Mass transfer in cellular material at solid–liquid contacting interface

The effective mass transfer (water and solute) and volume shrinkage were measured during solid–liquid contacting process for red beet material tissue under a wide range of process parameters. The mass transfer process of each component in the solid–liquid system is affected not only by operating parameters, but also by the matrix properties of cellular material. The main driving force for the mass transfer phenomena of water out of red beet tissue and sucrose taken into red beet tissue from sucrose solution is attributed to the concentration gradient between external and internal red beet material, and the interaction among water, sucrose fluxes and tissue matrix. The coupled mass transfer fluxes across the interface in an isothermal solid–liquid system were analysed by means of a film model as a function of the concentration gradients, based on the generalized multicomponent mass transfer theories. The relation between individual flux and the independent driving force is nonlinear. The mass transfer model and parameters proposed in the present study is applicable to the unit operation such as osmotic treatment of cellular porous biomaterial.     

High methoxyl pectin–methyl cellulose films with antioxidant activity at a functional food interface

The effect of using increasing proportions of methylcellulose (MC) for the development of glycerol plasticized films based on high methoxyl pectin (HMP) (30:70, 50:50 and 70:30 w/w HMP:MC) and carrying l-(+)-ascorbic acid (AA) was studied with the purpose of achieving higher stability of AA and localized antioxidant activity at food interfaces. MC and 30:70 HMP:MC systems could not be casted. The shelf-life of the other AA-active films was assessed by storage at 25 °C, constant relative humidity (RH: 33.3%, 57.7% and 75.2%) and vacuum conditions. The rate constant for AA hydrolysis increased with the RH and, hence, with water mobility. Browning and AA degradation rates were directly related. When stored at 75.2% RH, both decreased as MC proportion increased. Compared to HMP film, the highest proportion of MC (50:50 HMP:MC) showed the highest AA stabilization under vacuum and greater performance under air atmosphere. They also developed localized antioxidant activity preserving the tocopherol content of walnut oil.     

Heat transfer phenomena during thermal processing of liquid particulate mixtures—A review

During the past few decades, food industry has explored various novel thermal and non-thermal processing technologies to minimize the associated high-quality loss involved in conventional thermal processing. Among these are the novel agitation systems that permit forced convention in canned particulate fluids to improve heat transfer, reduce process time, and minimize heat damage to processed products. These include traditional rotary agitation systems involving end-over-end, axial, or biaxial rotation of cans and the more recent reciprocating (lateral) agitation. The invention of thermal processing systems with induced container agitation has made heat transfer studies more difficult due to problems in tracking the particle temperatures due to their dynamic motion during processing and complexities resulting from the effects of forced convection currents within the container. This has prompted active research on modeling and characterization of heat transfer phenomena in such systems. This review brings to perspective, the current status on thermal processing of particulate foods, within the constraints of lethality requirements from safety view point, and discusses available techniques of data collection, heat transfer coefficient evaluation, and the critical processing parameters that affect these heat transfer coefficients, especially under agitation processing conditions.     

Sequential adsorption of egg-white proteins at the air–water interface suggests a stratified organization of the interfacial film

The aim of this work was to get further insight into the formation of the interfacial film by ovalbumin and lysozyme in equimolar binary solutions, as well as the organization of these proteins inside the interfacial film. Our approach consisted in the sequential adsorption of the two proteins, with or without previous replacement of the sub-phase with protein-free buffer before injection of the second protein.     

Denaturation of soy proteins in solution and at the oil–water interface: A fluorescence study

Structural changes ensuing from denaturation of soy proteins in solution or occurring at the oil–water interface were studied by fluorescence spectroscopy. Studies were carried out on solutions and emulsions stabilized with β-conglycinin or glycinin. Tryptophan fluorescence spectroscopy was used to evaluate tertiary structural changes. The binding of fluorescent dyes and the accessibility of reactive cysteine thiols were also used to better identify structural changes of these proteins in solution. Protein conformational changes after interaction with the hydrophobic oil surface were compared with those ensuing from physical (temperature) or chemical denaturation (chaotropes). Results from solution denaturation experiments indicate that structural changes of β-conglycinin by both temperature and chaotropes are reversible under appropriate conditions, and result in a rearrangement of the supramacromolecular assembly of the protein structure. On the other hand, glycinin treated under the same conditions undergoes irreversible denaturation in solution at temperatures well below 90 °C. Both proteins undergo partial denaturation after adsorption on the lipid surface, and no further denaturation occurs upon heating of the emulsions prepared with either protein.     

