Enantiospecific synthesis of (R)-1,7-dioxaspiro [5.5]undecane [major component of olive fruit fly (Dacus Oleae) sex pheromone] from d-Fructose

The synthesis of the title compound13 has been carried out through the preparation of its precursor, (3R,4R,5S,6R)-3,4,5-trihydroxy-1,7-dioxaspiro[5.5]undecane (6), obtained fromd-fructose using Wittig's methodology, reduction, and spiroketalation. Compound6 was transformed into13 by a Barton deoxygenation at C-5 followed by a Corey dideoxygenation at C-3,4 of the appropriately protected derivatives.Enantiospecific synthesis of spiroacetals. Part II. For Part I, see Izquierdo and Plaza (1990).     

Photoelectric conversion of photosynthetic reaction center in multilayered films fabricated by layer-by-layer assembly

Multilayered protein films which contained ordered layers of photosynthetic reaction center (RC) from Rhodobacter Sphaeroides (RS601) were assembled by means of alternate electrostatic adsorption with positively charged poly(diallyldimethylammonium chloride) (PDDA). The assembly of RC was monitored by spectrometry and photocurrent measurement. Linear film growth was observed up to about 20 cycles of adsorption. For the monolayer film, the photocurrent was about 8.5 nA cm⁻². For the multilayered film, the total photocurrent was about 77 nA cm⁻² for the 24-layer RC film, while the average photocurrent increment per adsorption cycle was about 3.2 nA cm⁻². The overall light-to-electricity conversion efficiency for a 24-layer film was about eight times higher than that for the monolayer one. The effects of electrode potential and pH on the photocurrent were also measured to illustrate the light-to-electric converting mechanism.     

Preparation of Aluminum Nitride Powder from Aluminum Polynuclear Complexes

AIN powder was synthesized from aluminum polynuclear complexes. Basic aluminum chloride and basic aluminum lactate were used as the aluminum polynuclear complexes. These starting materials and glucose were dissolved in water and mixed homogeneously. AIN powder was obtained by calcining after drying and precalcining at 800°C under nitrogen gas flow. Then excess carbon was removed by firing in air. Nitridation in the system was investigated and compared with that in the alumina–carbon black system. It was found that in our reaction system nitridation began and proceeded at lower calcination temperatures above 1200°C than in the alumina–carbon black system. Using aluminum polynuclear complexes, AIN was synthesized through the nitridation of γ-alumina and produced in a very fine and sharp particle size distribution.     

甲缩醛空气氧化制甲醛催化剂的研制和工艺条件探讨

考察了铁钼催化剂对甲缩醛空气氧化制甲醛的催化性能。制备了多种不同钼铁比和第三、第四组分的催化剂,进行了活性评价和筛选,探讨了适宜的工艺条件范围。对于所选定的催化剂(钼铁比为1.82～1.88;铬铁比为0.1～0.38)在适宜的工艺条件(甲缩醛进料浓度4.5～5.5％;甲缩醛和氧气进料比1:2.0±0.2;空速12000～22000h~(-1);热点温度370～390℃)下,甲醛收率可达85％左右。     

合成气中氨含量测定方法的改进

用快速测定仪测定气体中的氨含量，采气量为50ml，可准确测出高含量氨体积百分比含量为80%-100%和低含量氨体积百分比含量为1%-20%的样气，该仪器结构简单，易于制造，测定过程简单，结果准确，一目了然。     

Reactive compatibilization of PE/PS blends. Effect of copolymer chain length on interfacial adhesion and mechanical behavior

This paper deals with in situ compatibilization of PE/PS blends via Friedel-Crafts reaction, performed at the interphase. Two polyethylenes having different molecular weights, and the same PS, were used along a wide range of catalyst concentration. The influence of the graft copolymer architecture and content on the efficiency of blend compatibilization was studied. The emulsifying effect, morphological aspects and mechanical behavior were also assessed for these blends. The amount of copolymer formed increases with catalyst concentration and the short chain length fraction of the homopolymers. The high molecular weight (MW) copolymers behaved as better compatibilizers as they showed, at the cmc, greater graft copolymer concentration than the low MW ones. A substantial increase in interfacial adhesion and particle size reduction was observed, even at catalyst concentrations as low as 0.3 wt%. In correspondence, mechanical properties, like ductility and yield strength, were enhanced by the effect of this Friedel-Crafts reaction's compatibilization.     

Enzymatic esterification of glycerol II. Lipase-catalyzed synthesis of regioisomerically pure 1(3)-rac-monoacylglycerols

Regioisomerically pure 1(3)-rac-monoacylglycerols are conveniently prepared in high yields (>75%) and in multigram quantities by enzymatic esterification of glycerol in the presence of various lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) with a variety of different acyl donors, such as free fatty acids, fatty acid alkyl esters, vinyl esters and triacylglycerols, as well as natural fats and oils. All reactions are carried out in aprotic organic solvents with low water content, namelyn-hexane, diethyl ether, tBuOMe or mixtures of these solvents. Essential for the success of these transformations were the following two factors. First, the creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol and the hydrophobic reaction medium by its adsorption onto a solid support. Second, a facile system for the separation of the desired monoacylglycerol from the reaction mixture, coupled with the continuous recycling of acyl donor and undesirable by-products.     

抗氧剂3114合成反应热力学和动力学的研究

研究了常温溶剂法合成抗氧剂3114反应热力学和动力学过程。控制温度在117±2℃,研究结果表明,反应是零级反应,反应速率常数k=1.91×10-3/min,反应的平衡常数K=138.4(mol/L)-6,反应活化能Ea=1366.2J/mol。     

聚合转化率对硫调型氯丁胶结构与性能的影响

研究了硫调型氯丁橡胶乳液聚合中转化率对产晶结构与性能的影响.结果表明,随单体转化率的提高,聚合物的凝胶量及其交联密度增大,致使断链速度减慢,所得断链胶的门尼粘度上升,残存凝胶量增加,分子支化程度增大,分子量分布变宽,焦烧时间缩短。而相应硫化胶的拉伸强度、撕裂强度、冲击弹性和硬度等提高,扯断伸长率和永久变形下降。这些变化一般在转化率为80——85％时有明显转折.综合考虑产量与质量,聚合转化率控制在82±2％较为适宜。     

Correlation of reactivity and electrical resistivity of coke

A correlation between the reactivity and electrical resistivity of a series of cokes was determined using cokes prepared from blends of medium- and high-volatile coals. After correcting for the ash yield of the coke and the density of the resistivity specimen, a statistically significant relation between reactivity and resistivity was established. As the resistivity test requires much less time to perform than the reactivity test, it can be considered as an alternative approach to reactivity testing currently performed for quality control purposes.