Effect of high-pressure/high-temperature processing on chemical pectin conversions in relation to fruit and vegetable texture

Heat sterilization of plant derived food products entails considerable organoleptic and nutritional quality losses. For instance, texture loss of fruits and vegetables occurs, next to turgor pressure losses, mainly due to chemical changes in the cell-wall pectic polysaccharides. High-pressure sterilization, i.e. the combination of high temperature (?90 °C) with high pressure (?500 MPa), could present a positive alternative assuring safety while minimizing quality losses. In this study, the potential of high-pressure sterilization in preserving fruit and vegetable texture was evaluated by investigating the effect of combined high-pressure/high-temperature (HP/HT) treatments on two texture related chemical pectin conversions in model sytems. First, a protocol was developed to perform reproducible kinetic studies at HP/HT under constant processing conditions. Subsequently, apple pectin solutions at pH 6.5 were subjected to different HP/HT combinations (500, 600 and 700 MPa/90, 110 and 115 °C) and the extent of chemical demethoxylation and β-eliminative depolymerization was determined. At atmospheric pressure, both zero-order reaction rate constants increased with increasing temperature. At all temperatures, demethoxylation showed a higher rate constant than β-elimination. However, a temperature rise resulted in a stronger acceleration of β-elimination than of demethoxylation. When combining high temperature with high pressure, β-elimination was retarded or even stopped, whereas demethoxylation was stimulated. These results are very promising in the context of the texture preservation of high-pressure sterilized fruits and vegetables, as β-elimination is accepted to be one of the main causes of thermal softening and low methoxylated pectin can enhance tissue strength by forming cross-links with calcium ions present.     

Degradation of high-methoxyl pectin by dynamic high pressure microfluidization and its mechanism

High-methoxyl pectin was degraded by dynamic high pressure microfluidization (DHPM). It was found that apparent viscosity, average molecular weight and particle size of pectin decreased, whereas the amount of reducing sugars increased with increasing DHPM pressure. At the same time, the surface topography of pectin was changed from large flake-like structure to smaller porous chips. The mechanism of DHPM-induced degradation of pectin was also investigated. Fourier transform infrared spectra showed DHPM had no effect on the primary structure of pectin. On the other hand, reducing sugars content increased linearly with decreasing average molecular weight, suggesting the degradation may derive from the rupture of glycosidic bond. The breakdown of glycosidic bond may not only result from intensive mechanical forces but also from acid hydrolysis, which was evidenced in the reduction of degradation when the concentration of H⁺ was lowered. In addition, neither β-elimination nor demethoxylation occurred with DHPM. Based on these results, a model was proposed to illustrate the degradation of pectin induced by DHPM.     

The influence of the storage conditions heat and humidity on conformation,state transitions and degradation behaviour of dried pectins

For testing the influence of long-term storage on pectins, differently prepared samples were incubated under defined temperature and relative humidity in a climate chamber. This caused pectin demethoxylation, depolymerisation and non-enzymatic browning and influenced the dissolution behaviour and pH. The extent of chemical changes and the reaction mechanisms depended on incubation conditions, type and “history” of the pectins and on their conformation (⁴C₁ or ¹C₄ chair). Higher temperature and higher humidity increased demethoxylation and browning. Depolymerisation was high even at low degree of methoxylation. Therefore, an additional mechanism besides β-elimination and glycosidic linkage cleavage was suggested.     

Effect of Novel Processing Techniques on Texture Softening and β-Carotene Content of Thermally Processed Carrots

Effect of novel processing methods was evaluated on product texture and β-carotene content of carrots following acidification to reduce pH from 6.0 to 4.4. Thermal treatments under Conventional (CH-T) and Ohmic heating (OH-T) conditions at 87, 92, and 97 °C, individually and/or in combination with high-pressure processing (HP-T; 400–600 MPa/40–60 °C), were given up to 90 min. A fractional conversion model was used to compute texture softening rate constant, k, and activation energy, E _a. Acid-infused carrot samples had lower k values than the control, implying a better texture retention in acidified products. In order to explore this further, acid-infused and control samples were subjected to selected processing methods for 0, 7, and 25 min representing minimal, optimum, and over-processing conditions, respectively. Texture value, pectin depolymerization by β-elimination, demethoxylation, cell microstructure modification, and β-carotene content were evaluated. Results showed that acid-infused samples retained significantly (p?≤?0.05) better texture than the untreated ones. Pectin depolymerization by β-elimination was greater (p?≤?0.05) in control samples than acid-infused samples. In contrast, pectin depolymerization by demethoxylation showed no such differences (p?>?0.05) with acid-infused samples. This indicates that pectin degradation was more dominated by β-elimination than demethoxylation, and these results concurred with the cell microstructure observations of processed carrots. Thermal and HP-T processing after acid infusion reduced the β-carotene content of carrots more than in control. However, mild heat treatment of carrots at 97 °C under CH-T and OH-T enhanced the β-carotene levels to higher than in raw control carrot samples.     

