全文获取类型
收费全文 | 468篇 |
免费 | 15篇 |
国内免费 | 4篇 |
专业分类
化学 | 300篇 |
力学 | 27篇 |
数学 | 77篇 |
物理学 | 83篇 |
出版年
2022年 | 6篇 |
2021年 | 4篇 |
2020年 | 7篇 |
2019年 | 5篇 |
2018年 | 12篇 |
2017年 | 2篇 |
2016年 | 15篇 |
2015年 | 16篇 |
2014年 | 25篇 |
2013年 | 36篇 |
2012年 | 35篇 |
2011年 | 35篇 |
2010年 | 15篇 |
2009年 | 11篇 |
2008年 | 18篇 |
2007年 | 18篇 |
2006年 | 18篇 |
2005年 | 19篇 |
2004年 | 20篇 |
2003年 | 12篇 |
2002年 | 11篇 |
2001年 | 12篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 4篇 |
1996年 | 8篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 9篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 3篇 |
1982年 | 11篇 |
1981年 | 6篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 5篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1957年 | 4篇 |
1955年 | 1篇 |
排序方式: 共有487条查询结果,搜索用时 928 毫秒
81.
Doye JP Louis AA Lin IC Allen LR Noya EG Wilber AW Kok HC Lyus R 《Physical chemistry chemical physics : PCCP》2007,9(18):2197-2205
The ability to control the crystallization behaviour (including its absence) of particles, be they biomolecules such as globular proteins, inorganic colloids, nanoparticles, or metal atoms in an alloy, is of both fundamental and technological importance. Much can be learnt from the exquisite control that biological systems exert over the behaviour of proteins, where protein crystallization and aggregation are generally suppressed, but where in particular instances complex crystalline assemblies can be formed that have a functional purpose. We also explore the insights that can be obtained from computational modelling, focussing on the subtle interplay between the interparticle interactions, the preferred local order and the resulting crystallization kinetics. In particular, we highlight the role played by "frustration", where there is an incompatibility between the preferred local order and the global crystalline order, using examples from atomic glass formers and model anisotropic particles. 相似文献
82.
Mangelings D Tanret I Meert V Eeltink S Schoenmakers PJ Kok WT Vander Heyden Y 《Journal of chromatographic science》2007,45(9):578-586
Polymeric methacrylate-based monoliths are evaluated in capillary electrochromatography (CEC) and pressurized capillary electrochromatography (p-CEC) for their potential in pharmaceutical analysis. Using a given polymerization mixture as a basis for the monolith synthesis, different mobile phase pH at constant organic modifier concentrations are tested in both CEC and p-CEC. The test set consists of basic, acidic, amphoteric, and neutral compounds, which are mainly pharmaceuticals. Because of the mainly hydrophobic character of the stationary phase, the interactions are largest when the compounds appear in an uncharged state, but some ion-exchange phenomena with negatively charged compounds can also be observed. In CEC, acidic substances are most retained at low pH. For amphoteric and neutral compounds, no preference regarding analyzing pH can be derived from these experiments. For basics, a high pH is chosen, but a reduced solvent strength is needed to enhance the retention of these compounds. The retention mechanism in p-CEC can also be assigned to both hydrophobic and ionic interactions. For acidic, amphoteric, and neutral compounds, acceptable retention is seen. For the basic compounds, the retention with a mobile phase containing 50% organic modifier is low, as in CEC. However, when the organic modifier content in the mobile phase is decreased, retention increases and the selectivity of the stationary phase is more pronounced. This mode of operation presents a possibility for separating some test mixtures, thus some potential for pharmaceutical analysis is seen. More efforts are needed to obtain higher efficiencies and better peak shapes, which might be solved by a further optimization of both the stationary phase synthesis and the mobile phase composition. 相似文献
83.
