全文获取类型
收费全文 | 379篇 |
免费 | 2篇 |
国内免费 | 1篇 |
专业分类
化学 | 247篇 |
力学 | 3篇 |
数学 | 53篇 |
物理学 | 79篇 |
出版年
2021年 | 9篇 |
2020年 | 8篇 |
2019年 | 4篇 |
2018年 | 9篇 |
2017年 | 4篇 |
2016年 | 7篇 |
2015年 | 6篇 |
2014年 | 12篇 |
2013年 | 30篇 |
2012年 | 17篇 |
2011年 | 28篇 |
2010年 | 18篇 |
2009年 | 11篇 |
2008年 | 19篇 |
2007年 | 21篇 |
2006年 | 18篇 |
2005年 | 19篇 |
2004年 | 10篇 |
2003年 | 20篇 |
2002年 | 14篇 |
2001年 | 4篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1998年 | 4篇 |
1997年 | 8篇 |
1996年 | 2篇 |
1995年 | 5篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 1篇 |
1985年 | 10篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1940年 | 1篇 |
1938年 | 1篇 |
排序方式: 共有382条查询结果,搜索用时 328 毫秒
71.
72.
Marini RD Servais AC Rozet E Chiap P Boulanger B Rudaz S Crommen J Hubert P Fillet M 《Journal of chromatography. A》2006,1120(1-2):102-111
Nonaqueous capillary electrophoresis (NACE) was successfully applied to the enantiomeric purity determination of S-timolol maleate using heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin (HDMS-beta-CD) as chiral selector. With a background electrolyte made up of a methanolic solution of 0.75 M formic acid, 30 mM potassium camphorsulfonate and containing 30 mM HDMS-beta-CD, the determination of 0.1% of R-timolol in S-timolol could be performed with an enantiomeric resolution of 8.5. Pyridoxine was selected as internal standard. The NACE method was then fully validated by applying a novel strategy using accuracy profiles. It is based on beta-expectation tolerance intervals for the total measurement error which includes trueness and intermediate precision. The uncertainty of measurements derived from beta-expectation tolerance intervals was estimated at each concentration level of the validation standards. To confirm the suitability of the developed and validated method, several real samples of S-timolol maleate containing R-timolol maleate at different concentrations were analysed and the results were compared to those obtained by liquid chromatography. 相似文献
73.
This article presents the validation results of a chiral liquid chromatographic (LC) method previously developed for the quantitative determination of R-timolol in S-timolol maleate samples. A novel validation strategy based on the accuracy profiles was used to select the most appropriate regression model, to assess the method accuracy within well defined acceptance limits and to determine the limits of quantitation as well as the concentration range.The validation phase was completed by the investigation of the risk profiles of various acceptable regression models in order to ensure the risk of obtaining the future measurements outside the acceptance limits fixed a priori.On the other hand, the present paper also shows how data used in this validation approach can be used to estimate the measurement uncertainty. The uncertainty derived from β-expectation tolerance interval (), which is equal to the uncertainty of measurements as well as the expanded uncertainty (Ux) using a coverage factor k = 2 was estimated. The uncertainty estimates obtained from validation data were finally compared with those obtained from interlaboratory and robustness studies. 相似文献
74.
New β,β′-aryl/heteroaryl 2,3-divinylfuran derivatives (9a-d) in which a hexatriene system is a part of heteroaromatic ring have been synthesized and their photochemical properties were investigated. The primary process observed was the isomerization to trans,trans-isomers 9a-d followed by photochemical rearrangement of the furan ring giving the phototransposition products (I-IV). Stilbenes (20, 21) and phenanthrenes (22, 25, and 26), formed as secondary products from the competitive intermolecular cycloadditions, were also observed. 相似文献
75.
Thi TD Pomponio R Gotti R Saevels J Van Hove B Van Ael W Matthijs N Vander Heyden Y Djan'geing'a RM Chiap P Hubert P Crommen J Fabre H Dehouck P Hoogmartens J Van Schepdael A 《Electrophoresis》2006,27(12):2317-2329
A CE method for metacycline (MTC) determination was investigated in an inter-laboratory experiment. Many problems were encountered in this study, most of which were related to the transfer of the method to different CE equipment. The reported problems could be classified into different categories: problems related to the precision, to the parameters in the protocol, and to the MTC peak shape. As the peak shape problem was partially responsible for the poor precision, a new CE method was developed in order to obtain a good MTC peak shape on all equipment. The precision of this new method for MTC determination was examined in an intermediate precision study, where the influence of the factors "time" and "equipment" was investigated. Although the new method could be transferred to different instruments, the precision remained poor mainly due to the contributions of the between-replicate and the between-injection variances. 相似文献
76.
