2-甲基-3-丁烯-2-醇合成3-甲基-2-丁烯-1-醇

[目的]2-甲基-3-丁烯-2-醇是异戊二烯间接皂化法生产3-甲基-2-丁烯-1-醇过程中产生的副产物,废物回收再利用是节能减排的有效措施.[方法]2-甲基-3-丁烯-2-醇经氯化、酯化和皂化得到3-甲基-2-丁烯-1-醇.[结果]结果表明:在优化条件下,氯化反应的产率可达87.25％,酯化和皂化反应的产率可达84.53％.[结论]该方法是2-甲基-3-丁烯-2-醇再利用的有效方法.     

2,3-二甲氧基-5-甲基-6-(3-甲基-2-烯-1-丁基)-1,4-苯酚的合成及其副产物的研究

2,3-二甲氧基-5-甲基-1,4-苯酚与2-甲基丁烯醇在BF3OEt2的催化下进行傅-克烷基化反应合成2,3-二甲氧基-5-甲基-6-(3-甲基-2-烯-1-丁基)-1,4-苯酚。对鲜见文献报道的副产物2,2,5-三甲基-3-氢-6-羟基-7,8-二甲氧基-苯并吡喃进行了结构鉴定并推测了其形成机理,在原料辅酶Q0、甲基丁烯醇和BR的配比为1：1.5：0.19(摩尔比),反应温度45℃,滴加时间30min,反应时间2h的条件下收率达90.24％。     

E-4-乙酰氧基-2-甲基-2-丁烯-1-醛的合成研究

根据Kornblum反应,采用二甲基亚砜(DMSO)氧化E-1-乙酰氧基-4-氯-3-甲基-2-丁烯(ACMB)合成E-4-乙酰氧基-2-甲基-2-丁烯-1-醛(AMBA)。在实验过程中,采用气相色谱跟踪,研究了反应时问、反应温度和催化剂用量等因素对主副产物收率的影响并确定了较佳反应条件;反应时间24h,反应温度80℃,原料缓慢滴加,KH2PO4：K2HPO4：ACMB=0．14：1．27：1(摩尔比),催化剂用量与原料ACMB比为0．12：1(摩尔比)。同时,对从未报道过的副产物E-1-乙酰氧基-4-甲巯基-3-甲基-2-丁烯(AMMB)进行了结构鉴定,并推测了其形成机理。     

6-(4-羟基-3,5-二叔丁基苯氨基)-2,4-二氯-1,3,5-三嗪的合成

本文通过还原2,6-二叔丁基-4-亚硝基苯酚得到2,6-二叔丁基-4-胺基苯酚,再与三聚氰氯反应,生成6-(4-羟基-3,5-二叔丁基苯氨基)-2,4-二氯-1,3,5-三嗪。考察了溶剂用量、反应时间、反应温度和物料配比等对反应的影响,确定了最佳反应条件,产品收率稳定在89%。     

3-乙基-2-羟基-2-环戊烯-1-酮的合成研究

以正丁酸乙酯和草酸二乙酯为主要原料,合成了香料化合物3-乙基-2-羟基-2-环戊烯-1-酮。首先由正丁酸乙酯和草酸二乙酯经Claisen缩合生成2-乙基-3-羰基-丁二酸乙酯,其与丙烯酸乙酯发生Michael加成,随后Dieckmann酯缩合得到5-乙基-3,5-二乙酯基-2-羟基-2-环戊烯-1-酮,然后经水解脱羧获得3-乙基-2-羟基-2-环戊烯-1-酮。初步考察并优化了各步反应的工艺条件,产品总收率达44.46%。     

10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物的合成

以9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO)和丙酮为原料,合成10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物。考察了原料摩尔比、反应温度和反应时间对产物收率的影响。结果表明,较优工艺条件为:n(丙酮)∶n(DOPO)=12∶1,反应温度为50℃,反应时间为30 min时,DOPO的转化率为99%,目标产物收率为90%。     

2,4,4-三甲基-3-(3-羰基-1-丁烯-1-基)-2-环己烯基-1-肟的合成研究

以环柠檬醛为原料,经过亚硝化、缩合两步反应得到2,4,4-三甲基-3-(3-羰基-1-丁烯-1-基)-2-环己烯基-1-肟,收率达65.1%。并分析了该反应中亚硝化的反应机理。     

4-氯-5-硝基-2-氨基苯酚的合成

本文以4-氯-2-氨基苯酚为起始原料合成了4-氯-5-硝基-2-氨基苯酚。4-氯-2-氨基苯酚经醋酐酰化制得2-乙酰氨基-4-氯苯酚,粗产率为92.4％,熔点为170.3℃～171 3℃。然后分别以氯苯,邻二氯苯为脱水剂在回流条件下反应15小时,经真空蒸馏得到5-氯-2-甲基苯并(?) 唑,熔点为52℃-54℃。将5-氯-2-甲基苯并(?)唑进行硝化反应,得到5-氯-6-硝基-2-甲基苯并(?)唑,粗产率84.76％,熔点为135.5℃-139.0℃。5-氯-6-硝基-2-甲基苯并(?)唑在强碱条件下水解后,经酸析得到4-氯-5-硝基-2-氨基苯酚,粗产率为90.10％.熔点为209.8～210.0℃。     

