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221.
Fascione MA Adshead SJ Mandal PK Kilner CA Leach AG Turnbull WB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):2987-2997
Sulfoxides are frequently used in organic synthesis as chiral auxiliaries and reagents to mediate a wide variety of chemical transformations. For example, diphenyl sulfoxide and triflic anhydride can be used to activate a wide range of glycosyl donors including hemiacetals, glycals and thioglycosides. In this way, an alcohol, enol or sulfide is converted into a good leaving group for subsequent reaction with an acceptor alcohol. However, reaction of diphenyl sulfoxide and triflic anhydride with oxathiane-based thioglycosides, and other oxathianes, leads to a different process in which the thioglycoside is oxidised to a sulfoxide. This unexpected oxidation reaction is very stereoselective and proceeds under anhydrous conditions in which the diphenyl sulfoxide acts both as oxidant and as the source of the oxygen atom. Isotopic labelling experiments support a reaction mechanism that involves the formation of oxodisulfonium (S-O-S) dication intermediates. These intermediates undergo oxygen-exchange reactions with other sulfoxides and also allow interconversion of axial and equatorial sulfoxides in oxathiane rings. The reversibility of the oxygen-exchange reaction suggests that the stereochemical outcome of the oxidation reaction may be under thermodynamic control, which potentially presents a novel strategy for the stereoselective synthesis of sulfoxides. 相似文献
222.
Sérandour AL Ledreux A Morin B Derick S Augier E Lanceleur R Hamlaoui S Moukha S Furger C Biré R Krys S Fessard V Troussellier M Bernard C 《Analytical and bioanalytical chemistry》2012,403(7):1983-1993
Human poisoning due to consumption of seafood contaminated with phycotoxins is a worldwide problem, and routine monitoring programs have been implemented in various countries to protect human consumers. Following successive episodes of unexplained shellfish toxicity since 2005 in the Arcachon Bay on the French Atlantic coast, a national research program was set up to investigate these atypical toxic events. Part of this program was devoted to fit-for-purpose cell-based assays (CBA) as complementary tools to collect toxicity data on atypical positive-mouse bioassay shellfish extracts. A collaborative study involving five laboratories was conducted. The responses of human hepatic (HepG2), human intestinal (Caco2), and mouse neuronal (Neuro2a) cell lines exposed to three known lipophilic phycotoxins-okadaic acid (OA), azaspiracid-1 (AZA1), and pectenotoxin-2 (PTX2)-were investigated. A screening strategy composed of standard operating procedures and a decision tree for dose-response modeling and assay validation were designed after a round of "trial-and-error" process. For each toxin, the shape of the concentration-response curves and the IC(50) values were determined on the three cell lines. Whereas OA induced a similar response irrespective of the cell line (complete sigmoid), PTX2 was shown to be less toxic. AZA1 induced cytotoxicity only on HepG2 and Neuro2a, but not on Caco2. Intra- and inter-laboratory coefficients of variation of cell responses were large, with mean values ranging from 35 to 54 % and from 37 to 48 %, respectively. Investigating the responses of the selected cell lines to well-known toxins is the first step supporting the use of CBA among the panel of methods for characterizing atypical shellfish toxicity. Considering these successful results, the CBA strategy will be further applied to extracts of negative, spiked, and naturally contaminated shellfish tissues. 相似文献
223.
T Courant VG Roullin C Cadiou M Callewaert MC Andry C Portefaix C Hoeffel MC de Goltstein M Port S Laurent LV Elst R Muller M Molinari F Chuburu 《Angewandte Chemie (International ed. in English)》2012,51(36):9119-9122
Do not tumble dry: Gadolinium-DOTA encapsulated into polysaccharide nanoparticles (GdDOTA?NPs) exhibited high relaxivity (r(1) =101.7?s(-1) mM(-1) per Gd(3+) ion at 37?°C and 20?MHz). This high relaxation rate is due to efficient Gd loading, reduced tumbling of the Gd complex, and the hydrogel nature of the nanoparticles. The efficacy of the nanoparticles as a T(1) /T(2) dual-mode contrast agent was studied in C6 cells. 相似文献
224.
