Glycation of caseinate by fructose and fructo‐oligosaccharides during controlled heat treatment in the ‘dry’ state

This paper investigates the controlled heating of caseinate with reducing sugars to produce glycoproteins with improved functionality for use in food. Caseinate was combined with inulin, fructose and a mixture of both inulin and fructose and the lyophilisates heated at a controlled water activity for up to 48 h. Caseinate–glucose and caseinate–lactose glycoconjugates were prepared for comparison. Conjugation between caseinate and fructose occurred readily at 60 °C and 67% relative humidity, modifying up to 75% of the lysine groups of caseinate within 48 h. Moreover, when reconstituted, the caseinate–fructose glycoconjugates showed a dramatic increase in viscosity relative to caseinate ‘dry’‐heated alone. At 80% relative humidity the reaction proceeded so rapidly that gels containing darkly coloured particulate matter were formed. Incorporation of inulin prevented formation of caseinate–fructose gels, and minimised browning development while still producing moderately viscous solutions. Based on ¹³C‐NMR, SDS‐PAGE and electron microscopy techniques, mechanisms by which inulin modified the reaction have been proposed. Copyright © 2005 Society of Chemical Industry     

An assessment of the texture of acidified sodium caseinate gels with added inulin using response surface methodology

This work evaluated the effect of inulin concentration (0–6.0% w/w) on the mechanical properties and microstructure of gels composed of sodium caseinate (CN) (1.5–6.5% w/w) at pH 4.6. Inulin did not statistically affect the elastic modulus and rupture properties of the studied gels but affected the nonlinear mechanical behaviour. Samples with higher inulin concentrations (6% w/w) presented strain‐weakening deformation behaviour, whilst gels with lower inulin concentrations were strain hardening. The presence of inulin resulted in a more closed‐pores network. Gel deformability increased as CN concentration was enhanced, reaching a maximum of 0.60 at 5.58% (w/w) CN, but was not affected by inulin concentration.     

Rheological,gelling and emulsifying properties of a glycosylated and cross‐linked caseinate generated by transglutaminase

The impacts of oligochitosan glycosylation and cross‐linking on some properties of a commercial caseinate were investigated in this study. The glycosylated and cross‐linked caseinate with glucosamine content of 4.74 g kg^?1 protein was generated by transglutaminase (TGase) and oligochitosan at pH 7.5 and 37 °C, with fixed substrate molar ratio of 1:3 (acyl donor to glucosamine acceptor), caseinate content of 50 g L^?1, TGase of 10 kU kg^?1 protein and reaction time of 3 h, respectively. In comparison with the caseinate, the glycosylated and cross‐linked caseinate had decreased reactable amino groups (0.58 vs. 0.51 mol kg^?1 protein), higher apparent viscosity, decreased emulsifying activity index (about 14.5%) and statistically unchanged emulsion stability index (92.6 vs. 90.5%). Based on the mechanical spectra of the acid‐induced gels, the glycosylated and cross‐linked caseinate showed shorter gelation time (95 vs. 200 or 220 min) than the caseinate or cross‐linked caseinate. The gels prepared from the glycosylated and cross‐linked caseinate also had enhanced hardness, springiness and cohesiveness. The results indicated that TGase‐mediated oligochitosan glycosylation and cross‐linking has the potential to obtain new protein ingredients.     

Assessment of Cross-Linking in Combined Cross-Linked Soy Protein Isolate Gels by Microbial Transglutaminase and Maillard Reaction

ABSTRACT:  Soy protein isolate (SPI) gels were produced using single cross-linking agents (SCLA) of microbial transglutaminase (MTG) via incubation for 5 or 24 h (SCLA-MTG). When powdered SCLA-MTG gels were heated for 2 h with ribose (R2) (2 g/100 mL), dark brown gels were formed, and these were designated as combined cross-linking agent (CCLA) gels: MTG5(R2) and MTG24(R2). The results showed that the levels of Maillard-derived browning and cross-links of MTG5(R2) and MTG24(R2) gels were significantly ( P  < 0.05) lower than a control gel produced without MTG (SCLA-R2) even though the percentage of ribose remaining after heating of these gels was similar, indicating that a similar amount of ribose was consumed during heating. ɛ-(γ-glutamyl)lysine bonds formed during incubation of SPI with MTG may have reduced the free amino group of SPI to take part in the Maillard reaction; nevertheless, ribose took part in the Maillard reaction and initiated the Maillard cross-linkings within the CCLA gels.     

