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The molecular structure of bis-5-hydroxypentylphthalate (BHPP) is like dihexyl phthalate but having appended to it two hydroxyl end groups, which contribute additional dipole moments and capacity for hydrogen-bond formation. In a previously published dielectric study of the primary and secondary relaxations of BHPP, it was found that all the dynamic properties are normal except for the anomalously large width of the primary relaxation loss peak. There are two secondary relaxations, the relaxation time of the slower one increases with increasing pressure, whereas that of the faster one is practically insensitive to pressure. Hence, the slower secondary relaxation is the "universal" Johari-Goldstein (JG) [J. Chem. Phys. 53, 2372 (1970); 55, 4245 (1971)] relaxation in BHPP. All is well except if the observed large width of the primary relaxation were an indication of a corresponding large coupling parameter n=0.45 in the coupling model. Then the predicted relations between the primary relaxation time tau(alpha) and the JG relaxation time tau(JG) found previously to hold in many glass formers would be violated. It was recognized that this singular behavior of BHPP is likely due to broadening of the primary loss peak by the overlapping contributions of two independent dipole moments present in BHPP, and the actual coupling parameter is smaller. However, at the time of publication of the previous work there were not enough data to support this explanation. By making broadband dielectric measurements of dibutyl phthalate (DBP) and dioctyl phthalate (DOP) that have chemical structures closely related to BHPP but with only one dipole moment, we show that all their dynamic properties are almost the same as BHPP but the widths of their primary relaxation loss peaks are significantly narrower corresponding to a smaller coupling parameter n=0.34. The new data presented here indicate that the coupling parameter of BHPP is about the same as DBP and DOP, and the predicted relations between tau(alpha) and tau(JG) of BHPP are brought back in agreement with the experimental data. 相似文献
3.
M. Paluch 《Colloid and polymer science》1998,276(7):648-652
The results of experimental studies of the adsorption at the solution/air interface from an aqueous mixture: 2,4,6-trimethylphenol–2,4,6-trichlorophenol
are presented. The surface properties of the above-mentioned mixture were studied by surface potential and surface tension
measurements. These measurements were carried out as a function of the concentration of 2,4,6-trimethylphenol aqueous solution
at a constant concentration of 2,4,6-trichlorophenol.
Using the results obtained and based on the Gibbs equation, Helmholtz formula and Motomura’s method the relative surface excesses
of adsorbed substances, effective dipole moments, surface molar fractions of solutes and miscibility of adsorbed films were
determined.
Received: 7 November 1997 Accepted: 26 February 1998 相似文献
4.
Jerzy Lisowski Marta Paluch Tadeusz Lis 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(1-2):123-129
The template condensation of (R)-2,2′-diamino-1,1′-binaphthyl and 2,6-diformylpyridine leads to lanthanide(III) complexes of the new chiral hexaaza macrocycle L that adopts highly twisted conformation in [LnL](NO3)3 complexes. The complexes have been characterised by ESI MS spectrometry and NMR spectroscopy. The analogous N2O4 chiral crown ether L2 that has the same carbon skeleton as L does not exhibit tendency to bind lanthanide(III) ions. The X-ray crystal structure of L2 exhibit squeezed conformation of the macrocycle and spatial disposition of donor atoms that does not predispose it for coordination of lanthanide(III) ions. 相似文献
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Jolanta Pyteraf Witold Jamrz Mateusz Kurek Joanna Szafraniec-Szczsny Daniel Kramarczyk Karolina Jurkiewicz Justyna Knapik-Kowalczuk Jacek Tarasiuk Sebastian Wroski Marian Paluch Renata Jachowicz 《Molecules (Basel, Switzerland)》2021,26(11)
The flexibility of dose and dosage forms makes 3D printing a very interesting tool for personalized medicine, with fused deposition modeling being the most promising and intensively developed method. In our research, we analyzed how various types of disintegrants and drug loading in poly(vinyl alcohol)-based filaments affect their mechanical properties and printability. We also assessed the effect of drug dosage and tablet spatial structure on the dissolution profiles. Given that the development of a method that allows the production of dosage forms with different properties from a single drug-loaded filament is desirable, we developed a method of printing ketoprofen tablets with different dose and dissolution profiles from a single feedstock filament. We optimized the filament preparation by hot-melt extrusion and characterized them. Then, we printed single, bi-, and tri-layer tablets varying with dose, infill density, internal structure, and composition. We analyzed the reproducibility of a spatial structure, phase, and degree of molecular order of ketoprofen in the tablets, and the dissolution profiles. We have printed tablets with immediate- and sustained-release characteristics using one drug-loaded filament, which demonstrates that a single filament can serve as a versatile source for the manufacturing of tablets exhibiting various release characteristics. 相似文献
8.
Paluch M Hensel-Bielowka S Ziolo J 《Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics》2000,61(1):526-531
The effect of pressure variation on dynamics of alpha relaxation process in poly[(phenyl glycidyl ether)-co-formaldehyde] has been investigated both under isothermal (T=293 K) and isobaric (P=0.1, 60, 120, 180, and 240 MPa) conditions using broad band dielectric spectroscopy (10(-2) to 10(6) Hz). The alpha relaxation is analyzed by means of the Havriliak-Negami relaxation function which has two shape parameters (alpha and gamma) to characterize non-Debye behavior. As a result we found that the shape parameters of the dielectric function collected for different pressures fall on master curves constructed by plotting alpha and alphagamma against the logarithm of relaxation time. The scaling of shape parameters for different pressure stems from pressure independence of fragility. This provides strong experimental evidence supporting correlation of non-Debye behavior with non-Arrhenius relaxation under high pressure. From an analysis of the shape parameters of relaxation function, in terms of the Schonhals and Schlosser model, we drew conclusions that the molecular mobility of PPG is controlled in the same way by temperature and pressure. The relaxation times exhibit a clear non-Arrhenius behavior under isothermal and isobaric condition. 相似文献
9.
The miscibility and interactions between components in mixed adsorbed films and micelles containing zwitterionic (dodecyl sulfobetaine--DSB) and cationic (dodecyltrimethylammonium bromide) or anionic (sodium dodecyl sulfonate) surfactant, respectively, have been investigated. The molecular interactions have been quantified by the values of the excess free energy of adsorption (DeltaGS,Exc) and micelle formation (DeltaGM,Exc). The obtained results indicate nonideal behavior of the investigated mixtures since the values of DeltaGS,Exc and DeltaGM,Exc) are negative. Moreover, it has been found that DSB interact more strongly with anionic surfactant as compared to cationic surfactant owing to different structure of mixed monolayers and micelles. 相似文献
10.
Kamil Kaminski Marian Paluch R. Wrzalik Jerzy Ziolo Radoslav Bogoslovov C. Michael Roland 《Journal of polymer science. Part A, Polymer chemistry》2008,46(11):3795-3801
The polymerization and crosslinking of tetraethylene glycol dimethacrylate were induced by high pressure. The product was analyzed by both swelling experiments and broadband dielectric spectroscopy to determine the structure, with IR measurements used to follow the extent of reaction and its temperature dependence. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3795–3801, 2008 相似文献