全文获取类型
收费全文 | 416篇 |
免费 | 8篇 |
国内免费 | 2篇 |
专业分类
化学 | 269篇 |
晶体学 | 1篇 |
力学 | 11篇 |
数学 | 62篇 |
物理学 | 83篇 |
出版年
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 6篇 |
2020年 | 4篇 |
2019年 | 2篇 |
2018年 | 5篇 |
2017年 | 3篇 |
2016年 | 8篇 |
2015年 | 11篇 |
2014年 | 11篇 |
2013年 | 23篇 |
2012年 | 27篇 |
2011年 | 26篇 |
2010年 | 24篇 |
2009年 | 16篇 |
2008年 | 20篇 |
2007年 | 25篇 |
2006年 | 20篇 |
2005年 | 11篇 |
2004年 | 19篇 |
2003年 | 11篇 |
2002年 | 8篇 |
2001年 | 16篇 |
2000年 | 13篇 |
1999年 | 8篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 6篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1985年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1970年 | 2篇 |
1966年 | 2篇 |
1957年 | 23篇 |
1956年 | 4篇 |
1888年 | 2篇 |
1885年 | 1篇 |
1884年 | 1篇 |
1880年 | 1篇 |
1879年 | 1篇 |
排序方式: 共有426条查询结果,搜索用时 0 毫秒
221.
In this paper we describe an approach to measure small glossy objects by illuminated film based on Phase Measuring Deflectometry (PMD) system. In this setup, the standard sinusoidal fringe patterns are produced by the photographic film frame (135-film), which is illuminated from behind using LED and diffuser, instead of the well-known LCD monitor plane or digital projector. This setup can avoid the influence of electronic noise and screen refreshing, and fulfill the test of small objects in low cost. Moreover the system is easily calibrated with its vertical setup. With the experiments of measuring a plastic contactless smartcard and a metal plate, it is proven that the setup can reach sub-micrometer accuracy with respect to the data of the Wyko white light interferometer. This setup will be promising in the small scale measurement field. 相似文献
222.
223.
Satu Strandman Petri Pulkkinen Heikki Tenhu 《Journal of polymer science. Part A, Polymer chemistry》2005,43(15):3349-3358
The effect of the steric hindrance on the initiating properties of two multifunctional resorcinarene‐based initiators in atom transfer radical polymerization (ATRP) was studied by using Cu(I)‐complexes of three multidentate amine ligands in the polymerization of tert‐butyl acrylate and methyl methacrylate. These ligands are less sterically hindered and have higher activities in the catalysis of ATRP of (meth)acrylates than 2,2′‐bipyridine. The polymerizations were faster and more controlled than with the 2,2′‐bipyridyl catalyst, but the tendency for bimolecular coupling increased. Even though the initiator was octafunctional, the resulting star polymers had only four arms. This indicates that the steric hindrance arising from the conformations of the initiators determines the structure of the polymer, but the ligand noticeably affects the controllability of the polymerization © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3349–3358, 2005 相似文献
224.
Agnes M. Stepan Alistair W. T. King Tia Kakko Guillermo Toriz Ilkka Kilpeläinen Paul Gatenholm 《Cellulose (London, England)》2013,20(6):2813-2824
In this study high molecular weight pure rye arabinoxylan and spruce arabinoglucuronoxylan were acetylated in ionic liquid (IL) systems. Two different ILs were used in our study. In both IL, using optimized procedures, it was possible to achieve acetylation within 5 min. The first system involved direct dissolution into 1-ethyl-3-methylimidazolium dimethylphosphate ([emim][Me2PO4]), followed by addition of acetyl chloride/pyridine (AcCl/Pyr) and additional chloroform (CHCl3), as co-solvent. The other system involved direct dissolution into the novel protic IL 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]), followed by acetic anhydride/1,5-diazabicyclo[4.3.0]non-5-ene (Ac2O/DBN) and no co-solvent added. The full acetyl substitution of the xylans was confirmed by FT IR and 1H NMR. The acetylated xylans maintained a high molecular weight, which was confirmed by gel permeation chromatography. The products were soluble in CHCl3 and dimethyl carbonate, which is considered as a ‘green’ reagent or solvent. This allowed for the casting of the materials into clear transparent films, opening opportunity for further processing and evaluation of these materials. 相似文献
225.
