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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 soft pectin.

Chemical Phenomena↗

The degree of methylation influences the degradation of pectin in the intestinal tract of rats and in vitro.

We investigated the degradation, metabolism, fate, and selected effects of pectin in the intestinal tract of rats. Conventional and germfree rats were fed for 3 wk diets containing 6.5% pectin (degree of methylation 34.5, 70.8 and 92.6%, respectively) or pectin-free diets. Pectin passes the small intestine as a macromolecule. The molecular weight distribution of pectins isolated from intestinal contents of germfree rats were unaffected by diet. No or very little galacturonan was found in cecum, colon or feces of most of the conventional rats. In colon contents of some conventional rats, di- and trigalacturonic acid were present. Total anaerobic and Bacteroides counts were greater in groups fed pectin. The concentration of short-chain fatty acids (SCFA) was higher in cecum and feces in all pectin-fed groups. With increasing degree of methylation, the formation rate of SCFA decreased in the cecum of conventional rats. During in vitro fermentation of pectin with fecal flora from rats, unsaturated oligogalacturonic acids appeared as intermediate products. Low-methoxyl pectin was fermented faster than high-methoxyl pectins in vivo and in vitro. Pectin-fed rats had greater ileum, cecum and colon weights. We conclude that structural parameters of pectin influence its microbial degradation in the intestinal tract.

Animals↗

Pectin secretion and distribution in the anther during pollen development in Lilium.

Using the monoclonal antibodies JIM 5 and 7, pectin was immunolocalized and quantitatively assayed in three anther compartments of Lilium hybrida during pollen development. Pectin levels in both the anther wall and the loculus increased following meiosis, were maximal during the early microspore stages and declined during the remainder of pollen ontogenesis. In the microspores/pollen grains, pectin was detectable at low levels during the microspore stages but accumulated significantly during pollen maturation. During early microspore vacuolation, esterified pectin epitopes were detected both in the tapetum cytoplasm and vacuoles. In the anther loculus, the same epitopes were located simultaneously in undulations of the plasma membrane and in the locular fluid. At the end of microspore vacuolation, esterified pectin epitopes were present within the lipids of the pollenkitt, and released in the loculus at pollen mitosis. Unesterified pectin epitopes were hardly detectable in the cytoplasm of the young microspore but were as abundant in the primexine matrix as in the loculus. During pollen maturation, both unesterified and esterified pectin labelling accumulated in the cytoplasm of the vegetative cell, concurrently with starch degradation. In the mature pollen grain, unesterified pectin epitopes were located in the proximal intine whereas esterified pectin epitopes were deposited in the distal intine. These data suggest that during early microspore development, the tapetum secretes pectin, which is transferred to the primexine matrix via the locular fluid. Further, pectin is demonstrated to constitute a significant component of the pollen carbohydrate reserves in the mature grain of Lilium.

Antibodies, Monoclonal↗

High-methoxyl pectin has greater enhancing effect on glucose uptake in intestinal perfused rats.

OBJECTIVE: Pectins have been known to decrease blood glucose levels. However, the mechanism of this effect is unclear. The direct action of various pectins (high- or low-methoxyl pectins) on the intestinal absorption of glucose was investigated in gut-perfused rats. METHODS: After equilibrium, jejunal and ileal segments were simultaneously perfused with an isotonic electrolyte solution (pH 7.4) containing glucose (10 mM/L) and high- or low-methoxyl pectins (10 g/L). Each test or control solution was perfused in a random sequence, with perfusion times of 30 min. Changes in glucose concentration of perfusate solution reservoir were determined over the experimental period. RESULTS: High- and low-methoxyl pectins in the perfusate significantly inhibited jejunal uptake of glucose compared with the control (P < 0.05). High-methoxyl pectins had greater inhibitive effect on intestinal absorption of glucose than low-methoxyl pectins. The observed changes in glucose and water absorptions caused by high- or low-methoxyl pectins were reversible by switching to a pectin-free perfusate. In addition, net water absorption changed to secretion after addition of high- or low-methoxyl pectins. CONCLUSIONS: These results suggest that the decrease in intestinal absorption of glucose observed after perfusion of high- or low-methoxyl pectins may be caused by viscosity-related increases in mucosal unstirred layer thickness.

Animals↗

Chemically methylated and reduced pectins: preparation, characterisation by 1H NMR spectroscopy, enzymatic degradation, and gelling properties.

The gelling properties of pectins are known to be closely related to the degree of methylation (DM) and the distribution of the ester groups. In order to investigate this dependency, a natural citrus pectin (DM 64%) has been methylated to pectins with higher DM or saponified to achieve pectins with lower DM. A simple method for determination of DM by 1H NMR spectroscopy is presented. New modified pectins have been prepared by treatment of pectins having different DM with NaBH(4) to reduce selectively the methyl esters to primary alcohols in the presence of free acids. The degree of reduction (DR) and the DM of the remaining carboxylic acids could likewise be determined by 1H NMR spectroscopy. The new reduced pectins are recognized by the pectin degrading enzymes polygalacturonase PGI and PGII as well as by pectin lyase, all from Aspergillus niger, but the enzymes exhibit lower specific activities as compared with unmodified pectin. The new reduced pectins exhibit high gelling properties.

