Effect of κ-carrageenan on milk protein polysaccharide mixtures

The effect of κ-carrageenan (0, 0.025, 0.05%) on phase separation between polysaccharides (0.36% of locust bean gum (LBG), guar gum, or xanthan gum) and milk proteins (from 10.5% skim milk powder) in solution was studied. Xanthan gum was seen to be the most incompatible with milk proteins, followed by guar gum and LBG. Casein micelles were more incompatible with all polysaccharides than whey proteins. Whereas at either concentration κ-carrageenan inhibited visual phase separation, it was seen by transmission electron microscopy that samples with κ-carrageenan showed microscopic phase separation. Samples with 0.05% κ-carrageenan and either LBG or guar gum and all samples with xanthan gum could be described rheologically as weak gels, while those with no or 0.025% κ-carrageenan and either LBG or guar gum could be described as concentrated solutions. Thus, no correlation was seen between the inhibition of macroscopic phase separation by κ-carrageenan and the formation of a weak gel in solution.     

Combining protein micro-phase separation and protein–polysaccharide segregative phase separation to produce gel structures

The ability of protein micro-phase separation and protein–polysaccharide segregative phase separation to generate a range of gel structures and textures was evaluated. Whey protein isolate/κ-carrageenan mixed gels were prepared with 13% (w/v) whey protein isolate, 0–0.6% (w/w) κ-carrageenan and 50, 100 or 250 mM NaCl. The microstructure of gels, determined by confocal laser scanning microscopy, varied from homogenous to protein continuous, bicontinuous, coarse stranded or κ-carrageenan continuous, depending on the κ-carrageenan concentration. Microstructure also varied from stranded to particulate (micro-phase separated) depending on the salt concentration. The rheological behavior of mixed gels corresponded to the shift in the continuous phase from protein to κ-carrageenan. At small concentrations of κ-carrageenan, where carrageenan-rich droplets were dispersed in a continuous protein-rich matrix, gel strength (fracture stress) and firmness (G′) increased due to increased local concentration of proteins caused by phase separation. At higher κ-carrageenan concentrations, gels were substantially less firm, weaker and less deformable (fracture strain). The change in the continuous phase from protein continuous to carrageenan continuous explained the major change in mechanical properties and water-holding properties. The shift in microstructure occurred at lower concentrations of κ-carrageenan when whey proteins were under micro-phase separation conditions. The results demonstrated how the combined mechanisms of ion-induced micro-phase separation of proteins and protein–polysaccharide phase separation and inversion can be used to alter gel structure and texture.     

The effect of pH on gel structures produced using protein–polysaccharide phase separation and network inversion

Forming heat-induced gels through combined effects of micro-phase separation of whey protein isolate (WPI; 5%, w/v, 100 mm NaCl) by pH change (5.5, 6.0, and 6.5), and addition of κ-carrageenan (0–0.3%, w/w), were evaluated. The microstructure of WPI gels was homogeneous at pH 6.0 and 6.5 and micro-phase separated at pH 5.5. Addition of 0.075% κ-carrageenan to WPI solutions caused the microstructure of the gel to switch from homogeneous (pH 6.0 and 6.5) to micro-phase separated; and higher concentrations led to inversion of the continuous network from protein to κ-carrageenan. Protein solutions containing 0.075% (w/w) κ-carrageenan produced gels with increased storage modulus (G′) at pH 6.5 and decreased G′ at pH 5.5. All gels containing 0.3% (w/w) κ-carrageenan had κ-carrageenan-continuous networks. It was shown that microstructural and rheological changes were different in WPI and κ-carrageenan mixed gels when micro-phase separation was caused by pH rather than ionic strength.     

卡拉胶/大豆11S蛋白共混体系相容性及凝胶性质研究

研究了大豆11S蛋白分别与3种不同荷电量卡拉胶组成共混体系的相容性、热性质、凝胶流变性质及微结构,并探讨了共混凝胶的成胶动力学及机理。结果表明:ι-卡拉胶对大豆11S蛋白的相容性比κ-卡拉胶弱,添加λ-卡拉胶样共混体系更易发生相分离;添加3种卡拉胶均提高了大豆11S蛋白的热变性温度,但降低了热焓值,影响效果依次是λ-卡拉胶﹥ι-卡拉胶﹥κ-卡拉胶;共混凝胶随卡拉胶所带负电荷的增加其弹性模量值呈降低趋势,且凝胶网络结构由蛋白-多糖双连续结构转变为蛋白凝胶网络单连续结构;增加卡拉胶所带负电荷可降低共混凝胶形成过程表观活化能,同时降低了温控程序终点的弹性模量值。     