A study on the preparation and some functional properties of a cross‐linked casein–gelatin composite by a microbial transglutaminase

A microbial transglutaminase (TGase) was used in this work as biocatalyst to prepare a cross‐linked casein–gelatin composite, a modified protein product with 4‐hydroxyproline about 41 mg g^?1 peptides. Some cross‐linking conditions such as total protein content, the ratio of caseinate to gelatin and original pH were fixed at 5% (w/v), 4:1 (w/w) and 7.5, respectively. Other suitable conditions selected by single factor trials were TGase addition of 20 U g^?1 peptides, reaction temperature of 45 °C and reaction time of 4 h. Peptide profiles from SDS‐PAGE analysis showed the composite was peptide polymers. Compared to that of the original caseinate or the cross‐linked caseinate, the dispersion of the composite exhibited a markedly enhanced apparent viscosity, storage modulus and viscous modulus. Meanwhile, the composite also showed a better water holding capacity, unchanged oil binding capacity and lower enzymatic digestibility in vitro, conferring its applicability as a new protein ingredient.     

The preparation of an oligochitosan‐glycosylated and cross‐linked caseinate obtained by a microbial transglutaminase and its functional properties

A glycosylated and cross‐linked caseinate (GCC) with glucosamine amount of 4.74 g/kg protein was generated from caseinate and oligochitosan by a microbial transglutaminase. The applied temperature, pH and molar ratio of acyl donor/acceptor were 37 °C, 7.5 and 1:3, respectively; while caseinate concentration, transglutaminase addition and reaction time selected from single‐factor trials were 50 g/L, 10 kU/kg protein and 3 h, respectively. Electrophoretic analysis revealed the cross‐linking and glycosylation of caseinate. Compared with caseinate, GCC showed improved solubility in pH 4–11, higher digestibility in vitro and water binding capacity, about 3‐fold, but lower surface hydrophobicity and oil binding capacity (34%).     

Correlating changes that occur in chemical properties with the generation of antioxidant capacity in different sugar-amino acid Maillard reaction models

Abstract: We investigated the development of antioxidant activity relative to the change of pH, fluorescent intensity, ultraviolet (UV) absorbance (A294), browning (A420), and alpha‐dicarbonyl compounds in sugar‐amino acid Maillard reaction (MR) model systems comprising fructose, glucose, or ribose each with glycine (Fru‐Gly, Glu‐Gly, and Rib‐Gly) or lysine (Fru‐Lys, Glu‐Lys, and Rib‐Lys), respectively, which were heated at 121 °C for 5 to 90 min. For hexose models, the change in pH was shown to fit a second‐order polynomial regression with A294 and A420. Antioxidant activity was significantly and positively correlated with UV absorbance (r = 0.905, P < 0.001) and browning products (r = 0.893, P < 0.001) rather than with fluorescent products or the alpha‐dicarbonyl compounds. Type of sugar was most important in evoking a change in UV absorbance, browning, alpha‐dicarbonyl compounds, and antioxidant activity of MR products (MRPs). In conclusion, the antioxidant activity of MRPs in six model systems was more closely associated with products derived at the intermediate‐to‐late stages of the reaction and influenced mostly by the type of sugar. Practical Application: We report on the different factors and their interactions that are important for understanding the functional attributes of food components that comprise the generation of Maillard browning products and the associated antioxidant activities generated during high‐temperature food processing.     

Maillard Reaction Products as Encapsulants for Fish Oil Powders

The use of Maillard reaction products for encapsulation of fish oil was investigated. Fish oil was emulsified with heated aqueous mixtures comprising a protein source (Na caseinate, whey protein isolate, soy protein isolate, or skim milk powder) and carbohydrates (glucose, dried glucose syrup, oligosaccharide) and spray‐dried for the production of 50% oil powders. The extent of the Maillard reaction was monitored using L*, a*, b* values and absorbance at 465 nm. Encapsulation efficiency was gauged by measurement of solvent‐extractable fat and the oxidative stability of the fish oil powder, which was determined by assessment of headspace propanal after storage of powders at 35 °C for 4 wk. Increasing the heat treatment (60 °C to 100 °C for 30 to 90 min) of sodium caseinate‐glucose‐glucose syrup mixtures increased Maillard browning but did not change their encapsulation efficiency. The encapsulation efficiency of all heated sodium caseinate‐glucose‐glucose syrup mixtures was high, as indicated by the low solvent‐extractable fat in powder (<2% powder, w/w). However, increasing the severity of the heat treatment of the sodium caseinate‐glucose‐glucose syrup mixtures reduced the susceptibility of the fish oil powder to oxidation. The increased protection afforded to fish oil in powders by increasing the temperature‐time treatment of protein‐carbohydrate mixtures before emulsification and drying was observed irrespective of the protein (sodium caseinate, whey protein isolate, soy protein isolate, or skim milk powder) and carbohydrate (glucose, glucose/dried glucose syrup, or oligosaccharide/dried glucose syrup) sources used in the formulation. Maillard reaction products produced by heat treatment of aqueous protein‐carbohydrate mixtures were effective for protecting microencapsulated fish oil and other oils (evening primrose oil, milk fat) from oxidation.     