Pectic Substance Degradation and Texture of Carrots as Affected by Pressurization

Heated pectin was degraded by transelimination (β-elimination) above pH 5 and by hydrolysis below pH 2, but pressurized pectin did not degrade. Thus cooked carrots decreased in firmness, but pressurized carrots did not. Pressurizing above 200 MPa slightly increased rupture strain. Galacturonic acid levels decreased in carrots cooked for 30 min. Total pectin in pressurized carrots was the same as in cooked for 3 min. However, with increased pressure, the amount of high methoxyl pectin in carrots decreased while low methoxyl pectin increased. Thus, the effects of pressurization on pectin degradation (transelimination) and texture of carrots were different from those of heating.     

The Effect of Brine Ingredients on Carrot Texture during Thermal Processing in Relation to Pectin Depolymerization due to the β-Elimination Reaction

ABSTRACT:  Thermal texture degradation of carrots was studied at a temperature of 100 °C in aqueous solutions containing sodium chloride, citric acid, ascorbic acid, and ethylenediaminetetraacetic acid (EDTA) at different concentrations. To enhance the texture of the final product, the carrot samples were pretreated at 65 °C for 30 min in an aqueous calcium chloride solution (5 g/L). For all case studies considered, the pH of the solutions was adjusted to pH = 6.0. In parallel, both the changes in degree of esterification (DE) and the progress of the β-elimination reaction of carrot pectin under the same conditions were investigated. The kinetic parameters for texture degradation (rate constant k_t and final texture value [TP_∞/TP₀]) were estimated using a fractional conversion model. The results indicate that both the rate constant for texture degradation ( k_t ) and the rate constant for the β-elimination reaction ( k_b ) increased with increasing additive concentration, while the final texture values (TP_∞/TP₀) and DE decreased with increasing additive concentration in all systems studied. A high correlation was observed between the relative rate constant for texture degradation and the relative rate constant for the β-elimination reaction on the one hand, and the relative final texture value and the relative rate constant for the β-elimination reaction on the other hand, suggesting that the influence of the solutes on texture degradation can be explained by their influence on the β-elimination reaction.     

THE CHEMISTRY OF TEXTURE IN FRUITS AND VEGETABLES

This review is concerned with the chemistry of the major primary cell wall components, pectins, hemicelluloses and cellulose, under conditions found during the normal handling of fruits and vegetables. These polymeric components are considered separately, then their combined changes during maturation, storage and processing are covered. The effects of tissue conditions, pH, enzymes and salt concentrations on the rate and degree of change are discussed. A large part of the review deals with the important texture-affecting reactions of pectic materials including glycosidic hydrolysis, β-elimination type depolymerization, demethoxylation, and complex formation.     

贮藏期间芦荟果胶含量变化及影响果胶粘度因素的研究

果胶作为由植物中提取的天然添加剂,具有良好的胶凝化和稳定化作用。从具有保健作用和药用价值的芦荟中提取果胶已广泛应用于食品工业、化妆品、医药等领域。本文对贮藏期间芦荟果胶含量态变化进行研究,并确定影响果胶粘度的因素,对芦荟果胶提取具有指导意义。本文采用酸水解醇析法提取芦荟中的果胶,确定提取果胶醇析过程中的最优pH和温度,并明确贮藏0～60d芦荟中果胶含量,此外还确定各种影响因素对果胶成品粘度的影响。结果表明,醇析过程中的最佳pH3.5,最佳温度为50℃。果胶成品的pH2.79（符合国标）,甲氧基含量为8.518%,属于高甲氧基果胶。贮藏0～60d库拉索芦荟中的果胶含量在贮藏10d时达到峰值。而后果胶含量随贮藏时间的延长而降低,并且在20d之后明显下降。因此,最适宜芦荟果胶提取和加工的时间为0～20d。所得芦荟果胶粘度与温度、柠檬酸和氯化钠添加量呈负相关,而与果胶浓度和蔗糖添加量呈正相关。     

