全文获取类型
收费全文 | 561篇 |
免费 | 26篇 |
国内免费 | 1篇 |
专业分类
化学 | 352篇 |
晶体学 | 1篇 |
力学 | 14篇 |
数学 | 46篇 |
物理学 | 84篇 |
无线电 | 91篇 |
出版年
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 6篇 |
2020年 | 10篇 |
2019年 | 10篇 |
2018年 | 9篇 |
2017年 | 5篇 |
2016年 | 14篇 |
2015年 | 11篇 |
2014年 | 19篇 |
2013年 | 20篇 |
2012年 | 41篇 |
2011年 | 47篇 |
2010年 | 29篇 |
2009年 | 29篇 |
2008年 | 39篇 |
2007年 | 32篇 |
2006年 | 28篇 |
2005年 | 34篇 |
2004年 | 31篇 |
2003年 | 27篇 |
2002年 | 27篇 |
2001年 | 12篇 |
2000年 | 13篇 |
1999年 | 5篇 |
1998年 | 13篇 |
1997年 | 4篇 |
1996年 | 10篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 2篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 1篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1966年 | 1篇 |
1937年 | 1篇 |
1928年 | 2篇 |
排序方式: 共有588条查询结果,搜索用时 0 毫秒
521.
Increasingly used in therapeutics, 5-methoxypsoralen (5-MOP), a linear furocoumarin, associated with UVA irradiation (PUVA), is now an established treatment for skin diseases such as vitiligo, mycosis funcoides and particularly psoriasis. Successful PUVA therapy depends on a sufficiently high peak 5-MOP plasma concentration coinciding with the UVA irradiation. However, as with most drugs, only the free plasma fraction is able to enter the target cells and has a pharmacological effect. In this work, the binding of 5-MOP to human albumin was studied in vitro, using a dialysis chamber. Bound and free 5-MOP fractions were quantified by a modification of Stolk's high-performance liquid chromatographic method. Dialysis was performed at 37 degrees C and pH 7.4 for 2 h, against a 4% albumin solution in phosphate buffer. The 5-MOP concentrations used were from 5 x 10(-5) to 5 x 10(-2) g/l in 1 x 10(-1) g/l steps. The 5-MOP bound strongly to human albumin in an unsaturable way. The mean 5-MOP binding to albumin was 95.3%. These results are in accordance with those published by Artuc et al. and not with those of Veronese et al., who found a lower saturable fixation (91%). These two research groups used tritiated 5-MOP. The technique used in this work is simple and inexpensive. It can be employed easily in vivo, e.g., for the assessment of 5-MOP free fractions in different therapeutic conditions. 相似文献
522.
Microfluidic devices are increasingly used to perform biological experiments on a single-cell basis. However, long-term stability of cell positions is still an issue. A novel biocompatible method for cell entrapment and release on a microchip is presented. It is based on the controlled formation of an alginate hydrogel by bringing two laminar flows of alginate and calcium ions in the range of 2 mM to 40 mM into contact. The resulting growth of a gel bar is used to enclose and immobilize yeast cells. Adding ethylenediaminetetraacetic acid (EDTA) to the alginate solution allows for control of the hydrogel growth, and by varying the ratio of Ca(2+) to EDTA concentrations gel growth or gel shrinkage can be induced at will. Trapped cells are released during shrinkage of the gel. The trapping efficiency for different cell speeds is investigated and the properties of gel growth are discussed using a diffusion model. Precise positioning of a single cell is demonstrated. The technique presented allows not only the reversible immobilization of cells under gentle conditions but also offers the potential of long-term cell cultures as shown by on-chip incubation of yeast cells. The procedure may provide a simple and fully biocompatible technique for a multitude of innovative experiments on cells in microsystems. 相似文献
523.
The radical homopolymerisation in acetonitrile of vinylidene fluoride (or 1,1-difluoroethylene, VDF) and the copolymerisation of VDF with hexafluoropropylene (HFP) initiated by bis(trifluoromethyl)peroxy dicarbonate are presented. Different reactions and different reactants were chosen to monitor the polymerisation in terms of initiating radicals generated from this initiator. Homopolymers and copolymers thus obtained were characterised by and NMR spectroscopy. From the assignments of the characteristic signals, an overall reaction mechanism is proposed that explains each step of the polymerisation. Particularly, an interpretation of the polymer microstructures and the presence of end-groups arising from the radical initiator as well as from eventual transfers is suggested. Among some of the microstructures, the trifluoromethoxy end-group was noted to be present in both PVDF and poly(VDF-co-HFP) (co)polymers, as generated from the decomposition of the initiator. This trifluoromethoxy end-group enabled the assessment of the molecular weights of PVDF and poly(VDF-co-HFP) (co)polymers. Thermal properties of the copolymers were also determined, showing that original fluoroelastomers possessing CF3 end-groups are obtained endowed with low Tg and good thermal stability. 相似文献
524.
B-Alkylcatecholboranes, prepared by rhodium(I)-catalyzed hydroboration of alkenes, are suitable radical precursors for conjugate addition to activated olefins. This procedure proved to be particularly useful for the control of the regio- and chemoselectivity of such tandem processes. Enantioselective hydroboration has also been successfully coupled with radical chain reaction in a one-pot process. 相似文献
525.
