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1.
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported.  相似文献   
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The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.  相似文献   
4.
The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.  相似文献   
5.
Ramos A  San Emeterio JL  Sanz PT 《Ultrasonics》2000,38(1-8):553-558
Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results.  相似文献   
6.
Two sets of cationic surfactants each with essentially the same alkyl chains but different headgroup structures were studied to investigate the effects of surfactant headgroup structure on micelle microstructures, drag reduction (DR) and rheological properties at certain counterion and surfactant concentrations. Cetyldimethylethylammonium bromide (CDMEAB) was compared with alkyltrimethyl ammonium bromide (CnTAB) and benzyldimethyl(hydrogenated tallow)ammonium chloride (DMHTB) was compared with alkyltrimethylammonium chloride (CmTAC), respectively. Surfactants with larger headgroups showed lower high temperature limits for DR. CDMEAB systems have better DR abilities than CnTAB below room temperature but the opposite is true at higher temperatures. DMHTB has stronger counterion binding ability than CmTAC, giving better DR properties than CmTAC at low counterion concentration, but has a lower upper temperature limit for DR. These results provide further understanding of the self-assembly nature of threadlike micelles of cationic surfactants and guidance for design of effective surfactant structures to meet particular DR requirements.  相似文献   
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Turbulent Couette flow between two circular cylinders has been used for drag reduction experiments using surfactants. In the experiments presented here, only the outer cylinder rotates, the inner cylinder remains at rest and accurate measurements of the torque at the inner cylinder are measured. Water is used as a reference fluid. A drag reducing surfactant called Arquad S-50 (Akzo Nobel Surface Chemistry LLC, Chicago, Ill., USA) (5 mM)+NaSal (12.5 mM) was used as the drag reduction agent. This surfactant can reduce the drag up to 70% (a Reynolds number of about 70,000–150,000) as measured by pressure drop in a pipe flow. Experiments in Couette flow also show drag reduction in the turbulent range. Two arrangements were used, (1) one small trip-wire on the inner cylinder, and (2) four larger trip-wires on the outer cylinder. These trips reduce the critical Reynolds number for transition from laminar to turbulent flow. In case (1), we obtained 18% drag reduction at 5,000<Re<15,000 and in case (2), we obtained an average reduction of about 20% at 2,000<Re<10,000, increasing up to 30% at Re=15,000. The paper also discusses two important problems. First, the shear rate is not constant in the radial gap in circular Couette flow. For non-Newtonian fluids, where the molecular viscosity is a function of the shear rate, this effect must be considered. Second, which viscosity should be used in the Reynolds number? For pipe flow measurements, most authors use the viscosity of the solvent (generally water and Newtonian). For measurements in the Couette flow, we use a different approach, which is described in this paper. We conclude that Couette flow is a useful method for drag reduction investigations. Its advantage is the much smaller geometry in comparison to those of conventional test facilities such as wind tunnels, water, or oil channels or in tubes.  相似文献   
9.
A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group.  相似文献   
10.
The zeros in the complex z plane of the Whittaker function Wc/z,µ(z),closely related to spherical waves in the quantum-mechanicalCoulomb problem, are investigated for varying real values ofthe parameters c and µ  相似文献   
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