1-甲基-3-丙基-4-硝基吡唑-5-羧酸的合成研究

以1-甲基-3-丙基吡唑-5-甲酸为原料,采用二氯甲烷为溶剂,合成了1-甲基-3-丙基-4-硝基吡唑-5-羧酸。试验研究了影响反应收率的多种因素,确定了最佳工艺条件:搅拌转速600 r/min;反应温度70°C;反应时间5~6 h;硫酸的浓度为90%。     

1-氨基-4-羟基-蒽醌的合成新方法

以1-氨基-2-溴-4-羟基-蒽醌和乙二醇为原料,在碱作用下脱溴得到1-氨基-4-羟基-蒽醌,收率92．O％。     

Failure of tannic acid to inhibit digestion or reduce digestibility of plant protein in gut fluids of insect herbivores

The rate of hydrolysis of the abundant foliar protein, ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBPC), in enzymatically active gut fluid ofManduca sexta larvae is very rapid and is unaffected by the presence of tannic acid, even when tannic acid is present in the incubation mixture in amounts in excess of the amount of RuBPC. When this protein is dissolved in the denatured gut fluids ofM. sexta larvae orSchistocerca gregaria nymphs, large amounts of tannic acid must be added to bring about the precipitation of significant quantities of protein. The ability of insect gut fluid to prevent the formation of insoluble tannin-protein complexes is due to the presence of surfactants. On the basis of our results and a review of the findings of other investigators, we argue that there is no evidence that tannins reduce the nutritional value of an insect's food by inhibiting digestive enzymes or by reducing the digestibility of ingested proteins and, further, that the failure of tannins to interfere with digestion is readily explained on the basis of well-documented characteristics of the digestive systems of herbivorous insects. In challenging the currently popular notion that tannins are digestibility-reducing substances, we do not challenge the general utility of either the apparency theory or resource availability theory of plant defense. In debating the merits of these two analyses of plant-herbivore interactions, however, the demise of tannins as all-purpose, dose-dependent, digestibility-reducing defensive substances must be taken into account.     

机制砂岩性与级配对混凝土抗硫酸盐侵蚀性能的影响

为了探究不同岩性、不同级配机制砂对混凝土性能的影响,对三种不同岩性机制砂混凝土及天然河砂混凝土的工作性和抗压强度进行研究。此外,对比分析了四种混凝土在干湿循环制度下的抗硫酸盐侵蚀性能。结果表明,天然河砂混凝土的工作性优于机制砂混凝土,钙质机制砂混凝土的工作性略好于硅质机制砂混凝土。机制砂混凝土的抗压强度优于天然河砂混凝土,在硫酸盐侵蚀循环作用下的力学性能变化趋势与天然河砂混凝土基本一致。在相同级配条件下,机制砂混凝土的抗蚀系数高于天然河砂混凝土;机制砂岩性并不会对混凝土抗硫酸盐侵蚀性能带来负面影响。级配良好的机制砂可以增强混凝土抗压强度和抗硫酸盐侵蚀性能。     

Functional properties of proteins in foods

The measurement of functionality of protein food ingredients has developed somewhat haphazardly, probably due to the wide range of proteins used as ingredients and the diversity of foods. Studies of the physiochemical properties of proteins should enable prediction of a proteins response to process environments and prove more fruitful than many of the empirical measurements of functionality. The effects of pH, salt type and concentration on the phase behaviour of the oilseed globulin and arachin, demonstrates the complexity of protein solubility and the inadequacies of simple tests that have arisen. Studies of the effects of salts and conditioning on meat fibres, coupled with measurement of the location of water in pellets from water holding tests enable the latter to be applied with increased confidence. Comparison of the endothermic transitions observed on heating with the development of storage and loss moduli allow the contributions of domains of skeletal muscle myosin to gel structure to be investigated.     

Aggregation pheromone system of adult gregarious desert locust schistocerca gregaria (forskal)

Six electrophysiologically active aromatic compounds, viz., anisole, benzaldehyde, veratrole, guaiacol, phenylacetonitrile, and phenol, were identified in the volatiles of older-adult male desert locust. Young adults and females of all age groups produced none or only trace quantities of these compounds. Comparison of the aggregation responses of young and older adults to the crude, older-adult, volatile extract and different synthetic blends of the six compounds showed that the aggregation pheromone system of the adult gregarious locust consists of phenylacetonitrile, guaiacol, phenol, and benzaldehyde. Like the crude volatile extract of older males, neither the synthetic blend of the six compounds nor the adult pheromone blend evoked any significant aggregation responses from nymphs. These results confirm our previous report of sexual differentiation in the production of adult aggregation pheromone in the desert locust and of the evidence of two distinct aggregation pheromone systems in the two stages of the insect.     

