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排序方式: 共有805条查询结果,搜索用时 15 毫秒
21.
Summary Cationic polymerization of p-methoxystyrene initiated by HI/ZnI2 in toluene afforded living polymers not only at low temperature (–15°C) but at room temperature (+25°C) as well. The number-average molecular weight of the polymers was directly proportional to monomer conversion and in excellent agreement with the calculated value assuming that one polymer chain forms per unit hydrogen iodide. On addition of a fresh feed of monomer at the end of the first-stage polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage; the polymer molecular weight further increased in direct proportion to monomer conversion and was close to the calculated value for living polymer. Throughout these reactions, the molecular weight distribution of the polymers stayed very narrow (¯Mw/¯Mn<1.1). This is the first example of living cationic polymerizations of styrene derivatives that proceed even at room temperature. 相似文献
22.
Saburo Komori Mitsuo Okahara Kenzo Okamoto 《Journal of the American Oil Chemists' Society》1960,37(10):468-473
Summary Since the long-chain fatty acid sucrose diesters inevitably produced in the synthesis of monoesters are only slightly soluble
in water, no important use can be found for them at the present time except as oilsoluble emulsifying agents.
In order to exploit new uses we have attempted to improve their solubility in water by introducing oxyethylene radicals into
the molecule.
The addition reaction of ethylene oxide with the sucrose diesters was carried out in an autoclave in the presence of alkaline
catalysts. With the reaction temperature maintained between 100–130° the pressure decreased as the reaction proceeded, and
one to two hours were required to consume the ethylene oxide used.
The addition products are yellow or orange oily materials soluble in water. Aqueous solutions showed good surface-active properties. 相似文献
23.
Toyama Mitsutoshi; Yamashita Mitsuo; Yoneda Morihide; Zaborowski Andrzej; Nagato Masaki; Ono Hisayo; Hirayama Noriaki; Murooka Yoshikatsu 《Protein engineering, design & selection : PEDS》2002,15(6):477-483
Despite the structural similarities between cholesterol oxidasefrom Streptomyces and that from Brevibacterium, both enzymesexhibit different characteristics, such as catalytic activity,optimum pH and temperature. In attempts to define the molecularbasis of differences in catalytic activity or stability, substitutionsat six amino acid residues were introduced into cholesteroloxidase using site-directed mutagenesis of its gene. The aminoacid substitutions chosen were based on structural comparisonsof cholesterol oxidases from Streptomyces and Brevibacterium.Seven mutant enzymes were constructed with the following aminoacid substitutions: L117P, L119A, L119F, V145Q, Q286R, P357Nand S379T. All the mutant enzymes exhibited activity with theexception of that with the L117P mutation. The resulting V145Qmutant enzyme has low activities for all substrates examinedand the S379T mutant enzyme showed markedly altered substratespecificity compared with the wild-type enzyme. To evaluatethe role of V145 and S379 residues in the reaction, mutantswith two additional substitutions in V145 and four in S379 wereconstructed. The mutant enzymes created by the replacement ofV145 by Asp and Glu had much lower catalytic efficiency forcholesterol and pregnenolone as substrates than the wild-typeenzyme. From previous studies and this study, the V145 residueseems to be important for the stability and substrate bindingof the cholesterol oxidase. In contrast, the catalytic efficiencies(kcat/Km) of the S379T mutant enzyme for cholesterol and pregnenolonewere 1.8- and 6.0-fold higher, respectively, than those of thewild-type enzyme. The enhanced catalytic efficiency of the S379Tmutant enzyme for pregnenolone was due to a slightly high kcatvalue and a low Km value. These findings will provide severalideas for the design of more powerful enzymes that can be appliedto clinical determination of serum cholesterol levels and assterol probes. 相似文献
24.
For the elucidation of the crystal structures of the two crystalline allomorphs of cellulose triacetate (CTA), namely CTA I and CTA II, two-dimensional (2D) solid-state through-bond 13C-13C and 1H-13C correlations NMR techniques applied to the two crystalline allomorphs of CTA. As a result, the 13C and 1H chemical shifts of the glucopyranose ring of CTA I and CTA II were completely assigned by the 2D NMR spectra of these allomorphs. On the 2D 13C-13C correlation spectrum of CTA II, two sets of the 13C-13C correlations from C1 to C6 were observed. This indicated that the CP/MAS 13C NMR spectrum of CTA II can be characterized by its overlapping of the 13C subspectra of two kinds of 2,3,6-triacetyl-anhydroglucopyranose units and that there are two magnetically non-equivalent sites in the unit cell of CTA II. In the case of CTA I, the numbers of respective 13C and 1H shifts of CTA I agreed with the those of the glucopyranose residue in the allomorph, strongly suggesting that the asymmetric unit of CTA I is only one glucose residue. In addition, conformational differences in the exocyclic C5-C6 bonds between CTA I and CTA II were strongly suggested by the notable differences in the 1H and 13C chemical shifts at the C6 sites of these allomorphs. 相似文献
25.