Hydrocolloids with emulsifying capacity. Part 2 – Adsorption properties at the n-hexadecane–Water interface

The ability to adsorb at n-hexadecane – water interface of natural hydrocolloids was quantified by dynamic drop tensiometry. Conventional and matured hydrocolloids samples from Acacia senegal, Acacia seyal (AcSey), Sugar Beet Pectin (SBP) and natural untreated Gum Ghatti (GG), were studied in aqueous solutions at pH 4.5. Maturation of A. senegal gum (Acacia (sen) SUPERGUM? EM2, designated as EM2) increased its ability to lower interfacial tension and the elastic characteristics of the interfacial film. This change in properties can be attributed to the increase in molecular weight and in arabino-galactan-protein (AGP) content. EM2 exhibited the best interfacial properties. Conventional and matured AcSey presented interfacial properties that were similar to conventional A. senegal (GAc), correlating with minimal changes observed in their structural features after maturation. Gum ghatti reacted similarly to EM2 and presented relatively fast kinetic profiles, revealing the good qualities of this gum. The kinetics associated with all the hydrocolloids at pH 4.5 have been described using a mathematical model, from which quantitative parameters as onset time or half-time of interfacial-tension-decrease were determined. Compared to the other hydrocolloids, SBP adsorbs by a different mechanism. However, pectin presented the lowest final interfacial tension and gave the more elastic interfacial film. Acidification of hydrocolloid solutions to pH 3.1 increased both the ability to lower the interfacial tension and the elastic characteristics of interfacial film. The effect of structural modifications on interfacial properties was demonstrated, and clarifies further the already observed emulsification behaviour of the studied hydrocolloid.     

The physicochemical characteristics and hydrophobicity of high amylose starch–glycerol films in the presence of three natural waxes

The film forming behaviour and hydrophobicity of high amylose (HA) starch in the presence of three different natural waxes (beeswax, candelilla wax and carnauba wax) were studied in the presence and absence of Tween-80. The HA starch:glycerol (G) ratio was maintained at 80:20 (on dry solid basis) and the concentration of wax was varied from 5% and 10% (w/w). The melted wax samples were homogenized with HAG dispersion with or without Tween-80 and the films were prepared by solution casting. The hydrophobicity and water-barrier properties in these films were determined by using contact angle (CA), water vapour permeability (K_w) tests, and water sorption isotherm at 0.529 RH and 20 °C. The K_w values of the HAG films decreased significantly (p < 0.05) with the addition of 5% concentration of these waxes. Then the addition of Tween-80 to the HAG + wax films increased the K_w values significantly (p < 0.05). The presence of these waxes in the presence and absence of Tween-80 resulted into different sorption isotherms and the water adsorptivity and moisture diffusion coefficient values were also affected. The presence of Tween-80 increased the CA in HAG + carnauba wax films while the CA was found to decrease in the case of other two waxes. The highest hydrophobicity was observed in HAG + carnauba wax + Tween-80 films in which the CA was >80.0° both at 5% and 10% (w/w) wax concentration. These higher CA values in HAG + carnauba wax + Tween-80 films were found to be related to the higher surface roughness in these films.     

Salting-out assisted liquid–liquid extraction with dansyl chloride for the determination of biogenic amines in food

Biogenic amines (BAs) are compounds present in foodstuff of animal origin that not only can be harmful to the consumer but can also serve as indicators of the product's edibility status. However, BAs’ analysis is rather complicated. Derivatisation methods have been employed to make their analysis less challenging. Salting-out assisted liquid–liquid extraction (SALLE) was herein applied to decrease time that the derivatising agent dansyl chloride (DNS-Cl) requires to be effective. DNS-Cl derivates were separated and analysed by high-performance liquid chromatography with UV and fluorescence detection (HPLC-UV/FD). It was by this way possible to analyse methylamine, dimethylamine, ethylamine, β-phenylethylamine, isopentylamine, putrescine, cadaverine, histamine, tyramine, spermidine and spermine in a straightforward manner in several fish-based and meat-based samples, obtaining results in the order of magnitude of about a few mg per kg. All calibrations curves had r² higher than 0.99, and limits of detection ranged from 0.0075 to 1.6 mg L⁻¹.     