In railway applications, the estimation of the wear at the wheel-rail contact is an important field of study, mainly correlated to the planning of maintenance interventions, vehicle stability and the possibility to carry out specific strategies for the wheel profile optimization. In this work Authors present a model conceived for the evaluation of the wheel profile evolution due to wear, which is organized in two parts, mutually interactive: a vehicle model for the dynamic analysis and a model for the wear estimation. The wheel wear evolution is reproduced by dividing the overall chosen mileage to be simulated in discrete spatial steps: at each step the dynamic simulations are performed by means of the vehicle model keeping the wheel profile constant, while the wheel geometry is updated through the wear model only at the end of the discrete step. Thus, the two parts of the whole model work alternately until the completion of the whole established mileage. Clearly, the choice of an appropriate step length is one of the most important aspect of the procedure and it affects directly the result accuracy and the required computational time to complete the analysis. The entire model has been validated in collaboration with Trenitalia S.p.A and RFI, which has provided the technical documentation and the experimental results relating to some tests performed on a scenery that exhibits serious problems in terms of wear represented by the vehicle ALn 501 “Minuetto” on the Aosta-Pre Saint Didier line. 相似文献
77.
Ketoreductases were utilized for the stereoselective synthesis of δ-hydroxy-β-keto esters, β-hydroxy-δ-keto esters, and β,δ-dihydroxy esters. Seven out of eight possible stereoisomers were obtained from the enzymatic reduction of the corresponding β,δ-diketo ester in high enantio- and diastereomeric excess. 相似文献
78.
Favaro M Guastoni A Marini F Bianchin S Gambirasi A 《Analytical and bioanalytical chemistry》2012,402(6):2195-2208
In this paper, we propose an analytical methodology for attributing provenance to natural lapis lazuli pigments employed in
works of art, and for distinguishing whether they are of natural or synthetic origin. A multitechnique characterization of
lazurite and accessory phases in lapis lazuli stones from Afghan, Siberian and Chilean quarries, on the pigments obtained
by their purification, and on synthetic ultramarine pigments was performed. According to the results obtained, infrared spectroscopy
is not a suitable technique for distinguishing the provenance of lapis lazuli, but a particular absorbance band makes it relatively
easy to determine whether it is of natural or synthetic origin. On the other hand, EDS elemental composition and XRD patterns
show the presence of specific mineral phases associated with specific lapis lazuli sources, and can be used to distinguish
the provenance of the stones as well as—albeit to a lesser extent—the corresponding purified blue pigments. In contrast, FEG-SEM
observations clearly show different stone textures depending on their provenance, although these distinctive features do not
persist in the corresponding pigments. PCA analyses of EDS data allow Afghan lapis lazuli stone to be distinguished from Chilean
and Siberian ones, and can distinguish between the pigments resulting from their purification as well as synthetic blue ones.
Although this methodology was developed using a limited number of samples, it was tested on lapis lazuli pigments collected
from three paintings (from the fourteenth to sixteenth centuries) in order to perform a preliminary validation of the technique,
and based on the results, the provenance of the blue pigments employed in those artworks is proposed. Finally, upon analytically
monitoring the process of purifying lapis lazuli to obtain the corresponding pigments, it was found that ion-exchange reactions
occur between the alkali modifiers of silicate/aluminosilicate phases and free carboxylic acids present in the doughy mixture
of natural terpenes and ground stone, namely pastello. These reactions favor (i) the retention of silicate phases in the organic mixture and (ii) the selective extraction of lazurite
due to the formation of Br?nsted acidic sites [Al(OH)Si], which are responsible for its high hydrophilicity in comparison
to the one of the other species present in the lapis lazuli stone. 相似文献
79.
Zhao P Ragam S Ding YJ Zotova IB Mu X Lee HC Meissner SK Meissner H 《Optics letters》2012,37(7):1283-1285
We implemented a singly resonant optical parametric oscillator based on adhesive-free-bonded periodically inverted KTiOPO4 plates. It has major advantages such as walk-off compensation and oscillation at four wavelengths. The threshold of the oscillation was measured to be 8 MW/cm2, which is about a factor of 4 lower than that based in two separate KTiOPO4 crystals. By frequency-mixing the dual-wavelength output in GaP stacks, we generated the terahertz radiation at 2.54 THz. The tuning range of the terahertz output was demonstrated to be 2.19-2.77 THz. 相似文献
80.
Hodgkinson JT Galloway WR Wright M Mati IK Nicholson RL Welch M Spring DR 《Organic & biomolecular chemistry》2012,10(30):6032-6044
Many species of bacteria employ a mechanism of intercellular communication known as quorum sensing which is mediated by small diffusible signalling molecules termed autoinducers. The most common class of autoinducer used by Gram-negative bacteria are N-acylated-L-homoserine lactones (AHLs). Pseudomonas aeruginosa is a clinically important bacterium which is known to use AHL-mediated quorum sensing systems to regulate a variety of processes associated with virulence. Thus the selective disruption of AHL-based quorum sensing represents a strategy to attenuate the pathogenicity of this bacterium. Herein we describe the design, synthesis and biological evaluation of a collection of structurally novel AHL mimics. A number of new compounds capable of modulating the LasR-dependent quorum sensing system of P. aeruginosa were identified, which could have value as molecular tools to study and manipulate this signalling pathway. Worthy of particular note, this research has delivered novel potent quorum sensing antagonists, which strongly inhibit the production of virulence factors in a wild type strain of this pathogenic bacterium. 相似文献