Kinetics of acid-catalysed de-esterification of pectin in a heterogeneous medium

The rate constants of acid-catalysed de-esterification at 30,40 and 50°C of apple, lemon, grapefruit, orange and carrot pectins, in ethanolic hydrochloric acid show that the reaction is a pseudo first-order reaction and is uninfluenced by the origin of the pectin.
The activation parameters (ΔS*= -107.2±2.6 J mol^-1 K^-1; ΔH*= 74.51±0.96 kJ mol^-1) were close to those calculated by Speiser, Eddy and Hills (1945) for homogeneous acid de-esterification of apple pectin, and thus the reaction mechanism appears to be the same as that in solution.
In most cases, (except grapefruit pectin) gel strength increased with the degree of es-terification and the duration of acid treatment: the maximum depends on the type of the pectin.     

Chemistry and uses of pectin — A review

Pectin is an important polysaccharide with applications in foods, Pharmaceuticals, and a number of other industries. Its importance in the food sector lies in its ability to form gel in the presence of Ca²⁺ ions or a solute at low pH. Although the exact mechanism of gel formation is not clear, significant progress has been made in this direction. Depending on the pectin, coordinate bonding with Ca²⁺ ions or hydrogen bonding and hydrophobic interactions are involved in gel formation. In low‐methoxyl pectin, gelation results from ionic linkage via calcium bridges between two carboxyl groups belonging to two different chains in close contact with each other. In high‐methoxyl pectin, the cross‐linking of pectin molecules involves a combination of hydrogen bonds and hydrophobic interactions between the molecules. A number of factors—pH, presence of other solutes, molecular size, degree of methoxylation, number and arrangement of side chains, and charge density on the molecule— influence the gelation of pectin. In the food industry, pectin is used in jams, jellies, frozen foods, and more recently in low‐calorie foods as a fat and/or sugar replacer. In the pharmaceutical industry, it is used to reduce blood cholesterol levels and gastrointestinal disorders. Other applications of pectin include use in edible films, paper substitute, foams and plasticizers, etc. In addition to pectolytic degradation, pectins are susceptible to heat degradation during processing, and the degradation is influenced by the nature of the ions and salts present in the system. Although present in the cell walls of most plants, apple pomace and orange peel are the two major sources of commercial pectin due to the poor gelling behavior of pectin from other sources. This paper briefly describes the structure, chemistry of gelation, interactions, and industrial applications of pectin.     

Improving the hardness of thermally processed carrots by selective pretreatments

The aim of this study was to improve the texture of thermally processed carrots by selective pretreatments modifying plant-intrinsic properties. Pretreatments were a combination of a thermal or high-pressure (HP) treatment followed by a 1 h soak in a specific solution. Lowering the degree of methyl-esterification (DM) of the carrot pectin was confirmed to be one strategy to reduce texture degradation. The thermal or HP pretreatment resulted in pectin with a lower DM which is less susceptible to β-eliminative depolymerization. A subsequent Ca²⁺ soak resulted in an even better texture by enhancing the amount of pectin cross-links within the cell wall. Lowering the pH of the carrots was proven to be another strategy. A thermal or HP pretreatment followed by soaking carrots in solutions of low pH proved to be effective in lowering the internal carrot pH, hereby retarding β-elimination and consequently texture degradation. The composition of the low pH solution was shown to be of importance; soak solutions containing cations and/or Ca²⁺ complexing agents have to be avoided. Ferulic acid proved to be a good acidifying candidate. In conclusion, for texture improvement of thermally processed carrots, lowering the susceptibility for β-elimination and enhancing cell wall cross-links are two main targets which both can be reached by manipulating different plant-intrinsic properties.     