Structure and rheology of the κ-carrageenan/locust bean gum gels

The structure and interaction of κ-carrageenan and locust bean gum (LBG) has been studied using rheology, cryo-SEM, conductivity and syneresis characterization. The rheological behaviour of the binary system has been characterized using both compression and shear measurements. Elimination of slip in the shear measurements yields G′ values of the order 10,000–30,000 Pa for a 1% κ-carrageenan gel in 0–0.2 M added KCl. These values are higher than previously reported. No synergistic peak was found with the addition of LBG as has been previously reported. The measured modulii for these gels yields a Poisson's ratio of 0.5. Compression rupture stress and strain were also monitored. The rupture measurements do show a synergistic peak indicating that the interaction does occur and is important at high strain amplitudes. The gel points as determined by conductivity for these systems show a decrease in temperature with increasing LBG concentration, which is consistent with rheological measurements. Syneresis results are reported for the range of κ-carrageenan/LBG ratios. The syneresis shown by the mixtures is the same as that shown by the same concentration of κ-carrageenan. Structures of the gels as determined by cryo-SEM are also reported. Characteristic length scales in these systems are of the order of tens of microns and show little change with LBG concentration. The reduction in the characteristic length scale with increasing LBG concentration is discussed in terms of the rheological behaviour.     

κ-卡拉胶对大豆分离蛋白乳浊凝胶特性的影响

研究了κ 卡拉胶在不同pH的条件下对大豆分离蛋白乳浊凝胶质构特性和流变特性的影响。研究结果表明 ,pH 7 3条件下的乳浊体系比 pH 6 8的体系更易形成凝胶。卡拉胶质量分数为 0 0 5 %时 ,因与大豆分离蛋白发生静电吸引相互作用形成连接型凝胶而显著提高了凝胶的质构特性和流变特性。 0 2 %时则形成相分离型凝胶 ,降低了凝胶的弹性和内聚性。     

Fabrication of κ-carrageenan fibers by wet spinning: Addition of ι-carrageenan

Taking advantage of the gelation process of κ-carrageenan, we have developed a wet-spinning process to fabricate micro-scale fibers from κ-carrageenan. Effects of three important spinning parameters, i.e. coagulation bath composition, spinning rate and post-spinning mechanical drawing, on fiber morphological and tensile properties have been discussed. In the present report, we studied the addition of ι-carrageenan on thermal and rheological properties of the bicomponent gels and the fibers spun from them. It was found that κ- and ι-carrageenan underwent phase separation in the bicomponent gel. Upon addition of ι-carrageenan, the diameter and compliance of the blend fiber was increased.     

Microscopic structure,viscoelastic behaviour and 3D printing potential of milk protein concentrate-hydrocolloid complex coacervates

To prepare a milk protein-enriched ink for extrusion-based 3D food printing, this study investigated the effects of a wide range of hydrocolloids on the microstructures, viscoelastic characteristics and 3D printing performance of milk protein concentrate (MPC). The distributions of hydrocolloids and milk protein in mixed coacervates were characterised by fluorescent covalent labelling and confocal laser scanning microscope (CLSM), and the microstructure of the coacervates was observed by scanning electron microscopy (SEM). In addition, the rheological properties of prepared protein coacervates, including steady shear test, dynamic oscillatory test, thixotropy and creep recovery were investigated. Meanwhile, Burger’s model was fitted to the creep behaviour to further study their viscoelastic properties. The results showed that κ-carrageenan, pectin, guar gum and sodium alginate significantly increased the zero-shear viscosity, thixotropy and solid-like behaviour while xanthan showed an opposite phenomenon. Results showed that the presence of hydrocolloids improved the 3D printability of MPC by forming a complex network between protein particles and hydrocolloids, and guar gum, pectin and κ-carrageenan better help maintain the deposited 3D structures of MPC ink than xanthan.     

