Björn Bergenståhl

Surface composition of spray-dried milk protein-stabilised emulsions in relation to pre-heat treatment of proteins.

Several important technical properties of spray-dried food powders depend on particle-liquid interactions (e.g. wettability, dispersability) and particle-particle interactions (e.g. flowability). It can be assumed that the chemical composition of the surface layer of the particles to a large extent determine these properties. The present study has been aimed to investigate the relation between the surface composition of spray-dried milk protein-stabilised emulsions and pre-heat treatment of the proteins. Solutions of WPC were heat-treated at low (60-90 degrees C) and high (140 degrees C) temperature and the degree of denaturation was determined, prior to the preparation of emulsions with rapeseed oil. The surface composition of the dry powders were established by using ESCA (electron spectroscopy of chemical analysis). The emulsions were characterised by droplet size distribution before spray drying and after dissolution of the powders. Also free fat extractions and estimations of wettability (dissolution rates) were performed. The powder surface coverage of protein decreased with increasing degree of protein denaturation before the emulsification, whereas the emulsion droplet size increased both before spray drying and after reconstitution of powders. The free fat extraction as well as the dissolution rate, whereof the latter decreased with increasing surface fat coverage, correlated well with the fat coverage of the powder surface.

The surface composition of spray-dried protein—lactose powders

Abstract The surface composition of spray-dried mixtures of lactose-protein and lactose-glycine were estimated by means of electron spectroscopy for chemical analysis (ESCA). The results show that even with a low concentration of protein (0.01 wt.%) in the solution to be dried, protein starts to appear on the surface of the powder. At a protein/lactose ratio of 1/99 the protein starts to dominate the powder surface. At a protein/lactose ratio of 20/80, about 70% of the surface is covered by protein. The results are similar for the proteins sodium caseinate and bovine albumin. The spray drying of mixtures of lactose and glycine gives a different result. In this case, the surface composition of the powder reflects the composition of the mixture to be dried. The surface tensions of the solutions show that the proteins have a higher surface activity than lactose, since even a small amount of protein added to a lactose solution lowers the surface tension considerably. Glycine affects the surface tension only to a minor extent. These results show that the composition of the air-water interface of the drying droplets is reflected in the surface composition of the dried powder. In addition, scanning electron micrographs show that the changes in the powder structure when protein is added to the solution are associated with the presence of protein on the surface. When the surface coverage of protein increases, dents start to appear in the particles. The powders made from lactose-glycine solutions are highly agglomerated regardless of the glycine concentration.

Spray-drying of trypsin — surface characterisation and activity preservation

In the present study trypsin mixed with various carbohydrates, i.e. lactose, sucrose, mannitol, alpha-cyclodextrin and dextrin, was spray-dried in order to investigate the effects of spray-drying on this enzyme, with particular emphasis on the effects of interactions between trypsin and the surface formed during spray-drying. The protein was strongly over-represented at the surface of the powder particles, the surface coverage ranging from 10 to 65%, depending on the amount of trypsin in the solids (0.2-5%). This indicates that the protein adsorbs at the air/liquid interface of the spray-droplets, and that this surface is also largely preserved after drying. The surface concentration of protein in the spray-dried powders could be controlled by adding a surfactant to the mixture before drying, since the surfactant adsorbs preferentially at the air/liquid interface of the spray droplets, thus expelling protein from the surface. In general, the residual activity of trypsin in these non-optimised formulations was 90% or higher, and in no case less than 82%. It was found that the loss of activity could partly be explained by inactivation of the protein adsorbed at the surface. For mannitol and sucrose, however, the level of inactivation was higher than could be explained by surface inactivation alone, and additional mechanisms must also be considered.

Spray-dried whey protein/lactose/soybean oil emulsions. 1. Surface composition and particle structure

Abstract Emulsions made of whey protein, lactose and soybean oil were spray-dried and the chemical surface composition of the dried powders estimated by electron spectroscopy for chemical analysis. In particular, the ability of whey protein to encapsulate fat was highlighted. Additionally, the structure of the spray-dried powder particles was studied by scanning electron microscopy. The powders were examined after storage in both dry and humid atmospheres (relative humidity 75%, 4 days). It was found that the ability of whey protein to encapsulate soybean oil is rather low compared with sodium caseinate, with a large part of the powder surface covered by fat after spray-drying. After storage in humid atmosphere there is a release of encapsulated oil onto the powder surface in most cases, and an increase in fat coverage. The release offat onto the powder surfaces causes the particle structure to change dramatically for powders containing a critical amount of lactose. Such powders agglomerate and lose structure completely. In comparison, powders containing no lactose storage under humid conditions also cause a release of fat onto the powder; however, in this case particle structure remains intact. Powders containing only a small amount of lactose, up to ~25% of emulsion dry weight, do not exhibit the release of fat onto the powder surfaces after storage under humid conditions and the structure of these powder particles does not change. The presence of lactose in whey protein-stabilized emulsions, however, does not increase fat encapsulation by whey protein, as reported earlier for sodium caseinate-stabilized emulsions that were spray-dried. During spray-drying of whey protein/lactose solutions there is a strong overrepresentation of surface-active whey protein on the powder surface. Whey protein coverage increases even further when the powders are stored under humid conditions, also making them lose structure.

