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61.
The ligand substitution reaction of [Co(an)6]2+ (an = acetonitrile) with 1,1,3,3-tetramethylurea (TMU) in the noncoordinating solvent, nitromethane, was spectrophotometrically investigated by titration. The observed spectral changes were analyzed using a model with the four steps of ligand substitution. The component complexes involved in the substitution were found to be 6-coordinate [Co(an)6]2+ and [Co(an)5(tmu)]2+, 5-coordinate [Co(an)3(tmu)2]2+ and [Co(an)2(tmu)3]2+, and 4-coordinate [Co(tmu)4]2+. The logarithmic values of the stepwise equilibrium constant are 2.17 +/- 0.26, 1.06 +/- 0.15, 1.19 +/- 0.06, and -0.4 +/- 0.4 at 25 degrees C. The decrease in the coordination number of the Co(II) ion from 6 to 5 during the formation of [Co(an)3(tmu)2]2+ and from 5 to 4 during the formation of [Co(tmu)4]2+ is ascribed to the steric repulsion between the coordinating bulky TMU molecules. 相似文献
62.
Transparent barium titanate (BaTiO3) wet gels synthesized by sol-gel processing using high-concentration Ba,Ti-alkoxide solution (1.0 mol/l) were subjected to optical measurements, X-ray diffraction analysis and transmission electron microscope observations. A systematic shift of the optical absorption edge was observed for the transparent BaTiO3 wet gels shrinking during aging at 30 and 50°C, while no shift was observed for the wet gels aged at 5°C. The crystallinity and crystallite size of the gels increased with increasing aging time and temperature. The shift of the optical absorption edge of the BaTiO3 gels during aging was found to have a close relation to an increase in the crystallite size of the gels. 相似文献
63.
Shiibashi Hiroyuki Matsuda Hirofumi Kuwabara Makoto 《Journal of Sol-Gel Science and Technology》1999,16(1-2):129-134
We have investigated on the synthesis of Ba1 – xSrxTiO3 (BST, x = 0.0–1.0) solid solution at low temperature by a sol-gel method using precursor solutions of Ba(OC2H5)2, Sr(OC2H5)2, and Ti(OCH(CH3)2)4 dissolved in 2-methoxyethanol. Crystalline BST solid solution monolithic gels were obtained as dried at 90°C. Crystalline fraction of BST gels increased with increasing concentration of the precursor solution and increasing amount of the hydrolysis water used. Ba0.4Sr0.6TiO3 (x = 0.6) gels from a precursor solution of 0.5 mol/l with hydrolysis water of H2O/Ti = 50 crystallized during aging at 30°C. 相似文献
64.
65.
A recent high pressure experiment on LaAlO3 has revealed that the compound is an exception for the "general rule" of displacive phase transition associated with zone-boundary phonons. In the present study, the experimental result is successfully confirmed by first principles calculations. The pressure dependence of phonon frequencies as well as the phase transition pressure is quantitatively well reproduced. We found that the behavior is not peculiar to LaAlO3 but rather ubiquitous. RAlO3 (R = La, Nd, Sm, and Gd) and LaGaO3 can be classified in the same group. 相似文献
66.
67.
Mihara F Kuwabara Y Yoshida T Yoshiura T Sasaki M Masuda K Matsushima T Fukui M 《Magnetic resonance imaging》2000,18(9):1167-1174
The purpose of this study is to investigate the correlation between lactate levels and cerebral vascular reactivity (VR) in regions outside an area of chronic cerebral infarction. Multivoxel proton magnetic resonance spectroscopy ((1)H-MRS) and positron emission tomography (PET) were performed in 11 patients who suffered chronic cerebral infarction. Of these 11 patients, 4 were examined before and after bypass surgery. Two regions-of-interests (ROIs) were placed outside the area of chronic infarction. One ROI was placed within a control region on the contralateral side. A lactate peak area was obtained in all ROIs. An N-acetyl aspartate (NAA) peak area was obtained in the ROI within the control region. The ratio of the lactate peak area and NAA peak area (Lct/NAA) was calculated for normalization of the lactate level, and was found to be 0.13 +/- 0. 10 (range, 0 to 0.43). The VR was recorded at 13.3 +/- 20.7% (range, - 44.3 to 68.9%), utilizing PET and administering acetazolamide. A significant negative correlation was observed between the Lct/NAA ratio and VR (r = - 0.709, p < 0.0001). These results suggest that lactate levels and VR are closely related in regions outside areas of chronic cerebral infarction. 相似文献
68.