Rheological characterization of experimental dairy creams formulated with locust bean gum (LBG) and λ-carrageenan combinations

The influence of the locust bean gum (LBG)–λ-carrageenan stabilizer combination on the rheology of dairy creams was analyzed. A central composite factorial design was used to choose the LBG–λ-carrageenan ratio, the weight fraction of each gum ranging from 0 to 0.1 g per 100 g cream. Cross’ rheological model was closely fitted to describe the flow curves of the samples and Cross parameters were correlated with gum concentrations. The rheological behaviour of model aqueous gum solutions, with the same pH, ionic strength, and competitive solute concentration as the cream serum, was also examined to analyze gum interactions. Strong interaction of λ-carrageenan with cream components, probably with caseins, may be anticipated based on a great increase in viscosity. The functional role of LBG seems to be associated with an increase in the emulsion shear stability.     

Stabilization of multilayered emulsions by sodium caseinate and κ-carrageenan

The influence of the κ-carrageenan concentration and pH on the properties of oil-in-water multilayered emulsions was studied. Multilayered emulsions were prepared by the mixture of a primary emulsion stabilized by 0.5% (w/v) sodium caseinate (Na-CN) with κ-carrageenan solutions with different concentrations (0.05–1% w/v). The emulsions were evaluated at pH 7 and 3.5. At pH 7, there was little adsorption of κ-carrageenan onto the droplet surface and a depletion flocculation was observed when the polysaccharide concentration exceeded 0.5% (w/v). At pH 3.5, a mixed κ-carrageenan–Na-CN second layer was formed around the protein-covered droplets and the emulsions showed bridging flocculation at lower polysaccharide concentrations (0.05–0.25% w/v). Stable emulsions could be formed with the highest κ-carrageenan concentration (1% w/v) at both pH values (7.0 and 3.5). Thus, stable emulsions were successfully produced using protein–polysaccharide interfacial complexes, and the oil droplet diameter, zeta potential and rheological properties of these emulsions were not affected by changes in the pH.     

κ-卡拉胶与魔芋胶复配胶的流变性能及其微观结构研究

研究κ-卡拉胶与魔芋胶(质量比为5.5:4.5)复配胶的流变特性,考察剪切速率、振动频率和温度等对复配胶流变特性的影响。研究结果表明:30℃时复配胶的储能模量G′高于κ-卡拉胶和魔芋胶单体胶的储能模量G′,其损耗模量G"低于κ-卡拉胶的损耗模量G",复配胶的凝胶性质更加明显。随着温度的升高,复配胶体系的G′始终大于G",具有典型黏弹性流体的特性。结构分析表明κ-卡拉胶与魔芋胶之间具有较好的协同作用,通过分子间氢键形成了以κ-卡拉胶网络结构为主,魔芋胶穿插其中的交联网络体系。     

Small and large deformation rheology and microstructure of κ-carrageenan gels containing commercial milk protein products

The rheological behaviour of commercial milk protein/κ-carrageenan mixtures in aqueous solutions was studied at neutral pH. Four milk protein ingredients; skim milk powder, milk protein concentrate, sodium caseinate, and whey protein isolate were considered. As seen by confocal laser microscopy, mixtures of κ-carrageenan with skim milk powder, milk protein concentrate, and sodium caseinate showed phase separation, but no phase separation was observed in mixtures containing whey protein isolate. For κ-carrageenan concentrations up to 0.5 wt%, the viscosity of the mixtures at low shear rates increased markedly in the case of skim milk powder and milk protein concentrate addition, but did not change by the addition of sodium caseinate or whey protein isolate. For κ-carrageenan concentrations from 1 to 2.5 wt%, small and large deformation rheological measurements, performed on the milk protein/κ-carrageenan gels, showed that skim milk powder, milk protein concentrate or sodium caseinate markedly improved the strength of the resulting gels, but whey protein isolate had no effect on the gel stength.     

Synergistic effects between κ-carrageenan and locust bean gum on physicochemical properties of edible films made thereof

The development of mixed systems, formed by locust bean gum (LBG), and κ-carrageenan (κ-car) can offer new interesting applications such as the development of edible films with particular properties. κ-car/LBG blend films with different ratios were developed, and their effects on films’ physical properties were assessed. Thermogravimetric analysis (TGA), X-ray diffraction (XRD) patterns, dynamic mechanical analysis (DMA) and Fourier-transform infrared (FTIR) spectroscopy techniques were used to highlight the interactions between the two polysaccharides. The addition of κ-car to LBG improved the barrier properties of the films leading to a decrease of water vapor permeability (WVP). Improved values of elongation-at-break (EB) were registered when the ratio of κ-car/LBG was 80/20 or 40/60 (% w/w). Moreover, the κ-car/LBG blend films enhance the tensile strength (TS) compared to κ-car and LBG films. FTIR results suggested that hydrogen bonds interactions between κ-car and LBG have a great influence in films’ properties e.g. moisture content, WVP. Therefore, different κ-car/LBG ratios can be used to tailor edible films with enhanced barrier and mechanical properties.     

