Obtaining 4-vinylphenols by decarboxylation of natural 4-hydroxycinnamic acids under microwave irradiation

4-Vinylphenols, useful compounds for industrial applications, were obtained by decarboxylation of 4-hydroxycinnamic acids under microwave irradiation in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as base and basic aluminum oxide as solid support. The reactions were fast (15-30 min). The selective extraction of the final products with ethyl acetate avoids chromatographic purifications. The conversions are quantitative and the yields are satisfactory. Only the unstable 4-vinylcatechol was obtained in moderate yield. This procedure was successfully extended to a natural sample of ferulic acid extracted from wheat bran to get the corresponding 4-vinylguaiacol, a FEMA GRAS (Flavor and Extract Manufacturer's Association; General Regarded as Safe) approved flavoring agent.     

高脂饮食对小鼠脂肪代谢和矿物元素代谢的影响

为探讨高脂饮食对小鼠脂肪代谢和矿物元素代谢的影响,用昆明(KM)小鼠24只,出生28 d后随机分成2组,各12只,分别给予高脂饲料与普通饲料,饲养至第9周眼球取血处死,取皮下、腹腔、肠系膜脂肪,毛,肝,血,计算体质量脂肪质量比,测定毛、肝、血中Zn、Ca、Cu、Mn、Mg、Fe含量。结果表明,高脂饮食小鼠体质量增加(P<0.05),单位腹腔脂肪及血Ch显著性增加(P<0.01)。肝Zn、Cu、Mg、Fe、Mn显著降低(P<0.01),血凝块Zn升高(P<0.05),Cu降低(P<0.05),毛Mg降低(P<0.05)。提示高脂饮食引起体质量与血脂增加,脂肪堆积,矿物元素代谢紊乱;不同器官矿物元素的代谢紊乱有差异,以肝脏最显著。     

TEQ-value determinations of animal feed; emphasis on the CALUX bioassay validation

Polyhalogenated aromatic hydrocarbons, such as polychlorinated dibenzo-p-dioxins are a large and diverse group of environmental pollutants. Their tendency to accumulate in the food chain and their toxicity make monitoring necessary. The reference analysis method is laborious and very expensive, therefore cheap and rapid bioassays have been developed. The chemical-activated luciferase bioassay (CALUX) bioassay uses a recombinant cell line, which responds to dioxins and dioxin-like molecules with Ah receptor (AhR)-dependent induction of firefly luciferase in a dose related response. The CALUX was tested for its use in the screening of feed. Aliquots of 20 g of enriched feed were extracted with a toluene:methanol mixture (20:4 v/v) and extracts were defatted on 33% H₂SO₄ silica columns and purified on carbon columns. Only the dioxin and furan fraction was analysed, the PCB fraction was discarded. The precision of the method is acceptable and in compliance with an R.S.D. <30% as suggested for cell-based bioassays in the Commission Directive 2002/70/EC of July 2002. The results evidence good agreement between TEQ-values obtained by either CALUX or GC–HRMS. The method is now routinely in use for a feed screening programme designed by the Federal Agency for the Safety of the Food chain. Approximately, 25 samples are analysed weekly. From the obtained results approximately 10% was confirmed by GC–HRMS. The false positive ratio is 1% and no false negatives were found, making the use of the CALUX technology advantageous.     

化学发光分析法测定动物蛋白粉等样品中的锰

基于Mn(Ⅱ) 邻菲罗啉对鲁米诺 KIO4化学发光体系的催化作用建立了测定Mn(Ⅱ)的分析方法。Mn(Ⅱ)质量浓度在2.0×10-6～5.0×10-5mg/mL范围与发光强度呈线性响应,回归方程为ICL=0.6+1.39×106ρ(mg/mL),检出限为2.0×10-6mg/mL。Cr3+、Fe2+、Co2+、Au3+等离子有干扰,使用EDTA、F-、8 羟基喹啉等为掩蔽剂可消除或降低干扰。将该法应用于生物化工产品丙酸钙、动物蛋白粉等中痕量锰的测定,加标回收率98%～102%,10次测定RSD为4 6%。将测定的结果与原子吸收法比较,相对偏差≤±3%。     

On-line enzymatic reaction,extraction, and chromatography of fatty acids and triglycerides with supercritical carbon dioxide

Supercritical carbon dioxide can be utilized both as an introduction solvent in capillary SFC and as a reaction medium; both possibilities are illustrated in this study. An off-line SFE unit was modified for on-line SFE-SFC. To facilitate rapid depressurization of the extraction cell and to prevent memory effects, a 6-port valve was installed at the outlet line of the extraction unit. An increased background signal was obtained when PEEK polymer was used in the construction of the extraction vessel; when stainless steel was used, the blanks improved. The synthesis of methyl esters and butyl esters of fatty acids from triglycerides in edible fat was examined using an immobilized lipase as a catalyst in on-line SFE-SFC. As a result of 30 minutes reaction – extraction time, high yields of fatty acid esters were obtained at a pressure of 150 bar and a temperature of 50°C.     

