全文获取类型
收费全文 | 234篇 |
免费 | 5篇 |
专业分类
化学 | 163篇 |
晶体学 | 8篇 |
力学 | 14篇 |
数学 | 34篇 |
物理学 | 20篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2020年 | 1篇 |
2019年 | 3篇 |
2018年 | 1篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 2篇 |
2014年 | 6篇 |
2013年 | 12篇 |
2012年 | 11篇 |
2011年 | 10篇 |
2010年 | 9篇 |
2009年 | 7篇 |
2008年 | 12篇 |
2007年 | 4篇 |
2006年 | 9篇 |
2005年 | 7篇 |
2004年 | 4篇 |
2002年 | 6篇 |
2001年 | 8篇 |
2000年 | 2篇 |
1999年 | 4篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1995年 | 2篇 |
1993年 | 1篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 12篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 9篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1915年 | 2篇 |
1914年 | 1篇 |
排序方式: 共有239条查询结果,搜索用时 15 毫秒
101.
Germain ME Vargo TR McClure BA Rack JJ Van Patten PG Odoi M Knapp MJ 《Inorganic chemistry》2008,47(14):6203-6211
Nitroaromatics and nitroalkanes quench the fluorescence of Zn(Salophen) (H2Salophen = N,N'-phenylene-bis-(3,5-di- tert-butylsalicylideneimine); ZnL(R)) complexes. A structurally related family of ZnL(R) complexes (R = OMe, di-tBu, tBu, Cl, NO2) were prepared, and the mechanisms of fluorescence quenching by nitroaromatics were studied by a combined kinetics and spectroscopic approach. The fluorescent quantum yields for ZnL(R) were generally high (Phi approximately 0.3) with sub-nanosecond fluorescence lifetimes. The fluorescence of ZnL(R) was quenched by nitroaromatic compounds by a mixture of static and dynamic pathways, reflecting the ZnL(R) ligand bulk and reduction potential. Steady-state Stern-Volmer plots were curved for ZnL(R) with less-bulky substituents (R = OMe, NO2), suggesting that both static and dynamic pathways were important for quenching. Transient Stern-Volmer data indicated that the dynamic pathway dominated quenching for ZnL(R) with bulky substituents (R = tBu, DtBu). The quenching rate constants with varied nitroaromatics (ArNO2) followed the driving force dependence predicted for bimolecular electron transfer: ZnL* + ArNO2 --> ZnL(+) + ArNO2(-). A treatment of the diffusion-corrected quenching rates with Marcus theory yielded a modest reorganization energy (lambda = 25 kcal/mol), and a small self-exchange reorganization energy for ZnL*/ZnL(+) (ca. 20 kcal/mol) was estimated from the Marcus cross-relation, suggesting that metal phenoxyls may be robust biological redox cofactors. Electronic structure calculations indicated very small changes in bond distances for the ZnL --> ZnL(+) oxidation, suggesting that solvation was the dominant contributor to the observed reorganization energy. These mechanistic insights provide information that will be helpful to further develop ZnL(R) as sensors, as well as for potential photoinduced charge transfer chemistry. 相似文献
102.
P. Germain C. de Brauer M. Diot J. M. Letoffe 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(3):205-212
Heat capacities of -CD·9.7H2O weremeasured by adiabatic calorimetry in the temperature range10–300 K. Differential scanning calorimetry wasused to follow the evolution of the thermalbehaviour versus hydration ratio between 170 and300 K. At least three different behaviours wereobserved, according to the number, n, of watermolecules: 0 < n < 7, 7 < n < 10, and n > 10.These macroscopic results are discussed in terms oforganization differences between the most or theleast hydrated -CD. The structuring effectof the hydration water molecules is emphasised. Theexistence of two energetically distinct -CDhydrates (n < 10 and n > 10) seems to be confirmed. Thishypothesis is discussed in comparison with previousspectroscopic and structural studies. 相似文献
103.
Youen Kervella Grégory Germain Benoît Gaurier Jean-Valéry Facq Florence Cayocca Patrick Lesueur 《European Journal of Mechanics - B/Fluids》2010,29(1):32-42
Oyster farming structures are artificial obstacles which disturb tidal flow and wave propagation. These effects can induce modifications of erosion and sedimentation patterns, turbidity changes, local silting up and can be threatening for the shellfish farming itself. The understanding of the impact of these structures in terms of hydrodynamics and sediment dynamics in the far-field, i.e. at the scale of a bay, is a very challenging task.In order to investigate the far-field impact, it is very important to understand in the first place all the changes which occur at a smaller scale, i.e. at the scale of a single table for a farm consisting of oyster tables made of metallic wire structures on which porous bags of oysters are laid. This work is carried out through the idealized representation of the in-situ flow in a free surface flume tank. The flow characteristics around the overall structure are determined from velocity measurements obtained by laser velocimetry. The results highlight an asymmetric development of the boundary layers which suggest the existence of preferential areas for silting up and suspended matter fragmentation under the table. 相似文献
104.
Pierre Germain 《Annales Henri Poincare》2008,9(5):927-943
In the case where the charge of the particle is small compared to its mass, we describe the asymptotics of the Lorentz–Maxwell
equation (Abraham model) for any finite-energy data. As time goes to infinity, we prove that the speed of the particle converges
to a certain limit, whereas the electromagnetic field can be decomposed into a soliton plus a free solution of the Maxwell
equation.
It is the first instance of a scattering result for general finite energy data in a field-particle equation.
Submitted: October 31, 2007. Accepted: April 21, 2008. 相似文献
105.
