全文获取类型
收费全文 | 455篇 |
免费 | 16篇 |
国内免费 | 4篇 |
专业分类
化学 | 231篇 |
力学 | 13篇 |
数学 | 101篇 |
物理学 | 130篇 |
出版年
2023年 | 4篇 |
2022年 | 18篇 |
2021年 | 21篇 |
2020年 | 4篇 |
2019年 | 14篇 |
2018年 | 22篇 |
2017年 | 7篇 |
2016年 | 30篇 |
2015年 | 22篇 |
2014年 | 22篇 |
2013年 | 43篇 |
2012年 | 28篇 |
2011年 | 33篇 |
2010年 | 23篇 |
2009年 | 13篇 |
2008年 | 26篇 |
2007年 | 22篇 |
2006年 | 15篇 |
2005年 | 11篇 |
2004年 | 9篇 |
2003年 | 13篇 |
2002年 | 7篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 8篇 |
1983年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1968年 | 1篇 |
1960年 | 1篇 |
1948年 | 1篇 |
1943年 | 2篇 |
1935年 | 1篇 |
1873年 | 1篇 |
排序方式: 共有475条查询结果,搜索用时 15 毫秒
41.
We prove surface and volume mean value formulas for classical solutions to uniformly parabolic equations in the divergence form with low regularity of the coefficients. We then use them to prove the parabolic strong maximum principle and the parabolic Harnack inequality. We emphasize that our results only rely on the classical theory, and our arguments follow the lines used in the original theory of harmonic functions. We provide two proofs relying on two different formulations of the divergence theorem, one stated for sets with almost C1-boundary, the other stated for sets with finite perimeter. 相似文献
42.
Dr. Alessandra Alberti Dr. Ioannis Deretzis Dr. Giovanna Pellegrino Dr. Corrado Bongiorno Dr. Emanuele Smecca Dr. Giovanni Mannino Dr. Filippo Giannazzo Prof. Guglielmo Guido Condorelli Dr. Nobuya Sakai Prof. Tsutomu Miyasaka Dr. Corrado Spinella Dr. Antonino La Magna 《Chemphyschem》2015,16(14):3064-3071
We investigate the degradation path of MAPbI3 (MA=methylammonium) films over flat TiO2 substrates at room temperature by means of X‐ray diffraction, spectroscopic ellipsometry, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI2. We describe how this degradation product is structurally coupled with the original MAPbI3 lattice through the orientation of its constituent PbI6 octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH3NH2 or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material. 相似文献
43.
Natural estrogens in dairy products: Determination of free and conjugated forms by ultra high performance liquid chromatography with tandem mass spectrometry
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Chiara Cavaliere Anna Laura Capriotti Patrizia Foglia Susy Piovesana Roberto Samperi Salvatore Ventura Aldo Lagan 《Journal of separation science》2015,38(20):3599-3606
Natural estrogens are synthesized by mammals in different amounts depending on the developmental stage and pregnancy/lactation period, and they may pass into milk, where they are mostly present as glucuronated and sulfated forms. In modern dairy practices, about 75% of milk is produced from pregnant cows; therefore, the amount of hormones that may pass into milk could be of concern. While estrogen determination in milk has been investigated in depth, the individual determination of estrogens and their conjugated forms in dairy products has not been fully addressed. The aim of this work was to develop and assess a sensitive method, using the peculiar retention properties of graphitized carbon black, to extract natural free estrogens and their major conjugated metabolites, without any enzymatic cleavage, from yogurt, cheese, and butter. The free and conjugated estrogens were eluted in two distinct fractions from the solid‐phase extraction cartridge and analyzed separately by ultra high performance liquid chromatography coupled to tandem mass spectrometry. Recoveries were higher than 80% for all the three sample typologies. The highest matrix effects were observed for butter, which was richest in lipid content, but was below 30%. A survey on some commercial dairy products suggests that production processes decreased estrogen content. 相似文献
44.
Emanuele Miserazzi Mario Alessandro SpottiRoberto Profeta Simone SpadaArnaldo Nalin Elisa MoroDaniele Andreotti 《Tetrahedron letters》2011,52(3):448-452
An interesting and surprising rearrangement was observed during the reaction of 4-N-benzyl piperazinone derivatives with Lawesson’s reagent as a thionating agent. Investigation into the possible mechanism responsible for these results is reported herein. 相似文献
45.
A fast analytical method has been developed for the determination of nine amino acids, together with serotonin, in wine samples of different origin and vintage. The method is based on capillary electrophoresis coupled to laser-induced fluorescence detection. Separation was obtained by using a fused-silica capillary (75?μm id, 74.0?cm total length, 60.0?cm length to detector) and a background electrolyte composed of carbonate buffer (20?mM, pH 9.2), applying a 20?kV voltage. Direct hydrodynamic injection of wine samples was made after an original microwave-assisted derivatisation step with 5-(4,6-dichlorotriazinyl)aminofluorescein. Fluorescence was induced by an Ar-Ion laser, exciting at 488?nm. Good linearity (r(2) >0.9990) was obtained for all considered analytes and sensitivity was also good, with limits of detection in the 7-50?ng/mL range. The method was successfully applied for the analysis of commercial Italian wines and thus seems to be suitable for the determination of the relevant amino acids and serotonin, providing good results in terms of accuracy and precision, together with the advantage of a very fast, microwave-assisted derivatisation procedure. Future applications of the method are planned to check for wine adulterations and commercial frauds. 相似文献
46.
