全文获取类型
收费全文 | 993篇 |
免费 | 3篇 |
专业分类
化学 | 721篇 |
晶体学 | 1篇 |
力学 | 39篇 |
数学 | 154篇 |
物理学 | 81篇 |
出版年
2023年 | 9篇 |
2022年 | 8篇 |
2021年 | 13篇 |
2020年 | 29篇 |
2019年 | 18篇 |
2018年 | 15篇 |
2017年 | 12篇 |
2016年 | 11篇 |
2015年 | 9篇 |
2014年 | 10篇 |
2013年 | 45篇 |
2012年 | 89篇 |
2011年 | 87篇 |
2010年 | 35篇 |
2009年 | 15篇 |
2008年 | 66篇 |
2007年 | 87篇 |
2006年 | 84篇 |
2005年 | 77篇 |
2004年 | 65篇 |
2003年 | 53篇 |
2002年 | 37篇 |
2001年 | 10篇 |
2000年 | 12篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1982年 | 6篇 |
1981年 | 6篇 |
1980年 | 5篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1973年 | 6篇 |
1972年 | 1篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有996条查询结果,搜索用时 656 毫秒
71.
Walter C. P. M. Blondel Bertrand Lehalle Gérard Maurice Xiong Wang Jean-François Stoltz 《Rheologica Acta》2000,39(5):461-468
Cryopreservation is widely used to preserve blood vessels for a while but is controversially suspected to affect the mechanical
behavior of these allografts. The aim of this study was to determine whether differences in the three-dimensional mechanical
behavior exist or not between fresh and cryopreserved arteries. Using a previously developed experimental system, in vitro
inflation tests were performed on twenty segments of human fresh and cryopreserved arteries, in static conditions. Opening
angles were also measured from images of rings in zero-stress state. The initial reference state was chosen as the unloaded
state and tests were performed on specimens stretched at natural “in vivo” length. Mechanical measures calculated are “natural”
(Hencky) strains (finite deformations), “true” (Cauchy) stresses in radial, circumferential, and longitudinal directions as
well as strain energy per unit volume. Tangent moduli are derived from radial and circumferential stress-strain characteristics
using non-linear curve fitting. Values of incremental and pressure-strain elastic parameters, wall stiffness, and compliance
per unit length are also calculated. Results are presented in terms of characteristics of stresses and strains in the three
directions, axial force, tangent moduli vs strains or stresses, and energy per unit volume, for both types of artery, with
reference to transmural pressure. Detailed numerical results are given at mean transmural pressure or in the physiological
range. Significant differences are indicated by statistic Student T-tests. Results obtained show that significant differences
exist between rheological properties of fresh and cryopreserved segments of human artery. Strains, stresses, axial force,
strain energy, and wall stiffness values highlight those differences whereas elastic parameters, compliance, and opening angle
do not. The usefulness of some parameters to compare the mechanical behavior existing between fresh and cryopreserved arteries
is therefore underlined.
Received: 3 January 2000 Revision received: 12 April 2000 Accepted: 8 May 2000 相似文献
72.
Nawel Cheikh Didier Villemin Nathalie Bar Jean-François Lohier Nourredine Choukchou-Braham Bachir Mostefa-Kara Jana Sopkova 《Tetrahedron》2013,69(3):1234-1247
In the course of our studies on Cerpegin analogues synthesis, a serendipitous reactivity of enaminolactone nitrile has been observed. Instead of expecting iminocerpegins, we have gained new class of substituted 2-aminopyridines. The methodology has been applied on a wide range of primary amines, as aliphatic, aromatic, heteroaromatic and also, diamines, hydrazines and chiral amines. 相似文献
73.
Jean-François Morfin Raphaël Tripier Michel Le Baccon Henri Handel 《Polyhedron》2009,28(17):3691-3698
The synthesis of new cyclam and cyclen derivatives (respectively L1 and L2), able to efficiently coordinate to Bi(III) are presented here. The two ligands bearing two different pendant arms (two-pycolyl and two (2-(2-hydroxyethoxy)ethyl)-2-aminoacetamide in trans position) were synthesized in the aim to obtain stable and water soluble complexes. The thermodynamic and kinetic of the formation of the corresponding complexes in aqueous solution were studied by means of NMR and potentiometric investigations. The fast kinetic of complexation and the high stability of the complexes are encouraging for further application with the alpha-emitting 213Bi isotope. 相似文献
74.
