全文获取类型
收费全文 | 396篇 |
免费 | 15篇 |
国内免费 | 5篇 |
专业分类
化学 | 337篇 |
晶体学 | 1篇 |
力学 | 9篇 |
数学 | 46篇 |
物理学 | 23篇 |
出版年
2023年 | 6篇 |
2022年 | 4篇 |
2021年 | 14篇 |
2020年 | 16篇 |
2019年 | 13篇 |
2018年 | 12篇 |
2017年 | 12篇 |
2016年 | 10篇 |
2015年 | 12篇 |
2014年 | 22篇 |
2013年 | 21篇 |
2012年 | 33篇 |
2011年 | 45篇 |
2010年 | 20篇 |
2009年 | 23篇 |
2008年 | 30篇 |
2007年 | 31篇 |
2006年 | 22篇 |
2005年 | 14篇 |
2004年 | 15篇 |
2003年 | 6篇 |
2002年 | 10篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1986年 | 1篇 |
1983年 | 2篇 |
1975年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有416条查询结果,搜索用时 62 毫秒
81.
Multiple-frequency EPR spectra of two aqueous Gd3+ polyamino polypyridine carboxylate complexes: a study of high field effects 总被引:1,自引:0,他引:1
Borel A Laus S Ozarowski A Gateau C Nonat A Mazzanti M Helm L 《The journal of physical chemistry. A》2007,111(25):5399-5407
In the search for highly efficient magnetic resonance imaging contrast agents, polyamino polypyridine carboxylate complexes of Gd3+ have shown unusual properties with both very rapid and very slow electron spin relaxation in solution observed by electron paramagnetic resonance. Since the relationship between the molecular structure and the electron spin properties remains quite obscure at this point, detailed studies of such complexes may offer useful clues for the design of Gd3+ compounds with tailored electronic features. Furthermore, the availability of very high-frequency EPR spectrometers based on quasi-optical components provides us with an opportunity to test the existing relaxation theories at increasingly high magnetic fields and observation frequencies. We present a detailed EPR study of two gadolinium polyamino polypyridine carboxylate complexes, [Gd(tpaen)]- and [Gd(bpatcn)(H2O)], in liquid aqueous solutions at multiple temperatures and frequencies between 9.5 and 325 GHz. We analyze the results using the model of random zero-field splitting modulations through Brownian rotation and molecular deformations. We consider the effect of concentration on the line width, as well as the possible existence of an additional g-tensor modulation relaxation mechanism and its possible impact on future experiments. We use (17)O NMR to characterize the water exchange rate on [Gd(bpatcn)(H2O)] and find it to be slow (approximately 0.6 x 10(6) s-1). 相似文献
82.
Hahn U Gégout A Duhayon C Coppel Y Saquet A Nierengarten JF 《Chemical communications (Cambridge, England)》2007,(5):516-518
Fullerene derivatives bearing a carboxylic acid function undergo self-assembly with n-butylstannonic acid (nBuSn(O)OH) to produce fullerene-rich nanostructures with a stannoxane core in almost quantitative yields. 相似文献
83.
Figueira-Duarte TM Gégout A Nierengarten JF 《Chemical communications (Cambridge, England)》2007,(2):109-119
Fullerene derivatives are attractive building blocks for the preparation of molecular and supramolecular photoactive devices. As a part of this research, combination of C60 with oligophenylenevinylene (OPV) subunits has generated significant research efforts. These results are summarized in the present account to illustrate the current state-of-the-art of fullerene chemistry for the development of new photoactive materials. 相似文献
84.
Nonat A Fries PH Pécaut J Mazzanti M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(30):8489-8506
The tripodal hexadentate picolinate ligand dpaa3- (H3dpaa=N,N'-bis[(6-carboxypyridin-2-yl)methyl]glycine) has been synthesised. It can form 1:1 and 1:2 lanthanide/ligand complexes. The crystal structure of the bis(aquo) lutetium complex [Lu(dpaa)(H2O)2] has been determined by X-ray diffraction studies. The number of water molecules was determined by luminescence lifetime studies of the terbium and europium complexes. The tris(aquo) terbium complex shows a fairly high luminescence quantum yield (22 %). The [Gd(dpaa)(H2O)3] complex displays a high water solubility and an increased stability (pGd=12.3) with respect to the analogous bis(aquo) complex [Gd(tpaa)(H2O)2] (pGd=11.2). Potentiometric and relaxometric studies show the formation of a soluble GdIII hydroxo complex at high pH values. A unique aquohydroxo gadolinium complex has been isolated and its crystal structure determined. This complex crystallises as a 1D polymeric chain consisting of square-shaped tetrameric units. In heavy water, the [Gd(dpaa)-(D2O)3] complex shows a quite high HOD proton relaxivity at high field (11.93 s(-1) mM(-1) at 200 MHz and 298 K) because of the three inner-sphere water molecules. The formation of ternary complexes with physiological anions has been monitored by relaxometric studies, which indicate that even under conditions favourable to the formation of adducts with oxyanions, the mean relaxivity remains higher than those of most of the currently used commercial contrast agents except for the citrate. However, the measured relaxivity (r1=7.9 s(-1) mM(-1)) in a solution containing equimolar concentrations of [Gd(dpaa)(D2O)3] and citrate is still high. The interaction with albumin has been investigated by relaxometric and luminescence studies. Finally, a new versatile method to unravel the geometric and dynamic molecular factors that explain the high-field relaxivities has been developed. This approach uses a small, uncharged non-coordinating probe solute, the outer-sphere relaxivity of which mimics that of the water proton. Only a routine NMR spectrometer and simple mathematical analysis are required. 相似文献
85.