Thermal transitions and fat droplet stability in ice-cream mixmodel systems

We studied thermal transitions and physical stability of oil-in-water emulsions containing different milk fat compositions, arising from anhydrous milk fat alone (AMF) or in mixture (2:1 mass ratio) with a high melting temperature (AMF–HMT) or a low melting temperature (AMF–LMT) fraction. Changes in thermal transitions in bulk fat and emulsion samples were monitored by differential scanning calorimetry (DSC) under controlled cooling and reheating cycles performed between 50 and –45°C (5°C min^–1). Comparison between bulk fat samples and emulsions indicated similar values of melting completion temperature, whereas initial temperature of fat crystallization (T_onset) seemed to be differently affected by storage temperature depending on triacylglycerols (TAG) composition. After storage at 4°C, T_onset values were very similar for emulsified and non-emulsified AMF–HMT blend, whereas they were lower (by approx. 6°C) for emulsions containing AMF or mixture of AMF–LMT fraction. After storage at –30°C, T_onset values of re-crystallization were higher in emulsion samples than in bulk fat blends, whatever the TAG fat composition. Light scattering measurements and fluorescence microscopic observations indicated differences in fat droplet aggregation-coalescence under freeze-thaw procedure, depending on emulsion fat composition. It appeared that under quiescent freezing, emulsion containing AMF–LMT fraction was much less resistant to fat droplet aggregation-coalescence than emulsions containing AMF or AMF–HMT fraction. Our results indicated the role of fat droplet liquid-solid content on emulsion stability.     

Agro-industrial waste enzymes: Perspectives in circular economy

According to the Food and Agriculture Organization of the United Nations, approximately 1.3 billion tons of food is wasted each year, equivalent to approximately one-third of world production. Agri-food wastes are the source of proteins, carbohydrates, lipids, and other essential minerals that have been exploited for value-added products by the development of biorefineries and sustainable business as important elements of circular economies. The innovation and materialization of these types of processes, including the use of disruptive technologies on microbial bioconversion and enzyme technology, such as nanotechnology, metabolic engineering, and multi-omics platforms, increase the perspectives on the waste valorization process. Lignocellulolytic enzymes, pectinases, and proteases are mainly used as catalyzers on agri-food waste treatment, and their production in house might be the trend in near future for agro-industrial countries. Another way to transform the agri-food wastes is via aerobic or anaerobic microbial process from fungal or bacterial cultures; these processes are the key to produce waste enzymes.     

Partially concurrent eluent evaporation with an early vapor exit; detection of food irradiation through coupled LC-GC analysis of the fat

This paper reports two subjects. It describes LC-GC transfer by partially concurrent eluent evaporation at a greatly accelerated rate, as required for optimal compatibility with 2–3 mm i.d. LC columns and LC flow rates up to some 500 μl/min. Evaporation rates around 200 μl/min were obtained using a 0.53 mm. i.d. uncoated pre-column and an early vapor exit. A stationary-phasecoated “retaining” pre-column was used for preventing escape of volatile solutes through the vapor exit. The technique was used for the detection of food irradiation by analyzing selected radiolysis products of triglycerides, namely alkanes/alkanes and aldehydes. Extracted fat of chicken, hazel-nuts, and soup mixes was injected in LO and the relevant fractions were transferred on-line to GC. For chicken and nuts, detection of irradiation was possible down to doses below 0.5 kGy. Detection limits were higher for soup mixes due to interfering peaks.     

Rapid determination of organochlorine pesticide residues in feeds by capillary gas chromatography

A simple micro-method is described for determination of 15 organochlorine pesticide residues in mixed feeds. Clean-up of the petroleum ether extract is by basic alumina minicolumn chromatography and quantitative identification is by capillary gas chromatography with electron capture detection. Cyanopropyl-polysiloxane chemically bonded fused silica capillary columns have been used to perform high resolution analyses in short time as well as to overcome possible interferences by PCBs. Recovery, repeatability, and detection limits of the proposed procedure are checked and results are also reported for non random samples of 180 feeds collected in Italy.     

A study for quality evaluation of Taxilli Herba from different hosts based on fingerprint-activity relationship modeling and multivariate statistical analysis

In this study, a fingerprint-activity relationship modeling between chemical fingerprints and antirheumatic activity was established, and multivariate statistical analysis was used to evaluate the quality of Taxilli Herba (TH) from different hosts. Characteristic fingerprints of 20 batches of TH samples were generated by high-performance liquid chromatography coupled with triple quadrupole-time of flight tandem mass spectrometry (HPLC-Triple TOF-MS/MS), and the similarity analysis was calculated based on thirteen common characteristic peaks by hierarchical clustering analysis (HCA). Subsequently, nine efficacy markers were discovered by combining fingerprints and antirheumatic activity through grey correlation analysis (GCA) and bivariate correlation analysis (BCA). Meanwhile, the content of 5 constituents in 9 markers was determined by high-performance liquid chromatography coupled with triple quadrupole-linear ion trap tandem mass spectrometry (HPLC-QTRAP-MS/MS). The comprehensive quality of TH was assessed using multivariate statistical analysis, including principal components analysis (PCA) and technique for order preference by similarity to ideal solution (TOPSIS). The results showed that a high dose of TH extract could markedly ameliorate arthritis damage compared to other doses, with flavonoids playing an important role in the antirheumatic activity. The comprehensive quality of samples from Morus alba L. (SS) was superior to those from Liquidambar formosana Hance (FXS). The present study will demonstrate the markers associated with efficacy, and provide an applicable strategy for more comprehensive quality control and evaluation of TH.