Molecular mechanics modelling of interfacial energy and flexibility on cellulose

Molecular mechanics modelling is used to calculate the energies of interaction, hence the molecular level energy of adhesion at the interface with crystalline cellulose I of three different photopolymerizable primers and of a polyester varnish at the interface with the primer/cellulose assembly. The energy of interactions for just one of the primers with the statistically most common conformation of amorphous cellulose has also been obtained for comparison. Experimental results of adhesion by a standard peel test and by thermomechanical analysis, in which the effect of viscoelastic energy dissipation by crack tip propagation has been respectively minimized or is not present, hence in which the energy of interfacial interaction is nothing else but the work of adhesion, correlated well with the energies of interaction calculated by molecular mechanics. An equation correlating the energy of interaction at each finish/cellulose interface with the deflection derived by thermomechanical analysis, and with the number of internal bond rotational degrees of freedom as well as the degree of networking of the finish, has been derived and is presented. A relationship between the intrinsic fracture energy Go and the molecular mechanics-derived energy of interaction at the interface equating this to the square of the work of adhesion is obtained and is presented.     

Distribution of birch (Betula SPP.), willow (Salix SPP.), and poplar (Populus SPP.) secondary metabolites and their potential role as chemical defense against herbivores

Isoprenoids and phenolics, major metabolites of important browse species, are reviewed in regard to concentrations, distribution within tissues, and between species. Seasonal variation of specific substances and changes with age of the plant are also considered. The distribution of substances may affect food selection and feeding behavior of animals. Wild mammalian herbivores tend to avoid plant parts rich in these substances, in spite of high nutritional content of the plant tissue. Possible mechanisms for defense by plants against depredation by mammalian herbivores are discussed within the framework of the plants' biochemistry.     

Sr改性Cu催化剂的果糖加氢制备甘露醇性能

使用共沉淀法制备负载Cu催化剂。通过添加碱土金属Sr，对Cu催化剂进行了改性，以提高Cu催化剂在果糖加氢制备甘露醇过程中的活性和选择性。采用ICP-MS、TEM、XRD、H₂-TPR、XPS和CO₂-TPD等对所制备的催化剂进行了系统表征。结果表明：Sr的添加能增大催化剂的比表面积，促进活性组分Cu的分散，从而提高了催化剂的活性，并且增加了催化剂的碱性，使果糖优先形成β-呋喃糖中间体，从而提高了甘露醇的选择性。在果糖浓度为1.1 mol·L^-1、催化剂用量为反应物质量的6%、反应温度为373 K、反应氢压为4.0 MPa、Cu/Sr原子比为7∶1的反应条件下，果糖转化率为99%，甘露醇的选择性为79%。催化剂循环使用了20次，其催化稳定性基本保持不变。     

接触式机械密封界面泄漏机理研究的关键科学问题

密封界面的泄漏机理是机械密封研究与应用的焦点问题之一,涉及泄漏通道表征、粗糙表面的接触力学模型、界面微观形貌变化以及介质流体在泄漏通道中的流动阻力等问题。回顾了近几十年国内外接触式机械密封泄漏通道模型的研究,深入分析了G-W模型、M-B模型和Persson模型3种粗糙表面接触力学模型的贡献和存在的问题,提出了一种基于逾渗理论的泄漏通道新模型;探讨了密封界面的分形参数、泄漏通道的流动阻力以及密封界面的有限尺寸效应对泄漏特性的影响,指出孔隙连通贯穿界面和流体流经贯穿通道的流动阻力小是密封界面产生泄漏的成因,以及泄漏通道的形成和泄漏通道内的流体流动特性是泄漏机理研究的主要方向。     

Measured kinetics of the acid-catalysed hydrolysis of sugar cane bagasse to produce xylose

Experimental trials of the water hydrolysis of bagasse to produce xylose, arabinose and glucose were conducted using a temperature-controlled microwave digester. The experimental variables were temperature, ratio of water mass to bagasse mass, type of bagasse material and reaction time. The pH of the liquid and concentration of dissolved xylose, arabinose and glucose were measured at the completion of each trial. Kinetic modelling of the global rates of formation of monosaccharide products was performed using schemes based on earlier researchers’ models of acid hydrolysis using mineral acids. For the most plentiful product, xylose, the most accurate kinetic model of the global reactions was determined to be two parallel pathways for hydrolysis of xylan to xylose followed by a single pathway for xylose decomposition. The calculated activation energies of the reactions were within the range reported by other researchers for the hydrolysis of a range of lignocellulosic materials using mineral acids.