Mussone PG Ip AW Schroeder SL Murray BS Miller AF 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3766-3773
The collapse of Langmuir monolayers of poly(vinyl stearate) (PVS) at the air-water interface has been investigated by combined measurements of the surface pressure-area isotherms and Brewster angle microscopy (BAM). Atomic force microscopy (AFM) has been used to gain out-of-plane structural information on collapsed films transferred onto a solid substrate by a modified version of the inverse Langmuir-Schaefer deposition method. At high areas per monomer repeat unit, BAM imaging revealed that the films are heterogeneous, with large solidlike domains (25-200 mum in diameter) coexisting with liquidlike domains. Upon film compression, the domains coalesced to form a homogeneous monolayer before the film collapsed at constant pressure, forming irreversible three-dimensional (3D) structures. BAM images showed that two 3D structures coexisted: buckles of varying width extending across the surface and perpendicular to the direction of the compression and dotted islandlike structures. Upon expansion, the film fractured and both 3D protrusions persisted, explaining the marked hysteresis recorded in the Langmuir isotherms. Experiments with AFM confirmed the 3D nature of both protrusions and revealed that many buckles contain substructures corresponding to narrow buckles whose heights are a multiple of a single bilayer. Additionally, many multilayer islands with diameters spanning from 0.2 mum to over 3.5 mum were characterized by varying heights between 2 nm and up to over 50 nm. The key to the formation of the irreversible 3D structures is the presence of large inhomogeneities in the PVS monolayer, and a generalized phenomenological model is proposed to explain the collapse observed. 相似文献
86.
Aline F. Miller 《Macromolecular Symposia》2005,222(1):109-114
Insulin protein was exposed to mildly denaturing conditions (heat and low pH) to encourage the formation of beta-sheet rich amyloid fibrils. This resulted in an increase in viscosity of our protein samples and the morphology and thermodynamics of the resulting hydrogel were monitored using environmental scanning electron microscopy and micro differential scanning calorimetry respectively. It was found that the beta-sheet fibrils aggregated further to form macrofibrils, 2 μm in diameter and several microns in length. These long, flexible macrofibrils became entangled to form hydrogels with controllable mesh size: the higher the incubation temperature the higher the number of entanglements, and consequently the smaller the mesh size. 相似文献
87.
Aline Salvi Corinne Brühlmann Eugenia Migliavacca Pierre‐Alain Carrupt Kurt Hostettmann Bernard Testa 《Helvetica chimica acta》2002,85(3):867-881
In this work, a convenient test of antioxidant activity was developed, with BChE‐contaminated HSA as the target of AAPH‐induced oxidation and its esterase activity as the marker of protein integrity or degradation. The method is relatively simple, of low cost, and convenient to use. Its application to natural polyphenols showed that quercetin ( 1 ), verbascoside ( 2 ), chlorogenic acid ( 3 ), caffeic acid ( 4 ), 1,3,6,7‐tetrahydroxyxanthone ( 5 ), and mangiferin ( 6 ), are good antioxidants (IC50<9 μM ). 1,5‐Dihydroxy‐3‐methoxyxanthone ( 7 ), flemichin D ( 8 ), and cordigone ( 9 ) showed modest activities (ca. 50 μM <IC50<350 μM ), whereas danthrone ( 10 ) was inactive. Complementary experiments with two of the more active antioxidants, namely quercetin ( 1 ) and chlorogenic acid ( 3 ) showed that both antioxidants were better radical scavengers than chain‐breaking antioxidants. The relative adiabatic oxidation potential (ΔHox), the relative H‐bond dissociation energy (ΔHabs), and the first oxidation potential measured by cyclic voltammetry were found to be related to the radical‐scavenging activity of these antioxidants. 相似文献
88.