Sodium caseinate/carboxymethylcellulose interactions at oil–water interface: Relationship to emulsion stability

The effect of carboxymethylcellulose (CMC) on the properties of oil-in-water emulsions prepared with sodium caseinate (CN) was studied at different pHs (4–7). At pH 7, the surface protein coverage increased gradually with increasing CMC concentration, followed by a preferential adsorption of β-casein. While at pH 4, a sharp decrease in surface protein coverage was noted between 0 and 0.3 wt.% CMC, and no obvious difference in protein composition was observed. ζ-Potential measurements indicated that CMC adsorbed onto the CN-coated droplets at pH 4–5, but not at pH 6–7. As a result, the excess of non-adsorbed CMC induced depletion flocculation in the neutral emulsions. However, the acidic emulsions containing high levels of CMC (>0.3 wt.%) remained stable after 60 days of storage due to the formation of multilayer structures. At pH 4, CMC desorbed from the droplet surfaces at high NaCl concentrations, leading to lower emulsion stability.     

Determination of Fusarium toxins in functional vegetable milks applying salting-out-assisted liquid–liquid extraction combined with ultra-high-performance liquid chromatography tandem mass spectrometry

ABSTRACT

Vegetable milks are considered as functional foods due to their physiological benefits. Although the consumption of these products has significantly increased, they have received little attention in legislation with regard to contaminants. However, they may contain mycotoxins resulting from the use of contaminated raw materials. In this work, ultra-high-performance liquid chromatography tandem mass spectrometry has been proposed for the determination of the most relevant Fusarium toxins (fumonisin B₁ and B₂, HT-2 and T-2 toxins, zearalenone, deoxynivalenol and fusarenon-X) in different functional beverages based on cereals, legumes and seeds. Sample treatment consisted of a simple salting-out-assisted liquid–liquid extraction with no further clean-up. The method provided limits of quantification between 3.2 and 57.7 µg L^?1, recoveries above 80% and precision with RSD lower than 12%. The method was also applied for studying the occurrence of these mycotoxins in market samples of vegetable functional beverages and deoxynivalenol was found in three oat-based commercial drinks.     

Enzymatic cross-linking of β-lactoglobulin in solution and at air-water interface: Structural constraints

Effective and controlled use of cross-linking enzymes in structure engineering of food systems depends on characterization of the favorable conditions for enzyme-substrate complex and the limiting factors for the desired modification. In this respect, we analyzed the susceptibility of bovine β-lactoglobulin (BLG) to enzymatic cross-linking by Trichoderma reesei tyrosinase (TrTyr) and transglutaminase (TG). Changes in BLG molecular structure were determined at pH 6.8, 7.5 and 9.0 before and after high-temperature heat treatment. The conformational change was linked to efficiency of protein cross-linking. BLG was not susceptible to TrTyr without heat treatment. TG, however, induced inter-molecular cross-links at pH 7.5 and 9.0. After the heat treatments, BLG molecules adopted a molten-globule-like conformation. Both of the enzymes were able to form inter-molecular cross-links between heat-denatured BLG molecules. Electrophoretic mobility and broadness of the oligomer bands created by both enzymes on SDS-PAGE gels showed differences which were linked to the availability and number of target amino acid residues. Evidence for intra-molecular cross-linking was obtained. Once adsorbed to air/water interface, BLG formed a viscoelastic surface film which was characterized by surface shear rheology. Application of cross-linking enzymes under a dense layer of BLG molecules at the interface led to decreasing G′ with time. Intra-molecular links were most probably favored against inter-molecular on packed BLG layer leading to constrained molecules. Results in general emphasize the importance of structural and colloidal aspects of protein molecules in controlling inter/intra-molecular bond formation by cross-linking enzymes.     

Mathematical modeling and microbiological verification of ohmic heating of a solid–liquid mixture in a continuous flow ohmic heater system with electric field perpendicular to flow

To ensure sterility of a solid–liquid mixture processed in continuous-flow ohmic systems, the slowest-heating solid particle needs to receive sufficient heat treatment at the outlet of the holding section. We describe herein, the development of a mathematical model for solid–liquid mixtures in a commercial ohmic heater with electric field oriented perpendicular to the flow. The fastest moving particle velocity was identified using over 299 particles and a radio-frequency identification technique, and used as an input to the model for the worst-case heating scenario. Thermal verification was conducted by comparing predicted and measured fluid temperatures at heater and hold tube outlets; the model showed good agreement between calculated and experimental fluid temperatures (P > 0.05) with a maximum error of 0.4 °C. The model predicted a hold tube length of 15.85 m at 134.0 °C process temperature to achieve a target lethal effect at the cold spot of the slowest-heating particle. Using this length of hold tube, microbiological tests were conducted using at least 299 chicken/alginate particles inoculated with Clostridium sporogenes spores per run. These tests showed the absence of viable microorganisms at the target treatment and positive growth when temperatures were below target, thereby verifying model predictions.     

