全文获取类型
收费全文 | 1242篇 |
免费 | 91篇 |
国内免费 | 4篇 |
专业分类
化学 | 995篇 |
晶体学 | 3篇 |
力学 | 47篇 |
数学 | 134篇 |
物理学 | 158篇 |
出版年
2023年 | 10篇 |
2022年 | 21篇 |
2021年 | 29篇 |
2020年 | 32篇 |
2019年 | 26篇 |
2018年 | 29篇 |
2017年 | 21篇 |
2016年 | 42篇 |
2015年 | 54篇 |
2014年 | 45篇 |
2013年 | 82篇 |
2012年 | 78篇 |
2011年 | 94篇 |
2010年 | 60篇 |
2009年 | 56篇 |
2008年 | 91篇 |
2007年 | 83篇 |
2006年 | 74篇 |
2005年 | 53篇 |
2004年 | 61篇 |
2003年 | 56篇 |
2002年 | 45篇 |
2001年 | 16篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 7篇 |
1996年 | 11篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 12篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 6篇 |
1988年 | 9篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 15篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 3篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有1337条查询结果,搜索用时 15 毫秒
121.
Julien Huser Sophie Bistac Christelle Delaite Didier Dentel Mickaël Derivaz Mohamed Zanouni 《Surface and interface analysis : SIA》2015,47(4):523-528
The grafting of trialkoxysilane molecules should also give rise to the formation of a siloxane network at the substrate's surface when trialkoxysilanes are used. Other candidates that might be able to act as adhesion promoters at metallic surfaces are dimethylalkoxysilanes. The advantage of dimethylalkoxysilanes is that only one silanol group is produced during the hydrolysis step, leading to the formation of a grafted monolayer onto the steel. Moreover, the chemical grafting of stainless steel, which exhibits a low surface reactivity, is of great interest for industrial applications such as adhesive bonding or coatings. The objective of this work was to chemically graft dimethylalkoxysilanes onto AISI 316L stainless steel and to analyze the grafted layer by X‐ray photoelectron spectroscopy (XPS). Investigation of the hydrolysis of these molecules in aqueous solutions was also performed by proton nuclear magnetic resonance spectroscopy (1H NMR). The grafting of 3‐(ethoxydimethylsilyl)propylamine (APDES) and 3‐glycidoxypropyldimethylethoxysilane (GPDES) was achieved onto stainless steel after a controlled hydrolysis reaction. A pH inferior or equal to 5 was necessary to obtain a sufficient hydrolysis of silanes. XPS results have evidenced the grafting of the silanes onto stainless steel. The signal of the Si 2p peak clearly showed the formation of a covalent bond between APDES and the stainless steel surface through the O atoms giving rise to a uniform layer of adsorbed molecules. Moreover, this grafted layer is strongly stable as no removal of the alkoxysilane was observed after immersion in hot water which is very critical for these molecules. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
122.
Cristina Díez Davy Guillarme Aline Staub Spörri Emmanuelle Cognard Didier Ortelli Patrick Edder Serge Rudaz 《Analytica chimica acta》2015
In this study, fourteen highly polar aminoglycoside (AGs) antibiotics were selected. Various stationary phases were tested, including Obelisc R, ZIC-HILIC, BEH amide and aminopropyl. The nature of the stationary phase, mobile phase (water or buffer solutions and acetonitrile), pH (percentage of formic acid), gradient conditions and injection solvents were systematically studied as relevant parameters for tuning retention selectivity and detectability of AGs in liquid chromatography electrospray tandem mass spectrometry (LC–(ESI)–MS/MS). Only the two zwitterionic phases (Obelisc R and ZIC-HILIC) achieved a proper chromatographic separation considering interferences due to the crosstalk effect in low resolution mass spectrometers. The water/acetonitrile mobile phase containing 1% formic acid used with Obelisc R provided more sensitivity than the highly concentrated buffered mobile phases required for ZIC-HILIC. A solid phase extraction (SPE) clean-up procedure with polymeric weak cation exchange (WCX) cartridges was optimized for honey, milk and liver samples. Different brands of cartridges and elution solvents were tested, and the Taurus WCX offered the best recovery rate with a buffer elution at pH 3. The final optimized method was validated in these matrices according to Decision 2002/657/EC. A monitoring campaign for sixty honey, milk and liver samples was carried out at the Food Authority Control in Geneva. The concentration of dihydrostreptomycin (DSTP) found in one ovine liver exceeded the established maximum residue levels (MRLs) within the European and Swiss legislations but it was compliant taking into account the validation data. 相似文献
123.
Computational Studies on Intramolecular Cycloadditions of Azidoenynes and Azidobutenenitriles to Give 6H‐Pyrrolo[1,2‐c][1,2,3]triazoles and 5H‐Pyrrolo[1,2‐d]tetrazoles 下载免费PDF全文
Gérard Audran Paul Brémond Douniazad El Abed Sylvain R. A. Marque Didier Siri Maurice Santelli 《Helvetica chimica acta》2015,98(7):1018-1027
Energetics of intramolecular cycloadditions of azidoenynes and azidobutenenitriles to give 6H‐pyrrolo[1,2‐c][1,2,3]triazoles and 5H‐pyrrolo[1,2‐d]tetrazoles have been calculated at the B3LYP/6.311++G(3df,3pd) level of theory in ideal gas and in H2O as solvent. Stabilities of the corresponding anions, tautomers, and isomers are discussed. Transition states of the cyclization of parent compounds are determined at the same level of theory. 相似文献
124.
