全文获取类型
收费全文 | 1305篇 |
免费 | 65篇 |
国内免费 | 1篇 |
专业分类
化学 | 1120篇 |
晶体学 | 1篇 |
力学 | 8篇 |
数学 | 107篇 |
物理学 | 135篇 |
出版年
2024年 | 4篇 |
2023年 | 21篇 |
2022年 | 49篇 |
2021年 | 48篇 |
2020年 | 29篇 |
2019年 | 39篇 |
2018年 | 24篇 |
2017年 | 27篇 |
2016年 | 56篇 |
2015年 | 53篇 |
2014年 | 57篇 |
2013年 | 91篇 |
2012年 | 73篇 |
2011年 | 90篇 |
2010年 | 50篇 |
2009年 | 50篇 |
2008年 | 73篇 |
2007年 | 81篇 |
2006年 | 63篇 |
2005年 | 57篇 |
2004年 | 52篇 |
2003年 | 40篇 |
2002年 | 31篇 |
2001年 | 14篇 |
2000年 | 10篇 |
1999年 | 11篇 |
1998年 | 15篇 |
1997年 | 7篇 |
1996年 | 15篇 |
1995年 | 10篇 |
1994年 | 11篇 |
1993年 | 11篇 |
1992年 | 6篇 |
1991年 | 6篇 |
1990年 | 9篇 |
1988年 | 4篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1978年 | 7篇 |
1977年 | 3篇 |
1921年 | 3篇 |
1919年 | 4篇 |
1917年 | 2篇 |
1916年 | 2篇 |
1914年 | 2篇 |
1913年 | 2篇 |
排序方式: 共有1371条查询结果,搜索用时 0 毫秒
81.
Elisabetta Coppi Federica Cherchi Martina Venturini Elena Lucarini Renato Corradetti Lorenzo Di Cesare Mannelli Carla Ghelardini Felicita Pedata Anna Maria Pugliese 《Molecules (Basel, Switzerland)》2022,27(6)
Ligands of the Gi protein-coupled adenosine A3 receptor (A3R) are receiving increasing interest as attractive therapeutic tools for the treatment of a number of pathological conditions of the central and peripheral nervous systems (CNS and PNS, respectively). Their safe pharmacological profiles emerging from clinical trials on different pathologies (e.g., rheumatoid arthritis, psoriasis and fatty liver diseases) confer a realistic translational potential to these compounds, thus encouraging the investigation of highly selective agonists and antagonists of A3R. The present review summarizes information on the effect of latest-generation A3R ligands, not yet available in commerce, obtained by using different in vitro and in vivo models of various PNS- or CNS-related disorders. This review places particular focus on brain ischemia insults and colitis, where the prototypical A3R agonist, Cl-IB-MECA, and antagonist, MRS1523, have been used in research studies as reference compounds to explore the effects of latest-generation ligands on this receptor. The advantages and weaknesses of these compounds in terms of therapeutic potential are discussed. 相似文献
82.
A spacer-equipped tetrasaccharide, p-aminocyclohexylethyl alpha-l-Colp-(1-->2)-beta-d-Galp-(1-->3)-[alpha-l-Colp-(1-->4)]-beta-D-GlcpNAc, containing a 4,6-cyclic phosphate in the galactose residue, has been synthesised. The structure corresponds to a part of the repeating unit of the capsular (and lipo-) polysaccharide of the endemic bacteria Vibrio cholerae type O139 synonym Bengal. The synthetic strategy allows continuous syntheses of the complete O139 hexasaccharide repeating unit as well as of the structurally related repeating unit of serotype O22. Starting from ethyl 2-azido-4,6-O-benzylidene-2-deoxy-1-thio-beta-D-glucopyranoside, a thioglycoside tetrasaccharide donor block was constructed through two orthogonal glycosylations with glycosyl bromide donors. First, a properly protected galactose moiety was introduced using silver triflate as promoter and subsequently the two colitose residues, carrying electron-withdrawing protecting groups for stability reasons, under halide-assisted conditions. The tetrasaccharide block was then linked to the spacer in a NIS-TMSOTf-promoted coupling. Transformation of the azido group into an acetamido group using H2S followed by removal of temporary protecting acetyl groups gave a 4',6'-diol, which was next phosphorylated with methyl dichlorophosphate and deprotected to yield the 4,6-cyclic phosphate tetrasaccharide target structure. 相似文献
83.
