Producing Fatty Acid Methyl Esters from Free Fatty Acids with Ionic Liquids as Catalyst

Three Brønsted acidic imidazole dicationic ionic liquids (ILs) with different length of alkyl chains, [C_n(Mim)₂][HSO₄]₂ (n = 3, 6, 12), were prepared and used as catalyst for the esterification reaction of free fatty acids and methanol. Taking oleic acid as model acid, the catalytic performances of the synthesized ILs for the esterification were evaluated. The main physicochemical properties of the ILs, thermal stability, acidity, solubility in common solvents, and causticity on Austenitic stainless steel 316, were examined. [C₃(Mim)₂][HSO₄]₂ demonstrated the highest catalytic activity and enabled to assess the preliminary optimum esterification condition of oleic acid and methanol. Under optimized reaction conditions, the yield of oleic acid methyl ester was up to 95 %. The ILs have great potential as catalysts for producing fatty acid methyl esters from long‐chain free fatty acids.     

Properties of mineral filled poly(lactic acid)/poly(methyl methacrylate) blend

This study examines the influence of three different minerals, that is, clay, calcium carbonate, and quartz on the physical, thermal, and mechanical properties of poly(lactic acid) (PLA)/poly(methyl methacrylate) blend. Rheological behavior and phase structure were initially studied by small-amplitude oscillatory shear rheology. Clay- and quartz-filled materials presented an increase in viscosity at low frequency associated with the presence of a yield stress. However, this behavior was not observed for calcium carbonate filled materials due to a matrix degradation effect. To elucidate this aspect, thermal stability and thermal properties were examined by thermogravimetric analysis and differential scanning calorimetry, showing that calcium carbonate promotes degradation of the PLA phase. No nucleating effect was observed in the presence of the minerals. Dynamical mechanical analysis and mechanical characterization revealed an increase of the overall softening temperature and, a reinforcing effect for clay- and quartz-based composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46927.     

Proton Nuclear Magnetic Resonance-Based Method for the Quantification of Epoxidized Methyl Oleate

Epoxidized methyl esters (EMO) with their high oxirane ring reactivity, acts as a raw material in the synthesis of various industrial chemicals including polymers, stabilizers, plasticizers, glycols, polyols, carbonyl compounds, biolubricants etc. EMO has been generally quantified by the gas chromatography (GC) and high-performance liquid chromatography (HPLC) techniques. Taking into the account of the limitations of these techniques, two qHNMR-based equations have been proposed for the quantification of EMO in the mixture of EMO and methylesters (MO). The validity of the proposed method was determined using standard mixtures of MO and EMO having different molar concentrations. The developed equations have been applied on the samples of EMO prepared from oleic acid in two-step process viz., esterification followed by epoxidation. The qHNMR-based EMO quantification showed acceptable agreement with the results obtained from HPLC analysis.     

甲醇转化制丙烯反应机理研究

以杂化轨道理论和关于含Si、Al元素催化剂酸中心的认识为理论依据和研究方法，从反应物与催化剂B酸中心相互作用为切入点，分析相互作用过程中甲醇与B酸中心分子结构变化，揭示甲醇制烯烃反应机理本质。研究结果表明甲醇转化制丙烯反应过程可分为3步：(1)B酸中心释放H+攻击甲醇分子中C-O键，C-O键断裂生成甲基碳正离子(CH+3)和H2O，CH+3中C原子外层有个空轨道，释放了H+后的B酸中心失去活性。(2)失活B酸中心从CH+3中获得H+，反应生成了一种新中间体H-form，H-form中C原子外层有1对孤对电子(e-)和1个空轨道，结构式为C↑↓〇H2；失活的B酸中心获得H+后恢复活性。第3步，有3个H-form结构的C原子，第1个C原子上的孤对e－占据第2个C原子上空轨道，第2个C原子上的孤对e－占据第1个C原子上空轨道，彼此共用2对e-，形成C=C键；第3个C原子上的空轨道与第1个C原子上C、H原子重叠轨道再次重叠，形成C、H和C三原子共用1对e－结构，结果是第1个C原子与第2个C原子形成C=C键，第1个C原子与第3个C原子形成C-C键，3个C原子形成C=C-C结构，即生成丙烯。     