125.
In this work, a two-phase film-flow model in a hygroscopic capillary tube is developed and extended to describe the two-phase capillary viscous transport in a network of parallel capillary tubes in terms of relative permeabilities. This film-flow approach is further considered to predict the longitudinal moisture transport in oak wood during drying. Numerical results obtained from this prediction are compared with data of convective drying experiments performed on samples of this wood. The comparison seems to confirm the physical relevance of a film-flow model to correctly represent the moisture transfer until the hygroscopic regime is reached. 相似文献
126.
We propose a model for describing mesoscale relaxation mechanisms in soft thermoplastic elastomers and also in the high-temperature
regime of filled rubbers. The model consists of hard spheres embedded in an elastic matrix. It is solved by dissipative particle
dynamics. We study the response of the model to deformations of various amplitudes. We show that it displays slow relaxation
processes of large amplitudes that are related to irreversible reorganizations at a mesoscopic scale. We characterize these
reorganizations as buckling of instabilities that change the local environment of the hard inclusions.
Paper presented at the 3rd Annual Rheology Conference, AERC 2006, April 27–29, 2006, Crete, Greece. 相似文献
127.
Scheen G Ziouche K Bougrioua Z Godts P Leclercq D Lasri T 《Langmuir : the ACS journal of surfaces and colloids》2011,27(10):6490-6495
Polyimide is of great interest in the field of MEMS and microtechnology. It is often used for its chemical, thermal, mechanical, and optical properties. In this paper, an original study is performed on controlled variation of polyimide film wettability. A two-step microtexturing method is developed to transform hydrophilic polyimide surfaces into a superhydrophobic surface with low magnitude of hysteresis (Δθ ≈ 0° and contact angle θ ≈ 158°). This method is based on the conception of a new kind of fakir surface with triangular cross-section micropillars, the use of a two-scale roughening, and a C(4)F(8) coating. We demonstrate that the absence of hysteresis is related to a combination of two scales of structuring and the pillar shape. The technology that has been developed results in the simultaneous fabrication of adjacent superhydrophobic and superhydrophilic small areas, which allows an effect of self-positioning of water droplets when deposited on such a checkerboard-like surface. 相似文献
128.
Stefanopoulos KL Romanos GE Vangeli OC Mergia K Kanellopoulos NK Koutsioubas A Lairez D 《Langmuir : the ACS journal of surfaces and colloids》2011,27(13):7980-7985
Small-angle neutron scattering (SANS), contrast-matching SANS, and nitrogen adsorption have been utilized to investigate the confined ionic liquid (IL) [bmim][PF(6)] phase in ordered mesoporous silica MCM-41 and SBA-15. The results suggest that the pores of SBA-15 are completely filled with IL whereas a small fraction of the pore volume, the pore "core", of MCM-41 is empty. The contrast-matching SANS measurements confirm the enhanced solubility of water in IL. In addition, they provide strong evidence that water does not enter the empty pore core of MCM-41, possibly because of the preferred orientation of the IL molecules in the adsorbed layer. 相似文献
129.
Catiau L Delval-Dubois V Guillochon D Nedjar-Arroume N 《Applied biochemistry and biotechnology》2011,165(5-6):1264-1273
Alpha-lactalbumin hydrolysate is of significant interest, due to its potential application as a source of bioactive peptides in nutraceutical and pharmaceutical domains. This study was focused on the cholecystokinin (CCK) family compounds which are small peptides involved in the satiety control. The action of chymotryptic hydrolysate of alpha-lactalbumin on cholecystokinin release from intestinal endocrine STC-1 cells was investigated. We demonstrated for the first time that a chymotryptic hydrolysate of alpha-lactalbumin was able to highly stimulate CCK-releasing activity from STC-1 cells. The peptidic hydrolysate was characterized by LC/MS and MS/MS, thus highlighting the presence of 11 fractions containing 21 peptides, each potentially having the desired activity. 相似文献
130.
Kamoun F Fguira IB Hassen NB Mejdoub H Lereclus D Jaoua S 《Applied biochemistry and biotechnology》2011,165(1):300-314
This study reports on the identification, characterization and purification of a new bacteriocin, named Bacthuricin F103,
from a Bacillus thuringiensis strain BUPM103. Bacthuricin F103 production began in the early exponential phase and reached a maximum in the middle of the
same phase. Two chromatographic methods based on high performance liquid chromatography and fast protein liquid chromatography
systems were used to purify Bacthuricin F103. Sodium dodecyl sulphate-polyacrylamide gel electrophoresis revealed that this
bacteriocin had a molecular weight of approximately 11 kDa. It also showed a wide range of thermostability of up to 80 °C
for 60 min and a broad spectrum of antimicrobial activity over a pH range of 3.0–10.0. This bacteriocin was noted, and for
the first time, to exhibit potent antimicrobial activity against Agrobacterium subsp. strains, the major causal agents of crown gall disease in tomato and vineyard crops, and against several challenging
organisms in food, such as Listeria monocytogenes and Bacillus cereus. Complete killing with immediate impact on cells was observed within a short period of time. The sequence obtained for Bacthuricin
F103 by direct N-terminal sequencing shared considerable homology with hemolysin. Bacthuricin F103 was noted to act through
the depletion of intracellular ions, which suggest that the cell membrane was a possible target to Bacthuricin F103. 相似文献