Monitoring of headspace volatiles in milk‐cereal‐based liquid infant foods during storage

The effect of storage (time and temperature) on the evolution of pentanal, hexanal, heptanal and pentane as volatile lipid oxidation products in two liquid ready‐to‐eat milk‐cereal‐based infant foods was studied. An SPME‐GC method was used to this effect. Samples were stored for 9 months at 25, 30 and 37 °C and tested eight times during this period. Freshly produced infant foods contained pentanal, hexanal and heptanal (mean values: 10.71, 71.5 and 1.2 µg/kg, respectively), which decreased during the first 3 months of storage, although from the fourth month onwards no significant differences among storage times were found. Aldehyde content was inversely proportional to storage temperature. Pentane content was directly proportional to storage temperature and increased (19.9 µg/kg at zero time) over all months of storage up to 43.1 µg/kg.     

Investigation of Lipid Oxidation in High- and Low-Lipid-Containing Topical Skin Formulations

Lipid oxidation can impact the odour of skin care products during storage. A study was conducted to identify and monitor representative markers for lipid oxidation in skin care products over time. Four lip care formulations and three skin care formulations with different lipid contents were stored at various cosmetic industry‐relevant conditions for 84 days. The skin care products were analysed for lipid hydroperoxides and secondary volatile oxidation products. A trained sensory panel performed an odour difference (triangle) test and odour‐profiled the products to detect and describe odour changes during storage. Several potential markers for lipid oxidation were identified. In skin care formulations, peroxide value (PV) analysis was a useful marker for lipid oxidation if the product was exposed to light during storage, but no clear changes were observed for PV in samples stored under other conditions. Furthermore, concentrations of several secondary volatile oxidation products increased during storage, and the highest increase was observed for products exposed to light. Pentanal and heptanal were found to be reliable markers for secondary volatile oxidation products in the skin care formulations (especially during exposure to light), whereas in the lip care formulations the best candidates were pentanal (especially during exposure to light and iron), 2‐methyl furan and 3‐methyl‐3‐buten‐2‐one (especially during exposure to light, iron and high temperatures).     

Effects of rainbow trout freshness on n‐3 polyunsaturated fatty acids in fish offal

The effects of rainbow trout cold storage on the quality of offal left after fish processing to fillets with skin were determined. The intact farmed rainbow trout were kept at 2 °C in ice for 0, 4, 7, and 14 days of storage. The offal was, immediately after processing, frozen at ?20 °C and analysed after a month‐long frozen storage; fillets (non‐frozen) were analysed as well. Non‐protein nitrogen, volatile bases, trimethylamine, lipid oxidation (peroxide value, anisidine value, UV‐VIS spectra, and fluorescence) and fatty acid composition were determined. The offal consists in 15% of protein and in about 20% of chloroform/methanol‐extractable lipids, with n‐3 polyunsaturated fatty acids (n‐3 PUFA) accounting for 20.37 ± 1.25% of the fatty acids. The fish storage duration was found to exert a significant (p = 0.05) effect on the changes in lipids and nitrogen compounds. No losses of long‐chain n‐3 PUFA in the offal were detected during the 2 wk of storage in ice plus 1 month at ?20 °C. The rainbow trout offal is a valuable – rich and stable – source of n‐3 PUFA.     

Influence of Temperature Stress on Lipid Stability of Atlantic Herring (<Emphasis Type="Italic">Clupea harengus</Emphasis>) Muscle During Frozen Storage

Unstable conditions are commonly encountered during industrial storage and transportation of frozen fish. Temperature stress and fluctuations may increase the amount of unfrozen water in the muscle and enzymatic activity and lipid oxidation can thus still take place during frozen storage. The aim of this study was to investigate the changes of characteristics of different muscle types of herring at unstable modelled conditions during storage and transportation. Compositional changes, lipid oxidation and lipid hydrolysis were monitored in light and dark muscle of Atlantic herring (Clupea harengus), during frozen storage, as affected by temperature stress (samples were stored at ? 25 °C for 2 months, then stressed at ? 12 °C for 1 month, followed by storage at a stable ? 25 °C for the remaining storage duration), and compared to samples stored at a stable ? 25 °C for 14 months. The dark muscle was more sensitive to lipid oxidation than the light muscle, leading to faster degradation. Increased lipid oxidation and lipid hydrolysis were observed in temperature‐stressed samples of both muscle types. The study demonstrated the importance of avoiding temperature stress during industrial frozen storage and transportation to improve the quality and shelf life of frozen herring products. Removal of dark muscle by deep skinning could benefit both processors and customers regarding the shelf life and nutritional value of the light herring muscle.     