Nijem N Veyan JF Kong L Wu H Zhao Y Li J Langreth DC Chabal YJ 《Journal of the American Chemical Society》2010,132(42):14834-14848
Infrared (IR) absorption spectroscopy measurements of molecular hydrogen in MOF-74-M (M = metal center) are performed as a function of temperature and pressure [to 45 kTorr (60 bar) at 300 K, and at lower pressures in the 20-200 K range] to investigate the nature of H(2) interactions with the unsaturated metal centers. A small shift (~?-30 cm(-1) with respect to the unperturbed H(2) molecule) is observed for the internal stretch frequency of H(2) molecules adsorbed on the metal site at low loading. This finding is in contrast to much larger shifts (~?-70 cm(-1)) observed in previous studies of MOFs with unsaturated metal centers (including MOF-74) and the general assumption that H(2) stretch shifts depend on adsorption energies (FitzGerald et al., Phys. Rev. B 2010, 81, 104305). We show that larger shifts (~?-70 cm(-1)) do occur, but only when the next available site ("oxygen" site) is occupied. This larger shift originates from H(2)-H(2) interactions on neighboring sites of the same pore, consistent with the short distance between H(2) in these two sites ~2.6 ? derived from an analysis of neutron diffraction experiments of D(2)-D(2) at 4 K (Liu et al., Langmuir 2008, 24, 4772-4777). Our results at 77 K and low loading can be explained by a diffusion barrier against pair disruption, which should be enhanced by this interaction. Calculations indicate that the vibrational shifts do not correlate with binding energies and are instead very sensitive to the environment (interaction potential and H(2)-H(2) interactions), which complicates the use of variable temperature IR methods to calculate adsorption energies of specific adsorption sites. 相似文献
75.
During continuing studies with a novel oxidative gold oxyarylation reaction, arylsilanes were found to be competent coupling partners, providing further evidence for an intramolecular electrophilic aromatic substitution mechanism. While providing yields complementary to those of the previously described boronic acid methods, the use of trimethylsilanes reduces the observation of homocoupling byproducts and allows for facile intramolecular coupling reactions. 相似文献
76.
Dr. Saida Majdoub Dr. Zoltán Garda Alexandre C. Oliveira Dr. Inga Relich Agnès Pallier Dr. Sara Lacerda Dr. Christelle Hureau Dr. Carlos F. G. C. Geraldes Dr. Jean-François Morfin Dr. Éva Tóth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):2009-2020
Metal chelates targeted to amyloid peptides are widely explored as diagnostic tools or therapeutic agents. The attachment of a metal complex to amyloid recognition units typically leads to a decrease in peptide affinity. We show here that by separating a macrocyclic GdL chelate and a PiB targeting unit with a long hydrophobic C10 linker, it is possible to attain nanomolar affinities for both Aβ1-40 (Kd=4.4 nm ) and amylin (Kd=4.5 nm ), implicated, respectively in Alzheimer's disease and diabetes. The Scatchard analysis of surface plasmon resonance data obtained for a series of amphiphilic, PiB derivative GdL complexes indicate that their Aβ1-40 or amylin binding affinity varies with their concentration, thus micellar aggregation state. The GdL chelates also affect peptide aggregation kinetics, as probed by thioflavin-T fluorescence assays. A 2D NMR study allowed identifying that the hydrophilic region of Aβ1-40 is involved in the interaction between the monomer peptide and the Gd3+ complex. Finally, ex vivo biodistribution experiments were conducted in healthy mice by using 111In labeled analogues. Their pancreatic uptake, ∼3 %ID g−1, is promising to envisage amylin imaging in diabetic animals. 相似文献
77.
78.
Jean-François Gal 《Chromatographia》2010,72(3-4):203-204
Some historical notes on the activities of Teodor Lippmaa and Mikhail S. Tswett at the University of Tartu. 相似文献
79.
Georgiana Surpateanu Jean-François Soulé Jean-Marie Beau Stéphanie Norsikian Bogdan I. Iorga 《Journal of carbohydrate chemistry》2013,32(2):114-129
The conformational flexibility of two glycal-type neuraminidase inhibitors has been studied, using several molecular modeling techniques. In agreement with the experimental data available, an intramolecular hydrogen bond, representing a key structural feature that controls the conformer distribution in solution, has been identified. The contribution of each substituent to the overall equilibrium was evaluated using simplified derivatives. Additionally, four methods for estimating NMR coupling constants from dihedral angles were evaluated and the Haasnoot method was found to be appropriate for this class of sugars. These results should allow a better understanding of the structural parameters governing physico-chemical properties of glycal-like compounds. Supplemental materials are available for this article. Go to the publisher's online edition of Journal of Carbohydrate Chemistry to view the free supplemental file. 相似文献
80.