Pesticide determination in tomatoes by solid–liquid extraction with purification at low temperature and gas chromatography

In this work, a simple and low cost method, based on solid–liquid extraction with low temperature purification (SLE–LTP), was optimized and validated for the determination of chlorpyrifos, λ-cyhalothrin, cypermethrin and deltamethrin in tomato samples. The analyses were performed by the GC–ECD and confirmed by the GC–MS. The method requires 4 g of tomato and an extraction mixture (8.0 mL acetonitrile, 0.5 mL water and 1.5 mL ethyl acetate), which was established by mixture experimental design. After optimization, pesticide recovery rates ranged from 79% to 97%, with a standard deviation of less than 5%. The SLE–LTP analytical characteristics were compared very favorably to the matrix solid phase dispersion technique, which used ethyl acetate and Florisil for extraction.     

Simulation of heat transfer for solid–liquid food mixtures in cans and model validation under pasteurization conditions

During processing of canned mixtures of solid–liquid foods, conduction and convection occur simultaneously. The literature lacks in a complete simulation study where a large number of solids are dispersed in the liquid phase, e.g. canned peas. Therefore, the objectives of this study were to determine temperature changes inside a can containing solid–liquid food mixtures. For this purpose, dispersed stationary solids (canned peas in water) in a 2D (axi-symmetrical) configuration were applied. Ansys V11 (Ansys Inc., Canonsburg, PA) was used to solve continuity, energy and momentum equations. For experiments, canned pea samples were prepared in 500 g cans, and heating process was conducted in a retort under pasteurization conditions at ≈98 °C. Temperature changes were measured using needle type thermocouples, and simulation results were validated against experimental data. This study is expected to be a significant contribution to the literature for further optimization studies and to form basis of an industrial project to improve canning process of solid–liquid mixtures.     

Release of active compounds from agar and agar–gelatin films with green tea extract

Active biodegradable films based on agar and agar–fish gelatin were developed by the incorporation of green tea aqueous extract to the film forming solution. The effect of the partial replacement of agar by fish skin gelatin as well as the addition of the green tea extract on the physical properties of the resultant films was evaluated. Special attention was given to the release of antioxidant and antimicrobial compounds from the agar film matrices with and without gelatin. Agar–gelatin films were less resistant and more deformable than agar films. The inclusion of green tea extract decreased tensile strength and elongation at break in both agar and agar–gelatin films. Water vapour permeability and water resistance was not affected either by the replacement of agar by gelatin or the addition of green tea extract, but the water solubility noticeably increased in the films containing green tea extract. The presence of gelatin in the agar–green tea matrix film hindered the release of total phenolic compounds, catechins and flavonols in water. As a consequence, the antioxidant power released by the films was lower in the case of films containing gelatin. However, the antimicrobial activity of the films was not affected by the presence of gelatin.     

Portuguese wild mushrooms at the “pharma–nutrition” interface: Nutritional characterization and antioxidant properties

The search for foods that might improve health or reduce disease risk, has been progressively gaining interest. Mushroom could be examples of these foods, presenting the additional advantage of being recognized as a delicacy. This feature might place mushrooms in the pharma–nutrition interface. Herein, eight different mushroom species were characterized in terms of nutrients (proteins, carbohydrates, fat, individual sugars, fatty acids) and bioactive compounds (tocopherols, carotenoids, organic acids and phenolic compounds) with recognized antioxidant properties. These medicinal properties are often related with the antioxidant potential presented by mushroom extracts. Boletus regius was the species with the highest levels of carbohydrates (88.79 g/100 g dw) and PUFA (56.55%), bioactive compounds such as tocopherols (763.80 μg/100 g dw), citric acid (3.32 g/100 g dw) and phenolic compounds (23.49 mg/100 g dw), including two chrysin derivatives, presenting also the highest antioxidant activity. The identified bioactive compounds might be used as nutraceuticals to prevent chronic diseases related with oxidative stress. Furthermore, all tested species are edible, and could be incorporated directly in diet acting as functional foods.     