84.
Zellner M Winkler W Hayden H Diestinger M Eliasen M Gesslbauer B Miller I Chang M Kungl A Roth E Oehler R 《Electrophoresis》2005,26(12):2481-2489
For the preparation of proteins for proteome analysis, precipitation is frequently used to concentrate proteins and to remove interfering compounds. Various methods for protein precipitation are applied, which rely on different chemical principles. This study compares the changes in the protein composition of human blood platelet extracts after precipitation with ethanol (EtOH) or trichloroacetic acid (TCA). Both methods yielded the same amount of proteins from the platelet preparations. However, the EtOH-precipitated samples had to be dialyzed because of the considerable salt content. To characterize single platelet proteins, samples were analyzed by two-dimensional fluorescence differential gel electrophoresis. More than 90% of all the spots were equally present in the EtOH- and TCA-precipitated samples. However, both precipitation methods showed a smaller correlation with nonprecipitated samples (EtOH 74.9%, TCA 79.2%). Several proteins were either reduced or relatively enriched in the precipitated samples. The proteins varied randomly in molecular weight and isoelectric point. This study shows that protein precipitation leads to specific changes in the protein composition of proteomics samples. This depends more on the specific structure of the protein than on the precipitating agent used in the experiment. 相似文献
85.
Structure of Framework Aluminum Lewis Sites and Perturbed Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR (3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics 下载免费PDF全文
Dr. Jiří Brus Libor Kobera Dr. Wolfgang Schoefberger Dr. Martina Urbanová Petr Klein Dr. Petr Sazama Dr. Edyta Tabor Dr. Stepan Sklenak Dr. Anna V. Fishchuk Dr. Jiří Dědeček 《Angewandte Chemie (International ed. in English)》2015,54(2):541-545
Zeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework AlFR Lewis acid sites are often found in their H‐forms. The formation of AlFR Lewis sites in zeolites is a key issue regarding their selectivity in acid‐catalyzed reactions. The local structures of AlFR Lewis sites in dehydrated zeolites and their precursors—“perturbed” AlFR atoms in hydrated zeolites—were studied by high‐resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)3AlOH groups and are characterized by a broad 27Al NMR resonance (δi=59–62 ppm, CQ=5 MHz, and η=0.3–0.4) with a shoulder at 40 ppm in the 27Al MAS NMR spectrum. Dehydroxylation of (SiO)3AlOH occurs at mild temperatures and leads to the formation of AlFR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)3Al Lewis sites exhibit an extremely broad 27Al NMR resonance (δi≈67 ppm, CQ≈20 MHz, and η≈0.1). 相似文献
86.
Polymersomes Prepared from Thermoresponsive Fluorescent Protein–Polymer Bioconjugates: Capture of and Report on Drug and Protein Payloads 下载免费PDF全文
Chin Ken Wong Alistair J. Laos Dr. Alexander H. Soeriyadi Prof. Jörg Wiedenmann Prof. Paul M. G. Curmi Prof. J. Justin Gooding Dr. Christopher P. Marquis Prof. Martina H. Stenzel Assoc. Prof. Pall Thordarson 《Angewandte Chemie (International ed. in English)》2015,54(18):5317-5322
Polymersomes provide a good platform for targeted drug delivery and the creation of complex (bio)catalytically active systems for research in synthetic biology. To realize these applications requires both spatial control over the encapsulation components in these polymersomes and a means to report where the components are in the polymersomes. To address these twin challenges, we synthesized the protein–polymer bioconjugate PNIPAM‐b‐amilFP497 composed of thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) and a green‐fluorescent protein variant (amilFP497). Above 37 °C, this bioconjugate forms polymersomes that can (co‐)encapsulate the fluorescent drug doxorubicin and the fluorescent light‐harvesting protein phycoerythrin 545 (PE545). Using fluorescence lifetime imaging microscopy and Förster resonance energy transfer (FLIM‐FRET), we can distinguish the co‐encapsulated PE545 protein inside the polymersome membrane while doxorubicin is found both in the polymersome core and membrane. 相似文献
87.
