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.     

Contamination of some foodstuffs marketed in Italy by fatty acid esters of monochloropropanediols and glycidol

ABSTRACT

Fatty acid esters of 3-monochloropropanediol (3-MCPD), 2-MCPD and glycidol (Gly) are food-processing contaminants that cause concerns about possible adverse health effects. The present study evaluates the contamination levels of the three ester classes in 130 samples of foodstuffs marketed in Italy covering 10 food categories, namely margarines, oils, roasted coffee, breakfast cereals, salted crackers, cookies, infant biscuits, rusks, breads and potato crisps. The analytical method employed is a so-called indirect method that entails MCPD/glycidol cleavage from their esterified forms, cleanup, derivatisation and GC-MS analysis. The MCPDs and glycidol concentrations (from esters) were found to be equal or a little higher than the levels reported in previous studies conducted in other European countries and described in the literature. 3-MCPD was the predominant compound in all foodstuffs analysed with the exception for rusks where Gly levels were slightly higher. Considering the sum of MCPD and Gly esters, the most contaminated foodstuffs were seed oils, followed by margarines and cookies, whereas roasted coffee, bread, rusks, cornflakes and infant biscuits were less contaminated with MCPDs and Gly concentrations often below LOQ or LOD values. Refined olive oil, potato chips and salted crackers showed contamination levels intermediate between the two above groups. The results of this study also confirm that the use of palm oil as an ingredient or frying medium is an important cause of increase of the levels of MCPD and Gly esters, especially in salted crackers, rusks and potato crisps. Finally, the Italian intake of 3-MCPD due to the various foods analysed has been calculated and related to TDI. The MoE for Gly was also estimated.     

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.     

The comparison of several lipid extraction methods on infant formula for 3-monochloropropanediol esters and glycidyl esters analysis

This study aimed to determine the best lipid extraction method for infant formula; therefore, it can be used as a routine analysis. The samples were some commercial infant formulas in Indonesia. The research was conducted with three steps: (i) Lipid extraction of infant formula using five lipid extraction methods; (ii) 3-monochloropropanediol esters (3-MCPDE) and glycidyl esters (GE) analysis of lipid extract from three lipid extraction methods in the first step; and (iii) 3-MCPDE and GE analysis of six commercial infant formulas using the best lipid extraction method. The results showed that lipid extraction using the Dubois method gave the best results than other lipid extraction methods. The level of 3-MCPDE and GE also had no significant difference with the addition of NaCl in the Folch method, compared with the addition of Na₂SO₄. The level of 3-MCPDE and GE using the Dubois method was significantly different and higher compared with the other lipid extraction methods. 3-MCPDE and GE levels of commercial infant formula were 6.62–52.84 µg kg⁻¹ and <1.43–17.06 µg kg⁻¹, respectively. The values obtained were still within the standard according to Commission Regulation EU 2018/290 by the European Food Safety Authority (125 µg kg⁻¹ for 3-MCPDE (on progress) and 50 µg kg⁻¹ for GE).     

Hybrid dual-curable cyanate ester/boron phosphate composites via sequential thiol-ene photopolymerization and thermal polymerization

The aim of this study was to improve hybrid dual-curable cyanate ester/boron phosphate composites via sequential thiol-ene photopolymerization and thermal polymerization for high performance applications such as aerospace and electronic devices. A novel 2,2′-diallylbisphenol A dicyanate ester (DA-BADCy) which is the allyl group containing cyanate ester was synthesized and characterized. DA-BADCy, silicon containing monofunctional thiol compound, trifunctional thiol compound and boron phosphate were cured using both ultraviolet (UV) and thermal methods. Using thiol-ene system, cyanate ester formulations, which are normally prepared at high temperatures, were prepared at room temperature. This study maintains ease of application for cyanate esters. Thermal stability, flammability and thermal conductivity of the samples were evaluated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), limiting oxygen index (LOI) and laser flash method, respectively. The samples were characterized with the following analysis; gel content, water absorption capacity and stress–strain test. Hydrophobicity of the samples was determined by the contact angle measurements. Moreover, the surface morphology of the samples was investigated by a scanning electron microscopy (SEM–EDS). The obtained results prove that the composites have good thermal and mechanical properties and with the help of easier preparation techniques, they can be used in many applications such as aerospace, electronic devices, materials engineering.