改进β-紫罗兰酮的合成方法

以氢氧化锂/助催化剂为催化剂体系,柠檬醛为原料合成β-紫罗兰酮。此催化剂体系有良好选择性,用量少、成本低、对环境污染小。同时对反应溶剂、温度、反应时间等因素进行优化,使其适用于工业生产,最终摩尔收率可达86%以上。     

山苍子油在合成香料中的应用

简介近十几年来从山苍子油中柠檬醛出发合成的有关香料，并对有发展前景和应用前景的紫罗兰酮类、大马酮类和环高柠檬醛等香料的合成方法作一评述。     

四氯化锡掺杂聚苯胺催化合成柠檬醛1,2-丙二醇缩醛

以柠檬醛、1,2-丙二醇为原料,四氯化锡掺杂聚苯胺（PAn-SnCl4）为催化剂催化合成柠檬醛1,2-丙二醇缩醛。研究了醛醇物质的量比、催化剂质量、反应时间等因素对产品收率的影响。结果表明,在n（柠檬醛）/n（1,2-丙二醇）=1∶3,催化剂质量为反应物料总质量的2.0%,带水剂环己烷质量为反应物总质量的40%,反应时间2.0h的最佳反应条件下,柠檬醛1,2-丙二醇缩醛的收率可达94.65%。催化剂重复使用5次,产品收率仍达88.39%。     

Selective hydrogenation of citral over gold nanoparticles on alumina

Gold nanoparticles have been supported on alumina by wet impregnation in the presence of sodium citrate and polyvinyl alcohol. The catalytic performance of these catalysts for the selective hydrogenation of 3,7-dimethyl-2,6-octadienal (citral) in the liquid phase has been evaluated. The presence of polyvinyl alcohol significantly improved the selectivity to cis-3,7-dimethyl-2,6-octadien-1-ol (nerol).     

Base-catalyzed condensation of citral and acetone at low temperature using modified hydrotalcite catalysts

A study on the catalytic properties of properly activated hydrotalcite (HT) with special attention to the nature and amount of active sites present in this solid base catalyst has been undertaken. Only a small fraction (5%) of the available basic sites in the rehydrated calcined HT is active in liquid-phase aldol condensations. These sites exhibit high catalytic activity and are most likely localized at the edges of the HT-platelets. Besides a high activity, these modified HTs also show a high selectivity. No further condensation products other than diacetone alcohol (DAA) in the acetone self-condensation could be observed. Initial results with the citral–acetone condensation show that even at 273 K this reaction is catalyzed by modified HTs with a conversion of 65% and a selectivity of 90%, when the citral concentration is not too high (1 wt.%). At higher citral concentrations, no reaction is observed indicating a negative order in citral concentration.     

Modeling the inactivation of Escherichia coli O157:H7 and Uropathogenic E. coli in ground beef by high pressure processing and citral

Escherichia coli O157:H7 are a well-known intestinal foodborne pathogen which were responsible for numerous foodborne illness outbreaks. Uropathogenic E. coli (UPEC) are common contaminants in meat and poultry, and may cause urinary tract infections after colonizing the gastrointestinal tract followed by accidental transfer of contaminated feces from the anus to the urethra. High pressure processing (HPP) has been demonstrated an effective means in reducing pathogenic E. coli levels in meat and poultry. Citral, an antimicrobial, also demonstrated some inactivation effect on pathogenic E. coli in ground beef (ca. 0.5–1.0 log CFU/g reduction at 1% w/w without HPP). With HPP alone, to achieve 5 log CFU/g reduction required a 500 MPa level and 15 min (for both O157:H7 and UPEC). However, 1% of citral addition may lower the pressure requirement to 380 MPa and 15 min which could reduce the food quality damage. To effectively inactivate E. coli O157:H7 and UPEC in meat, high pressure processing (HPP) in combination with the antimicrobial citral was studied. Ground beef inoculated with E. coli O157:H7 or UPEC were treated at different HPP conditions (250–350 MPa; 10–20 min), and citral (0.75–1.25%, w/w) following a central composite experimental design. Quadratic linear regression equations were developed to describe and predict the reductions of E. coli O157:H7 (R² = 0.93, p < 0.001) and UPEC (R² = 0.92, p < 0.001). Dimensionless nonlinear models consisting of three impact factors were also developed and compared with the linear models. These models were experimentally validated. Citral enhanced the inactivation of pathogenic E. coli, increasing the effectiveness of the HPP process. The models may assist the food industry and regulatory agencies in risk assessment of E. coli O157:H7 and UPEC on ground meats.     