The crystalline–noncrystalline structure and its structural changes from thermal treatments for ethylene ionomers have been investigated with solid‐state 13C and 23Na NMR spectroscopy. 13C spin–lattice relaxation time (T1C) measurements reveal that as‐received ethylene ionomers have much enhanced molecular mobility in the crystalline region in comparison with conventional polyethylene samples. By appropriate annealing, however, polyethylene‐like morphological features reflecting T1C behavior can also be observed. 13C spin–spin relaxation time (T2C) measurements for the noncrystalline region reveal the existence of two components with different T2C values, and these two components have been assigned to the crystalline–amorphous interfacial and rubbery–amorphous components. These results indicate that the structure of the major part of the noncrystalline region in the ethylene ionomers is similar to that of bulk‐crystallized polyethylene samples, regardless of possible ionic aggregates. The origin of the lower temperature endothermic peak in the heating process of the differential scanning calorimetry curve observed for the as‐received sample has also been examined somewhat in detail. As a result, it is proposed that the melting of smaller crystallites produced during storage at room temperature is the origin of the lower temperature peak. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1142–1153, 2002 相似文献
69.
Potassium gallate in which gallium ions are partially substituted by aluminium, K2O·(5 ? x)Ga2O3·xAl2O3, has been prepared by sintering a mixture of K2CO3, Ga2O3, Al2O3 at 1500°C. It was found from X-ray diffraction that the gallate had the beta-alumina type β phase and that solid solutions were formed on substituting Ga by Al. The potassium gallate thus obtained was revealed to be a relatively high potassium ion conductor by a.c. conductivity and ionic transport number measurements. The potassium ion conductivity decreases monotonically with the aluminium content. In order to analyze the decreasing behavior of the conductivity isotherm, the slot width was calculated from the lattice parameters and the apparent porosity was evaluated using the apparent and theoretical densities. The change of the potassium ion conductivity with the substituted amount of aluminium was explained well by the variation of the slot width. 相似文献
70.
Kuwabara T Aoyagi T Takamura M Matsushita A Nakamura A Ueno A 《The Journal of organic chemistry》2002,67(3):720-725
The heterodimerization behavior of dye-modified beta-cyclodextrins (1-6) with native cyclodextrins (CDs) was investigated by means of absorption and induced circular dichroism spectroscopy in an aqueous solution. Three types of azo dye-modified beta-CDs (1-3) show different association behaviors, depending on the positional difference and the electronic character of substituent connected to the CD unit in the dye moiety. p-Methyl red-modified beta-CD (1), which has a 4-(dimethylamino)azobenzene moiety connected to the CD unit at the 4' position by an amido linkage, forms an intramolecular self-complex, inserting the dye moiety in its beta-CD cavity. It also associates with the native alpha-CD by inserting the moiety of 1 into the alpha-CD cavity. The association constants for such heterodimerization are 198 M(-1) at pH 1.00 and 305 M(-1) at pH 6.59, which are larger than the association constant of 1 for beta-CD (43 M(-1) at pH 1.00). Methyl red-modified 2, which has the same dye moiety as that for 1 although its substituent position is different from that of 1, does not associate even with alpha-CD due to the stable self-intramolecular complex, in which the dye moiety is deeply included in its own cavity of beta-CD. Alizarin yellow-modified CD (3), which has an azo dye moiety different from that of 1 and 2, caused a slight spectral variation upon addition of alpha-CD, suggesting that the interaction between 3 and alpha-CD is weak. On the other hand, phenolphthalein-modified beta-CD (4), which forms an intermolecular association complex in its higher concentrations, binds with beta-CD with an association constant of 787 M(-1) at pH 10.80, where 4 exists as the dianion monomer in the absence of beta-CD. p-Nitorophenol-modified beta-CDs (5 and 6), each having p-nitorophenol moieties with a different connecting part with an amido and amidophenyl group, respectively, associated with alpha-CD with association constants of 66 and 16 M(-1) for 5 and 6, respectively. The phenyl unit in the connecting part of 6 may prevent the smooth binding with alpha-CD. All these results suggest that the dye-modified CDs, in which the dye part is not tightly included in its CD cavity, associate with the native CD to form heterodimer composed of two different CD units by inserting the dye moiety into the native CD unit. The resulting heterodimers have a cavity that can bind another appending moiety of host molecules. On this basis, more ordered molecular arrays or the supramolecular hereropolymers can be constructed. 相似文献