Influence of heating time and oxygen availability on lipid oxidation in meat emulsions

The aim of the present study was to investigate the effect of heating time and oxygen availability on lipid oxidation during chill storage, using different step indicators, in a meat emulsion model. Lipid oxidation was measured by conjugated dienes, hydroperoxides and 2‐thiobarbituric acid reactive substances formation on raw and cooked meat emulsion at 80 °C in different oxygen availability bags, at 0 °C during 35 d. The results obtained showed that heat treatment and oxygen availability affected conjugated dienes, hydroperoxides and 2‐thiobarbituric acid reactive substances formation during chill storage. Besides cooked meat emulsion did not have a similar behaviour to that of raw samples. Thus, is very important to follow primary and secondary products of oxidative deterioration to understand the effect of heat treatment and oxygen availability overall lipid oxidation process in meat emulsion.     

Oxidative stability during storage of structured lipids produced from fish oil and caprylic acid

Structured lipids produced by enzymatic or chemical methods for different applications have been receiving considerable attention. The oxidative stability of a randomized structured lipid (RFO), produced by chemical interesterification from fish oil (FO) and tricaprylin, and a specific structured lipid (SFO), produced by enzymatic interesterification from the same oil and caprylic acid, was compared with the stability of FO. Oils were stored at 2°C for 11 wk followed by storage at 20°C for 6 wk. In addition, the antioxidative effect of adding the metal chelators EDTA or citric acid to SFO was investigated. FO contained the largest amount of PUFA and RFO the lowest. However, SFO had a higher PV initially and during storage at 2°C, whereas the PV of FO was highest during storage at 20°C. The level of volatile oxidation products was highest in SFO during the entire storage period, and off-flavors were more pronounced in SFO. The lower oxidative stability of SFO was probably related to the initially lower quality (regarding oxidation products), which is apparently a result of the long production procedure required. Addition of metal chelators did not reduce the oxidation of the SFO.     

Stability of refined olive oil and olive‐pomace oil added by phenolic compounds from olive leaves

Refined olive oil and olive‐pomace oil were enriched with olive leaf phenolic compounds in order to enhance its quality and bring it closer to virgin olive oil. The changes that occurred in the concentrations of pure oleuropein, oleuropein aglycone, hydroxytyrosol acetyl and α‐tocopherol at 400 µg/kg of oil during the storage of refined olive oil and olive‐pomace oil under accelerated conditions (50 °C) were investigated. In a period of 4 months, α‐tocopherol decomposed by 75% whereas less than 40% of the phenols were lost. During storage, enzymatic olive leaf extract hydrolysate that contains two major compounds, hydroxytyrosol and oleuropein aglycone showed the highest antioxidant activity and the lowest detected stability, followed by oleuropein. The oleuropein in olive leaf extracts exhibited similar degradation profiles, reducing by 60–50% and 80% for the olive oil and olive‐pomace oil in 6 months, respectively. The acetylated extract, however, displayed a loss of 10 and 5% in olive oil and olive‐pomace oil, respectively. In the fatty acid composition, an increase in oleic acid and a decrease in linoleic acid were observed. The antiradical activities of the olive oil and olive‐pomace oil enriched with olive leaf phenolic compounds at 400 ppm showed that enzymatic hydrolysate extract had the highest protective effect against oil oxidation. Based on the Rancimat method, the oils with added leaf enzymatic hydrolysate extract had the lowest peroxide value and the highest stability. After 6 months of storage and at 120 °C, the oxidative resistance of refined olive oil and olive‐pomace oil reached 0.71 and 0.89 h, respectively, whereas that of the non‐enriched samples fell to zero.     

Prediction of Amine‐Based Liquid Rocket Propellant Shelf Life

The storage stability of amine based rocket fuel called Samine was studied over 9 months for the first time. It was found that storage stability significantly depends on fuel oxidation with the air trapped in the storage tanks. A reduction of the triethylamine concentration from 50.2 % (wt) to less than 48 % was taken as the end of shelf life of the propellant. After obtaining experimental data from accelerated storage stability tests, the shelf life of Samine was estimated using the Arrhenius equation. According to the kinetic studies, the oxidation reaction of fuel was a zero order reaction and the shelf lives of Samine in stainless‐steel tanks at 20 °C, 25 °C, and 30 °C were obtained to be 5.7, 3.7, and 2.4 years, respectively. Additionally, it was observed that for long time storage of amine based fuels like Samine it is better to use stainless‐steel or aluminum tanks, which are charged with an inert gas like nitrogen.     

