全文获取类型
收费全文 | 664篇 |
免费 | 27篇 |
专业分类
化学 | 503篇 |
晶体学 | 5篇 |
力学 | 23篇 |
数学 | 76篇 |
物理学 | 84篇 |
出版年
2023年 | 4篇 |
2022年 | 8篇 |
2021年 | 18篇 |
2020年 | 14篇 |
2019年 | 18篇 |
2018年 | 7篇 |
2017年 | 11篇 |
2016年 | 18篇 |
2015年 | 21篇 |
2014年 | 20篇 |
2013年 | 33篇 |
2012年 | 49篇 |
2011年 | 47篇 |
2010年 | 30篇 |
2009年 | 35篇 |
2008年 | 51篇 |
2007年 | 35篇 |
2006年 | 51篇 |
2005年 | 29篇 |
2004年 | 36篇 |
2003年 | 21篇 |
2002年 | 20篇 |
2001年 | 9篇 |
2000年 | 9篇 |
1999年 | 8篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 13篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 12篇 |
1991年 | 6篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1976年 | 2篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1967年 | 1篇 |
1933年 | 1篇 |
1931年 | 1篇 |
1930年 | 4篇 |
1928年 | 1篇 |
1924年 | 1篇 |
1881年 | 2篇 |
1880年 | 1篇 |
排序方式: 共有691条查询结果,搜索用时 15 毫秒
1.
Martin Kellert Jan-Simon Jeshua Friedrichs Nadine Anke Ullrich Alexander Feinhals Jonas Tepper Peter Lnnecke Evamarie Hey-Hawkins 《Molecules (Basel, Switzerland)》2021,26(7)
The development of novel, tumor-selective and boron-rich compounds as potential agents for use in boron neutron capture therapy (BNCT) represents a very important field in cancer treatment by radiation therapy. Here, we report the design and synthesis of two promising compounds that combine meta-carborane, a water-soluble monosaccharide and a linking unit, namely glycine or ethylenediamine, for facile coupling with various tumor-selective biomolecules bearing a free amino or carboxylic acid group. In this work, coupling experiments with two selected biomolecules, a coumarin derivative and folic acid, were included. The task of every component in this approach was carefully chosen: the carborane moiety supplies ten boron atoms, which is a tenfold increase in boron content compared to the l-boronophenylalanine (l-BPA) presently used in BNCT; the sugar moiety compensates for the hydrophobic character of the carborane; the linking unit, depending on the chosen biomolecule, acts as the connection between the tumor-selective component and the boron-rich moiety; and the respective tumor-selective biomolecule provides the necessary selectivity. This approach makes it possible to develop a modular and feasible strategy for the synthesis of readily obtainable boron-rich agents with optimized properties for potential applications in BNCT. 相似文献
2.
Thermodynamic study of transthyretin association (wild‐type and senile forms) with heparan sulfate proteoglycan: pH effect and implication of the reactive histidine residue
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ambre Geneste Claire André Nadine Magy‐Bertrand Lydie Lethier Gharbi Tijani Yves Claude Guillaume 《Biomedical chromatography : BMC》2015,29(4):514-522
The tetramer destabilization of transthyretin into monomers and its fibrillation are phenomena leading to amyloid deposition. Heparan sulfate proteoglycan (HSPG) has been found in all amyloid deposits. A chromatographic approach was developed to compare binding parameters between wild‐type transthyretin (wtTTR) and an amyloidogenic transthyretin (sTTR). Results showed a greater affinity of sTTR for HSPG at pH 7.4 compared with wtTTR owing to the monomeric form of sTTR. Analysis of the thermodynamic parameters showed that van der Waals interactions were involved at the complex interface for both transthyretin forms. For sTTR, results from the plot representing the number of protons exchanged vs pH showed that the binding mechanism was pH‐dependent with a critical value at a pH 6.5. This observation was due to the protonation of a histidine residue as an imidazolium cation, which was not accessible when TTR was in its tetrameric structure. At pH >6.5, dehydration at the binding interface and several contacts between nonpolar groups of sTTR and HSPG were also coupled to binding for an optimal hydrogen‐bond network. At pH <6.5, the protonation of the His residue from sTTR monomer when pH decreased broke the hydrogen‐bond network, leading to its destabilization and thus producing slight conformational changes in the sTTR monomer structure. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
3.