Maria Valentina Dinu Mariana Spulber Kasper Renggli Dalin Wu Christophe A. Monnier Alke Petri‐Fink Nico Bruns 《Macromolecular rapid communications》2015,36(6):507-514
Polymersomes that encapsulate a hydrophilic polymer are prepared by conducting biocatalytic atom transfer radical polymerization (ATRP) in these hollow nanostructures. To this end, ATRPase horseradish peroxidase (HRP) is encapsulated into vesicles self‐assembled from poly(dimethylsiloxane)‐block‐poly(2‐methyl‐2‐oxazoline) (PDMS‐b‐PMOXA) diblock copolymers. The vesicles are turned into nanoreactors by UV‐induced permeabilization with a hydroxyalkyl phenone and used to polymerize poly(ethylene glycol) methyl ether acrylate (PEGA) by enzyme‐catalyzed ATRP. As the membrane of the polymersomes is only permeable for the reagents of ATRP but not for macromolecules, the polymerization occurs inside of the vesicles and fills the polymersomes with poly(PEGA), as evidenced by 1H NMR. Dynamic and static light scattering show that the vesicles transform from hollow spheres to filled spheres during polymerization. Transmission electron microscopy (TEM) and cryo‐TEM imaging reveal that the polymersomes are stable under the reaction conditions. The polymer‐filled nanoreactors mimic the membrane and cytosol of cells and can be useful tools to study enzymatic behavior in crowded macromolecular environments.
226.
Antti Pohjakallio Prof. Petri M. Pihko Ulla M. Laitinen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(37):11325-11339
The formation of 3‐unsubstituted 2‐isoxazolines by means of condensation reactions between α,β‐unsaturated aldehydes and oximes proceeds readily in the presence of catalytic amounts of anilinium salts. Mechanistically, the process involves a fast conjugate addition of the oxime and a slower intramolecular oxime‐transfer reaction. The rate of oxime transfer was found to correlate with the acidity of the catalyst. This finding enabled us to discover an enantioselective process in which the fragile conjugate‐addition product generated in the first stage is rapidly cyclized into the stable isoxazoline under acidic conditions, with conservation of enantiomeric excess. In summary, herein we describe synthetically useful protocols for accessing 3‐unsubstituted 2‐isoxazolines in both the enantioselective and racemic manner. The mechanism of the condensation reaction catalyzed by the anilinium salt was also investigated by NMR spectroscopy experiments in which the effect of differently substituted aldehydes and oximes as well as water on the reaction rate was studied. The results point to the rate‐limiting elimination of water from the 3‐hydroxy‐2‐isoxazolidine intermediate. 相似文献
227.
Kaj Backfolk Rob Holmes Petri Ihalainen Petri Sirvi Nick Triantafillopoulos Jouko Peltonen 《Polymer Testing》2007,26(8):1031-1040
The glass transition temperature (Tg) for two latices with different styrene/butadiene compositions was determined by the thermal SPM probe resonance frequency method. The results were compared with the Tg values obtained by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), process rheometer (PR) and thermo-mechanical analyzer (TMA) measurements. The Tg values detected by the thermal SPM method agreed well with the Tg values obtained by DSC and calculated by the Fox–Flory equation. DMA, on the other hand, showed a significantly higher Tg value for both latices than those obtained from theoretical calculations, the thermal SPM method and DSC. The Tg obtained from the PR curve was slightly higher for the latex with a low styrene content, whereas good agreement was obtained with the thermal SPM data for the latex with a high styrene content. The glass transition temperature determined by TMA agreed fairly well with the thermal SPM data for the latex with the low styrene content, whilst the value of Tg for the second latex was much less than those obtained by the other methods. The thermal SPM method detects changes in thermal behavior (thermal diffusivity, heat capacity) during heating of the latex films rather than changes in the mechanical properties. Information about the sample history could be seen in the thermal SPM curves, which was further associated with the degree of latex film formation, especially when the roughness of the films was taken into consideration. 相似文献
228.