Stability Assessment of Virgin Coconut Oil‐Based Emulsion Products

In recent years, there has been dramatic growth in the market for virgin coconut oil (VCO). VCO, a promising functional food oil, has gained popularity and captured public attention worldwide. Two VCO‐based emulsion products were developed as a new nutritional food supplement with the aim of increasing the consumption of VCO. The stability of VCO‐based emulsion products was assessed during a storage period of 3 months to gauge the quality of the optimized VCO‐based emulsions. The particle‐size distributions of the VCO‐based emulsions remained stable throughout the 3‐month storage period at 25 and at 50°C. However, a slight increase in the particle sizes was observed in the VCO‐based emulsions samples after 2 months of storage at 4 °C. Nevertheless, phase separation did not occur in either of the VCO‐based emulsions products throughout the storage‐stability assessment period. No signs of microbial growth were detected in the emulsion products during the storage period. Furthermore, no significant changes in the free fatty acid contents of the emulsion products were observed during storage at 4 or 25°C throughout the storage period. The VCO‐based emulsion products possessed sufficient emulsion stability to withstand changes at different storage temperatures.     

Profiles of volatile compounds in milk containing fish oil analyzed by HS‐SPME‐GC/MS

Long‐chain polyunsaturated fatty acids (LC‐PUFA) have various positive biological effects. Fish oil represents a major source of LC‐PUFA; therefore it is extensively used to enrich food products as, for example, infant formulae, dairy products and fruit juices. However, in the presence of oxygen and metals, LC‐PUFA readily degrade, producing off‐flavors and decreasing the nutritional value of the product. The deterioration of sensory properties (taste and odor) can be easily perceived by the consumer, due to the formation of volatile compounds that are formed by decomposition of lipid hydroperoxides, also known as primary oxidation products. In this study, we used the headspace solid‐phase microextraction‐gas chromatography/mass spectrometry technique (HS‐SPME‐GC/MS) to characterize and quantify volatile compounds in a food matrix supplemented with fish oil. We demonstrated that the HS‐SPME‐GC/MS method is a valuable tool to monitor lipid oxidation at early stages. We identified t‐2‐hexenal and c‐4‐heptenal as possible oxidation markers during the storage of milk enriched with 5% of cod oil.     

Effects of lipid oxidation on fish lipids — amylopectin interactions

The results of studies on fish lipid oxidation effects on lipid‐amylopectin starch interactions are presented. Particular attention is paid to fish lipid availability (extractability from the system) and fatty acid contributions to individual lipid groups after mixing‐provoked interaction and after a 30‐day storage at —18 °C. The study involved model systems containing fish lipids at different levels of oxidation, lipids containing an antioxidant (BHA), and gelatinised amylopectin starch in a 10% aqueous solution. The lipid to starch ratio was 1:1. The test systems were subjected to selective extraction. The extracts were assayed for lipid content, peroxide value, anisidine value, fluorescence, and fatty acid composition. Compared to fresh fish lipids, those lipids, which were oxidised to a higher extent were shown to be more amenable to complexing with amylopectin, but they were also more readily released during frozen storage. On the other hand, addition of BHA stabilised the lipid‐amylopectin starch interaction during storage at —18 °C. In the entire systems tested, polyunsaturated fatty acids, eicosapentaenoic and docosahexaenoic acids in particular, proved to be most susceptible to binding, up to 90% of the latter being complexed.     

Synthesis,Surface Activity,and Antimicrobial Efficacy of Diaryliodonium Salt‐Derived Amphiphiles

Two sets of 19 amphiphiles derived from diaryliodonium salt in the form of 4‐methylbenzenesulfonate salts and trifluoromethanesulfonate salts were synthesized in good yields through the oxidation of 17 different aryl iodides using oxone (potassium peroxymonosulfate) as the oxidation agent in Route I and meta‐chloroperoxybenzoic acid as the oxidation agent in Routes II and III, followed by Friedel–Crafts reaction with (2‐(2‐(2‐methoxyethoxy)ethoxy)ethoxy)benzene to obtain the target compounds ( 1 – 19 ). Their structures were characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR, and high‐resolution mass spectrometry studies. Their surface activities were evaluated on the basis of surface tension and critical micelle concentration measurements by the Wilhelmy plate method at 25 °C. With their good water solubility, diaryliodonium salts ( 1 – 19 ) have excellent short‐term bactericidal efficacy against Bacillus cereus in the concentration of 600 ppm at 20 °C. After compounding 1 or 18 with the broad‐spectrum but skin‐irritating antibacterial agent Kathon CG (methylchloroisothiazolinone in combination with methylisothiazolinone) in the ratio of 1:1 by mass, both formulations maintained lethality rate of >90% after 48 h.     

