PECTIC SUBSTANCES AND FIRMNESS OF CUCUMBER PICKLES AS INFLUENCED BY CACL2, NACL AND BRINE STORAGE1

The effects of brine treatments (CaCl₂ and NaCl) and storage on pectic substances and texture of cucumber pickles were examined. Firmness of cucumber pickles was closely associated with the solubility characteristics and degree of esterification (DE) of pectic substances. Brining, storage, time of CaCl₂ addition and concentration of NaCl and CaCl₂ were all observed to influence the characteristics of pectic substances. Important to preventing softening was maintenance of pectic substances not extractable (NXP) by conventional methods, i.e., by water (WSP), the chelator sodium hex-ametaphosphate (CSP), and dilute alkali (OHSP). Erosion of NXP consistently resulted in increased levels of CSP and reduced firmness. Reducing the amount of demethylation of pectins was also associated with maintaining firmness. Although the DE declined rapidly during brining, tissues from treatments that enhanced firmness had pectic substances with the highest DE. CaCl₂ added to brine at the beginning of fermentation was most effective in preventing the demethylation of pectins and solubilization of NXP. In contrast, delayed addition of CaCl₂ and storage in low NaCl concentration (5% or less) caused greater pectin demethylation, erosion of NXP with concomitant increases in CSP and tissue softening.     

Firmness and Cell Wall Characteristics of Pasteurized Jalapeño Pepper Rings as Affected by Preheating and Storage

Changes in cell wall pectic substances, degree of pectin methylation, bound calcium and firmness were determined in preheated and nonpreheated fresh pack jalapeño pepper rings stored for 5 mo. Pepper rings preheated for 60 min at 50°C in a brine solution (8% NaCl and 0.2% CaCl₂, were firmer, had more nonextrctable pectins (NXP), more bound calcium, less water-soluble and chelator-soluble pectins (CSP), and less pectin methylation than nonpreheated pepper rings. The greater formation and maintenance of nonextractable pectins, which resisted acid hydrolysis during pasteurization and storage is probably an important factor in firming.     

Relationship Between Degree of Pectin Methylation and Tissue Firmness of Cucumber Pickles

The relationship between pectin methylation and tissue firmness was examined in cucumber pickles exposed to pre-brining and brining treatments. Tissue treated with CaCl₂ prior to or during brining, blanched before brining or held at 2°C during brine storage resisted softening. Although all treatments reduced the degree of esterification (DE) of pectic substances, less demethylation occurred in treatments that protected against softening. Join point regression analysis of the data indicated that maximum firmness of mesocarp tissue was attained when the DE of pectins was 12.3 ± 1.2 or greater. Firmness declined concomitantly when the DE declined below 12.3 ± 1.2. Methods that protect against excessive demethylation of pectins appear to be important in retarding softening of cucumber pickle tissue during storage in brine.     

Bound Cations in Cucumber Pickle Mesocarp Tissue as Affected by Brining and CaCl2

The effects of brining, fermentation, storage, time of CaCl₂ addition and concentration of NaCl and CaCl₂ on Ca⁺⁺, Mg⁺⁺, Na⁺, and K⁺ bound to middle lamella-cell wall material of cucumber pickle mesocarp tissue were examined. Changes in the amount of each bound cation occurred rapidly during the first 2 days of brining; levels then remained relatively stable during fermentation and storage if concentrations of NaCl or CaCl₂ in brines were not altered. NaCl reduced levels of bound Ca⁺⁺, Mg⁺⁺, and K⁺, and the presence of CaCl₂ increased the amount of bound Ca⁺⁺ by displacing the other cations. Delayed addition of CaCl₂ to brines enhanced the content of bound Ca⁺⁺, indicating that levels of bound Ca⁺⁺ may not be related to maintenance of firmness.     