Fat encapsulation in spray-dried food powders

The surface composition of spray-dried sodium caseinate/lactose emulsions having different oil phases were estimated using electron spectroscopy for chemical analysis (ESCA), and the particle structure was studied using scanning electron microscopy (SEM) both before and after storage under humid conditions. After spray-drying, powders in which the oil phases consisting of fats with intermediate melting points, such as hardened coconut oil and butter fat, had the highest surface coverage of fat, approximately 34%. The powder with soybean oil as the oil phase had a surface coverage of fat of approximately 15%. The high-melting hardened rapeseed oil was almost completely encapsulated after spray-drying. After storage in a humid atmosphere, fat was released onto all the powder surfaces (surface fat after storage, between 50–65%) except for those with hardened rapeseed oil in which the fat remained encapsulated. These observations are consistent with the powder structure observed by SEM. The surface composition estimated by ESCA for spray-dried sodium caseinate/lactose-containing emulsions with different amounts of soybean oil and a constant lactose/sodium caseinate ratio showed an almost completely encapsulated oil-phase after drying. Storage of these powders in a humid atmosphere leads to a release of fat onto the powder surface even if the soybean oil content is low (1% of the dry weight). Powders made from soybean oil emulsions with sodium caseinate alone exhibit a much lower degree of encapsulation than in the system where lactose is present.

Interactions between iron, phenolic compounds, emulsifiers, and pH in omega-3-enriched oil-in-water emulsions

The behavior of antioxidants in emulsions is influenced by several factors such as pH and emulsifier type. This study aimed to evaluate the interaction between selected food emulsifiers, phenolic compounds, iron, and pH and their effect on the oxidative stability of n-3 polyunsaturated lipids in a 10% oil-in-water emulsion. The emulsifiers tested were Tween 80 and Citrem, and the phenolic compounds were naringenin, rutin, caffeic acid, and coumaric acid. Lipid oxidation was evaluated at all levels, that is, formation of radicals (ESR), hydroperoxides (PV), and secondary volatile oxidation products. When iron was present, the pH was crucial for the formation of lipid oxidation products. At pH 3 some phenolic compounds, especially caffeic acid, reduced Fe(3+) to Fe(2+), and Fe(2+) increased lipid oxidation at this pH compared to pH 6. Among the evaluated phenols, caffeic acid had the most significant effects, as caffeic acid was found to be prooxidative irrespective of pH, emulsifier type, and presence of iron, although the degrees of lipid oxidation were different at the different experimental conditions. The other evaluated phenols were prooxidative at pH 3 in Citrem-stabilized emulsions and had no significant effect at pH 6 in Citrem- or Tween-stabilized emulsions on the basis of the formation of volatiles. The results indicated that phenol-iron complexes/nanoparticles were formed at pH 6.

Spray-dried whey protein/lactose/soybean oil emulsions. 2. Redispersability, wettability and particle structure