Microencapsulation of fish oil with n‐octenylsuccinate‐derivatised starch: Flow properties and oxidative stability

Fish oil with 33% long‐chain polyunsaturated fatty acids was microencapsulated in a matrix of n‐octenylsuccinate‐derivatised starch and glucose syrup and stored at varying temperatures (5, 20 and 40 °C) and relative humidities (11, 33, 48–59 and 75%). Development of lipid oxidation parameters upon storage depended to a certain extent on temperature, but to a much greater extent on relative humidity. Temperature had no significant effect on the development of lipid oxidation parameters when samples were stored at 11 or 33% relative humidity. Hydroperoxide concentration doubled over the storage period and reached from 88 to 146 mmol/kg oil in the samples stored at 11 and 33% relative humidity, respectively. An increase in hydroperoxide concentration with increasing storage temperature was observed at 48–59% relative humidity. In all samples, the increase in the lipid oxidation parameters was not linear or exponential and significantly differed from the course as it is described in the literature for bulk oils and emulsions. Based on data for colour measurement, moisture sorption and extractable fat, the course of lipid oxidation is discussed. Finally, the use of silica derivatives and tricalciumphosphate efficiently improved the flowing properties of microencapsulated fish oil without affecting the oxidative stability of the products.     

Lipid oxidation products of heated soybeans as a possible cause of protection from ruminal biohydrogenation

Heating oilseeds has been shown to improve the milk fatty acid profile when given to dairy cows, compared to raw oilseeds. However, results from published studies are conflicting. The conditions of heating and storage of the oilseeds could be responsible for these differences, probably partly through their effects on lipid oxidation, the products of which could act on ruminal biohydrogenation (BH). Thus, 15 different treatments were applied to ground soybeans: three levels of heating (no heating, 30 min at 110 or 150°C) × 5 ambient storage durations (0, 1, 2, 4, or 6 months). Soybeans were incubated in vitro with ruminal fluid for 6 h. Triacylglycerol (TAG) polymers, hydroperoxides and hydroxyacids (HOA), aldehydes, and fatty acids were assayed in soybeans and ruminal culture. No TAG polymer was detected in any treatment. Soybeans stored for a long time had a high content of HOA, whereas those heated at 150°C, whatever the storage duration, had high aldehyde contents. The percentage disappearance of cis‐9,cis‐12 18:2 and cis‐9,cis‐12,cis‐15 18:3 in incubates decreased significantly in cultures with heated soybeans, especially at 150°C, suggesting that this partial protection of polyunsaturated fatty acids (PUFA) from BH was at least in part linked to the aldehyde content of the heated soybeans. Practical applications: Oilseeds given to ruminants are often heated, and heat treatment is known to generate oxidation products. Knowing what oxidation products influence ruminal biohydrogenation of unsaturated fatty acids could result in technological processes allowing a better transfer of unsaturated fatty acids from oilseeds to ruminant products.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

Retention of Eucalyptol,a Natural Volatile Insecticide,in Delivery Systems Based on Hydroxypropyl‐β‐Cyclodextrin and Liposomes

Eucalyptol (Euc) is a natural monoterpene with insecticide effects. Being highly volatile and sensitive to ambient conditions, its encapsulation would enlarge its application. Euc‐loaded conventional liposomes (CL), cyclodextrin/drug inclusion complex, and drug‐in‐cyclodextrin‐in‐liposomes (DCL) are prepared to protect Euc from degradation, reduce its evaporation, and provide its controlled release. The liposomal suspension is freeze‐dried using hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) as cryoprotectant. The liposomes are characterized before and after freeze‐drying. The effect of Euc on the fluidity of liposomal membrane is also examined. A release study of Euc from delivery systems, in powder and reconstituted forms, is performed by multiple head extraction at 60 °C after 6 months of storage at 4 °C. CL and DCL suspensions are homogeneous, show nanometric vesicles size, spherical shape, and negative surface charge before and after freeze‐drying. Moreover, HP‐β‐CD does not affect the fluidity of liposomes. CL formulations present a weak encapsulation for Euc. The loading capacity of eucalyptol in DCL is 38 times higher than that in CL formulation. In addition, freeze‐dried DCL and HP‐β‐CD/Euc inclusion complex show a higher retention of eucalyptol than CL delivery system. Both carrier systems HP‐β‐CD/Euc and Euc‐loaded DCL decrease Euc evaporation and improve its retention. Practical Applications: Eucalyptol is a natural insecticide. It is highly volatile and poorly soluble in water. To enlarge its application, its encapsulation in three delivery systems (conventional liposomes, cyclodextrin/drug inclusion complex, combined system composed of cyclodextrin inclusion complex and liposome) is studied. In this paper it is proved that cyclodextrin/eucalyptol inclusion complex and eucalyptol‐in‐cyclodextrin‐in‐liposome are effective delivery systems for encalyptol encapsulation, retention, and release.     