Effect of κ-carrageenan on rheological properties, microstructure, texture and oxidative stability of water-in-oil spreads

The effect of κ-carrageenan concentration (0-7.5 g kg⁻¹) on the rheology, microstructure, texture and oxidative stability of water-in-oil (W/O) spreads (600 g fat kg⁻¹ emulsion) was examined over 60 days storage time. Results showed that increasing the κ-carrageenan concentration to 7.5 g kg⁻¹ significantly increased the viscosity of the aqueous phase (to 42.7 mPa s at 60 °C) resulting in gelation of the aqueous phase on cooling. The microstructure of the spreads was disrupted by higher levels of κ-carrageenan, resulting in a less homogeneous distribution of the aqueous phase. Melt temperature (where tan δ > 1) decreased significantly from 62 to 56.2 °C with increasing κ-carrageenan concentration from 0 to 7.5 g kg⁻¹. The firmness and the G′ at 6 °C for all samples were significantly increased after 60 days storage with only small effects due to κ-carrageenan levels. Oxidation of the fat phase was evident by the significant increases in peroxide values of all spreads on storage, with κ-carrageenan exhibiting no antioxidant behaviour. While increased κ-carrageenan levels modified the microstructure of W/O spreads in terms of the droplet size of the aqueous phase and its distribution few changes were evident in the continuous fat phase.     

Rheological characterisation of yolk-based gels and Staphylococcus growth

Model yolk-based (10% v/v) gels with different concentrations of κ-carrageenan (0–2% w/w) were characterised employing rheological measurements, textural analysis and scanning electron microscopy. Additionally, the effect of the microstructure of the model gels on the growth rate of Staphylococcus was also evaluated. In all cases, the nature of the gel was dominated by the elastic component, specifically, 1.5, 1.75 and 2% κ-carrageenan samples can be described as ‘true gels’ (tan δ < 0.1). Maximum strength of the interactions between rheological units (A) was observed with 1.75% κ-carrageenan (4.74 ± 0.38 kPa), which indicates that the strength of interactions was determined not only by κ-carrageenan concentration, but also by the amount of yolk. Finally, an inverse linear correlation was found between the maximum specific growth rate of Staphylococcus and rheological data (R² > 0.99).     

温敏型胶体对玉米淀粉3D打印固化性能的影响

目的:利用温敏型胶体的相转变特性,辅助实现淀粉在打印过程中的成型固化,并揭示不同种类胶体-淀粉体系的固化性能变化规律。方法:将不同比例的温敏型胶体(低酰基结冷胶、明胶、κ-卡拉胶)与玉米淀粉进行复配并测定其流变性能,通过打印圆柱及空心球模型、测试产品力-位移曲线、温度扫描流变、全质构分析及微观结构观测评估体系可打印及固化性能。结果:结冷胶和卡拉胶在2%～4%添加量,明胶在0%～2%添加量时,体系具有适宜的流变性能及良好的可打印性能。添加4%结冷胶及4%卡拉胶的产品表现出显著的塑性,固化效果较好;添加明胶的打印产品无显著塑性,打印产品不固化。结冷胶-淀粉混合体系的固化温度在35～43℃之间;卡拉胶-淀粉混合体系的固化温度在30～40℃之间,随着胶体含量增加,固化温度上升,固化速度加快。而随着明胶含量增加,固化温度从25℃下降至20℃以下且固化速度减慢。4%低酰基结冷胶产品具有更致密的凝胶网络,硬度高于4%κ-卡拉胶产品。明胶对硬度、弹性都有削弱作用,但使粘附力大幅提高。结论:适宜含量的低酰基结冷胶和κ-卡拉胶能够实现淀粉的成型固化,且卡拉胶固化性能优于结冷胶,而明胶则无辅助固化能力。     