Comprehensive multi-residue method for the target analysis of pesticides in crops using liquid chromatography-tandem mass spectrometry 总被引:1,自引:0,他引:1
A liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS) multi-residue method for the simultaneous target analysis of a wide range of pesticides and metabolites in fruit, vegetables and cereals has been developed. Gradient elution has been used in conjunction with positive mode electrospray ionization tandem mass spectrometry to detect up to 171 pesticides and/or metabolites in different crop matrices using a single chromatographic run. Pesticide residues were extracted/partitioned from the samples with acetone/dichloromethane/light petroleum. The analytical performance was demonstrated by the analysis of extracts from lettuce, orange, apple, cabbage, grape and wheat flour, spiked at three concentration levels ranging from 0.01 to 0.10 mg/kg for each pesticide and/or metabolite. In general, recoveries ranging from 70 to 110%, with relative standard deviations better than 15%, were obtained. The recovery and repeatability data are in good accordance with EU guidelines for pesticide residue analysis. The limit of quantification for all targeted pesticides and metabolites tested was 0.01 mg/kg. The selectivity and robustness of the LC-MS/MS method was demonstrated by a 1-year comparison of its analytical results with those obtained from our validated GC and LC multi-residue methods applied to more than 3500 routine samples. The validated LC-MS/MS method has been implemented in our analytical scheme since 2004, replacing four of the conventional detection methods, i.e. GC-flame-photometric detection (acephate, methamidophos, etc.), GC-nitrogen-phosphorus detection, LC-UV detection (carbendazim, thiabendazole, imazalil and prochloraz) and LC-fluorescence detection (N-methylcarbamate pesticides). During a 3-year period, the LC-MS/MS method has been applied to the analyses of more than 12,000 samples. 相似文献
84.
A novel series of monodisperse, multi-dipolar zigzag oligoaryleneethynylenes DA(n) and D-Ar-A(n), bearing electron-donating dibenzothiophene and electron-accepting dibenzothiophene dioxide as arenes, with up to six charge-transfer (dipolar) units have been designed and synthesized by palladium-catalyzed Sonogashira coupling reactions. The linear and nonlinear optical properties of these multi-dipolar oligoaryleneethynylenes can easily be modified or enhanced by incorporating/extending with various central aryleneethynyl moieties such as phenylethynyl, oligo(9,9-dibutylfluorenyl)ethynyl, and oligothienylethynyl within the donor-acceptor units. Interestingly, the absorption and emission of these zigzag oligoaryleneethynylenes are not dependent on the number of covalently linked dipolar chromophores; however, the fluorescence quantum efficiencies consistently decrease with increased number of covalently linked dipolar units. These zigzag oligoaryleneethynylenes exhibit a linear increase in the two-photon absorption (TPA) cross-sections with increased number of covalently linked dipolar units without red-shifting the absorption and emission spectra. In addition, very large TPA cross-sections in the femtosecond regime (sigma(800) = 1306 GM in DMF or sigma(750) = 1522 GM in CH(2)Cl(2)) were obtained for D-TF-A(4) despite the moderate strength of the donor-acceptor pair. Our results suggest that the TPA properties of these zigzag oligoaryleneethynylenes including TPA wavelength and TPA cross-section can easily be tuned by means of modifying the central aryleneethynylene units and increasing the number of dipolar units, respectively. This approach provides an alternative means to tune or enhance the TPA cross-section at a specific wavelength. 相似文献
85.
CHEN Ying-Tian ZHANG Yang HU Sen Ho Tso-Hsiu Boon Ham Lim Chen Sin Lim Kok Keong Chong Boon Kok Tan 《理论物理通讯》2009,(10):750-760
In this article, we report the principle and conceptual design of a fundamentally different technology in fabricating high precision aberration free optical devices. The tip-tilt of facet in a mirror array is produced by digitally controlled line-tilts of rows and columns. It has not only provided a cost-effective designing methodology in optical physics but also led to a much finer precision of 1 mili arc sec or less. As examples of the application of the proposed digitalised optics, two case studies have been given: a 10 m Schmidt telescope (off-axis) and an 8 m Cassegrain telescope (on-axis). 相似文献
86.
Ionara R. Pizzutti René J.J. Vreuls André de Kok Rafael Roehrs Samile Martel Caroline A. Friggi Renato Zanella 《Journal of chromatography. A》2009,1216(15):3305-3311
In this study, a new modulator that is simple, robust and presents low operation costs, was developed. This modulator uses compressed air to cool two small portions in the first centimeters of the second chromatographic column of a comprehensive multidimensional gas chromatography (GC × GC) system. The results show a variation in the peak area less than 3 and 5% to alkanes and pesticides, respectively. The standard deviations for the retention times in the first and second dimension are around 0.05 min and 0.05 s for all the compounds. The system was optimized with n-alkanes. The GC × GC system proposed was applied in the determination of pyrethroid pesticides (bifenthrin, cypermethrin, deltamethrin, fenvalerate, esfenvalerate, cis- and trans-permethrin) in grape samples. Samples were extracted by the mini-Luke modified method and pesticides were quantified by comprehensive multidimensional gas chromatography with micro electron-capture detection (μECD). The values of method limit of quantification (LOQ) were 0.01–0.02 mg kg−1 for all studied pyrethroid and the values of recovery were between 94.3 and 115.2%, with good precision (RSD < 18.4%), demonstrating that the performance of the total method consisting of a modified Luke extraction method and determination by GC × GC-μECD are satisfactory. This study also showed that the system using a modulator with a double jet of compressed air has the potential for application in the analysis of a wider range of pesticide residues in other commodities since it provides low values of LOQ with acceptable accuracy and precision. 相似文献
87.