A variational approach is proposed to study some properties of the adiabatic Holstein–Hubbard model which describes an assembly of fermionic charges interacting with a static atomic lattice. The sum of the electronic energy and the lattice elastic energy is proved to have minima with a many-polaron structure in a certain domain of model parameters. Our analytical work consists in expanding these energy minima from the zero electronic transfer limit which remarkably holds for a finite amplitude of the onsite Hubbard repulsion and for an unbounded lattice size. 相似文献
4.
5.
Claude Didierjean Julien Marin Emmanuel Wenger Jean‐Paul Briand Andr Aubry Gilles Guichard 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(3):o200-o203
X‐ray studies reveal that tert‐butyl (6S)‐6‐isobutyl‐2,4‐dioxopiperidine‐1‐carboxylate occurs in the 4‐enol form, viz. tert‐butyl (6S)‐4‐hydroxy‐6‐isobutyl‐2‐oxo‐1,2,5,6‐tetrahydropyridine‐1‐carboxylate, C14H23NO4, when crystals are grown from a mixture of dichloromethane and pentane, and has an axial orientation of the isobutyl side chain at the 6‐position of the piperidine ring. Reduction of the keto functionality leads predominantly to the corresponding β‐hydroxylated δ‐lactam, tert‐butyl (4R,6S)‐4‐hydroxy‐6‐isobutyl‐2‐oxopiperidine‐1‐carboxylate, C14H25NO4, with a cis configuration of the 4‐hydroxy and 6‐isobutyl groups. The two compounds show similar molecular packing driven by strong O—H⋯O=C hydrogen bonds, leading to infinite chains in the crystal structure. 相似文献
6.
Apart from specific methods amenable to specific problems, symplectic Runge-Kutta methods are necessarily implicit. The aim
of this paper is to construct explicit Runge-Kutta methods which mimic symplectic ones as far as the linear growth of the
global error is concerned. Such method of orderp have to bepseudo-symplectic of pseudosymplecticness order2p, i.e. to preserve the symplectic form to within ⊗(h
2p
)-terms. Pseudo-symplecticness conditions are then derived and the effective construction of methods discussed. Finally, the
performances of the new methods are illustrated on several test problems. 相似文献
7.
Three new porphyrins bearing in the meso positions 4-(pyrazol-1-yl)-2,3,5,6-tetrafluorophenyl substituents have been prepared and characterized by nmr spectroscopy. 相似文献
8.
9.
Cédric Kalinski Michael Umkehrer Nadine Jäger Wolfgang Hiller 《Tetrahedron letters》2006,47(12):2041-2044
A combinatorial synthetic route yielding fused tetrazolo[1,5-a]quinoxalines is described. The use of 2-fluorophenylisocyanide in the Ugi-tetrazole reaction (tetrazole-U-4CR) followed by a nucleophilic aromatic substitution (SNAr) affords the tricylic tetrazolo[1,5-a]quinoxaline moiety in good yields and with high diversity. 相似文献
10.
Nadine Metz 《European Polymer Journal》2007,43(4):1202-1209
Acetone oxime acrylate has been synthesized as a new active ester monomer. Free radical polymerization yielded a reactive polymer soluble in various organic solvents, such as chloroform, dioxane, DMSO, acetone, methanol, dichloromethane, DMF, and ethanol. Controlled radical polymerization of acetone oxime acrylate was successfully conducted using the RAFT, NMP and Iniferter method. Partly polymer analogous reaction with N-isopropylamine resulted in the reactive copolymer poly(N-isopropylacrylamide-co-acetone oxime acrylate), which featured a lower critical solution temperature (LCST) of 61 °C in water. Further, the reactivity of the copolymer was exemplary proven by complete reaction with ammonia yielding poly(N-isopropylacrylamide-co-acrylamide), which does not possess a LCST. 相似文献