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91.
Crystallization of polyethylene (PE) blends of low and high molecular weight components under shear flow was studied using time-resolved depolarized light scattering (DPLS), focusing on effects of the high molecular weight component on the shish-kebab structure formation. Anisotropic two-dimensional scattering pattern due to shish-like structure formation was observed above a certain concentration of the high molecular weight PE. The threshold was about 2.5-3 times larger than the chain overlap concentration, suggesting an important role of entanglements of the high molecular weight component. On the basis of these results a gel-spinning-like mechanism for the shish-like structure formation has been proposed. The DPLS results also implied that the shish-like structure was mainly formed from the high molecular weight PE. This was confirmed by small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) measurements on an elongated PE blend of low molecular weight deuterated PE and high molecular weight hydrogenated PE (3 wt%). 相似文献
92.
制备了不同类型的单皂和复皂润滑脂,测定了其理化性能。采用分子模拟技术对润滑脂滴点进行了初步预测,并计算了润滑脂中各种金属皂分子间氢键键长和分子体积模量。结果表明,复合钙皂和复合锂皂的分子体积模量分别大于钙皂和锂皂的分子体积模量。金属皂分子体积模量与其所形成的润滑脂的滴点呈对应关系,即分子体积模量大的,其形成的润滑脂滴点也高,反之则反。采用分子模拟技术可以从分子的层次指导润滑脂的研究。 相似文献
93.
固载于SBA-15分子筛中的同双核金属配合物催化剂 总被引:3,自引:1,他引:2
合成了3种同双核金属配合物[M2LCl3]Cl(L代表配体三亚乙基四胺,M代表Co,Cu,Cr),采用微波加热法合成了SBA-15分子筛,采用浸渍法将3种同双核金属配合物分别固载在表面官能化的SBA-15分子筛(SBA-15-NH2分子筛)中制得负载型催化剂。傅里叶变换红外光谱、X射线衍射、紫外可见光谱和热分析表征结果表明,同双核金属配合物被固载后,其结构仍保持完整。以环己烷氧化反应为探针反应,考察了[Co2LCl3]Cl/SBA-15-NH2,[Cu2LCl3]Cl/SBA-15-NH2,[Cr2LCl3]Cl/SBA-15-NH2催化剂的活性,环己烷转化率分别为11.0%,49.5%,57.9%;对于[Cr2LCl3]Cl/SBA-15-NH2催化剂,当分别以乙睛、丙酮和冰醋酸为溶剂时,环己烷转化率分别为57.9%,52.1%,34.2%,3次重复实验的环己烷转化率分别为57.9%,47.8%,46.5%,表明该催化剂具有较好的活性和重复使用性。 相似文献
94.
Vinit D. Makwana L. Javier Garces Jia Liu Jun Cai Young-Chan Son Steven L. Suib 《Catalysis Today》2003,85(2-4):225-233
Manganese oxides having a tunnel structure (OMS-2) have been utilized as selective catalysts for alcohol oxidation. In this study manganese oxide catalysts were synthesized in different media and modified by exchanging the tunnel cation by H+, using acid treatment or exchanging with NH4+ followed by thermolysis. Various alcohol oxidations were performed using these catalysts to ascertain the influence of synthesis method on their activity. A correlation is made between lattice oxygen instability and activity of the catalysts, which indicates involvement of the lattice oxygen in the mechanism. The exchange of the tunnel cation with the smaller H+ ions leads to weakening of the Mn–O bond, as verified by temperature programmed desorption (TPD) results. Only the chemisorbed oxygen on the surface (O−) and the lattice oxygen in the layers close to the surface is involved in the oxygen transfer during the reaction. 相似文献
95.
Ioannis Arvanitoyannis John M. V. Blanshard Ioannis Kolokuris 《Polymer International》1992,27(1):7-15
Mastication of gutta percha (trans-polyisoprene) resulted in the selective scission of molecules, producing a narrower distribution of lower molecular weights. The mechanical properties of the samples also underwent a significant change due to mastication. The greater the content of incompatible substances (salts and oxides) in commercial gutta percha. the more substantial were these effects. The atmosphere (air, N2, O2) in which the experiments were conducted yielded significantly different results. The decrease in molecular weight was far greater in an O2 atmosphere than under a current of nitrogen or air, owing to the combination of double bonds with O2. 相似文献
96.