In the present paper redispersion and wettability experiments of spray-dried whey protein-stabilized emulsions are presented. Emulsion droplet size after redispersion gives information about eventual coalescence between emulsion droplets in the powder matrix during drying or storage, resulting in an increase in emulsion droplet size after redispersion. Results from redispersion experiments are combined with previously presented knowledge about powder surface composition and particle structure to elucidate internal processes in the powder matrix and external processes on the powder surface during drying and storage of whey protein powder. The results show that with addition of lactose to whey protein-stabilized emulsions, emulsion droplet structure remains intact in the powder matrix during drying since the emulsion droplet size in the redispersed spray dried emulsion is unchanged. In the absence of lactose there is a growth in emulsion droplet size after redispersion of the spray-dried whey protein-stabilized emulsion, showing that a coalescense of emulsion droplets occurs during the drying or redispersion process. Storage of the whey protein-stabilized powders in a humid atmosphere (relative humidity 75%, 4 days) induces changes in some powders. When the powder contains a critical amount of lactose there is a remarkable increase in emulsion droplet size after redispersion of humid stored powders compared with the emulsion before drying and with the redispersed dry stored powder. In addition, there is a release of encapsulated fat after humid storage of lactose-containing powders detected by electron spectroscopy for chemical analysis. For powders which do not contain any lactose there is no increase in emulsion droplet size after storage in a humid atmosphere compared with the redispersed dry stored emulsion. Addition of only a small amount of lactose prevents coalescence of emulsion droplets and the subsequent increase in droplet size during drying. If the lactose content is kept rather low neither an effect on the droplet size after storage under humid conditions nor a release of fat onto powder surfaces is detected. Furthermore, wettability of the spray-dried whey protein-stabilized emulsions by water is presented. It is concluded that it is beneficial to wettability in water to have as high a coverage of lactose on the powder surface as possible. In addition, a review of particle structure for powders of various composition is presented.

Sintering of fat crystal networks in oil during post-crystallization processes

Several foods contain semi-solid fats that consist of solid crystals dispersed in a liquid oil. In oil-continuous margarine, butter, and chocolate, fat crystals determine properties such as consistency, stability against oiling-out, and emulsion stability. Trends toward foods with less fat and/or less saturated fat create a need for understanding and controlling the properties of fat crystal dispersions. Fat crystals form a network in oil due to mutual adhesion. One source of strong adhesion is formation of solid bridges (sintering), which has been studied in this work through sedimentation and rheological experiments. Results indicate that sintering may be created by crystallization of a fat phase with a melting point between that of the oil and the crystal. Generally speaking, β′ crystals were sintered by β′ fat bridges, favored by rapid cooling, and β crystals by β fat bridges, favored by slow cooling. The existence of the same polymorphic form of the crystal and bridge indicated that solid bridges, rather than bridges formed by small crystal nuclei, were formed. A maximum in sintering ability for an optimal sintering fat concentration occurred due to competition between bridge formation and other crystallization processes. Some emulsifiers influenced the sintering process. For example, monooolein made it more pronounced, while technical lecithin had the opposite effect.

The effect of rheological behaviour of a topical anaesthetic formulation on the release and permeation rates of the active compound.

The objective of this study was to investigate the possibility of developing a topical cream that allows maximum release rate of the active compound while having suitable consistency, i.e., sufficient apparent plasticity. A submicron (o/w) emulsion containing a model compound was investigated in the presence and absence of different polymers: sodium carboxymethylcellulose (CMC), Carbopol 934P (C934), polyethylene glycol 400 (PEG400) and polyethylene glycol 4000 (PEG4000). Various concentrations of the polymers were used in order to produce different rheological behaviours. The amount of drug passing through the membrane was measured as a function of time, using static diffusion cells with either Silastic sheeting 500-1 or guinea pig skin as membrane. The emulsion without polymer was used as reference. Rheological measurements were performed, giving the viscosity and the apparent yield stress of the formulations. Furthermore, theoretical values for diffusion coefficients and diffusion pathways were estimated and compared with the experimental data to discuss different diffusion models. Gelling polymers have been shown to produce an increase in the macroviscosity, thus inhibiting the diffusion of the oil droplets in the formulation without affecting the molecular diffusion. However, we suggest that when a compound of limited solubility is emulsified, the intact oil droplets contribute to the transport of the compound through the formulation. Thus, both release and permeation rates are decreased as the apparent yield stress, i.e., the macroviscosity of the formulation, is increased sufficiently by addition of gelling polymers.

Inhibition of Ostwald ripening in local anesthetic emulsions by using hydrophobic excipients in the disperse phase

The stability of submicron emulsions of different local anesthetic/analgesic substances was investigated in the presence and absence of different hydrophobic excipients (ripening inhibitors). Ostwald ripening was believed to be the underlying mechanism for the instability of these emulsions. In the absence of ripening inhibitors, the mean droplet size of the emulsions increased from 100 nm to about 4-5 microm within an hour of manufacture. The addition of a small amount of a second component of lower solubility to the disperse phase decreased the rate of Ostwald ripening, producing good stability of the emulsions. The efficiency of the ripening inhibitors was directly proportional to their solubility in the disperse phase, i.e. the water. The lower the solubility, the more effective the stabilization of the emulsions. The experimentally observed rates of increase in droplet size in the emulsions were closely correlated with those predicted according to the Liftshitz-Slezov-Wagner (LSW) theory.