Fumiaki Kobayashi Toru Ogawa Mitsuo Akabori Yoshio Kato 《Journal of the American Ceramic Society》1995,78(8):2279-2281
Uranium-plutonium nitride is a candidate fuel for fast reactors, but its major drawback is 14 C formation from natural nitrogen. One would probably have to use highly 15 N-enriched nitrogen. A pyrochemical process with molten-salt electroreflning has been proposed as a means to increase the nuclear proliferation resistance of the fuel cycle. Molten-salt electroreflning could also be applied to nitride fuels to make possible the recycling of 15 N. The anodic dissolution behavior of UN in LiCI-KCI melt was studied to provide the basis for a feasibility study of electroreflning of irradiated nitride fuels. 相似文献
26.
Summary Cationic polymerization of CH2=CH-O-CH2CH2C(COOC2H5)3, a vinyl ether with three pendent esters, initiated by the HI/I2 system in toluene at –40 °C afforded living polymers with a controlled molecular weight (
= 103–104) and a narrow molecular weight distribution (
= 1.1–1.2). The number-average molecular weight of the polymers was directly proportional to monomer conversion and the monomer-to-initiator (HI) feed ratio. The polymers obtained with BF3O(C2H5)2 had a fairly high molecular weight (
105,
5 × 104) and a broad molecular weight distribution. The triester vinyl ether was similar in reactivity to alkyl counterparts and one order of magnitude more reactive than the corresponding mono- and diester vinyl ethers. 相似文献
27.
The recoverable shear strain (SR) for the liquid crystal‐forming hydroxypropyl cellulose solutions was determined by means of a concentric cylinder rotational apparatus as functions of shear stress prior to recovery and concentration of the solutions at 30°C. SR greatly depended on shear stress and concentration; the phase of the solution (the single phase or biphase) governed the dependences of SR on stress and concentration. SR increased with increasing stress for the single phase and decreased for the biphase. SR seemed to be related to the die swell (B): SR ∝ Bn. SR exhibited a maximum and a minimum with respect to concentration. SR for the cellulosic cholesteric liquid crystalline solutions was greater than that for the isotropic solutions. A model was proposed for explaining the greater SR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 865–872, 2002 相似文献
28.
Upper and lower critical solution temperatures have been determined for solutions of poly(ethylene glycol) in t-butyl acetate and water over the molecular weight range of Mη = 2.18 × 103 to ~1020 × 103. The phase diagram for solutions of poly(ethylene glycol) (Mη = 719 × 103) in t-butyl acetate was expressed as the ‘hour glass’ type, while the phase diagram for solution of poly(ethylene glycol) (Mη = 2.18 × 103 to ~2.29 × 103) in water was expressed as the ‘closed loop’ type. The value of the pressure dependence of the lower critical solution temperature in the poly(ethylene glycol) (Mη = 1020 × 103)/water system over the pressure range of 0 to ~50 atm was negligibly small and positive. 相似文献
29.
A series of organic-soluble naphthalocyanine derivatives (YmMNcX4) have been synthesized. Their spectroscopic properties in organic solutions and in thin films were studied. MNcX4 such as MNc(t-Bu)4 (5a-5c) and MNc(On-Bu)4 (5j) formed H-aggregates even in dilute solutions. MNc(CO2R')4 (5d-5i) had much stronger H-aggregation properties compared with those ofMNc(t-Bu)4 and MNc(On-Bu)4. Especially, MNc(CO2R')7 complexes (M=Cu, Pd and Ni) existed exclusively without monomers in the aggregated state even in highly dilute solutions. MNcX4, which has strong H-aggregation properties, showed merely H- aggregate absorption maxima in thin films. In contrast, Y2MNcX4 (4), which has sterically hindered Y groups, showed monomerically pure characteristics in solution. However, thin films of Y2MNcX4 have a J-type molecular arrangement, exhibiting a red shift of Q-band absorption. The monomeric properties of Y2MNcX4 in solutions and J-type molecular arrangement in thin films arise from steric hindrance of two Y groups, such as R3SiO-in Y2MNcX4, which prevents strong H-aggregation of naphthalocyanine. 相似文献
30.
Summary The first example of the living cationic polymerization of isobutyl vinyl ether via the phosphate counteranion has been achieved in toluene below 0°C with a new initiating system that consists of diphenyl phosphate and zinc iodide, (C6H50)2P(0)0H/ZnI2. The number-average molecular weight of the polymers increased in direct proportion to monomer conversion, and was in excellent agreement with the calculated value assuming that one polymer chain forms per unit diphenyl phosphate. On addition of a fresh feed of monomer at the end of the polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage, and the polymer molecular weight further increased in direct proportion to monomer conversion. Throughout the reaction, the molecular weight distribution of the polymers stayed very narrow (¯M/¯Mn 1.1). At room temperature (+25 °C), however, the molecular weight distribution of the polymers slightly broadened (¯Mw/¯Mn 1.2) at high conversions where the polymer molecular weight became smaller than the calculated value. Evidently, the (C6H50)2-P(0)0H/ZnI2 system indeed generates a propagating species of a long life-time at room temperature, but the perfectly living polymerization by this system operates below 0°C.Living cationic polymerization of vinyl ethers by electrophile 相似文献