Sensory evaluation of the odour of a sunflower oil emulsion throughout oxidation

Oxidation of unsaturated fatty acids is responsible for off‐flavours, often described as rancid flavours. This study was aimed at describing the evolution of the odour of a sunflower oil‐in‐water emulsion during oxidation at 50 °C in the dark. Appearance of an odour and occurrence of oxidation were first tested for at short‐time aging (0–4 h) by the triangle test and measurements of oxygen consumption, respectively. The odour of the emulsion oxidised for up to 240 h was then characterised by sensory profile, while volatiles issued from lipid oxidation were analysed in the headspace by SPME. From 1 h of aging, while oxygen consumption remained weak, a significant change of the odour was detected by the panel. Up to 21 volatile compounds were identified in the headspace of long‐time‐oxidised emulsions. Beyond the rancid attribute, seven attributes were chosen to describe the odour of oxidised emulsions, four of which referring to solutions of a single volatile oxidation compound. The contribution of the fresh oil attribute, initially dominant, was progressively overtaken from 6 to 24 h of aging by the deep‐fried attribute, which later declined in favour of the painty attribute, predominant after 100 h. Evolution of intensity scores and contribution to odour profiles of attributes could not be easily related to one reference volatile compound or another, confirming the complex relationship between the generated volatile compounds and the perceived odour.     

Stabilization of refined olive oil by enrichment with chlorophyll pigments extracted from Chemlali olive leaves

This paper presents the first investigation on the effect of enrichment refined olive oil by chlorophyll pigment extracted from Chemlali olive leaves during storage (6 months). The changes that occurred in the quality indices, fatty acids, sterol, and phenolic content were investigated during the storage of refined olive oil under RT (20°C) and accelerated conditions (50°C) in the dark. Additionally, the pigments (chlorophyll and carotene) changes during 6 months of oil storage were evaluated. At the end of the storage, more than 90% of chlorophyll pigments decomposed in all samples, while, carotene pigment loss was lower showing up to 60 and 85% loss for oil stored at 20 and 50°C, respectively, at the end of storage. The reduction of total phenolic compounds exhibited similar degradation profiles, being reduced by 5% and up to 60% for the enriched refined olive oil stored at 20 and 50°C in 6 months, respectively. In the fatty acid composition, an increase in oleic acid and a decrease in linoleic and linolenic acids were less significant in enriched than non‐enriched refined olive oil. On the other hand, sterol composition was less affected by storage in enriched oil samples. However, the sterol concentration of the oil samples showed an increase in β‐sitosterol, 24‐methylene cholesterol, stigmasterol, and a decrease in cholesterol, Δ5, 24‐stigmastadienol percentage at the end of storage. Based on the Rancimat method, the oils with added leaf pigment extract had the lowest peroxide value and the highest stability. After 6 months of storage, the oxidative resistance of refined olive oil fell to 0.2 and to zero for enriched refined olive oil stored at 20 and 50°C, respectively.     

Preparation and high‐temperature behavior of HfC–SiC nanocomposites derived from a non‐oxygen single‐source‐precursor

A single‐source precursor for the preparation of HfC‐SiC ceramics was synthesized via a Grignard reaction using bis(cyclopentadienyl)hafnium(IV) dichloride, trans‐1,4‐dibromo‐2‐butene, and (chloromethyl)trimethylsilane as raw materials. The composition, structure, pyrolysis process and high‐temperature behavior of the precursor were investigated. The results show that the precursor with a backbone comprising Hf–C, Si–C and CH=CH groups exhibits good solubility in common solvents, such as tetrahydrofuran, dimethylbenzene, and chloroform. Pyrolysis of the precursor at 1000°C yielded a microcrystalline HfC phase with a ceramic yield of 63.86 wt%. The pyrolytic products at 1600°C were HfC–SiC nanocomposite ceramics, which exhibited good thermal stability up to 2400°C. The formation of a (Hf,Si)C solid‐solution would be beneficial for densification during the sintering process. The non‐oxygen structure, high ceramic yield, homogeneous composition and excellent high‐temperature behavior of the pyrolytic products make the as‐prepared precursor a promising material for the preparation of high‐performance ultra‐high‐temperature ceramics.