Colon-specific drug delivery: Influence of solution reticulation properties upon pectin beads performance.

In this study, pectinate gel beads were produced by ionotropic gelation method with different solutions of cross-linking agents and ketoprofen was entrapped as model drug. The influence of these formulation parameters was investigated upon bead properties and upon their performance to target the colon. Zinc pectinate beads obtained with 10% of counter-ions solution at pH 1.6 exhibited the strongest gel network due to "egg-box" dimmer formation helped by hydrogen bonding. Furthermore the gel network formed at low pH was arranged in a compact three-fold conformation. Thus, this matrix structure in enteric capsules induced the lowest drug release in the upper gastro-intestinal tract (pH 1.2 following by pH 7.4). However ketoprofen release occurred specifically in the colon thanks to the presence of pectinolytic enzymes and the release rate can be modulated by the counter-ion concentration during the reticulation process. Therefore this approach using pectinate beads is very promising as efficient carrier for specific delivery of drug into the colon, after oral administration.

Functional properties of edible agar-based and starch-based films for food quality preservation.

Edible films made of agar (AG), cassava starch (CAS), normal rice starch (NRS), and waxy (glutinous) rice starch (WRS) were elaborated and tested for a potential use as edible packaging or coating. Their water vapor permeabilities (WVP) were comparable with those of most of the polysaccharide-based films and with some protein-based films. Depending on the environmental moisture pressure, the WVP of the films varies and remains constant when the relative humidity (RH) is >84%. Equilibrium sorption isotherms of these films have been measured; the Guggenheim-Anderson-de Boer (GAB) model was used to describe the sorption isotherm and contributed to a better knowledge of hydration properties. Surface hydrophobicity and wettability of these films were also investigated using the sessile drop contact angle method. The results obtained suggested the migration of the lipid fraction toward evaporation surface during film drying. Among these polysaccharide-based films, AG-based film and CAS-based film displayed more interesting mechanical properties: they are transparent, clear, homogeneous, flexible, and easily handled. NRS- and WRS-based films were relatively brittle and have a low tension resistance. Microstructure of film cross section was observed by environmental scanning electron microscopy to better understand the effect of the structure on the functional properties. The results suggest that AG-based film and CAS-based films, which show better functional properties, are promising systems to be used as food packaging or coating instead of NRS- and WRS-based films.

Modified arabinoxylan-based films. Part B. Grafting of omega-3 fatty acids by oxygen plasma and electron beam irradiation.

Arabinoxylans (AXs) are byproducts of the cereal milling industry. To obtain high-value products, AXs have been used as a film-forming agent. Hence, AX-based films are poor water vapor barriers. The objectives of this study were to graft omega-3 (omega3) fatty acids onto AX polymeric chains by using two new technologies: cold plasma and electron beam (EB) irradiation. Results show that the surface hydrophobicity of the modified films is higher than that of a waxy coating or a low-density polyethylene (LDPE) film. In addition, FTIR spectroscopy analysis reveals vibration bands attributed to new chemical functions. Finally, a decrease in water vapor permeability (WVP) is obtained for the film treated with the alpha-linolenic acid-rich oil. This result could be explained by a better diffusion of this shorter polyunsaturated fatty acid into the AX network. Linseed oils provide better barrier properties and a higher surface hydrophobicity than oils extract from marine oils. Edible oils were chosen for edible application of these films to retard moisture transfers in stuffed biscuits.

Influence of physicochemical interactions between amylose and aroma compounds on the retention of aroma in food-like matrices.

In food matrices, where starch is often used as a gelling or texturing agent, the occurrence of amylose-aroma complexes and their effect on the release of aroma compounds are difficult to determine. Indeed, thick or gelled systems are known to reduce the diffusion rate of flavor molecules, resulting in an increase of retention. Moreover, interactions between aroma compounds and matrix components might increase the retention of aroma compounds. The complexing behavior of three aroma compounds with amylose was studied by DSC and X-ray diffraction to determine the relative importance of these two factors. Their interaction properties were different: two of them formed complexes, and the third did not. These aroma compounds were added in food matrices containing different starches that induced different textures. Their retention was studied by static headspace analysis. The retention of aroma compounds appeared to depend on the amylose/amylopectin ratio of starch, both from the formation of complexes and by a viscosity effect.

Retention of aroma compounds in starch matrices: competitions between aroma compounds toward amylose and amylopectin.

The retention of three aroma compounds-isoamyl acetate, ethyl hexanoate, and linalool--from starch-containing model food matrices was measured by headspace analysis, under equilibrium conditions. We studied systems containing standard or waxy corn starch with one or two aroma compounds. The three studied aroma compounds interact differently: ethyl hexanoate and linalool form complexes with amylose, and isoamyl acetate cannot. However, in systems containing one aroma compound, we observed with both starches a significant retention of the three molecules. These results indicate that amylopectin could play a role in the retention of aroma. In systems containing two aroma compounds in a blend, the retentions measured for isoamyl acetate and for linalool were either equal to or less than those in systems where they were added alone. This phenomenon was attributed to competition between aroma compounds to bind with starch. The retention of aroma compounds blended in starch-based systems gave us additional information which confirmed that interactions occur not only with amylose but also with amylopectin.