Mechanistic insight into common bean pectic polysaccharide changes during storage,soaking and thermal treatment in relation to the hard-to-cook defect

Different mechanisms responsible for the development of the hard-to-cook defect in common beans during storage, their soaking behavior and softening during thermal treatment have been previously suggested. However, these mechanisms have not been sufficiently confirmed by direct molecular evidence. This research aimed at gaining a detailed mechanistic insight into changes occurring in Canadian wonder bean pectic polysaccharides during storage, soaking and/or thermal treatment in different brine solutions in relation to the development and manifestation of the hard-to-cook (HTC) defect. Both fresh or easy-to-cook (ETC) and stored (HTC) bean samples were either soaked or soaked and thermally treated in demineralized water, solutions of Na₂CO₃ and CaCl₂ salts followed by extraction of cell wall materials. Pectic polysaccharide properties examined included sugar composition, degree of methylesterification (DM), extractability and molar mass (MM). The DM of pectin from ETC and HTC beans was similar but low (< 50%). Upon (pre)treatment in a Na₂CO₃ solution, solubilization of pectic polysaccharides, especially the strongly bound chelator- (CEP) and Na₂CO₃- (NEP) extractable pectins was enhanced leading to increased amounts of water extractable pectin (WEP). Also, there was a decrease in high MM polymers paralleled by an increase in β-elimination degradation products. These observations are in line with the fast cooking behavior of beans (pre)treated in a Na₂CO₃ solution. In contrast, (pre)treatment in a CaCl₂ solution hindered softening leading to the failure of the beans to cook. The beans (pre)treated in a CaCl₂ solution showed increased high MM polymers and lack of cell wall separation. Therefore, it can be inferred that development of the hard-to-cook defect in Canadian wonder beans during storage and its manifestation during soaking and subsequent thermal treatment is largely reflected by the pectic polysaccharide properties in line with the pectin hypothesis. Our data suggest the release of Ca⁺⁺ leading to pectin cross-linking and the increase or decrease of β-elimination depolymerization. However, the relatively high amounts of neutral sugars and strongly bound NEP in HTC seeds do not allow to rule out the possible existence of non-Ca⁺⁺ based pectin cross-linking.     

Cell Wall Characteristics of Gamma-Radiated Refrigerated Cucumber Pickles

The effect of gamma radiation (0, 0.5, and 1.0 kGy) on firmness and changes in cell wall polysaccharides of mesocarp tissue from refrigerated cucumber pickles was examined. Softening of mesocarp tissue of pickles exposed to 1.0 kGy was a response associated with altered solubility characteristics of pectic substances. Ionizing radiation reduced nonsoluble and alkali soluble pectic substances, while levels of water and chelator soluble pectic substances were increased. Radiation reduced the degree of esterification of pectic substances and increased the amount of bound calcium. Except for a small reduction in galactose caused by 1.0 kGy, levels of other neutral sugars in the cell wall were not significantly affected by any of the treatments.     

Thermal and Calcium Pretreatment Affects Texture, Pectinesterase and Pectic Substances of Frozen Sweet Cherries

Freezing causes loss of turgidity and firmness in sweet cherries. Thermal pretreatment at 50°C for 10 min followed by immersion in 100 mM CaCl₂ and thermal pretreatment at 70°C/2 min with or without immersion in 100 mM CaCl₂ prevented freezing-induced loss of firmness. Thermal pretreatments increased the pectin fraction soluble in EDTA, reduced the degree of pectin esterification, and increased both the concentration of divalent cations in the cell wall and the pectinesterase activity bounded to the cell wall. Immersion in CaCl₂ increased the concentration of Ca²⁺ cations in the cell wall and enhanced the effect of thermal pretreatments on pectinesterase activity.     

ELEVATED CALCIUM CHLORIDE IN CUCUMBER FERMENTATION BRINE PROLONGS PICKLE PRODUCT CRISPNESS

ABSTRACT

The effects of treating cucumbers with calcium chloride (CaCl₂) during fermentation and alum during desalting on changes in crispness of processed pickle mesocarp tissue during storage were determined from probe penetration forces, measurements of sound frequencies and sensory panel ratings. Penetration forces of mesocarp tissues from salt‐stock and desalted pickles that had been treated with CaCl₂ were similarly higher than untreated tissues. After processing and storage, crispness and its retention was significantly correlated to the amount of residual Ca⁺⁺. A high level of crispness was retained during 52 weeks of storage in only the tissues containing elevated residual Ca⁺⁺ (1,248 and 1,490 ppm). Tissues containing 96 ppm Al⁺⁺⁺ and 655 ppm Ca⁺⁺ were substantially crisper than tissues with less than 900 ppm Ca⁺⁺ and without Al⁺⁺⁺; however, retention of crispness was better in tissues containing elevated Ca⁺⁺. It is concluded that alum can be replaced by elevating residual Ca⁺⁺.