Influence of pectin structure on texture of pectin–calcium gels

A library of pectins with varying degree and pattern of methoxylation was produced by demethoxylating a parent pectin by use of NaOH or pectinmethylesterase from plant or fungal origin. Additionally, pectin was chemically depolymerised by a heat treatment. The resulting pectins were characterised in terms of degree and pattern of methoxylation (“(absolute) degree of blockiness”) and the extent of depolymerisation. Pectin–calcium gels were prepared and their texture was studied by performing compression tests. From the resulting force vs. distance curves, the modulus of elasticity under low strain and the fracture stress and strain were determined. The modulus of elasticity under low strain increased with decreasing degree of methoxylation. At very low degree of methoxylation, gels were brittle, resulting in low fracture stress. Both modulus of elasticity and fracture stress correlated more with degree of blockiness and absolute degree of blockiness as compared to degree of methoxylation. Gel strength increased with increasing Ca²⁺ or pectin concentration. Depolymerisation of pectin resulted in formation of brittle gels.Industrial relevancePectin with low degree of methoxylation can form a gel in presence of calcium. Therefore, it is widely used in the food industry. In addition, pectin-calcium interactions are of importance for the texture of fruits and vegetables, since crosslinked pectin in the cell wall provides cell-cell adhesion and mechanical strength of tissues. This research is focused on textural characteristics of pectin-calcium gels. It is shown that pectin structural properties influence texture of gels. As a result, control of pectin structure allows fine-tuning of functional properties.     

Influence of pectin modification on water binding properties

Water can be bound to food components and products as non-freezing, freezing-bound and free water. The interactions are crucial for any application as well as for food consumption and digestion. DSC was applied to examine the amounts of the different types of water bound to pectin, a biomacromolecule that is used as gelling and stabilising agent in many food products. One commercial high-methoxylated citrus pectin and three modified samples, prepared by acidic and alkaline demethoxylation as well as amidation, were tested. The water content of dry samples depended mainly on the molecular parameters, especially the content of hydrophilic groups at the galacturonic acid that was increased by demethoxylation and amidation, as well as on monovalent cations of the pectins. The water–pectin interactions of wetted materials were additionally influenced strongly by the availability of hydrophilic groups that depended on material properties such as amorphous or crystalline state, powder bulk and solid density and porosity as well as particle size, surface and porosity. Small amorphous porous particles, whose polar groups were rapidly available without prior softening and swelling, accelerated water uptake. Non-freezing and freezing-bound water, bound closely to the pectin molecules, depended on the number and type of polar groups. Free water, bound in micro- and macro-capillaries as well as voids within and between the pectin particles, was influenced by hydrophilic as well as hydrophobic groups of the samples. There was a strong impact of the pre-treatment during processing and modification.     

Influence of intrinsic and extrinsic factors on rheology of pectin–calcium gels

Pectin was selectively demethoxylated by use of NaOH or pectinmethylesterase from plant or fungal origin in order to produce a library of pectins with varying degree and pattern of methoxylation. In addition, pectin was chemically depolymerised by a heat treatment. The resulting pectin products were characterised by studying the degree and pattern of methoxylation and the extent of depolymerisation. The pattern of methoxylation was estimated quantitatively by determining the “degree of blockiness” (DB and DB_abs). Pectin–calcium gels were prepared at varying concentrations of both components. Rheological properties of these gels were studied by performing small deformation oscillatory tests. Gel strengths were better explained by the pattern of methoxylation than by the degree of methoxylation. The relation between rheological properties and calcium or pectin concentration depended on the pattern of methoxylation. Depolymerisation had a detrimental effect on gel strength, especially at low calcium concentration.     

Effect of Methyl Ester Content on Heat Degradation of Chelator-Soluble Carrot Pectin

Chelator-soluble pectin was isolated from carrot under mild conditions and used as a model compound for an investigation of the heat degradation mechanism of pectin in an aqueous environment. Methyl ester content was modified with minimal changes in the polymer size. At pH 6.1 the heated pectin preparation degraded primarily through β-eliminative cleavage of the chain. The higher the methyl ester content the greater the degradation. Evidences also indicated a-small amount of hydrolytic cleavage of glycosidic bonds which was not affected by the presence of the methyl ester content. De-esterification of methyl ester groups proceeded at a faster rate than the eliminative cleavage of the chain; however, under the test conditions, it did not terminate the β-elimination.     

Extraction and partial characterization of Solanum lycocarpum pectin

In this work Solanum lycocarpum fruits were used as a source of pectin. The parameters of pectin extraction were examined using a 2³ factorial design, with temperature, pH and extraction time as independent variables. The extracted S. lycocarpum pectin and dried pulp were analyzed for the presence of antinutritional compounds, such as amylase and trypsin inhibitors, hemagglutinin, tannins, saponins, alkaloids and phytate. Pectin was characterized by measuring its methoxylation degree, intrinsic viscosity and molecular weight. The best pectin extraction conditions yielded as much as 33.6% (dry matter). The S. lycocarpum pectin was determined to be highly methoxylated (77.15%), and it showed an intrinsic viscosity 4.6% lower than that of citrus pectin, probably due to its lower molecular weight (177.76 kDa versus 224.48 kDa of that of citrus pectin). Although there were tannins and phytate in the dried pulp, the pectin fraction was free of these compounds.     