Pierre Germain 《Journal d'Analyse Mathématique》2008,105(1):169-196
This article is devoted to the study of the nonhomogeneous incompressible Navier-Stokes system in dimension d ≥ 3. We use new a priori estimates, which enable us to deal with low-regularity data and vanishing density. In particular,
we prove new well-posedness results which improve the results of Danchin [6] by considering a less regular initial density,
without a lower bound. Also, we obtain the first uniqueness criterion for weak solutions which is at the scaling of the equation. 相似文献
106.
David St‐Germain Lavoie Floriane Pailleux Pascal Vachon Francis Beaudry 《Biomedical chromatography : BMC》2013,27(7):882-888
ABSTRACT: Xylazine is an α2‐adrenoceptor agonist and it is widely used in veterinary anesthesia in combination with ketamine. There is limited information on the metabolism of xylazine. A quantitative method for the determination of xylazine by HPLC‐ESI/MS/MS was developed. The method consisted of a protein precipitation extraction followed by analysis using liquid chromatography electrospray tandem mass spectrometry. The chromatographic separation was achieved using a Thermo Betasil Phenyl 100 × 2 mm column combined with an isocratic mobile phase composed of acetonitrile, methanol, water and formic acid (60:20:20:0.4) at a flow rate of 300 μL/min. The mass spectrometer was operating in selected reaction monitoring mode and the analytical range was set at 0.05–50 μm . The precision (%CV) and accuracy (%NOM) observed were 2.3–7.2 and 88.2–96.4%. In vitro metabolism studies were performed in rat liver microsomes and results showed moderate cytochrome P450 affinity (Km = 10.1 μm ) and a low metabolic stability of xylazine with a half‐life of 4.1 min in rat liver microsomes. Five phase 1 metabolites were observed. The main metabolite observed was an oxidation of the thiazine moiety at m/z 235 and, to a lesser extent, we observed the formation of N‐(2,6‐dimethylphenyl)thiourea at m/z 181 and three distinctive hydroxylated metabolites at m/z 237. Further experiments with ketamine and ketoconazole strongly supported that the metabolism of xylazine to its main metabolite is mediated by CYP3A in rat liver microsomes. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
107.
Chaudhuri RK Lascu Z Puccetti G Deshpande AA Paknikar SK 《Photochemistry and photobiology》2006,82(3):823-828
Di-2,2'-diethylhexyl-3,5-dimethoxy-4-hydroxy-benzylidenemalonate (INCI name diethylhexyl syringylidene malonate, DESM), the target photostabilizer, was synthesized in one step by condensation of 3,5-dimethoxy-4-hydroxy benzaldehyde (Syringaldehyde) with di-2,2'-diethylhexyl malonate. Photostability data in sunscreen formulations showed that DESM is photostable and improves the photostability of avobenzone significantly when compared to control (without a photostabilizer). Photostable broad-spectrum sunscreen formulations with high SPF (>30) have been achieved by combining avobenzone, DESM and UV-B sunscreens, such as homosalate, octisalate or other UV-B sunscreens. It seems that (a) triplet-state energy transfer from avobenzone to DESM and (b) scavenging of reactive species are responsible for the observed stabilization of avobenzone. In vitro study of the two formulations containing DESM clearly showed critical wavelength of well over 370 nm and can thus be categorized as broad-spectrum sunscreens. DESM does not have any contribution to in vivo SPF; instead it boosts SPF by about 5 units in high-SPF products. DESM was found to be an excellent singlet-oxygen quencher, thereby reducing photodegradation of avobenzone caused by singlet oxygen. In short, the multiplicity of effects and formulation benefits seen with DESM makes it an ideal choice as a unique antioxidant photostabilizer for a variety of cosmetic products targeting young and mature skin alike. 相似文献
108.
Jean-Michel Thomassin Christophe Pagnoulle Giuseppe Caldarella Albert Germain Robert Jrme 《Journal of membrane science》2006,270(1-2):50-56
Direct methanol fuel cells (DMFCs) that use a proton exchange membrane (PEM) as electrolyte, is a promising alternative source of energy for the future. However, methanol crossover from the anodic side to the cathodic one is a major problem in DMFC. Proper dispersion of layered silicates within the fuel cell membrane has been proposed as a strategy for improving the barrier properties of the membrane. The validity of this approach has been tested in case of a model membrane consisting of phosphotungstic acid doped poly(vinyl alcohol). A solvent casting technique has been used, which allows the nanofiller to be delaminated by an ultrasonic pre-treatment, as confirmed by TEM and XRD analysis. The layered silicates have a favourable impact on the methanol permeability, whose the decrease overcompensates some loss in ionic conductivity. 相似文献
109.
David Touboul Sandrine Roy Dominique P. Germain Pierre Chaminade Alain Brunelle Olivier Laprvote 《International journal of mass spectrometry》2007,260(2-3):158
Fabry disease is an X-linked disorder of glycosphingolipid metabolism, in which a partial or total deficiency of α-galactosidase A, a lysosomal enzyme, results in the progressive accumulation of neutral glycosphingolipids (globotriaosylceramide and digalactosylceramide) in most fluids and tissues of the body. Few information is available about the composition and distribution in tissues of the accumulated glycosphingolipids species. Mass spectrometry imaging is an innovative technique, which can provide pieces of information about the distribution of numerous biological compounds, such as lipids, directly on the tissue sections. MALDI-TOF and cluster-TOF-SIMS imaging approaches were used to study the localization of lipids (cholesterol, cholesterol sulfate, vitamin E, glycosphingolipids …) on skin and kidney sections of patients affected by the Fabry disease. Numerous information on pathophysiology were enlightened by both techniques. 相似文献
110.