PRACTICAL APPLICATIONS

Augmenting calcium chloride in cucumber fermentation brines to increase the residual concentration of Ca⁺⁺ in the processed pickle product provides manufacturers the opportunity to improve retention of crispness without using alum. Elimination of Al⁺⁺⁺ without compromising texture should improve marketability of products, since Al⁺⁺⁺ is objectionable to some distributors and consumers.     

Firming of fruit tissues by vacuum-infusion of pectin methylesterase: Visualisation of enzyme action

Apple pieces were vacuum-impregnated with either a pectin methylesterase (PME) and calcium solution or with water prior to pasteurization. Pasteurized apple pieces impregnated with PME and calcium showed a significantly higher firmness. Moreover, solid state ¹³C NMR spectroscopy of apple cell wall residues revealed an increase of their molecular rigidity. Exogenous PME addition involved a decrease from 82% to 45% of apple pectin degree of methyl-esterification. Microscopic observations of apple slices immunolabelled with antibodies specific for pectins showed that (i) demethyl-esterification was more intense in the cell wall region lining intercellular spaces (demonstrating a key role for these intercellular channels in the enzyme penetration in the tissue during vacuum-infusion) and that (ii) the number of calcium-dimerized deesterified homogalacturonan chains increased. The results corroborate the hypothesis that vacuum-impregnated PME action liberates free carboxyl groups along pectin chains that could interact with calcium, increasing the rigidity of pectins and finally the mechanical rigidity of apple tissue.     

Effects of Salts Added After Cooking on the Texture of Canned Snap Beans

Soaking bean pods in NaCl solutions caused decreases in firmness and increases in Ca⁺⁺ solubilization as the NaCl concentration increased. CaCl₂ soak solutions increased firmness of pods previously softened by soaking in KCl solutions. Chlorides of Na⁺, K⁺, Li⁺, NH₄⁺, and Mg⁺⁺, and Na acetate caused softening. LiCl caused the most softening, while MgCl₂ caused the greatest solubilization of Ca⁺⁺. Salt-induced softening was accompanied by Ca⁺⁺ displacement. Firmness of salt-softened pods was further decreased by subsequent removal of the salt, indicating an electrostatic component as a minor factor in pod texture.     

Freezing of strawberries by immersion in CaCl2 solutions

The present investigation studied the freezing of strawberries by immersion in CaCl₂ solutions, analysing drip loss, pectin content and the degree of esterification of the pectins, total and cell-wall bonded calcium contents, the ratio bonded calcium/total calcium, and textural parameters. In addition, the effect of immersion in pectin methylesterase (PME) solutions prior to immersion freezing (IF) was analysed. The firmness of thawed fruit decreased by approximately 74% with respect to fresh strawberries, and neither IF-CA (freezing by immersion in CaCl₂ solution) nor PME–IF-CA (immersion in PME solution + freezing by immersion in CaCl₂ solution) provided significant benefit in maintaining firmness when compared to slow freezing (SF). However, IF provided a significant benefit in reducing drip loss of thawed strawberries when compared to SF, but pre-treatment with PME did not provide any additional benefit.     

Firmness and Cell Wall Characteristics of Pasteurized Jalapeño Pepper Rings Affected by Calcium Chloride and Acetic Acid

Pepper rings packed in brine containing CaCl₂ were firmer, had higher bound calcium, chelator soluble pectin and pectin DE, and less water-soluble pectin (WSP) than peppers packed in brine containing no CaCl₂. Pepper rings packed in low acid brines (1% and 1.2% acetic acid) were firmer and had less WSP than those packed in high acid brine. Those samples (4% acetic acid) resulted in softening and pectin solubilization, but CaCl₂ resulted in less softening. Monosaccharide composition of cell walls was not affected by CaCl₂ or acetic acid. Firmness retention in CaCl₂ treated samples was probably due to greater association between calcium ions and pectic substances, which resisted acid hydrolysis.     