Arrival time distributions of product ions reveal isomeric ratio of deprotonated molecules in ion mobility–mass spectrometry of hyaluronan‐derived oligosaccharides 下载免费PDF全文
Martina Hermannová Andreea‐Maria Iordache Kristína Slováková Vladimír Havlíček Helena Pelantová Karel Lemr 《Journal of mass spectrometry : JMS》2015,50(6):854-863
Hyaluronic acid is a naturally occurring linear polysaccharide with substantial medical potential. In this work, discrimination of tyramine‐based hyaluronan derivatives was accessed by ion mobility–mass spectrometry of deprotonated molecules and nuclear magnetic resonance spectroscopy. As the product ion mass spectra did not allow for direct isomer discrimination in mixture, the reductive labeling of oligosaccharides as well as stable isotope labeling was performed. The ion mobility separation of parent ions together with the characteristic fragmentation for reduced isomers providing unique product ions allowed us to identify isomers present in a mixture and determine their mutual isomeric ratio. The determination used simple recalculation of arrival time distribution areas of unique ions to areas of deprotonated molecules. Mass spectrometry data were confirmed by nuclear magnetic resonance spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
88.
Christof Schmitz Ahmed Mourran Helmut Keul Martin Möller Martina Keerl Walter Richtering 《Colloid and polymer science》2009,287(10):1183-1193
The effect of microstructure on the aggregation behaviour of symmetrical di- and triblock copolymers P(BMA)-b-P(MAA) and P(BMA)-b-P(BMA-co-MAA)-b-P(MAA) with a molecular weight of 40,000 g/mol was studied. The critical micelle concentration, hydrodynamic radius and morphology
of the micelles were determined by fluorescence spectroscopy, dynamic light scattering and scanning force microscopy (SFM).
Whereas no effect of the microstructure on the critical micelle concentration could be detected, the hydrodynamic radius decreased
from di- to triblock copolymer from 53 to 36 nm. The decrease of about 32% corresponds to the length of the random middle
block within the triblock copolymer so that the reduction in hydrodynamic radius was caused by a complete orientation of the
random middle block at the core corona interface. Finally, the SFM investigation showed that dehydration of micelles on a
substrate is accompanied by formation of a physisorbed monolayer with a thickness of 2 nm on which the micelles are deposited. 相似文献
89.
Study of the development of thermoresistance in human pancreatic carcinoma cell lines using proteome analysis 总被引:3,自引:0,他引:3
In order to find candidate proteins that are potentially associated with the thermoresistant phenotype in combination with drug resistance, we analyzed the differential protein expression in vitro in the human pancreatic cancer cell line EPP85-181-P and classical and atypical multidrug-resistant variants and their thermoresistant counterparts using proteomics. This study identifies sets of proteins that may lead to the development of thermoresistance. These results provide a fundamental basis to elucidate the molecular mechanism of thermoresistance and chemoresistance phenomena that may assist the therapy of inoperable cancers. 相似文献
90.
We develop a semi-quantitative analytical theory to describe adhesion between two identical planar charged surfaces embedded in a polymer-containing electrolyte solution. Polymer chains are uncharged and differ from the solvent by their lower dielectric permittivity. The solution mimics physiological fluids: It contains 0.1 M of monovalent ions and a small number of divalent cations that form tight bonds with the headgroups of charged lipids. The components have heterogeneous spatial distributions. The model was derived self-consistently by combining: (a) a Poisson-Boltzmann like equation for the charge densities, (b) a continuum mean-field theory for the polymer profile, (c) a solvation energy forcing the ions toward the polymer-poor regions, and (d) surface interactions of polymers and electrolytes. We validated the theory via extensive coarse-grained Molecular Dynamics (MD) simulations. The results confirm our analytical model and reveal interesting details not detected by the theory. At high surface charges, polymer chains are mainly excluded from the gap region, while the concentration of ions increases. The model shows a strong coupling between osmotic forces, surface potential and salting-out effects of the slightly polar polymer chains. It highlights some of the key differences in the behaviour of monomeric and polymeric mixed solvents and their responses to Coulomb interactions. Our main findings are: (a) the onset of long-ranged ion-induced polymer depletion force that increases with surface charge density and (b) a polymer-modified repulsive Coulomb force that increases with surface charge density. Overall, the system exhibits homeostatic behaviour, resulting in robustness against variations in the amount of charges. Applications and extensions of the model are briefly discussed. 相似文献