Rio-Echevarria IM Tavano R Causin V Papini E Mancin F Moretto A 《Journal of the American Chemical Society》2011,133(1):8-11
The stabilizing action of C(α)-tetrasubstituted α-amino acids inserted into a sequence of short peptides allowed for the first time the preparation of water-soluble nanoparticles of different materials coated with a helix-structured undecapeptide. This peptide coating strongly favors nanoparticle uptake by human immune system cells. 相似文献
47.
Euterpio MA Cavaliere C Capriotti AL Crescenzi C 《Analytical and bioanalytical chemistry》2011,401(9):2977-2985
Pressurized hot water extraction (PHWE, also known as subcritical water extraction) is commonly considered to be an environmentally
friendly extraction technique that could potentially replace traditional methods that use organic solvents. Unfortunately,
the applicability of this technique is often limited by the very low water solubility of the target compounds, even at high
temperatures. In this paper, the scope for broadening the applicability of PHWE by adjusting the pH of the water used in the
extraction is demonstrated in the extraction of curcumin (which exhibits very limited water solubility) from untreated turmeric
(Curcuma longa L.) rhizomes. Although poor extraction yields were obtained, even at high temperatures when using degassed water or neutral
phosphate buffer as the extraction medium, yields exceeding those obtained by Soxhlet extraction were achieved using highly
acidic pH buffers due to curcumin protonation. The influence of the temperature, pH, and buffer concentration on the extraction
yield were investigated in detail by means of a series of designed experiments. Optimized conditions for the extraction of
curcumin from turmeric by PHWE were estimated at 197 °C using 62 g/L buffer concentration at pH 1.6. The relationships between
these variables were subjected to statistical analysis using response surface methodology. 相似文献
48.
Capriotti AL Caracciolo G Cavaliere C Crescenzi C Pozzi D Laganà A 《Analytical and bioanalytical chemistry》2011,401(4):1195-1202
The knowledge about the interaction between plasma proteins and nanocarriers employed for in vivo delivery is fundamental
to understand their biodistribution. Protein adsorption onto nanoparticle surface (protein corona) is strongly affected by
vector surface characteristics. In general, the primary interaction is thought to be electrostatic, thus surface charge of
carrier is supposed to play a central role in protein adsorption. Because protein corona composition can be critical in modifying
the interactive surface that is recognized by cells, characterizing its formation onto lipid particles may serve as a fundamental
predictive model for the in vivo efficiency of a lipidic vector. In the present work, protein coronas adsorbed onto three
differently charged cationic liposome formulations were compared by a shotgun proteomic approach based on nano-liquid chromatography–high-resolution
mass spectrometry. About 130 proteins were identified in each corona, with only small differences between the different cationic
liposome formulations. However, this study could be useful for the future controlled design of colloidal drug carriers and
possibly in the controlled creation of biocompatible surfaces of other devices that come into contact with proteins into body
fluids. 相似文献
49.
Accolla M Congiu E Dulieu F Manicò G Chaabouni H Matar E Mokrane H Lemaire JL Pirronello V 《Physical chemistry chemical physics : PCCP》2011,13(17):8037-8045
The morphology of water ice in the interstellar medium is still an open question. Although accretion of gaseous water could not be the only possible origin of the observed icy mantles covering dust grains in cold molecular clouds, it is well known that water accreted from the gas phase on surfaces kept at 10 K forms ice films that exhibit a very high porosity. It is also known that in the dark clouds H(2) formation occurs on the icy surface of dust grains and that part of the energy (4.48 eV) released when adsorbed atoms react to form H(2) is deposited in the ice. The experimental study described in the present work focuses on how relevant changes of the ice morphology result from atomic hydrogen exposure and subsequent recombination. Using the temperature-programmed desorption (TPD) technique and a method of inversion analysis of TPD spectra, we show that there is an exponential decrease in the porosity of the amorphous water ice sample following D-atom irradiation. This decrease is inversely proportional to the thickness of the ice and has a value of ?(0) = 2 × 10(16) D-atoms cm(-2) per layer of H(2)O. We also use a model which confirms that the binding sites on the porous ice are destroyed regardless of their energy depth, and that the reduction of the porosity corresponds in fact to a reduction of the effective area. This reduction appears to be compatible with the fraction of D(2) formation energy transferred to the porous ice network. Under interstellar conditions, this effect is likely to be efficient and, together with other compaction processes, provides a good argument to believe that interstellar ice is amorphous and non-porous. 相似文献
50.