Influence of Processing Methodology on Quality of Cucumber Pickles

A study was conducted on the influence of fruit size, blanch temperature, treatment with calcium, and type of acid in cover brine on quality attributes and carbohydrates in nonfermented and fermented cucumber pickles. Firmness was improved by blanching, especially in CaCl₂ solution in both fermented and fresh-pack pickles. Fermentation and acetic acid brine treatments produced the firmest pickles. Size of fruit and length of storage affected quality attributes. The carbohydrate fractions, water-soluble pectin and sodium hexametaphosphate-soluble (SPS) pectin, were correlated with shearpress and sensory firmness. It was concluded that method of processing had a significant effect on quality of pickles.     

Quality attributes and cell wall properties of strawberries (Fragaria annanassa Duch.) under calcium chloride treatment

Effects of CaCl₂ (0%, 1% and 4%) treatment on quality attributes and cell wall pectins of strawberry fruits stored at 4 °C for 15 d were investigated. Strawberry firmness was not significantly affected by CaCl₂ treatment. Compared to the other groups, the 1% CaCl₂ group had better quality attributes, including decay rate, weight loss and soluble solids content. The treatment with 4% CaCl₂ inhibited weight loss but caused phytotoxicity. During storage, the chain widths and lengths of water-soluble pectin (WSP), chelate-soluble pectin (CSP) and sodium carbonate-soluble pectin (SSP) decreased. Strawberry softening seemed to be due to modifications of CSP and SSP, especially the side chains. CaCl₂ treatment significantly slowed the breakdown of CSP and SSP chains by strengthening the ionic crosslinkages among these pectin molecules. These results illustrate the fundamental CaCl₂ effects and will help improve the application of CaCl₂ to postharvest fruits.     

Effect of Calcium Chloride and Alum on Fermentation, Desalting, and Firmness Retention of Cucumber Pickles

The effects of CaCl₂ in cucumber pickle fermentation and storage brines on fermentation, desalting and retention of mesocarp firmness after processing were determined. Also, the influence of post-desalting treatments with alum and CaCl₂ on firmness of processed pickle was evaluated. Fermentation and desalting were unaffected by CaCl₂ treatment of fermentation brines. However, exposure of pickles to CaCl₂ during fermentation and brine storage substantially reduced softening after processing. Post-desalting treatment with alum and/or CaCl₂ of pickles not previously exposed to CaCl₂ also reduced softening. Retention of firmness was maximized in pickles processed from fermentation and storage brines containing CaCl₂ and treated with alum or CaCl₂ after desalting.     

Towards a better understanding of the pectin structure-function relationship in broccoli during processing: Part I—macroscopic and molecular analyses

To investigate the structure-function relationship of pectin during (pre)processing, broccoli samples (Brassica oleracea L. cultivar italica) were subjected to one of the following pretreatments: (i) low-temperature blanching (LTB), (ii) LTB in combination with Ca²⁺ infusion, (iii) high-pressure pretreatment (HP), (iv) HP in combination with Ca²⁺ infusion, or (v) no pretreatment (control sample), whether or not in combination with a thermal treatment of 15 min at 90 °C. The macroscopic attributes of broccoli were linked to the chemical structure of broccoli pectin. By enhancing the cross-linking of pectic polymers, both LTB and HP reduced the texture loss that occurred during thermal processing of broccoli. During these pretreatments, homogalacturonan was de-esterified by pectin methylesterase, which led to changes in pectin solubility. When LTB or HP was combined with Ca²⁺ infusion, changes in the structure of pectin occurred, however not always reflected at the macroscopic level. The degree of esterification of pectin in Ca²⁺-soaked broccoli samples was lower compared to non-Ca²⁺-soaked samples and, in addition, a higher amount of ionically cross-linked pectin was retrieved.     