Response surface modelling of lead pre-concentration from food samples by miniaturised homogenous liquid–liquid solvent extraction: Box–Behnken design

In this study, a new method called miniaturised homogenous liquid–liquid extraction, followed by graphite furnace atomic absorption spectrometry, was developed for the extraction and determination of lead from food samples. The procedure was based on the fast extraction of lead from an acetic acid sample solution into 0.5 mL chloroform, as an extraction solvent. After adding water into the mixture, the extracting solvent phase immediately formed a distinct water-immiscible phase below the vial, which could easily be separated, evaporated and re-dissolved in 1.0 mL nitric acid 0.1 mol L⁻¹ for further analysis. The effects of various experimental parameters in extraction step were studied using two optimisation methods, one variable at a time and Box–Behnken design. The results showed that the amount of salt and extraction time did not have effect on the extraction efficiency. Therefore, a three-level Box–Behnken experimental design with three factors, which combined the response surface modelling, was used to optimise lead extraction. Three independent variables, including pH of solution (ranging from 6.5 to 10.5), concentration of dithizone as chelating agent (ranging from 0.05 to 0.5 μg L⁻¹) and extracting solvent volume (ranging from 300 to 900 μL) were respectively coded as pH, D and V at three different levels (−1, 0 and 1). In this study, the optimum condition was determined at pH 8.4, a volume of chloroform at 0.45 mL, and concentration of dithizone at 0.5 μg L⁻¹. Under the optimum condition, the limit of detection (LOD) was 0.05 μg L⁻¹. Furthermore, the relative standard deviation of the ten replicate was <5.0%. The developed procedure was applied to the extraction and determination of lead in the food samples.     

Determination of phenolic compounds in olive oil: New method based on liquid–liquid micro extraction and ultra high performance liquid chromatography-triple–quadrupole mass spectrometry

A novel analytical approach has been performed and evaluated for the identification and quantification of phenolic compounds (phenolic alcohols, secoiridoid derivates, lignans, flavonoids, phenolic acids and aldehydes) which can be found in both virgin olive oil (VOO) and extra virgin olive oil (EVOO). An improved liquid–liquid micro extraction (LLME) method combining with ultra high performance liquid chromatography (UHPLC) coupled to electrospray ionization source (ESI) and tandem mass spectrometry (MS/MS) in Dynamic Multiple Reaction Monitoring (DMRM) mode has been developed, reducing the amount of sample, reagents and time consumed. The proposed methodology was applied to standard solutions, and the quality control parameters obtained were compared with those achieved in spiked refined olive oil (SROO). Generally, these parameters showed lower values in SROO than in standard solutions. Matrix effect, recovery and process efficiency have been studied using SROO. The recoveries were around 90% and the process efficiency of the whole method was higher than 80% for most of the phenolic compounds studied. Examination of these parameters revealed that work straight in the olive oil matrix, which is closer to behave as a real sample, provides better results. The applicability and reliability of this methodology have been confirmed using real samples.     

Dispersive liquid–liquid microextraction combined with sweeping micellar electrokinetic chromatography for the determination of some neonicotinoid insecticides in cucumber samples

A rapid, simple and sensitive method has been developed for the analysis of some neonicotinoid insecticides in cucumber samples by using dispersive liquid–liquid microextraction (DLLME) coupled with sweeping in micellar electrokinetic chromatography (MEKC). Under optimised conditions, the enrichment factors were achieved in the range from 4000 to 10,000. The linearity of the method was in the range from 2.7 to 200 ng g⁻¹ for thiacloprid, acetamiprid and imidacloprid, and in the range from 4.0 to 200 ng g⁻¹ for imidaclothiz in cucumber samples, with the determination coefficients (r²) ranging from 0.9924 to 0.9968. The limits of detection (LODs, S/N = 3) ranged from 0.8 to 1.2 ng g⁻¹. The relative standard deviations (RSDs) at the concentration levels of 10.0 and 50.0 ng g⁻¹ each of the neonicotinoid insecticides in cucumber samples varied from 3.8% to 6.3%. The developed method has been successfully applied to the analysis of the neonicotinoid insecticides in cucumbers with a satisfactory result.