Anjana Bhattacharya Jagannath Das Swapan Mitra Sisir K. Roy 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》1992,54(4):399-407
Silicoaluminophosphate (SAPO-5) molecular sieves have been synthesised from reaction mixtures having a molar composition of: 0.7–1.0 Al2O3:0.7–1.0 P2O5:0.01–2.0 SiO2:xR:40 H2O (where R = (C2H3)3N or (C2H3)4NOH and x = 1.5–2.5 for (C2H5)5N and 0.5 for (C2H5)4NOH, at 473 K using various sources of alumina and silica. The effects of (i) varying the crystallinity of the alumina source (boehmite) and (ii) the use of different silica sources such as freshly prepared silica either from sodium silicate or paddy husk extract, silica gel from commercial water-glass, and tetraethyl orthosilicate have been studied. The crystallinity of boehmite has been found to have a strong effect on its reactivity towards the formation of SAPO-5. The activity of boehmite for SAPO-5 formation increased with a decrease in its crystallinity (or with increase in its moisture content). Any silica source devoid of sodium ions could be employed for the synthesis of SAPO-5. The process of crystallisation started as early as within 1.5 h of reaction and incorporation of silicon into the AlPO4 framework has been noted at this stage. Formation of some tridymite phase as impurity has been observed under conditions such as (i) SiO2 concentration > 1.7 mole and (ii) x > 2.0 when R = (C2H5)3N. 相似文献
97.
Summary In flow through porous media, solutions of poly(ethylene oxide) (PEO) exhibit extension thickening, whereas hydroxypropyl
guar (HPG) solutions are shear-thinning at high concentrations. The results show that the extension-thickening exhibited by
PEO solutions becomes less critical with increasing flow rate as the concentration of HPG in the solution is increased. At
high concentrations of HPG, the presence of PEO inhibits the shear-thinning behaviour, without increasing the apparent viscosity
of the solution. The presence of HPG reduces the rate and extent of degradation of PEO in the flowing solution. 相似文献
98.
Bogusz Stephen; Boxer Adam; Busath David D. 《Protein engineering, design & selection : PEDS》1992,5(4):285-293
To examine the feasibility of a ß structure for thepore-lining region of the voltage-gated potassium channel, wehave characterized a family of 12 antiparallel ß-barrels.Each is comprised of four identical pairs of ß-strandsorganized with approximate 4-fold symmetry about a channel axis.The Cand N-termini of the ß-strand pairs are assumedto be at the extracellular end of the channel, and each pairis connected by a hairpin turn at the intracellular end of thechannel. The models differ in the residues located in the hairpinturn and in the orientation of the two strands of each pairin the barrel, i.e. whether the C-terminus of a pair is clockwise(CW) or counterclockwise (CCW) from the N-terminus when thechannel is viewed from outside the cell. Following known structureprecedents and potential energy predictions, the barrel is assumedto be right-twisting in all cases. All models have crowded layersof inward-projecting aromatic sidechains near the center ofthe channel which could regulate channel selectivity. The modelswith an odd number of amino acids in the hairpin turn have theadvantage of predicting that F433 points into the barrel, butthe disadvantage that V438 does not. Of these models, two ofthe models are most consistent with the external tetraethylanunonhim(TEA) block data, and of those, one (T439 CCW 3:5) is most consistentwith the internal TEA block data. 相似文献
99.
A molecularly imprinting polymer (MIP) was synthesized via bulk polymerization under different conditions using anti-ague drug cinchonine (CN) as template. Infrared spectra (IR) results show that the template CNand functional monomer α-methyl acrylic acid (MAA) formed complexes before polymerization and the structure of complexes was simulated by Hyperchem. The results indicate that there are hydrogen bond or ionic bond between functional monomer and template molecule in acetonitrile solution. The MIP made in cold-initiated photo-polymerization has higher separation performance than that in the therm-initiated polymerization. The separation of the isomers CN and cinchonidine (CD) can be successfully obtained when its separate factor α reaches 1.82. Scatchard analysis suggests that the MIP recognizing CN with two classes of binding sites. The partition coefficient Kd, 1 and apparent maximum number nmax, 1 of binding sites with high affinity are 131.43 μmol/L and 58. 90 μmol/g, respectively,while Kd, 2 and nmax, 2 of binding sites with low affinity are 2.32 mmol/L and 169.08 mmol/g, respectively. 相似文献
100.
Auguste Commeyras Hlne Collet Laurent Boiteau Jacques Taillades Odile Vandenabeele‐Trambouze Herv Cottet Jean‐Philippe Biron Raphaël Plasson Louis Mion Olivier Lagrille Herv Martin Franck Selsis Michel Dobrijevic 《Polymer International》2002,51(7):661-665
Addressing the still open question of the prebiotic origin of sequential macromolecules (peptides, nucleic acids) on the primitive Earth, we describe a molecular engine (the primary pump), which works at ambient temperature and continuously generates, elongates and complexifies sequential peptides. This new scenario is based on a cyclic reaction sequence, whose keystep is the activation of amino acids into their N‐carboxyanhydrides (NCA) through nitrosation by NOx. This process could have taken place on tidal beaches; it requires a buffered ocean, emerged land and a nitrosating atmosphere. With the help of geochemical studies and computer simulations of atmosphere photochemistry, we show that the primitive Earth during the Hadean may have satisfied all these requirements. © 2001 Society of Chemical Industry. 相似文献