Arabinoxylan-lipid-based edible films and coatings. 3. Influence of drying temperature on film structure and functional properties.

This work is a contribution to better knowledge of the influence of the structure of films obtained from emulsions based on arabinoxylans, hydrogenated palm kernel oil, and emulsifiers on their functional properties. The sucrose esters (emulsifiers) have a great effect on the stabilization of the emulsified film structure containing arabinoxylans and hydrogenated palm kernel oil. The structure and stability of the emulsion during drying strongly affect barrier and mechanical properties of films. The higher are creaming and coalescence phenomena in films, the lower is the water vapor permeability. Emulsion destabilization is favored by high drying temperature and tends to give films having a "bilayer-like" structure, which tends to improve the functional properties of arabinoxylans-based edible films.

Transfer of aroma compounds through the lipidic-aqueous interface in a complex system.

The transfer kinetics of aroma compounds from the aqueous phase to the lipidic phase (miglyol) and from miglyol to the aqueous phase have been studied in the presence or absence of a protein, beta-lactoglobulin, and at different pH values. In the presence of beta-lactoglobulin, the transfer at the interface from the aqueous to the lipidic phase decreases, with a greater effect of the presence of the protein at pH 3 than at pH 6. This barrier effect of the protein plays a role in the transfer of the aroma compounds between the different phases of the matrix.

Arabinoxylan-lipids-based edible films and coatings. 2. Influence of sucroester nature on the emulsion structure and film properties.

This work is a contribution to better knowledge of the influence of the structure of films on their functional properties obtained from emulsions based on arabinoxylans, hydrogenated palm kernel oil (HPKO), and emulsifiers. The sucroesters (emulsifiers) have a great effect on the stabilization of the emulsified film structure containing arabinoxylans and hydrogenated palm kernel oil. They improve the moisture barrier properties. Several sucroesters having different esterification degrees were tested. Both lipophilic (90% of di and tri-ester) and hydrophilic (70% of mono-ester) sucrose esters can ensure the stability of the emulsion used to form the film, especially during preparation and drying. These emulsifiers confer good moisture barrier properties to emulsified films.

Competitive binding of aroma compounds by beta-cyclodextrin.

Retention of six aroma compounds has been studied after dehydration of ternary mixtures of aroma water and beta-cyclodextrin. A maximal retention of a mole of aroma per mole of beta-cyclodextrin has been observed for five of the aroma compounds, whereas retention of benzyl alcohol can be twice as high. Retention of a mixture of aroma compounds has also been studied. It has been noted that when volatile compounds compete for the same binding sites on beta-cyclodextrin, ethyl hexanoate, 2-methylbutyric acid, and benzyl alcohol are, respectively, better retained than ethyl propionate, hexanoic acid, and hexanol. Preferential retention observed with esters can be simply explained by their difference of physicochemical properties, but for the acids and alcohols a study at the molecular scale has been necessary. The better retention of 2-methylbutyric acid can be explained by differences in the nature of interaction between the acids and their carrier. At least selectivity of retention noted for the alcohol could be due to a difference in the location of the guest and also a difference in the number of aroma molecules that can be bound per polysaccharide molecule.

Aroma compound sorption by oak wood in a model wine.

Oak wood used for wine barrels was immersed into a model wine containing eight aroma compounds (e.g., aromatic and terpene alcohols, ethyl esters, and aldehyde), for which activity coefficients in water and model wine were determined using the mutual solubility measurement. A mass balance of these volatiles considering their reactivity in model wine was established. For most of the studied aroma compounds, and mainly for linalool and ethyl octanoate, a sorption behavior into wood was reported for the first time. This phenomenon was selective and could not be related to the solubilities in model wine and hydrophobicities of the studied aroma compounds, suggesting that acid-base and polar characteristics of wood were more involved in this sorption mechanism. This study has also shown that the level of sorption is a function of the ratio of wood surface area/solution volume.

Influence of the food matrix structure on the retention of aroma compounds.

The retention of the aroma compounds in a multicomponent medium like the food matrix is influenced by their affinity with the protein when lipid is present at a low level (0.5%). The effect of the structure of the media is also studied by using two media with the same composition; one was emusified, and the other was not. Among the studied aroma compounds, 2-nonanone and isoamyl acetate present opposite behaviors: the volatility of isoamyl acetate is not affected by the change of the medium structure whereas that of 2-nonanone increases. The decrease of retention of 2-nonanone in an emulsified system would be due to a modification of the fixation site for this compound on the protein or to a competition between the lipid and the aroma compound while the protein is adsorbed at the lipid-water interface.

Influence of the physical state of water on the barrier properties of hydrophilic and hydrophobic films.

Water transfer through different films, as a function of the physical state of water in contact with the film, the relative humidity difference, and the water vapor pressure difference, was investigated. The films were two synthetic packagings (hydrophobic polyethylene and hydrophilic cellophane) and an edible film. The physical state of water affects water sensitive films, such as cellophane, inducing a higher liquid water transfer due to interactions with the polymer. For hydrophobic polymers, such as polyethylene, neither the physical state of water nor the relative humidity has an influence on the water permeability. In complex system, such as an edible film composed of hydrophilic particles dispersed in a lipid phase, barrier efficiency is influenced by the continuous hydrophobic phase but could also be affected by the physical state of water due to the presence of hydrophilic compounds.