Changes in browning‐related components of apple slices during different stages of instant controlled pressure drop‐assisted hot air drying (AD‐DIC)

The effect of instant controlled pressure drop‐assisted hot air drying (AD‐DIC) on browning‐related components in apple slices was studied. Results showed the AD temperature had no significant effect on colour index of final apple slices. The aspartic acid, glutamic acid, lysine, histidine, arginine, sucrose and dehydroascorbic acid (DHAA) in apple slices increased firstly during the AD process and then decreased during DIC process. The fructose, glucose, reduced ascorbic acid and major phenolic compounds reduced with the abrupt increase of 5‐hydroxymethylfurfural (5‐HMF) during AD‐DIC. There were significant correlations (P < 0.05) among moisture content (w.b.), water activity (a_w), water state, reduced ascorbic acid, DHAA, chlorogenic acid, procyanidin B₁, (+)‐catechin, (?)‐epicatechin and phlorizin during AD‐DIC. The colour difference showed that the major browning reaction of apple slices during the predrying process was enzymatic browning, while nonenzymatic browning played a crucial role on green‐red value (CIE a* value) during DIC.     

Relationship between postmortem changes and browning of boiled, dried, and seasoned product made from Japanese common squid (Tedarodes pacificus) mantle muscle

ABSTRACT:  To clarify the process that possibly causes discoloration in boiled, dried, and seasoned squid products ("sakiika" or "ikakun" in Japanese), we investigated the relationship of squid freshness with the rate of browning using the boiled, freeze-dried, and ground squid product model. ATP and its related compounds in Japanese common squid ( Tedarodes pacificus ) decomposed gradually during storage, yielding hypoxanthine and ribose at 24 h postmortem. The browning rate of the model during preservation as revealed by the increase of the b * value showed a high coefficient in the linear regression against ribose content ( R² = 0.767). Only the model made from the squid stored for 24 h postmortem turned brown. These results strongly suggest that ribose produced during storage plays a major role in the browning of dried and seasoned squid products.     

Rheological properties of modified lupin proteins

The properties of acetylated, succinylated and phosphorylated protein isolates extracted from the flour of yellow lupins (L. luteus) were studied by means of oscillatory rheology. The flow behaviour of protein dispersions (15% w/w) and the properties of thermotropic gels were distinctly influenced by the modification. Succinylation increased the viscosity of the dispersions of unmodified protein isolate (LPI) from 99 mPas to 515 mPas and results in the lowest gel point (T = 30.5°C). Acetylation and phosphorylation enhance the pseudoplastic flow behaviour of the dispersions. Acylated lupin samples formed the strongest gels with a small visco‐elastic range while phosphorylation leads to weak and “rubber‐like” gels.     

Preparation,characterisation and selected functional properties of hydrolysed sodium caseinate–maltodextrin conjugate

Sodium caseinate was hydrolysed to a limited, moderate or extensive degree. The hydrolysates were conjugated with maltodextrin by a Maillard‐type reaction by dry‐heat treatment at 60 °C and 79% relative humidity for 2 or 4 days. Conjugates were characterised by SDS–PAGE and gel permeation chromatography. In comparison with the hydrolysates themselves, the conjugated hydrolysates had improved solubility, particularly around the isoelectric pH of the protein. The emulsifying properties of these conjugates were assessed in oil‐in‐water (o/w) emulsions; on emulsion formation, each conjugate‐stabilised emulsion had lower mean fat globule size than the corresponding hydrolysate‐stabilised emulsion. After storage for 7 days under accelerated shelf life testing conditions, the limited and moderate hydrolysate conjugate–stabilised emulsions had improved storage stability compared with hydrolysate‐stabilised emulsions; however, further research is required to optimise the hydrolysate fraction prior to conjugation for the production of novel low molecular weight emulsifiers.     