Synthesis and Application of Methyl N,O-Hydroxylamine Muramyl Peptides

The innate immune system's interaction with bacterial cells plays a pivotal role in a variety of human diseases. Carbohydrate units derived from a component of bacterial cell wall, peptidoglycan (PG), are known to stimulate an immune response. Nonetheless, access to modified late-stage peptidoglycan intermediates is limited due to their synthetic complexity. A method to rapidly functionalize PG fragments is needed to better understand the natural host–PG interactions. Here methyl N,O-hydroxylamine linkers are incorporated onto a synthetic PG derivative, muramyl dipeptide (MDP). The modification of MDP maintained the ability to stimulate a nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) immune response dependent on the expression of nucleotide-binding oligomerization domain-containing protein 2 (Nod2). Intrigued by this modification's maintenance of biological activity, several applications were explored. Methyl N,O-hydroxylamine MDP was amendable to N-hydroxylsuccinimide (NHS) chemistry for bioconjugation to fluorophores as well as a self-assembled monolayer for Nod2 surface plasmon resonance analysis. Finally, linker incorporation was applicable to larger PG fragments, both enzymatically generated from Escherichia coli or chemically synthesized. This methodology provides rapid access to PG probes in one step and allows for the installation of a variety of chemical handles to advance the molecular understanding of PG and the innate immune system.     

Improved compatibility of PET/HDPE blend by using GMA grafted thermoplastic elastomer

ABSTRACT

Herein, graft-modified ethylene-1-octene copolymer (POE-g-GMA) and styrene-butadiene-styrene triblock copolymer (SBS-g-GMA) were found to be excellent reactive compatibilizers for immiscible poly(ethylene terephthalate) (PET)/high-density polyethylene (HDPE) blends via in-situ reaction compatibilization. With increase in compatibilizer amount, uniform phase morphology was observed in all the blends. Thus, exhibiting enhanced mechanical properties, especially, the notched Izod impact strength. In comparison with SBS-g-GMA, compatibilizer POE-g-GMA demonstrated greater impact on the compatibility. The addition of 15% POE-g-GMA produced blends with best mechanical properties. Besides, both POE-g-GMA and SBS-g-GMA enhanced the melt viscosity of PET/HDPE blends.     

高效液相色谱串联质谱法测定植物油中香兰素、 甲基香兰素和乙基香兰素

目的建立高效液相色谱串联质谱同时检测植物油中香兰素、甲基香兰素和乙基香兰素的分析方法。方法样品经乙腈提取后,以正己烷除脂净化,采用C_(18)色谱柱进行分离,以0.1%(V/V)甲酸水和甲醇为流动相进行梯度洗脱,质谱采用电喷雾正离子电离进行多反应监测模式监测(multiple reaction monitoring,MRM)。结果方法加标回收率(n=6)为83.4%~96.8%,相对标准偏差为3.1%~4.6%,检出限为23~30μg/kg,定量限为76~100μg/kg。采用该方法对50批次市售植物油进行检测,只有香兰素被检出,检出浓度为160~830μg/kg。结论该方法操作简便、检测准确、分析速度快,适合植物油中香兰素、甲基香兰素和乙基香兰素的快速检测。     

蓖麻酸甲酯水解反应性能研究

以自制蓖麻酸甲酯为原料,对其进行了水解反应性能的研究。采用单因素试验考察了反应温度、水与蓖麻酸甲酯体积比、酸碱性及反应时间对蓖麻酸甲酯水解率的影响。结果表明:按碱性、中性、酸性水解顺序蓖麻酸甲酯水解率依次减小;反应温度越低,蓖麻酸甲酯水解率越小;水与蓖麻酸甲酯体积比越小,蓖麻酸甲酯水解率越小;反应时间缩短,蓖麻酸甲酯水解率减小;在酸性介质、水与蓖麻酸甲酯体积比1∶1、反应温度25℃、反应时间60 min条件下,蓖麻酸甲酯水解率为4.2%。选择在酸性介质、较低温度、较少水量条件下对蓖麻酸甲酯进行快速水洗对降低其水解损失是有利的。     

聚苯乙烯/交联丙烯酸甲酯共混物的制备及其发泡性能研究

将聚苯乙烯（PS）颗粒溶解到二乙烯基苯（DVB）、丙烯酸甲酯（MA）与偶氮二异丁腈（AIBN）的混合物中，通过加热引发MA聚合，获得PS/交联PMA共混物, 采用釜压法制备了PS/交联PMA共混物泡沫。采用全自动视频光学接触角测试仪、差示扫描量热仪、傅里叶变换红外光谱仪、动态力学分析仪对PS/交联PMA共混物的结构和性能进行了表征，并通过扫描电子显微镜对PS/交联PMA共混物泡沫的结构进行了表征。结果表明，交联PMA的引入能提高体系的成核效率，随着MA用量的增加，PS/交联PMA共混物的接触角从PS的100.5 °降至86.1 °；当MA的用量为9.6份（质量份，下同）时，PS/交联PMA共混物的泡孔尺寸主要分布在40~60 μm之间，泡孔尺寸分布明显变窄，泡孔密度达到了1.2×10⁸ 个/cm³。