大目金枪鱼皮明胶与κ-卡拉胶复配胶凝胶特性探究

将大目金枪鱼皮明胶和κ-卡拉胶按不同配比混合制成复配胶,测定了复配胶的凝胶强度、流变学性质、凝胶持水性、质构、红外光谱和电镜。结果表明:复配胶的凝胶强度、粘度、储能模量和耗能模量均随着κ-卡拉胶比例的增大而增大。复配胶的凝胶持水率在明胶/κ-卡拉胶比例为7:3时为75.9%,远低于单组分明胶凝胶的97.1%,但继续增大κ-卡拉胶的比例会出现显著增大的趋势,质构特性与持水率有相同的变化趋势。红外光谱分析结果表明κ-卡拉胶与明胶之间的交互作用随着κ-卡拉胶比例的增大而减小,说明复配胶中形成了以κ-卡拉胶为主体的结构。电子扫描结果显示复配胶中出现褶皱与聚集,进一步说明κ-卡拉胶与明胶以不同比例混合后通过氢键发生了不同程度的交互作用。实际生产中,可通过改变明胶/κ-卡拉胶的配比来调节复配凝胶的特性,适应不同产品的需要。     

Whey protein aggregate formation during heating in the presence of κ-carrageenan

The effect of a negatively charged polymer, κ-carrageenan, on the aggregation behaviour of whey proteins during heating was studied. Aqueous solutions of whey protein isolate (WPI) at 0.5% were heated in the presence of κ-carrageenan (0.1%) at pH 7.0. This concentration was chosen as optimal in the detection of the intermediate aggregates during chromatographic analysis. The residual unaggregated protein, the intermediate aggregates and the soluble aggregates were all examined as a function of heating time and temperature, using size-exclusion chromatography coupled with light scattering detection. The presence of κ-carrageenan did not affect the aggregation of whey proteins heated at 75 °C; however, a change in the mechanism of aggregation seemed to occur at higher temperatures, and intermediates with higher molecular mass formed at 85 °C. At 90 °C, in the presence of κ-carrageenan, the extent of WPI aggregation was much larger, as soluble aggregates were no longer present and less residual protein was recovered in the unaggregated peak.     

Optimisation of conditions for precipitation of collagen from solution using κ-carrageenan. Studies on collagen from the skin of Baltic cod (Gadus morhua)

The effects of the concentration of collagen (0.025–3%), extracted from the skins of Baltic cod (Gadus morhua) and the concentration of κ-carrageenan (0.04–1%), in the presence of NaCl (0–5%), on the yield of precipitated collagen fibrils at 0 °C and at pH 2.2–8 were determined. The yield of precipitated collagen was directly proportional to the ratio, κ-carrageenan to collagen, within the range 0.015–0.4. Collagen dissolved in citric acid could be completely precipitated using κ-carrageenan if the weight ratio of dry reagents was 1:0.4 within a protein concentration of 1.5–0.08%. The maximal yield of precipitated collagen fibrils using κ-carrageenan could be achieved in the pH range 2.2–3. In this range of pH, the presence of NaCl in the system did not affect the efficiency of precipitation of collagen fibrils with κ-carrageenan. The yield of precipitated collagen was lower at 20 °C than at 0 °C.     

Study of the functionality of selected hydrocolloids and their blends with κ-carrageenan on storage quality of vanilla ice cream

In the present paper, the functionality of hydrocolloids related to the rheological, physical and sensory characteristics of ice cream mixes and frozen ice cream was studied. Carboxylmethylcellulose, guar gum, sodium alginate and xanthan gum were used as primary stabilizing agents, whereas κ-carrageenan as secondary. The hydrocolloid concentrations were 0.1 and 0.2% and the primary to secondary ratio was 9:1. The ice cream samples were stored under quiescent frozen conditions. Samples were taken after 4, 8 and 16 weeks of storage and examined for the functionality of the stabilizing systems.The addition of hydrocolloids significantly reinforced the shear thinning behavior, particularly in the case of sodium alginate, xanthan gum, and κ-carrageenan which was attributed to gelation phenomena. Sodium alginate attained the better stabilizing effect improving textural quality and acceptance of ice creams even after 16 weeks of storage, whereas the presence of κ-carrageenan found to be a crucial factor for the cryoprotection. Xanthan gum was also evaluated as an effective stabilizing agent, indicating that gelling hydrocolloids may remarkably amend ice cream shelf life.Moreover, principal components and cluster analysis of instrumental and sensory data furnished important information for the correlation of objective and sensory properties and discrimination of stabilizing systems based on quality criteria.