高酰基结冷胶/酪蛋白酸钠复合凝胶粘弹行为的研究

本文研究了酪蛋白酸钠浓度、结冷胶浓度、离子和测试条件对高酰基结冷胶/酪蛋白酸钠复合凝胶粘弹性的影响。结果表明:高酰基结冷胶/酪蛋白酸钠共混体系为典型的切力变稀流体,表观粘度随着酪蛋白酸钠浓度的升高而降低,而随着阳离子浓度的增大出现先增大后减小的变化趋势。压缩速度对复合凝胶硬度几乎无影响,而内聚性和弹性则随着压缩速度的增加而增大。内聚性随着压缩应变的增大出现先增大后减小的变化趋势。复合凝胶的硬度和弹性随着酪蛋白酸钠浓度的增加而下降,但复合凝胶的内聚性对酪蛋白酸钠浓度不敏感。高酰基结冷胶浓度越高,复合凝胶的硬度和弹性越大。相对于一价离子而言,二价离子形成的凝胶更强且用量更少。钾离子的添加对复合凝胶保水性影响较弱,而钙离子的添加则可以提高复合凝胶的保水性。     

Isolation,structural features and rheological properties of water‐extractable β‐glucans from different Greek barley cultivars

β‐Glucans were isolated from six Greek barley cultivars (Persefoni, Kos, Thessaloniki, Athinaida, Dimitra and Triptolemos) by water extraction at 47 °C, enzymatic removal of starch and protein and subsequent precipitation of the water‐soluble β‐glucans with 37% (w/v) ammonium sulfate saturation. The purity of barley β‐glucans was high (>93% dry basis) with some small contamination by protein (<3.84%). The molecular size of the β‐glucan isolates was determined by high‐performance size‐exclusion chromatography (HPSEC); the weight‐average molecular weights and the intrinsic viscosities ranged between 0.45 × 10⁶ and 1.32 × 10⁶ and 2.77 and 4.11 dl g^?1, respectively. Structural features of barley β‐glucans were revealed by ¹³C NMR spectroscopy and high‐performance anion‐exchange chromatography (HPAEC) of the oligomers released by the hydrolytic action of lichenase. Lichenase degradation showed that β‐glucans from all barley cultivars consisted of blocks of cellotriosyl and cellotetraosyl units, accounting for 90.6–92.3% of the total oligomers released, with a molar proportion of these units between 2.31 and 2.77. Rheological measurements of aqueous solutions/dispersions of β‐glucans showed the behaviour of non‐interacting polysaccharides and a transition from the typical viscoelastic response to gel‐like properties after a time period that depended on the molecular size of the polysaccharide. The lowest molecular size β‐glucans from the Triptolemos cultivar showed shorter gelation times than their higher molecular weight counterparts. The effect of sugar incorporation (glucose, fructose, sucrose, xylose and ribose), at a concentration of 30% (w/v), to the β‐glucans gels (6% w/v) on compression parameters seemed to be related to the type of sugar used; the pentose sugars substantially reduced gel firming. Copyright © 2004 Society of Chemical Industry     

Milk Protein Coatings Prevent Oxidative Browning of Apples and Potatoes

ABSTRACT Color analysis on apple and potato slices coated with calcium caseinate or whey protein solutions showed that the 2 coatings efficiently delayed browning by acting as oxygen barriers. The antioxidant properties of the films were realized using a model allowing the release of oxidative species by electrolysis of saline buffer. Whey proteins were a better antioxidant capacity than calcium caseinate. Furthermore, addition of carboxymethyl cellulose (CMC) to the formulations significantly improved their antioxidative power. Best scavenging of oxygen free radicals and reactive oxygen species was found for films based on whey proteins and CMC which inhibited by 75% the formation of colored compounds produced by the reaction of the oxidative species with N,N‐diethyl‐p‐phenylenediamine.     

Meaty flavour compounds formation from the submerged liquid culture of Pleurotus ostreatus

The capacity of oyster mushroom (Pleurotus ostreatus) mycelium to produce meaty flavour compounds in the presence of amino acids and sugars was studied. The submerged liquid culture of P. ostreatus mycelium along with base medium made of defatted soybean powder, sucrose, potassium phosphate, and magnesium sulphate was incubated for 3 days at 25 °C. Cysteine, glutamine, or methionine and fructose, galactose, ribose, or xylose were added to the base medium to study the effect of amino acids and sugars on meaty flavour formation by trained panelists. The flavour compounds were isolated and identified by GC–MS and GC retention time of authentic compounds. The base medium required P. ostreatus, cysteine, ribose, and heat treatment to produce meaty flavour. The sulphur containing heterocyclic compounds such as 2,5‐diethylthiophene, 2‐formyl‐5‐methylthiophene, 3‐ethyl‐2‐formylthiophene, and dimethylformyl thiophene were responsible for meaty flavour. These compounds were formed by non‐enzymatic browning reaction between ribose and cysteine during heat treatment.     