Dr. Cédric Rouxel Dr. Céline Le Droumaguet Yohan Macé Sophie Clift Dr. Olivier Mongin Dr. Emmanuel Magnier Dr. Mireille Blanchard‐Desce 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(39):12487-12497
Novel tripodal derivatives with a triphenylamine core and that bear “superacidifiers” (i.e., fluorinated sulfoximinyl blocks) or novel sulfiliminyl moieties as peripheral groups were synthesized. These new chromophores show strong absorption in the near‐UV region and emission in the visible region. The fluorinated sulfoximinyl moieties were found to behave as potent auxochromic and electron‐withdrawing (EW) groups, thus leading to redshifted absorption and emission. These moieties promote a core‐to‐periphery intramolecular charge transfer (ctp‐ICT) transition, the energy of which was found to be correlated to their EW strength. In this study, we provide evidence of a linear correlation between the Hammett constant (σp) values and the electronic gap between the ground and first excited state of the three‐branched derivatives. This in turn was used to derive σp values of fluorinated sulfoximinyl moieties. These EWGs show unprecedentedly high σp values, up to 1.45 relative to 0.8 for NO2. Also, by using this method, the sulfiliminyl moiety was shown to exhibit similar EW strength as NO2, while promoting improved transparency and solubility. Finally, the superior EW strength of the fluorinated sulfoximine peripheral moieties was shown to induce significant enhancement of the two‐photon absorption responses in the red near‐IR region of the three‐branched derivatives relative to similar octupoles that bear more usual strong EW groups. These characteristics (improved nonlinear responses or transparency) open new routes for the design of nonlinear optical (NLO) chromophores for optical limiting or electro‐optical modulation. Such building blocks could also be of interest for optoelectronic applications, including the development of solar cells. 相似文献
225.
Guillerm B Darcos V Lapinte V Monge S Coudane J Robin JJ 《Chemical communications (Cambridge, England)》2012,48(23):2879-2881
Well-defined graft copolymers were obtained using a copper-catalysed azide-alkyne Huisgen's cycloaddition click reaction from both biocompatible and non-toxic poly(ε-caprolactone) and poly(2-methyl-2-oxazoline) homopolymers. Resulting amphiphilic copolymers proved to form micelles that could be used as potential drug carriers. 相似文献
226.
A pair of interpenetrated and non-interpenetrated chiral metal-organic frameworks with the same catalytic sites but different open channel sizes catalysed asymmetric cyclopropanation of substituted terminal alkenes with excellent diastereoselectivities (up to 9.6) and enantioselectivities (up to >99%). 相似文献
227.
228.
Sensitivity of stratospheric ozone lidar measurements to a change in ozone absorption cross-sections
Sophie Godin-Beekmann Prijitha J. Nair 《Journal of Quantitative Spectroscopy & Radiative Transfer》2012,113(11):1317-1321
The effect of a change in ozone absorption cross-section data is evaluated for stratospheric ozone lidar measurements, which are regularly performed for the monitoring of the ozone layer. The change is analysed for the measurements based on both the elastic and Raman scattering of the laser light by the atmosphere. The latter technique is essentially used for measurements performed in the presence of volcanic aerosol layers in the stratosphere. The discrepancy in ozone number densities is evaluated for various ozone cross-section data sets, using an atmospheric model for the evaluation of ozone cross-section temperature dependence. Results show that the difference in both elastic and Raman DIAL retrievals is below 1.5% in absolute values from 10 to 30 km. Above 30 km, the difference, estimated for the elastic DIAL retrieval only, is maximum around 45 km, with largest differences reaching 1.8% in the tropics. 相似文献
229.
We investigate the steady-state rheological behaviour of the lamellar phase of a lyotropic system (CpCl, hexanol, brine)
and of a thermotropic system (8CB). Power laws characterize the behaviour of the imposed stress as a function of the measured
shear rate and similarities are observed for both systems; the same regime γ˙∼σ
m
with m≈1.7 is obtained at low shear stresses corresponding to a texture of oily streaks oriented in the direction of the flow, as
shown by microscopic observations. The “onion state” only exists in the case of dilute samples of the lyotropic lamellar phase;
the stress then varies as γ˙∼σ
m
with m≈4.8, as already observed by other groups with different systems. Rheological measurements at different temperatures allow
determination of different activation energies relating to the still badly understood processes involved in the different
rheological regimes. We propose a model which reproduces the experimental power laws and which is based on an analogy with
the theory of high-temperature creep in metals and alloys.
Received: 19 October 1999/Accepted: 1 November 1999 相似文献
230.
Sophie Peeterbroeck Fouad Laoutid Benjamin Swoboda Jos‐Marie Lopez‐Cuesta Nicolas Moreau Janos B. Nagy Michaël Alexandre Philippe Dubois 《Macromolecular rapid communications》2007,28(3):260-264
Nanocomposites based on an ethylene–vinyl acetate copolymer (27 wt.‐% vinyl acetate) and multiwall carbon nanotubes (MWNTs) have been prepared by melt blending and their thermal degradation and flame retardant properties have been evaluated. Special attention has been paid to the influence of the nanotube nature on the flammability properties and more particularly on the time to ignition (TTI) as measured by cone calorimetry. It has been shown that there is a strong influence of the nature of carbon nanotubes on the fire behaviour of the composites, especially previous MWNTs crushing proved to substantially delay the TTI while maintaining much reduced heat release rate (HRR). Such a remarkable behaviour might be explained by the chemical reactivity of radical species present at the surface/extremities of crushed MWNTs during the combustion process.