Nevin Gürbüz Bekir Çetinkaya Jean-Luc Renaud Bernard Demerseman 《Tetrahedron letters》2006,47(4):535-538
Benzimidazolium halides are used for the first time as ligand precursors in ruthenium-catalyzed substitution of allylic carbonates and chlorides by carbon nucleophiles and phenols, respectively. After generation of diaminocarbene species upon deprotonation by tBuOK, their association with [Cp*Ru(MeCN)3]PF6 induces a very high regioselectivity in favor of the branched isomers when cinnamyl derivatives are used as starting substrates. They also provide good regioselectivities for the allylation of phenols by unsymmetrical aliphatic allylic substrates such as 3-chloro-4-phenylbut-1-ene, and thus provide a straightforward access to new allylic phenyl ethers. 相似文献
526.
The series of mixed hexacyanoferrates M2Zn3[Fe/CN/6]2.xH2O (M=K+, Na+, Cs+) present zeolitic properties. The adsorption water vapour isotherms were determined by TG at 303 K. The differential heats of adsorption of water vapour were measured by microcalorimetry; the molar integral entropy of the sorbed phase was calculated. The data obtained show that (i) the H2O-sorbent interactions are very weak at the beginning of cavity filling, whereas the sorbed molecules exhibit the same mobility as in the vapour phase; (ii) during the filling, the H2O-H2O interactions increase up to a maximum; (iii) close to total filling, the adsorption phenomenon is comparable to a vapour-liquid transition and the sorbed phase has the same molar entropy as that of the liquid phase. 相似文献
527.
The synthesis of a new perfluorovinyl ether monomer containing phosphonic acid functionality is reported. It started from 4-[(α,β,β-trifluorovinyl)oxy]bromo benzene prepared in two steps from the nucleophilic substitution of 4-bromophenate to 1,2-dibromotetrafluoroethane. The [(α,β,β-trifluorovinyl)oxy]benzene dialkyl phosphonate was prepared according to various methods of phosphonation like a Michaelis-Arbuzov or a Michaelis-Becker or a palladium catalysed arylation in the presence of various reactants. The influence of the nature of the method and of the reactants onto the yields is discussed. It was shown that reaction involving a palladium triphenyl phosphine catalyst led to the best yield. All different aromatic intermediates and fluoromonomers were characterised by , and NMR, mass spectrometry (EI), and by FTIR. 相似文献
528.
Enantiomerically Pure Pyrrolidine Derivatives from trans-4-Hydroxy-L -proline by Electrochemical Oxidative Decarboxylation and Titanium-Tetrachloride-Mediated Reaction with Nucleophiles Preparative electrolysis of N-methoxycarbonyl-O-[(t-butyl)dimethylsilyl]hydroxyproline 4 in MeOH leads to substitution of the COOH by a MeO group (oxidative decarboxylation). The mixture 5 of the two diastereoisomers (ca 1:1) thus obtained was reacted in CH2Cl2 with nucleophilic silylated compounds (such as allylsilane, silyl cyanide and 1-phenyl-1-silyloxyethane) or with trimethyl phosphite in the presence of TiCl4 to give 2-allyl-, 2-cyano-, 2-(2-oxo-2-phenylethyl)- and 2-phosphono-substituted hydroxypyrrolidines, respectively, with high diastereoselectivities (≥ 90%, products 6-12 ). The configuration of two of the products ( 6/7 and 8/9 ) was shown to be cis. 相似文献
529.
Electrochemical Oxidation of (S)-Malic-Acid Derivatives: a Route to Enantiomerically Pure Alkylmalonaldehydic Esters The 3,3-dialkymalic-acid diesters, prepared by the previously described diastereoselective alkylations through dilithium alkoxide enolates, are saponified to the monoesters containing a free α-hydroxycarboxylic-acid moiety(Scheme 3). The monoesters are subjected to electrochemical oxidative decarboxylation in MeOH . If the intermediate monoacids are purified, the malonaldehydic esters (2-formy1-2-alkylcaroxylates) Obtained by this procedure are enantiomerically pure; they have the same structural features, i.e. two enantiotopic functionalized branches on the (persubstituted) stereogenic center, as the well known 3-hydroxy-2-methylpropanoic acid (‘Roche acid’) which was employed frequently as a starting material for the preparation of either enantiomer of various target molecules. 相似文献
530.
Nikodem Tomczak Renaud A.L. Vallée Erik M.H.P. van Dijk Laurens Kuipers G. Julius Vancso 《European Polymer Journal》2004,40(5):1001-1011
The use of single molecules to study local, nanoscale polymer dynamics is presented. Fluorescence lifetime fluctuations were used to extract the number of polymer segments (Ns) taking part in the rearranging volume around the probe molecule below the glass transition temperature. Ns was dependent on the temperature and it decreased with increasing temperature. Above the glass transition, rotational motion of single molecules was followed in time and typical time-scales of the rotational diffusion were extracted. These two approaches allowed us to obtain non-averaged information about the heterogeneous dynamics present in polymer systems, on the nanoscale, above and below glass transition temperatures. 相似文献