ylide 19 afforded hexahydro‐1H‐pyrrolizinones (−)‐ 25 and (−)‐ 26 (Scheme 5). The absolute configuration of the target compounds was determined by a combination of NMR studies (Figs. 1 and 2) and X‐ray crystallographic analysis (Fig. 3). 相似文献
65.
In this work, snapshot proper orthogonal decomposition (POD) is used to study a pulsed jet in crossflow where the velocity fields are extracted from stereoscopic particle image velocimetry (SPIV) results. The studied pulsed jet is characterized by a frequency f = 1 Hz, a Reynolds number Re j = 500 (based on the mean jet velocity ${\overline{U}_{j}}$ = 1.67 cm/s and a mean velocity ratio of R = 1). Pulsed jet and continuous jet are compared via mean velocity field trajectory and Q criterion. POD results of instantaneous, phase-averaged and fluctuating velocity fields are presented and compared in this paper. Snapshot POD applied on one plane allows us to distinguish an organization of the first spatial eigenmodes. A distinction between “natural modes” and “pulsed modes” is achieved with the results obtained by the pulsed and unforced jet. Secondly, the correlation tensor is established with four parallel planes (multi-plane snapshot POD) for the evaluation of volume spatial modes. These resulting modes are interpolated and the volume velocity field is reconstructed with a minimal number of modes for all the times of the pulsation period. These reconstructions are compared to orthogonal measurements to the transverse jet in order to validate the obtained three-dimensional velocity fields. Finally, this POD approach for the 3D flow field reconstruction from experimental data issued from planes parallel to the flow seems capable to extract relevant information from a complex three-dimensional flow and can be an alternative to tomo-PIV for large volume of measurement. 相似文献
66.
Ratan Kotipalli Bart Vermang Viktor Fjällström Marika Edoff Romain Delamare Denis Flandre 《固体物理学:研究快报》2015,9(3):157-160
The benefits of gallium (Ga) grading on Cu(In,Ga)Se2 (CIGS) solar cell performance are demonstrated by comparing with ungraded CIGS cells. Using drive‐level capacitance profiling (DLCP) and admittance spectroscopy (AS) analyses, we show the influence of Ga grading on the spatial variation of deep defects, free‐carrier densities in the CIGS absorber, and their impact on the cell's open‐circuit voltage Voc. The parameter most constraining the cell's Voc is found to be the deep‐defect density close to the space charge region (SCR). In ungraded devices, high deep‐defect concentrations (4.2 × 1016cm–3) were observed near the SCR, offering a source for Shockley–Read–Hall recombination, reducing the cell's Voc. In graded devices, the deep‐defect densities near the SCR decreased by one order of magnitude (2.5 × 1015 cm–3) for back surface graded devices, and almost two orders of magnitude (8.6 × 1014 cm–3) for double surface graded devices, enhancing the cell's Voc. In compositionally graded devices, the free‐carrier density in the absorber's bulk decreased in tandem with the ratio of gallium to gallium plus indium ratio GGI = Ga/(Ga + In), increasing the activation energy, hindering the ionization of the defect states at room temperature and enhancing their role as recombination centers within the energy band. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
67.
68.
J.P. Romain A. Migault J. Jacquesson 《Journal of Physics and Chemistry of Solids》1976,37(12):1159-1165
The Grüneisen ratio of crystalline solids is shown to be dependent on a parameter n whose values are characteristic of each solid, and can be determined by two independent ways: from experimental shock data and from the pressure derivative of Poisson's ratio. The determinations are made for several metals, using data on the pressure derivatives of polycrystalline elastic moduli or of the second order elastic constants measured on single crystals, and giving the pressure derivatives of Poisson's ratio by means of the Voigt-Reuss-Hill averaging procedure. The values of the parameter n deduced from shock data are found to be in good agreement with those deduced from the pressure derivatives of Poisson's ratio. Positive and negative values of parameter n correspond respectively to increasing and decreasing Poisson's ratio with increasing pressure. Discussion of the results is made using the linear and the quadratic relationships between shock velocity and particle velocity. It is shown that shock wave data cannot yield directly an accurate estimation of the derivative of the initial slope of the Hugoniot. 相似文献
69.
K. Jaouadi N. Zouari T. Mhiri A. Daoud F. Romain 《Journal of Raman spectroscopy : JRS》2007,38(3):344-348
Raman spectra (10–1200 cm−1) of polycrystalline samples of Rb2(HSeO4)(H2PO4) were studied at temperatures ranging from 300 to 423 K. An assignment of most of the observed bands is proposed. The first‐order phase transition previously detected at 382 K was characterized as: This superionic‐protonic transition is believed to be governed by librations of the HSe/PO42− ion and the A OH (A = Se, P) stretching mode. It corresponds to the weakening of Se(P) O H˙˙˙ H O Se(P) hydrogen bonds and to the melting of the proton sublattice into a quasi‐liquid state in which the protons and the HSe/PO42− ions contribute to the unusually high conductivity. The activation energy that was determined from the plot Δν1/2 versus temperature for the ν (A OH) band has the same order of magnitude as that determined from conductivity measurements. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
70.
Souhir Boujday Romain Briandet Michèle Salmain Jean-Marie Herry Pierre-Guy Marnet Michel Gautier Claire-Marie Pradier 《Mikrochimica acta》2008,163(3-4):203-209
We describe the elaboration of ultra-sensitive immunosensors, to detect the bacterial pathogen Staphylococcus aureus. We utilized commercially available polyclonal anti-S. aureus antibody as receptor. Immunosensors were elaborated by building a self-assembled monolayer (SAM) of thiolamine onto planar gold-coated sensor chips. Then, Protein A was covalently linked to the thiolated SAM using glutaraldehyde as cross-linking agent. After a blocking step by Bovine Serum Albumin (BSA), the antibody was immobilized by affinity to Protein A. This step-by-step construction was monitored by Polarization Modulation Reflection Absorption Infrared Spectroscopy (PM-RAIRS) and Quartz Crystal Microbalance with Dissipation (QCM-D). In a first stage, the parameters of immunosensor elaboration were optimized using a model rabbit IgG. The accessibility of receptors and the homogeneity of their distribution were checked by PM-RAIRS, QCM-D, and by immuno-gold scanning electron microscopy. Then, the specific rabbit anti-S. aureus antibody was immobilized and the resulting sensing layer was applied to the detection of the pathogen target. Independent detection of bacteria immobilized on the sensors by fluorescent imaging allowed validation of the specificity of recognition toward the pathogen as well as a quantitative response of the sensor. Using PM-RAIRS as transducing technique allowed us to enhance sensitivity and reach a very competitive detection level (105 CFU mL?1). 相似文献