Pectin from low quality ‘Golden Delicious’ apples: Composition and gelling capability

Pectin was acid-extracted from low quality ‘Golden Delicious’ apple fruit, yielding 16% (w pectin/w apple fruit). Composition and some of its physicochemical and functional properties were assessed. The pectin fraction presented a galacturonic acid content of 65% (w/w), an esterification degree of 57%, an intrinsic viscosity, [η], of 307 ml/g and a molecular weight (Mw) of 112 kDa. Pectin gels were obtained in 60% (w/v) fructose and pH 2.7. Pectin gels at 2.0% and 3.0% (w/v) presented hardness values of 10.2 and 20.4 g after 12 h at 4 °C. The gel hardness was greatly affected by aging (20% and 25% decrease in 48 h for gels at 2% and 3%, respectively). The results attained suggest the use of this gum as a potential texturing agent for the food industry.     

Influence of pH,NaCl and pre‐incubation on utilisation of surimi wash water in generation of antioxidative material by using the Maillard reaction

Maillard reaction products (MRPs) were generated from reaction mixtures of surimi wash water (SWW) with glucose or fructose (5%w/v) heated at 95 °C for 2–12 h. The effects of pH, NaCl and pre‐incubation of SWW on the Maillard reaction and antioxidant capacity of MRPs were investigated. The antioxidative capacity of MRPs was determined by measuring free DPPH° radical scavenging activity and reducing power. The highest colour intensity (OD₄₂₀) as well as antioxidative capacity was noted in the reaction mixture containing fructose at pH 9.0. The addition of NaCl (0.5–2.5%w/v) caused reduction in browning intensity but enhanced antioxidative capacity of the MRPs. Pre‐incubation of SWW at 45 °C for 4 h decreased soluble protein but increased the Maillard reaction and antioxidative capacity of MRPs. A positive effect of salt or pre‐incubation of SWW on the antioxidative capacity of MRPs was not associated with the soluble protein content in the reaction mixture.     

Influence of fortification with sodium–calcium caseinate and whey protein concentrate on microbiological,textural and sensory properties of set‐type yoghurt

The effect of fortification of yoghurt with sodium–calcium caseinate (SCC) and whey protein concentrate (WPC) on some properties of set‐type yoghurt were investigated. The addition of WPC enhanced the viability of Lactobacillus delbrueckii subsp. bulgaricus more than SCC. The highest firmness values were obtained from SCC‐fortified yoghurts, whereas yoghurts fortified with WPC had the highest water‐holding capacity during storage. The yoghurts fortified with 4% w/w SCC or 4% w/w WPC had the highest viscosity. Yoghurts fortified with 2% w/w SMP, SCC or WPC showed similar taste and overall acceptability scores; however, samples containing 4% w/w SCC or 4% w/w WPC had the lowest scores.     

Effects of inulin/oligofructose on the thermal stability and acid-induced gelation of soy proteins

ABSTRACT:  Differential scanning calorimetry (DSC) and dynamic oscillatory shear testing were performed to study the influence of inulin (Raftiline^® HP-gel and Raftiline^® ST-gel) and oligofructose (Raftilose^® P95) on the thermal stability and gelation (using glucono-δ-lactone [GDL] as a coagulant) of soy protein isolate (SPI) dispersions. Addition of 10% (w/v) inulin/oligofructose or sucrose increased ( P < 0.05) the peak denaturation temperatures ( T_m ) of 7S and 11S soy proteins in SPI dispersion (5%[w/v], pH 7.0) by an average of 1.9 and 2.3 °C, respectively. GDL induced SPI thermal gelation, and the gel rheology was affected by both the pH decline and the specific temperature of heating. Addition of inulin/oligofructose (8%, w/v) improved the gelling properties of preheated SPI dispersion (8%, w/v) coagulated with GDL, showing 14.4 to 45.6% increase ( P < 0.05) in gel rigidity ( G ' value) at the end of heating (81 °C). Microstructural examination revealed a denser protein cross-linking structure and reduced pore sizes in SPI gels containing inulin/oligofructose. In general, inulin was more capable of improving SPI gelation than oligofructose, suggesting that the degree of fructose polymerization in the fructans was of thermal and rheological importance.