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排序方式: 共有62条查询结果,搜索用时 406 毫秒
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Warunee Klinklai Tomonobu Mizumo Jitladda Tangpakdee Sakdapipanich Hiroyuki Ohno 《European Polymer Journal》2003,39(8):1707-1712
Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (Tg) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH4)2S2O8 in the presence of propanal. The resulting liquid epoxidized rubber (Mn≈104) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li+ as an ionic conducting medium, that is, solid polymer electrolyte. 相似文献
4.
By the application of the Vilsmeier-Haack reaction to various o-hydroxyacetophenone derivatives, 4-oxo-4H-1-benzopyran-3-carboxaldehydes were synthesized in one step. Their IR, NMR and mass spectra were studied. In the mass spectra characteristic fragmentation pathways were observed. 相似文献
5.
Oikawa H Nakamura K Toshima H Toyomasu T Sassa T 《Journal of the American Chemical Society》2002,124(31):9145-9153
To examine the mechanism of the cyclization reaction catalyzed by aphidicolan-16beta-ol synthase (ACS), which is a key enzyme in the biosynthesis of diterpene aphidicolin, a specific inhibitor of DNA polymerase alpha, skeletal rearrangement of 2a and biomimetic cyclization of 4b were employed. The structures of the reaction products, which reflect penultimate cation intermediates, allowed us to propose a detailed reaction pathway for the Lewis acid-catalyzed cyclizations and rearrangements. Isolation of these products in an aphidicolin-producing fungus led us to speculate that the mechanism of the ACS-catalyzed cyclization reaction is the same as that of a nonenzymatic reaction. Ab initio calculations of the acid-catalyzed reaction intermediates and the transition states indicate that the overall reaction catalyzed by ACS is an exothermic process though the reaction proceeds via an energetically disfavored secondary cation-like transition state. In conjunction with the solvent effect in the acid-catalyzed reactions, this indicates that the actual role of ACS is to provide a template which enforces conformations of the intermediate cations leading to the productive cyclization although it has been believed that the cation-pi interaction between cation intermediates and aromatic amino acid residues in the active site is important for the enzymatic catalysis. This study provided important information on the role of various cationic species, especially secondary cation-like structures, in both nonenzymatic and enzymatic reactions. 相似文献
6.
The bidentate phosphine oxide compounds bis(diphenylphosphinyl)methane (BDPPM) and bis(diphenylphosphinyl)ethane (BDPPE) were synthesized and the liquid—liquid extraction equilibria of some divalent metal ions such as Co(II), Ni(II), Zn(II) and Cd(II) with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP) and the neutral phosphine oxide compounds were investigated. BDPPM was found to be much more powerful than BDPPE and the monodentate neutral ligand trioctylphosphine oxide (TOPO). The composition of the extracted species were determined by a graphical method to be M(PMBP)2(TOPO)s (s = 2 for Co, Ni, Cd and s = 1 for Zn), M(PMBP)2(BDPPM) and M(PMBP)2(BDPPE). The adduct formation constants between the acylpyrazolone chelates and the neutral ligands were determined and are discussed in terms of the molecular structure. 相似文献
7.
Kazuhisa Uomi Masahiro Aoki Tomonobu Tsuchiya Atsushk Takai 《Fiber and Integrated Optics》1994,13(1):17-29
The high-speed modulation properties of 1.5 μm multiquantum-well λ/4-shifted DFB lasers are filly reviewed. In particular, the dependence of intrinsic dynamic properties, such as relaxation oscillation frequency, nonlinear damping phenomenon, and spectral chirping under 10 Gbit/s direct modulation, on the number of quantum wells is systematically investigated and compared with those of bulk lasers. The results indicate that the dependence of the above three factors on the number of wells is clearly explained by the linear gain saturation of the quantum-well lasers and that the optimum number of wells should be more than ten in order to increase the modulation bandwidth. 相似文献
8.