Thermoanalytical characterisation of processing-dependent structural changes and state transitions of citrus pectin

Pectins are stabilised by inter- and intramolecular attraction forces, such as hydrophobic interactions and hydrogen bonds, and destabilised for example by electrostatic repulsion forces and steric hindrances. These interactions are changed during the processing in dependence on the methods and conditions. Two original high methoxylated citrus pectins were modified and the derivatives were tested for their molecular parameters (degree of methoxylation, DM; galacturonan content, GC; intrinsic viscosity, [η]; ash content, cations) and for their thermal degradation and dissolution behaviour. It was found that pectins were degraded later after removing side chains, low-molecular sugars and cations by washing with acidified ethanol as well as after amidation with ethanolic ammonia. The materials were degraded earlier after re-precipitation and acidic (HCl) or alkaline (K₂CO₃) demethoxylation. Additionally, for all pectins the pre-drying treatment and drying procedure were of considerable importance with respect to state and state transitions. The characteristic degradation temperatures and other parameters of the thermal analysis gave important information on the stability and homogeneity of the materials as well as on the molecular interactions and the preferred conformation. Conformations and conformational changes are assumed to be detectible to a certain extent by thermal analysis. Altogether, the thermal analysis proved to be a quick and reproducible method for the detection of changes of several material properties of dry pectins that result from modifications and processing.     

Hydrolysis of apple pectin by the coordinated activity of pectic enzymes

The hydrolysis of pectin from apples, cv. Budimka fruit (Pyrus mahus L.), by individual and/or combined action of fungal polygalacturonase from Aspergillus niger (FPG), fungal pectin esterase from A. niger (FPE) and plant tomato pectin esterase (PPE) was studied. The optimum pH values for individual actions of FPG, FPE and PPE on 1% apple pectin were determined to be 4.5, 3.5 and 6.5, and the optimum temperatures were 40, 45, and in the range 45–50 °C, respectively. FPE was found to be more efficient for the hydrolysis of the apple pectin than was PPE from tomato. By measuring the initial velocities on 1% apple pectin it was confirmed that the PG expressed no effect on the PE activity. By using the combination of FPG (162 U/l) and FPE (60 U/l), e.g., in a respective ratio of 2.5, an efficient pectin degradation process, with a viscosity reduction of η/η₀ = 1.05, could be reached in less than 2 h. This process produced about 160 ppm of methanol in the pectin digest. The long term hydrolysis reaction of the apple pectin with FPG (162 U/l) and FPE (27 U/l) achieved a degree of hydrolysis of around 29% after 12 h and consisted mostly of trimers (28.4%).     

不同部位柚子果胶提取率与理化特性相关性研究

采用酸处理乙醇沉淀法从柚子黄皮、白皮、囊衣、果肉中提取果胶,计算提取率,对提取的柚子果胶进行pH、半乳糖醛酸、酯化度、溶解度、黏度等理化特性的测定,并分析果胶液的热稳定性、提取率与理化特性的相关性。结果表明,柚子不同部位果胶的提取率表现为：果肉>白皮>囊衣>黄皮,pH为：黄皮>囊衣>白皮>果肉,半乳糖醛酸含量：白皮>黄皮>囊衣>果肉,酯化度：囊衣>白皮>果肉>黄皮,溶解度：果肉>白皮>囊衣>黄皮;各部位提取率、半乳糖醛酸、酯化度均存在极显著差异（p <0.01）,黄皮、囊衣、白皮果胶之间pH差异不显著（p> 0.05）;柚子果胶提取率与pH呈显著负相关（r=-0.973,p<0.05）;柚子各部位果胶的黏度均优于市售果胶,但高温降低了柚子果胶的热稳定性。     

Effect of pH on the Degradation and Regeneration of Betanine

The influence of pH (3.0–7.0) on betanine stability in solution was studied based on proposed reversible reaction kinetics. The forward and reverse rate constants and their activation energies were determined and found to be pH dependent. The influence of pH on two degradation products showed that betalamic acid was most stable as the pH of the reaction increased, while cyclodopa-5–0-glucoside was more stable as the pH decreased. The results support the reported conclusion that betanine is most stable at an intermediate pH range (4.0–5.0).