The aim of this paper is to present a thorough reassessment of the Snyman–Fatti (SF) Multi-start Global Minimization Algorithm with Dynamic Search Trajectories, first published twenty years ago. The reassessment is done with reference to a slightly modified version of the original
method, the essentials of which are summarized here. Results of the performance of the current code on an extensive set of
standard test problems commonly in use today, are presented. This allows for a fair assessment to be made of the performance
of the SF algorithm relative to that of the popular Differential Evolution (DE) method, for which test results on the same
standard set of test problems used here for the SF algorithm, are also given. The tests show that the SF algorithm, that requires
relatively few parameter settings, is a reliably robust and competitive method compared to the DE method. The results also
indicate that the SF trajectory algorithm is particularly promising to solve minimum potential energy problems to determine
the structure of atomic and molecular clusters. 相似文献
88.
Eeltink S Desmet G Vivó-Truyols G Rozing GP Schoenmakers PJ Kok WT 《Journal of chromatography. A》2006,1104(1-2):256-262
A method is proposed for the comprehensive characterization and comparison of columns in the high-performance liquid chromatographic (HPLC) and capillary electrochromatographic (CEC) modes. Using this approach, column parameters such as the number of plates, the eddy-diffusion and mass-transfer contributions to peak broadening, the permeability, and the analysis time are incorporated in a single graph and a comparison in terms of efficiency and speed is obtained. The chromatographic performance of silica-based and polymer-based monolithic capillary columns is discussed and a comparison is made with the performance of packed columns. Also, the potential of ultra-high-pressure liquid chromatography is discussed in this context. In the HPLC mode, the best results were obtained with silica monoliths; in the CEC mode, the low-density methacrylate-ester-based monoliths showed the best performance. 相似文献
89.
In this review research papers on the application of CEC are summarized that have been published between May 2003 and May 2005. First, a short overview is given of trends and developments in CEC that may increase the applicability of the separation technique. Next, application-oriented research using CEC is described in biochemical studies, including proteomics and genomics, in the analysis of food and natural products, and in pharmaceutical, industrial, and environmental analysis. 相似文献
90.
Tyrsted C Pauw BR Jensen KM Becker J Christensen M Iversen BB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(18):5759-5766
Understanding nanoparticle-formation reactions requires multi-technique in situ characterisation, since no single characterisation technique provides adequate information. Here, the first combined small-angle X-ray scattering (SAXS)/wide-angle X-ray scattering (WAXS)/total-scattering study of nanoparticle formation is presented. We report on the formation and growth of yttria-stabilised zirconia (YSZ) under the extreme conditions of supercritical methanol for particles with Y(2)O(3) equivalent molar fractions of 0, 4, 8, 12 and 25 %. Simultaneous in situ SAXS and WAXS reveals a quick formation (seconds) of sub-nanometre amorphous material forming larger agglomerates with subsequent slow crystallisation (minutes) into nanocrystallites. The amount of yttria dopant is shown to strongly affect the crystallite size and unit-cell dimensions. At yttria-doping levels larger than 8 %, which is known to be the stoichiometry with maximum ionic conductivity, the strain on the crystal lattice is significantly increased. Time-resolved nanoparticle size distributions are calculated based on whole-powder-pattern modelling of the WAXS data, which reveals that concurrent with increasing average particle sizes, a broadening of the particle-size distributions occur. In situ total scattering provides structural insight into the sub-nanometre amorphous phase prior to crystallite growth, and the data reveal an atomic rearrangement from six-coordinated zirconium atoms in the initial amorphous clusters to eight-coordinated zirconia atoms in stable crystallites. Representative samples prepared ex situ and investigated by transmission electron microscopy confirm a transformation from an amorphous material to crystalline nanoparticles upon increased synthesis duration. 相似文献