Effect of debranching on the rheological properties of Ca-pectin gels

Water-soluble pectin (WSP) extract was subjected to controlled carrot pectin methylesterase treatment, thereby producing de-esterified pectin (DEP). Both WSP and DEP were incubated with a mixture of endo-arabinanase and α-L-arabinofuranosidase to yield partially debranched pectins (WSP_DBr and DEP_DBr respectively). Pectin samples were characterised in terms of degree of methylesterification (DM), neutral sugar content, and degree of branching (DBr). The characterised pectins were used for the preparation of pectin gels with high and low calcium ion (Ca²⁺) concentrations. The rheological characteristics of the produced gels were evaluated by means of small-amplitude oscillatory tests. These characteristics include network development of the gel, gel strength (G′), gel elastic character and gel type. Partial debranching of pectin resulted in a reduction of the arabinose content (by approximately 50%) and caused a slight decrease in polymer DBr. Gels produced from semi-dilute solutions of partially debranched pectins showed network development profiles similar to those prepared from semi-dilute solutions of the corresponding non-debranched polymers. Yet, the former gels showed lower G′ values, poor gel elastic character and a “weaker” nature as compared to the latter. Next to Ca²⁺ cross-links, the presence of long arabinose-containing side chains is suggested to play an important role in the rheological characteristics of Ca²⁺-pectin gels.     

Effects of Ca++, Mg++ and Na+ on Heat Aggregation of Whey Protein Concentrates

Effect of Ca⁺⁺ on the heat aggregation of whey protein concentrates (WPC) was compared with that of Na⁺ and Mg⁺⁺. On the alkaline side of the isoelectric zone, aggregation of WPC was increased by the addition of CaCl₂, MgCl₂ or NaCl, among which CaCl₂ showed the greatest effect. The denaturation temperature of WPC determined by differential scanning calorimetry significantly decreased in the presence of CaCl₂ or MgCl₂, but increased slightly in the presence of NaCl. In the electrophoretic patterns of heated WPC, the most sensitive protein to Ca⁺⁺ was β-lactoglobulin.     

Butternut and beetroot pectins: Characterization and functional properties

The physicochemical characteristics and functional properties of butternut (Cucumis moschata Duch. ex Poiret) and beetroot (Beta vulgaris L. var. conditiva) pectins obtained by enzymatic extraction from by-products of vegetable processing have been evaluated. The molecular mass distribution was determined using Gel Permeation Chromatography using light scattering, refractive index and UV detectors and the samples were found to be highly heterogeneous and polydisperse. M_w values of 136,000 and 1,309,000 g/mol were determined for butternut and beetroot pectins respectively. Butternut pectin had a high degree of methyl esterification. In the presence of high concentrations of sugar and at low pH, this pectin did not form gels but instead produced viscous solutions. Solutions showed pseudoplastic flow behaviour with a shear thinning index of 0.68 as determined from the Power law model. Beetroot pectin had a low degree of methyl esterification and formed gels with addition of Ca²⁺ at concentrations of 10 mg/g pectin or higher. The maximum value of the storage modulus was obtained at a Ca²⁺/GalA ratio of 0.25. The thermal stability of gels suggested that hydrogen bond interactions prevailed in the absence of Ca²⁺, whereas electrostatic junction zones increasingly developed between pectin chains as the calcium concentration increased. Aqueous solutions of butternut and beetroot pectins significantly reduced surface tension and both samples were able to form stable oil-in-water emulsions. It was found that protein and/or polyphenol – rich fractions present in the pectins adsorbed at the oil–water interface and were responsible for the emulsification properties.     

Effect of Cooking and Pre-Cooking on Cell-Wall Chemistry in Relation to Firmness of Carrot Tissues

The aim of this work was to investigate heat-induced changes in cell wall polysaccharides of carrot in relation to texture. Discs of fresh carrot (Daucus carota cv Amstrong) tissue were subjected to cooking (100°C, 20 min), with or without a pre-cooking treatment (50°C, 30 min). Alcohol-insoluble residues were prepared from the tissues and were extracted sequentially with water, NaCl, CDTA, Na₂CO₃ and 0·5 M KOH to leave a residue. These were analysed for their carbohydrate compositions, their degree of methyl esterification and the molecular size of selected soluble polysaccharides. Cooking caused tissues to soften. This involved cell separation, an increase in water- and salt-soluble, high-molecular-weight pectic polysaccharides and a concomitant decrease in the pectic polymers in all wall extracts and the residue. Pre-cooking prior to cooking enhanced cell–cell adhesion and reduced the extent of softening. This was accompanied by a general reduction in the degree of methylesterification of cell-wall pectic polymers, and a decrease in the cooking-induced modification to all pectic fractions. The firming effect of pre-cooking could be reversed by extracting the precooked+cooked tissue with CDTA, a chelating agent. The role of Ca²⁺ cross-linked polymers and pre-cooking in the enhancement of firmness are discussed. © 1997 SCI.