Ono Y Minami A Noike M Higuchi Y Toyomasu T Sassa T Kato N Dairi T 《Journal of the American Chemical Society》2011,133(8):2548-2555
Fusicoccin A and cotylenin A are structurally related diterpene glucosides and show a phytohormone-like activity. However, only cotylenin A induces the differentiation of human myeloid leukemia cells. Since the cotylenin A producer lost its ability to proliferate during preservation, a study on the relationship between structure and activity was carried out and a modified fusicoccin A with hydroxyl group at the 3-position showed a similar biological activity with that of cotylenin A. We then searched for an enzyme source that catalyzes the introduction of a hydroxyl group into the 3-position and found that brassicicene C, which is structurally related to fusicoccin A with hydroxyl group at the 3-position, was produced by Alternaria brassicicola ATCC96836. We recently cloned a brassicicene C biosynthetic gene cluster including the genes encoding fusicocca-2,10(14)-diene synthase and two cytochrome P450s, which were responsible for the formation of fusicocca-2,10(14)-diene-8β,16-diol. In this study, we report that a α-ketoglutarate dependent dioxygenase, the gene coding for which was located in the cluster, catalyzed a hydroxylation at the 3-position of fusicocca-2,10(14)-diene-8β,16-diol. On the other hand, a α-ketoglutarate-dependent dioxygenase, which had been identified in a fusicoccin A biosynthetic gene cluster, catalyzed the 16-oxidation of fusicocca-2,10(14)-diene-8β,16-diol to yield an aldehyde (8β-hydroxyfusicocca-1,10(14)-dien-16-al), although both dioxygenases had 51% amino acid sequence identity. These findings suggested that the dioxygenases played critical roles for the formation of the fusicoccin A-type and cotylenin A-/brassicicene C-type aglycons. Moreover, we showed that short-chain dehydrogenase/reductase located in the fusicoccin A biosynthetic gene cluster catalyzed the reduction of the aldehyde to yield fusicocca-1,10(14)-diene-8β,16-diol. 相似文献
9.
Mikiyasu Shirai Matthew Beard James T. Pearson Takashi Sonobe Hirotsugu Tsuchimochi Yutaka Fujii Emily Gray Keiji Umetani Daryl O. Schwenke 《Journal of synchrotron radiation》2013,20(3):441-448
Synchrotron radiation microangiography is a powerful tool for assessing adverse changes in pulmonary vessel density associated with primary pulmonary hypertension (PH). Congestive heart failure (CHF) leads to a `secondary' onset of PH, yet it is unknown whether secondary PH is also associated with reduced vessel density. This study utilized synchrotron radiation to assess both pulmonary vessel density and endothelial function in a Dahl rat model of CHF with secondary PH. High salt‐fed Dahl salt‐sensitive (Dahl‐S) and salt‐resistant (Dahl‐R) rats were anesthetized and microangiography was performed to assess the pulmonary vessel density and vascular responses to (i) sodium nitroprusside (5.0 µg kg?1 min?1), (ii) acetylcholine (3.0 µg kg?1 min?1) and (iii) ET‐1A receptor blockade, BQ‐123 (1 mg kg?1). Dahl‐S rats developed CHF and secondary PH as evident by endothelial dysfunction, impaired vasodilatory responses to acetylcholine, enhanced vasodilatory responses to BQ‐123 and extensive pulmonary vascular remodeling. Consequently, the pulmonary vessel density was adversely reduced. Interestingly, the etiology of secondary PH manifests with structural and functional changes that are comparable with that previously reported for primary PH. One important discrepancy, however, is that ET‐1 modulation of pulmonary vessels is most striking in vessels with a diameter range of 100–200 µm in secondary PH, in contrast to a range of 200–300 µm in primary PH. Such discrepancies should be considered in future studies investigating primary and secondary forms of PH. 相似文献
10.
Hiroshi Mukai Shoji Miyazaki Shigeo Umetani Sorin Kihara Masakazu Matsui 《Analytica chimica acta》1989
Solvent extraction of europium (III), zinc (II) cobalt (II) with α-acyl-d-camphor and optically active isomers of quinine and quinidine was studied in order to obtain information on chirality recognition based on adduct formation between a chiral metal chelate and optically active isomers. It was possible to differentiate clearly between the adduct formation of quinine and that of quinidine in the synergic extraction of cobalt and europium with 3-heptafluorobutyryl- d-camphor and cobalt with 3-trifluoroacetyl-d-camphor. 相似文献