Lidia Moreira Lima Tiago Fernandes da Silva Carlos Eduardo da Silva Monteiro Cristiane Aparecida-Silva Walfrido Bispo Júnior Aline Cavalcanti de Queiroz Magna Suzana Alexandre-Moreira Gisele Zapata-Sudo Eliezer J. Barreiro 《Molecules (Basel, Switzerland)》2021,26(16)
Acylhydrazones are still an important framework to the design of new bioactive compounds. As treatment of chronic pain represents a clinical challenge, we decided to modify the structure of LASSBio-1514 (1), previously described as anti-inflammatory and analgesic prototype. Applying the homologation as a strategy for molecular modification, we designed a series of cyclopentyl- (2a–e), cyclobutyl- (3a–e), and cyclopropylacylhydrazones (4a–e) that were synthetized and evaluated in murine models of inflammation and pain. A comparison of their in silico physicochemical and drug-like profile was conducted, as well as their anti-inflammatory and analgesic effect. Compounds 4a (LASSBio-1755) and 4e (LASSBio-1757) displayed excellent in silico drug-like profiles and were identified as new analgesic lead-candidates in acute and chronic model of pain, through oral administration. 相似文献
89.
Marjorie C. L. C. Freire Gabriela D. Noske Natlia V. Bitencourt Paulo R. S. Sanches Norival A. Santos-Filho Victor O. Gawriljuk Eduardo P. de Souza Victor H. R. Nogueira Mariana O. de Godoy Aline M. Nakamura Rafaela S. Fernandes Andre S. Godoy Maria A. Juliano Bianca M. Peres Cecília G. Barbosa Carolina B. Moraes Lucio H. G. Freitas-Junior Eduardo M. Cilli Rafael V. C. Guido Glaucius Oliva 《Molecules (Basel, Switzerland)》2021,26(16)
The COVID-19 outbreak has rapidly spread on a global scale, affecting the economy and public health systems throughout the world. In recent years, peptide-based therapeutics have been widely studied and developed to treat infectious diseases, including viral infections. Herein, the antiviral effects of the lysine linked dimer des-Cys11, Lys12,Lys13-(pBthTX-I)2K ((pBthTX-I)2K)) and derivatives against SARS-CoV-2 are reported. The lead peptide (pBthTX-I)2K and derivatives showed attractive inhibitory activities against SARS-CoV-2 (EC50 = 28–65 µM) and mostly low cytotoxic effect (CC50 > 100 µM). To shed light on the mechanism of action underlying the peptides’ antiviral activity, the Main Protease (Mpro) and Papain-Like protease (PLpro) inhibitory activities of the peptides were assessed. The synthetic peptides showed PLpro inhibition potencies (IC50s = 1.0–3.5 µM) and binding affinities (Kd = 0.9–7 µM) at the low micromolar range but poor inhibitory activity against Mpro (IC50 > 10 µM). The modeled binding mode of a representative peptide of the series indicated that the compound blocked the entry of the PLpro substrate toward the protease catalytic cleft. Our findings indicated that non-toxic dimeric peptides derived from the Bothropstoxin-I have attractive cellular and enzymatic inhibitory activities, thereby suggesting that they are promising prototypes for the discovery and development of new drugs against SARS-CoV-2 infection. 相似文献
90.
Aline G. Cunha Gloria Fernández-Lorente Melissa L. E. Gutarra Juliana V. Bevilaqua Rodrigo V. Almeida Lúcia M. C. Paiva Roberto Fernández-Lafuente Jose M. Guisán Denise M. G. Freire 《Applied biochemistry and biotechnology》2009,156(1-3):133-145
Lipases are an enzyme class of a great importance as biocatalysts applied to organic chemistry. However, it is still necessary to search for new enzymes with special characteristics such as good stability towards high temperatures, organic solvents, and high stereoselectivity presence. The present work’s aim was to immobilize the lipases pool produced by Penicillium simplissicimum, a filamentous fungi strain isolated from Brazilian babassu cake residue. P. simplissicimum lipases were separated into three different fractions using selective adsorption method on different hydrophobic supports (butyl-, phenyl-, and octyl-agarose) at low ionic strength. After immobilization, it was observed that these fractions’ hyperactivation is in the range of 131% to 1133%. This phenomenon probably occurs due to enzyme open form stabilization when immobilized onto hydrophobic supports. Those fractions showed different thermal stability, specificity, and enantioselectivity towards some substrates. Enantiomeric ratio for the hydrolysis of (R,S) 2-O-butyryl-2-phenylacetic acid ranged from 1 to 7.9 for different immobilized P. simplissicimum lipase fractions. Asymmetry factor for diethyl 2-phenylmalonate hydrolysis ranged from 11.8 to 16.4 according to the immobilized P. simplissicimum lipase fractions. Those results showed that sequential adsorption methodology was an efficient strategy to obtain new biocatalysts with different enantioselectivity degrees, thermostability, and specificity prepared with a crude extract produced by a simple and low-cost technology. 相似文献