Interactions between aroma and edible films. 1. Permeability Of methylcellulose and low-density polyethylene films to methyl ketones.

This work contributes to the study of aroma transfers through edible and plastic packaging films. Permeability, sorption, and diffusivity of three methyl ketones (2-heptanone, 2-octanone, and 2-nonanone) in and through low-density polyethylene and methylcellulose-based edible films have been determined. Permeability was measured using a dynamic method coupled with a gas chromatograph. The methyl ketone permeability of polyethylene films mainly depends on diffusivity of the penetrant in the polymer. In the case of 2-heptanone, a saturation of the polymer network is observed at high vapor concentrations. The formation of clusters could take place when concentrations are higher in the vapor phase. Physicochemical interactions between aroma compounds and components of the methylcellulose-based film induce structural changes such as plasticization. Therefore, the diffusion step depends on the aroma concentration differential, and permeability is essentially driven by the sorption.

Transfer of aroma compounds in water-lipid systems: binding tendency of beta-lactoglobulin.

Interactions of volatile aroma compounds with protein in aqueous solutions, especially whey proteins, have received significant attention in recent years. This work attempts to improve our understanding of the mass transfer in multiphasic systems, such as emulsions at the lipid-water interface, and to reveal the role of beta-lactoglobulin in the release rate of solutes. For this purpose the rotating diffusion cell has been used. From a practical point of view it enables evaluation of the transfer through the aqueous phase, through the oil and the interfacial transfer. The effect of beta-lactoglobulin, medium pH, and solute concentration has been investigated. Benzaldehyde and 2-nonanone have been studied, and miglyol has been chosen as an oil phase. It has been demonstrated that mass transfer has a rate-limiting step, which depends on physicochemical parameters such as hydrophobicity of the volatile, diffusion and partition coefficients, and rheological properties of the aqueous phase.

Qualitative and quantitative evaluation of mono- and disaccharides in D-fructose, D-glucose and sucrose caramels by gas-liquid chromatography-mass spectrometry. Di-D-fructose dianhydrides as tracers of caramel authenticity.

The monosaccharide (D-fructose, D-glucose, anhydrosugars), disaccharide (glucobioses) and pseudodisaccharide (di-D-fructose dianhydrides) content of D-fructose, D-glucose and sucrose caramels has been determined by gas-liquid chromatography-mass spectrometry (GLC-MS) of their trimethylsilyl (TMS) or TMS-oxime derivatives. The chromatographic profiles revealed significant differences in the disaccharide/pseudodisaccharide distribution depending on the caramel source: a D-fructose caramel contains prominent proportions of di-D-fructose dianhydrides, a D-glucose caramel mainly D-glucobioses, and a sucrose caramel similar proportions of both disaccharide/pseudodisaccharide series. It is noteworthy that di-D-fructose dianhydrides are found in all three types of caramels and might then be used as specific tracers of the authenticity of caramel, i.e., a product resulting from the controlled heat treatment of food-grade carbohydrates for use as food additives.

Interphase Transport of Benzoic Acid in Emulsions.

The kinetics of transport of benzoic acid in triglyceride-in-water emulsions stabilized by Tween 80 was measured by a continuous flow kinetic apparatus. The determination of the liquid-liquid partitioning of the solute in two-phase systems enabled estimation of the retention of benzoic acid by the triglycerides and the micellar solution and calculation of the solute theoretical distribution in emulsions. The initial rates of release of benzoic acid from 2 to 5 mmol m-2 s-1 were found proportional to the initial concentration of benzoic acid in the emulsions. Copyright 1998 Academic Press.

Influence of water on the mobility of small molecules dispersed in a polymeric system.

The rotational mobility of paramagnetic solutes dispersed in partially hydrated macromolecules (proteins, polysaccharides, synthetic polymers) was measured using Electron Spin Resonance. A critical minimum amount of water was observed to be necessary for these molecules to reach a level of mobility of the same order as in dilute solutions. This amount of water depended on the size of the diffusing solute and on the microporosity of the macromolecule. Above this critical moisture range, a progressive increase of the proportion of mobile solute occurred over a hydration range determined by the size of the diffusing solute. At the same time, the rotational diffusivity of the mobile solute increased linearly with water content. The mobilization pattern of spin-labelled side chains of caseinates was observed to be similar to that of the solute. Results are discussed with reference to free volume theory.

Patterns of aeration in a solid substrate fermentor through the study of the residence time distribution (RTD) of a volatile tracer.

The injection of a volatile tracer in the gas flow allowed to describe the residence time distribution (RTD) in a solid substrate reactor. The chromatographic analysis of Dirac impulses of acetone led to identify the fermentor as a first-order rate system. The evolution of the time constant (lambda) of the system versus the gas flow rate gave a flow rate value that permitted a homogeneous aeration of the fermentor.