Structure−Activity Relationships of Cinnamate Ester Analogues as Potent Antiprotozoal Agents

Protozoal infections are still a global health problem, threatening the lives of millions of people around the world, mainly in impoverished tropical and sub-tropical regions. Thus, in view of the lack of efficient therapies and increasing resistances against existing drugs, this study describes the antiprotozoal potential of synthetic cinnamate ester analogues and their structure-activity relationships. In general, Leishmania donovani and Trypanosoma brucei were quite susceptible to the compounds in a structure-dependent manner. Detailed analysis revealed a key role of the substitution pattern on the aromatic ring and a marked effect of the side chain on the activity against these two parasites. The high antileishmanial potency and remarkable selectivity of the nitro-aromatic derivatives suggested them as promising candidates for further studies. On the other hand, the high in vitro potency of catechol-type compounds against T. brucei could not be extrapolated to an in vivo mouse model.     

邻苯二甲酸酯鼓泡生物降解

该课题测试了邻苯二甲酸酯类化合物的鼓泡生物降解行为。结果表明，邻苯二甲酸酯的降解速率常数（kb)与其烷基链长度之间存在良好的相关性，kb=0.0009x^2-0.019x 0.1123，相关系数r=0.9906；浓度超过500mg/L时，邻苯二甲酸二乙酯可抑制自身的生物降解；中间产物邻苯二甲酸浓度超过50mg/L时，也对邻苯二甲酸二乙酯的生物降解有明显的抑制作用。     

燃料甲酯应用研究浅析

本阐述了分别使用燃料甲酯及柴油时由柴油机以加俐到的示功图，烟度及过量空气系统等的对比结果。经分析认为：当燃料甲酯取代柴油机时，用户可不必对柴油机另作调整，因而十分方便。     

Preparation of fatty acid methyl esters for gas-chromatographic analysis of lipids in biological materials

Theoretically, preparation of fatty acid methyl esters (FAMEs) deals with reversible chemical reactions in a complex system. Methodologically, there are numerous ways, generally characterized by the type of catalysts used and steps involved. Although there are more than a half dozen common catalysts, the majority fall into either acidic (HCl, H₂SO₄ and BF₃) or alkaline types (NaOCH₃, KOH and NaOH), with each having its own catalytic capability and application limitations. In terms of steps, many conventional methods, including those officially recognized, consist of drying, digestion, extraction, purification, alkaline hydrolysis, transmethylation/methylation and postreaction work-up. Although these methods are capable of providing reliable estimates if some precautions are taken, they are cumbersome, time-consuming and cost-inefficient. A new approach has been to transmethylate lipidsin situ. Due to its simplicity, high sensitivity, comparable reliability and capability to determine total fatty acids, the method of direct transmethylation is finding a unique place in lipid determination. Regardless of which method is used, quantitative methylation requires chemists to take precautions at every step involved, particularly during FAME formation and subsequent recovery steps. Evidently, there is an urgent need for more systematic studies, guided by the chemical principle of reactions involved and physicochemical properties of regents and end products, into factors affecting these steps. Hopefully, this will lead to an improved method, which measures lipid composition in biological materials not only with high accuracy but also with high efficiency and minimum costs.     

Contribution oftrans-18∶1 acids from dairy fat to european diets

Twelve commercial samples of French butter, purchased in October–November, and 12 other samples, purchased in May–June, were analyzed with particular attention to theirtrans-octadecenoic acid contents. The isomeric fatty acids were quantitated by a combination of gas-liquid chromatography (GLC) of total fatty acids as isopropyl esters on a polar capillary column (CPSil 88) and of silver nitrate-impregnated thin-layer chromatography followed by GLC of the pooled saturated (used as internal standards) andtrans-octadecenoic acid fractions. Autumn butters contained 3.22±0.44%trans-octadecenoic acids (relative to total fatty acids), whereas those collected during the spring contained 4.28±0.47% (P<0.01). Minimum and maximum values for the two sets of butters were 2.46 (autumn) and 5.10% (spring), respectively. The annual mean value for thetrans-octadecenoic acid content in all butter samples was 3.8% of total fatty acids (ca. 2% for thetrans-11 18∶1 acid). This value allows calculation of the daily individual intake oftrans-octadecenoic acids from dairy products by populations of member states of the European Economic Community (EEC). It varies from 0.57 g (Portugal) to 1.66 g (Denmark). The mean value for the twelve countries of the EEC is 1.16 g/person/d, which is close to data published for the United States. In France, the consumption oftrans octadecenoic acids from dairy fat is higher than that from margarines (ca. 1.5 vs. 1.1 g/person/d).     