Human very-low-density lipoprotein (VLDL) particles were immobilised on the inner wall of electrochromatographic fused-silica capillaries, and the applicability of these capillary columns in oxidation studies was investigated. Capillaries coated with radiolabelled VLDL particles showed a coating efficiency of 97%, and allowed estimation of the amount of VLDL present in a capillary. Radioactivity measurements and atomic force microscopy with tapping mode confirmed the presence of VLDL particles as a monolayer. The pI determined for the VLDL was 4.7-4.8 varying with the human source. The effects of VLDL concentration, coating time and pH on the coating stability were clarified, and the stability was examined in terms of the repeatability of EOF and retention factors of selected steroids. The repeatability of run-to-run and the coating-to-coating reproducibility ranged from 2.6 to 4.9% and 3.2 to 6.6%, respectively. The lifetime of a coating was at least 7 days or 84 consecutive runs. The in situ copper-mediated VLDL oxidation carried out in the capillary with optimised VLDL coating showed that, during the oxidation of VLDL particles, the negative charges of the particles are increased, leading to enhanced EOF mobilities. Several oxidation parameters, including copper sulfate concentration, amount of EDTA needed to stop the reaction, pH and the oxidation procedure, were examined. Effect of the oxidation process on the stability of the coating in one capillary, and in five different capillaries ranged between 0.4-4.1% and 0.8-6.6%, respectively. The in situ oxidation of VLDL particles was compared with that of low-density lipoproteins. 相似文献
229.
Paakkunainen M Kilpeläinen J Reinikainen SP Minkkinen P 《Analytica chimica acta》2007,595(1-2):209-215
Sampling and uncertainty of sampling are important tasks, when industrial processes are monitored. Missing values and unequal sources can cause problems in almost all industrial fields. One major problem is that during weekends samples may not be collected. On the other hand a composite sample may be collected during weekend. These systematically occurring missing values (gaps) will have an effect on the uncertainties of the measurements. Another type of missing values is random missing values. These random gaps are caused, for example, by instrument failures. Pierre Gy's sampling theory includes tools to evaluate all error components that are involved in sampling of heterogeneous materials. Variograms, introduced by Gy's sampling theory, have been developed to estimate the uncertainty of auto-correlated process measurements. Variographic experiments are utilized for estimating the variance for different sample selection strategies. The different sample selection strategies are random sampling, stratified random sampling and systematic sampling. In this paper both systematic and random gaps were estimated by using simulations and real process data. These process data were taken from bark boilers of pulp and paper mills (combustion processes). When systematic gaps were examined a linear interpolation was utilized. Also cases introducing composite sampling were studied. Aims of this paper are: (1) how reliable the variogram is to estimate the process variogram calculated from data with systematic gaps, (2) how the uncertainty of missing gap can be estimated in reporting time-averages of auto-correlated time series measurements. The results show that when systematic gaps were filled by linear interpolation only minor changes in the values of variogram were observed. The differences between the variograms were constantly smallest with composite samples. While estimating the effect of random gaps, the results show that for the non-periodic processes the stratified random sampling strategy gives more reliable results than systematic sampling strategy. Therefore stratified random sampling should be used while estimating the uncertainty of random gaps in reporting time-averages of auto-correlated time series measurements. 相似文献
230.
Soares KV Masini JC Torresi RM Carmona-Ribeiro AM Petri DF 《Langmuir : the ACS journal of surfaces and colloids》2005,21(18):8515-8519
The synthesis of hybrid particles was carried out by emulsion polymerization of styrene in complexes formed by carboxymethyl cellulose (CMC), a polyanion, and a cationic surfactant, cetyltrimethylammonium bromide (CTAB). CMC chains with variable molecular weights and degrees of substitution were tested. The polymerization condition chosen was that corresponding to CMC chains fully saturated with CTAB and to the onset of pure surfactant micelle formation, namely, at the critical aggregation concentration. The hybrid particles were characterized by zeta potential and light scattering measurements. The period of colloidal stability in the ionic strength of 2.0 mol L(-)(1) NaCl was observed visually. Upon increasing the CMC chain length, the particle characteristics remained practically unchanged, but the colloid stability was increased. The increase in the CMC degree of substitution led to particles with more negative zeta potential values. The adsorption of copper ions (Cu(2+)) on the surface of hybrid particles could be described by the Langmuir model, as determined by potentiometric measurements. The increase in the mean zeta potential values and X-ray absorption near-edge spectra evidenced the immobilization of Cu(2+) ions on the hybrid particles. 相似文献