Characterization of bimetallic rhodium-germanium catalysts prepared by surface redox reaction

The preparation of bimetallic rhodium-germanium/silica and rhodium-germanium/alumina catalysts was investigated by controlled surface reaction. Their catalytic performances were measured for two gas phase reactions (toluene hydrogenation at 323 K and cyclohexane dehydrogenation at 543 K) and for a liquid phase reaction (citral hydrogenation at 343 K).

Elemental analysis of bimetallic catalysts showed that germanium can be deposited by redox reaction between hydrogen activated on a parent monometallic rhodium catalyst and germanium tetrachloride dissolved in water (catalytic reduction method). EDX microanalysis of rhodium-germanium/silica catalysts indicated that rhodium and germanium were deposited in close contact on the silica support. However, on alumina-supported catalysts, germanium deposition occurred also separately on the support. For the different test reactions, the catalytic properties of rhodium were strongly altered by the addition of germanium. On alumina-supported catalysts, interesting catalytic effects were observed in citral hydrogenation when not only close contact exists between both metals but when, in addition, the second metal was deposited on the support in the close vicinity of rhodium.     

Stability of citral in protein- and gum arabic-stabilized oil-in-water emulsions

Citral is a major flavor component of citrus oils that can undergo chemical degradation leading to loss of aroma and formation of off-flavors. Engineering the interface of emulsion droplets with emulsifiers that inhibit chemical reactions could provide a novel technique to stabilize citral. The objective of this study was to determine if citral was more stable in emulsions stabilized with whey protein isolate (WPI) than gum arabic (GA). Degradation of citral was equal to or less in GA- than WPI-stabilized emulsion at pH 3.0 and 7.0. However, formation of the citral oxidation product, p-cymene was greater in the GA- than WPI-stabilized emulsion at pH 3.0 and 7.0. Emulsions stabilized by WPI had a better creaming stability than those stabilized by GA because the protein emulsifier was able to produce smaller lipid droplets during homogenization. These data suggest that WPI was able to inhibit the oxidative deterioration of citral in oil-in-water emulsions. The ability of WPI to decrease oxidative reactions could be due to the formation of a cationic emulsion droplet interface at pH 3.0 which can repel prooxidative metals and/or the ability of amino acids in WPI to scavenge free radical and chelate prooxidative metals.     

Combined effect of carvacrol and citral on the growth of Listeria monocytogenes and Listeria innocua and on the occurrence of damaged cells

The aim of this study was to evaluate the growth kinetics of Listeria innocua Serovar 6a (CECT 910) and Listeria monocytogenes Serovar 4b (CECT 4032) exposed to combinations of carvacrol and citral (0.0 μL/mL (control), 0.050 μL/mL of carvacrol and 0.075 μL/mL of citral, 0.050 μL/mL of carvacrol and 0.125 μL/mL of citral, 0.085 μL/mL of carvacrol and 0.075 μL/mL of citral, and 0.085 μL/mL of carvacrol and 0.125 μL/mL of citral), with two initial inoculum concentrations, and also the occurrence of sublethal damage in these cell populations. The terpene combinations exhibited antibacterial activity against L. innocua and L. monocytogenes and the effects were dependent on the concentration of terpenes present in the culture medium (p ≤ 0.05). When terpene-treated L. innocua and L. monocytogenes were incubated in TSB, significant differences in lag phase and growth rate were observed between low and high inoculum concentrations (p ≤ 0.05), indicating that the inoculum level should be taken into account in modeling studies. When bacterial cells were exposed to terpenes the proportion of sublethally injured cells increased with the increase in the terpene dose (p ≤ 0.05). In conclusion, all of these results show that carvacrol and citral can be used in combination at 25% of the MIC in order to control Listeria growth.     

Modelling of citral hydrogenation kinetics on an Ni/Al2O3 catalyst

The kinetics of citral hydrogenation in ethanol over an Ni/Al₂O₃ catalyst was studied in a slurry reactor operating at atmospheric pressure and at a temperature range of 60–77°C. Citronellal was the primary reaction product, whereas the amounts of unsaturated alcohols were very minor. Citronellol was the dominating product, generated mainly through the hydrogenation of the carbonyl group of citronellal. Based on the experimental data, a kinetic model was developed for hydrogenation. The model comprises competitive and rapid adsorption steps as well as rate-determining hydrogenation steps. The mass transfer limitation of hydrogen was included in the mathematical model. The kinetic parameters and the mass transfer parameter of hydrogen were estimated from the experimental data. A comparison of the model predictions with the experimental data revealed that the proposed kinetic approach gave a satisfactory reproduction of the data.