Process conditions for separating fatty acid esters by supercritical CO2

The solubilities of ethyl palmitate, ethyl oleate, ethyl eicosapentaenoate (EPA) and ethyl docosahexaenoate (DHA) in supercritical carbon dioxide were determined by a continuous flow method. The solubilities of fatty acid ethyl esters increased with pressure and decreased as the temperature was increased. An empirical equation, similar to Chrastil's equation, was used to describe the relationship between solute solubility and the density of carbon dioxide. The empirical equation was further used to qualitatively estimate the separation efficiency of isolating EPA and DHA ethyl esters from fatty acid esters. The operating conditions yielding high solubility gave fast extraction rate but resulted in low separation efficiency. Experiments were conducted to separate ethyl EPA and ethyl DHA from a model mixture containing four fatty acid ethyl esters and from esterified squid visceral oil. The experimental data compared closely with the calculated values.     

Enzymatic biodiesel production: Technical and economical considerations

It is well documented in the literature that enzymatic processing of oils and fats for biodiesel is technically feasible. However, with very few exceptions, enzyme technology is not currently used in commercial‐scale biodiesel production. This is mainly due to non‐optimized process design and a lack of available cost‐effective enzymes. The technology to re‐use enzymes has typically proven insufficient for the processes to be competitive. However, literature data documenting the productivity of enzymatic biodiesel together with the development of new immobilization technology indicates that enzyme catalysts can become cost effective compared to chemical processing. This work reviews the enzymatic processing of oils and fats into biodiesel with focus on process design and economy.     

Enzymatic Synthesis of Glucose- and Xylose Laurate Esters Using Different Acyl Donors,Higher Substrate Concentrations,and Membrane Assisted Solvent Recovery

Glucose- and xylose laurate esters are enzymatically synthesized using equimolar substrate concentrations in 2-methyl-2-butanol, comparing free lauric acid with methyl- and vinyl-laurate as acyl donors. All reactions result in ≥70% acyl donor conversions after 72 h but the activated donors are also partially hydrolyzed to lauric acid, highlighting the difficulty in controlling water presence in this particular reaction system. The esterification of xylose generates a complex product profile, with several regioisomers of monoesters and diesters. The esterification of glucose is quite selective, forming mainly the 6-O monoester (≥96%) with a small presence of two diester isomers (4%). Increasing substrate concentration up to 800 millimoles kg⁻¹ results in lower conversion values (down to 58%) but shows that the reaction proceeds successfully even in the presence of high amounts of insoluble glucose. However, the reaction is less selective and the proportion of diester increases, becoming up to 46% (molar fraction) of the final product. Solvent recovery after esterification can be achieved by organic solvent nanofiltration through a polymeric membrane able to retain ≥80% of all reaction substrates and products. Practical Applications: The use of high substrate concentrations during the enzymatic synthesis of sugar ester biosurfactants leads to product titers that are more industrially appealing, without the need to find a solvent that can solubilize all initial substrate. The sustainability of the enzymatic conversion at mild temperatures can be enhanced by recycling of the reaction solvent through organic solvent nanofiltration, an energy efficient alternative to other traditional methods like distillation.     

Synthesis and characterization of maltose fatty acid monoesters as biosurfactants

Maltose long-chain fatty acid esters (MFAE), esterified at the 6 and 6′ position, were synthesized with stearic, palmitic, myristic, and oleic groups. Synthesis yields were 15–20% based on initial maltose present, and structural confirmation was obtained using plasma desorption mass spectrometry and nuclear magnetic resonance spectroscopy. These surfactants have surface tensions in the range of 34–36 dyn/cm at their critical micelle concentrations (CMC) of approximately 10⁻⁵–10⁻⁶ mol/L. The increased chain lengths have a marked effect, reducing CMC values for MFAE by approximately three orders of magnitude over similar carbohydrate-based dodecyl chain sources. Within chain lengths between 14 and 18 carbons, the rate of change in CMC is significant and decreases with increasing chain length for MFAE. The melting points of MFAE are approximately 40°C, and the heat capacities range from 1.6 to 1.9 J/g·K. These numbers are comparable to those of sucrose esters, indicating their applicability in similar uses. However, because MFAE, unlike sucrose, possess an anomeric carbohydrate carbon position, these surfactants maintain their reducing nature and are susceptible to further derivatization. They are also synthesized from renewable, economical carbohydrates and lipids and may provide an excellent alternative to pertrochemical-derived products.     

Isolation,identification, and function of the Dufour gland secretion ofXylocopa virginica texana (Hymenoptera: Anthophoridae)

The Dufour's gland secretion ofXylocopa virginica texana possesses short-term repellency for conspecifics when applied to passion flowers. This secretion contains a number of straight-chain hydrocarbons. The two major components are the methyl esters of palmitic and myristic acid. A mixture of the two esters and two of the available hydrocarbons were as effective as the Dufour's gland extract in eliciting a response in females to the passion flower,Passiflora incarnata, to which the extract was applied.Approved as TA13387 by the Director, Texas Agricultural Experiment Station and conducted in cooperation with the USDA. Supported in part by NSF-DEB-76-03963.