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201.
Kohji Yagi Tatsuru Miyazaki Hiroyuki Okitsu Fujio Toda Yoshio Iwakura 《Journal of polymer science. Part A, Polymer chemistry》1972,10(4):1149-1156
The anionic polymerization of three monomers, 2-isopropenyl-4,5-dimethyloxazole(I), 2-isopropenylthiazole(II), and 2-isopropenylpyridine(III), was studied in THF. These monomers produced red-colored living polymers on addition of sodium naphthalene or living α-methylstyrene tetramer as an initiator. It was observed that a considerable amount of monomer remained in the respective living polymer–monomer system, indicating that an equilibrium between the polymer and the monomer existed as in the case of α-methylstyrene. At lower temperatures, the conversion of the monomer to the polymer increased. The equilibrium monomer concentrations [Me] were determined at different temperatures, and the heats (ΔH) and the entropies (ΔS°) of polymerization were obtained by plotting In(1/[Me]) against 1/T as ΔH = ?9.4, ?6.8, and ?6.2 kcal/mole, ΔS°S = ?22.9, ?16.5, and ?16.6, eu for I, II, and III, respectively. 相似文献
202.
Katsuhiko Fujio Tsunehiro Mitsui Hiroshi Kurumizawa Yoshikazu Tanaka Yuhei Uzu 《Colloid and polymer science》2004,282(3):223-229
In order to investigate the effect of added salt on micelle size, shape, and structure the solubilization of Orange OT in aqueous NaBr solutions of decylpyridinium bromide (DePB), dodecylpyridinium bromide (DPB), tetradecylpyridinium bromide (TPB), and hexadecylpyridinium bromide (CPB) has been examined. The solubilization powers of DePB and DPB micelles increase with increasing NaBr concentration up to 2.86 and 3.07 mol dm–3, respectively, but above these concentrations remain unaltered. This suggests that spherical micelles of DePB and DPB can have a maximum and constant size at NaBr concentrations higher than these threshold concentrations. On the other hand, the solubilization powers of TPB and CPB micelles increase in the whole range of NaBr concentration studied. The dependencies of the solubilization powers of their micelles on the counterion concentration change at 0.10 and 0.03 mol dm–3 NaBr, respectively, as suggests that TPB and CPB micelles undergo the sphere–rod transition at those concentrations. Orange OT is a more suitable probe for detecting the presence of the maximum- and constant-size spherical micelle than Sudan Red B. 相似文献
203.
Second-order rate constants have been measured for reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with a series of alicyclic secondary amines. The reaction proceeds through S-O and C-O bond fission pathways competitively. The S-O bond fission occurs more dominantly as the amine basicity increases and the substituent X in the sulfonyl moiety becomes more strongly electron withdrawing, indicating that the regioselectivity is governed by the amine basicity as well as the electronic nature of the substituent X. The S-O bond fission proceeds through an addition intermediate with a change in the rate-determining step at pK(a) degrees = 9.1. The secondary amines are more reactive than primary amines of similar basicity for the S-O bond fission. The k(1) value has been determined to be larger for reactions with secondary amines than with primary amines of similar basicity, which fully accounts for their higher reactivity. The second-order rate constants for the S-O bond fission result in linear Yukawa-Tsuno plots while those for the C-O bond fission exhibit poor correlation with the electronic nature of the substituent X. The distance effect and the nature of reaction mechanism have been suggested to be responsible for the poor correlation for the C-O bond fission pathway. 相似文献
204.
Fujio Suganuma Hiroshi Mitsui Sueo Machi Miyki Hagiwara Tsutomu Kagiya 《Journal of polymer science. Part A, Polymer chemistry》1968,6(11):3127-3137
The gamma-radiation-induced polymerization of ethylene in the presence of 13–30 ml of tert-butyl alcohol was carried out under a pressure of 120–400 kg/cm2 at a dose rate of 1 × 103 to 2.5 × 104 rad/hr at 30°C with a 100 ml reactor. The polymerization rate and the molecular weight of the polymer increased with reaction time and pressure and decreased with amount of tert-butyl alcohol. The polymer yield increased almost proportionally with the dose rate, while the molecular weight was almost independent of it. These results were graphically evaluated, and the rate constants of initiation, propagation, and termination for various conditions were determined. No transfer was observed. On the basis of these results the role of tert-butyl alcohol in the polymerization is discussed. 相似文献
205.
A simple one-dimensional mass transfer model has been proposed for the oxygen transport through a bronchial tree to alveolar
tissues as well as the carbon dioxide removal from the tissues in the human respiratory system. The proposed model mathematically
describes the mass transfer between the airway inlet and the red blood cell interior in the pulmonary capillaries. The quasi
steady one-dimensional analysis based on the model reveals that the bronchial tree is constructed such that it promotes the
easiest access to the external air. Naturally, there exists the optimal number of the bifurcation levels, namely, 23, that
yields the minimum overall mass transfer resistance for the mass transport from the external air to the red blood cells. 相似文献
206.
Tokuji Ikeda Hirosuke Tatsumi Hajime Katano Mizue Wanibuchi Takao Hibi Tsutomu Kajino 《Analytical sciences》2008,24(2):237-241
The thermal stability of a redox enzyme, bilirubin oxidase (BOD), has been quantitatively evaluated by measuring the inactivation kinetics of BOD at several temperatures. The enzyme activity is directly related to the mediated bioelectrocatalytic current for the BOD-catalyzed reduction of O(2). Thus, the inactivation process is measured by the time-dependent decrease in the bioelectrocatalytic current. The results reveal that the inactivation obeys first-order kinetics, whose rate constants (k) are determined at pH 7.0 and at 50 - 70 degrees C. The half life of BOD activity, calculated from the k value at 50 degrees C is 114 min, which is in harmony with the thermal-stability data given in a catalog by Amano Enzyme Inc. The bioelectrocatalysis method allows in situ measurements of the inactivation kinetics in the period of a few minutes at relatively high temperatures. The rate constants show a large temperature dependence, leading to a large Arrhenius activation energy (E(A)) of 221 kJ mol(-1). The activation Gibbs energy (DeltaG(not equal)), activation enthalpy (DeltaH(not equal)), and activation entropy (DeltaS(not equal)) are also determined. 相似文献
207.
Fujio Shimizu 《Hyperfine Interactions》1992,74(1-4):259-267
The characteristics of laser cooling and trapping of Li, Ne, Ar, Kr, Ca, and Sr are described. The effect of the hyperfine
structure, level multiplicity and population leakage on the trapping efficiency are discussed. 相似文献
208.
209.
Koji Yagi Shigeo Tsuyama Fujio Toda Yoshio Iwakura 《Journal of polymer science. Part A, Polymer chemistry》1976,14(5):1097-1105
An interesting effect of pyridine on the anionic polymerization of styrene in THF is described. Pyridine forms a complex with living polystyrene and greatly slows the polymerization rate without changing the degree of polymerization. From kinetic and spectroscopic studies, it was clear that there exist two active species in this system and the complex between living polystyrene and pyridine was of the 1:1 type, which itself had a weak ability to grow. The formation constant of the complex K was found to be about 4 × 105 l./mole. The effect of substituted pyridine was also studied and the nature of the complex was discussed. 相似文献
210.