Aspergillus niger↗

Pectin anaphylaxis and possible association with cashew allergy.

BACKGROUND: Inhalation of pectin has been identified as a cause of occupational asthma. However, allergic reactions to orally ingested pectin have not been reported. OBJECTIVES: To describe a child with pectin-induced food anaphylaxis and to discuss its possible relationship to cashew allergy. METHODS: A 3 1/2-year-old boy developed anaphylaxis once after eating cashews and later after eating a pectin-containing fruit "smoothie." He also has a history of generalized pruritus after eating grapefruit. Skin tests or radioallergosorbent tests (RASTs) were performed to pectin and other suspected food allergens. RESULTS: The child had a positive skin prick test reaction to pectin and a high RAST reaction to cashew and pistachio. He had a low-level positive RAST reaction to grapefruit. Results of allergy tests for the other potential food allergens were negative. The pectin in the smoothie was confirmed to be of citrus origin. Review of previous case reports of pectin-induced occupational asthma revealed several patients with allergies to and cross-reactivity with cashew. CONCLUSIONS: Ingestion, not only inhalation, of pectin can cause hypersensitivity reactions. Cashew, and possibly pistachio, allergy may be associated with pectin allergy, and the possibility of pectin allergy should be considered in cashew- or pistachio-allergic patients who have unexplained allergic reactions.

Anacardium↗

Production and characterization of oil-in-water emulsions containing droplets stabilized by beta-lactoglobulin-pectin membranes.

Oil-in-water emulsions containing droplets stabilized by beta-lactoglobulin (beta-Lg)-pectin membranes were produced using a two-stage process. A primary emulsion containing small droplets (d(32) approximately 0.3 microm) was prepared by homogenizing 10 wt % corn oil with 90 wt % aqueous solution (1 wt % beta-Lg, 5 mM imidazole/acetate buffer, pH 3.0) using a high-pressure valve homogenizer. The primary emulsion was then diluted with pectin solutions to produce secondary emulsions with a range of pectin concentrations (5 wt % corn oil, 0.45 wt % beta-Lg, 5 mM imidazole/acetate buffer, 0-0.22 wt % pectin, pH 3.0). The electrical charge on the droplets in the secondary emulsions decreased from +33 +/- 3 to -19 +/- 1 mV as the pectin concentration was increased from 0 to 0.22 wt %, which indicated that pectin adsorbed to the droplet surfaces. The mean particle diameter of the secondary emulsions was small (d(32) < 1 microm) at relatively low pectin concentrations (<0.04 wt %), but increased dramatically at higher pectin concentrations (e.g., d(32) approximately 13 microm at 0.1 wt % pectin), which was attributed to charge neutralization and bridging flocculation effects. Emulsions with relatively small mean particle diameters (d(32) approximately 1.2 microm at 0.1 wt % pectin) could be produced by disrupting flocs formed in secondary emulsions containing highly negatively charged droplets, for example, by sonication, blending, or homogenization. The particles in these emulsions probably consisted of small flocs containing a number of protein-coated droplets bound together by pectin molecules. These emulsions had good stability to further particle aggregation up to relatively high ionic strengths (< or =500 mM NaCl) and low pH (pH 3). The interfacial engineering technology used in this study could lead to the creation of food emulsions with improved physicochemical properties or stability.

Chemical Phenomena↗

Stabilization of caseinate-covered oil droplets during acidification with high methoxyl pectin.

Polysaccharides are widely used in the food industry to modify the stability of protein-based drinks. However, an in depth knowledge of the interactions occurring in the system is still lacking. In this study, the interactions between sodium caseinate and high methoxyl pectin under acidification conditions were studied nondestructively and without dilution using transmission diffusing wave spectroscopy. Oil-in-water emulsions were prepared with 10% soybean oil and 0.5% sodium caseinate. Various concentrations of pectin (ranging from 0 to 0.2%) were added, and the emulsions were acidified with glucono-delta-lactone. With acidification, a "sol-gel" transition occurred and emulsions containing pectin were more stable at lower pH than those without pectin. Furthermore, the sol-gel transition of the mixtures was more sudden for control emulsions without pectin. While in control samples the final solidlike emulsion after gelation tended to be more inhomogeneous and more dissimilar to the starting emulsion, emulsions with pectin in solution gelled later under acidification. With a sufficient amount of pectin, the emulsions showed no aggregation and the destabilization pH varied depending on the amount of pectin present in the emulsions. At intermediate pH values (pH > 5.5), the emulsions displayed a decrease in particle size, more pronounced in samples containing pectin. The results collected using light scattering in concentrated systems, 10% (v/v) in our case, suggested that pectin stabilizes the emulsion oil droplets forming a network of oil droplets loosely connected by strands of pectin.

Caseins↗

The effect of dietary citrus pectin on the excretion of human fecal neutral and acid steroids and the activity of 7alpha-dehydroxylase and beta-glucuronidase.

The purpose of this study was to investigate the effects of citrus pectin on human fecal neutral and acid steroid excretion and beta-glucuronidase and 7alpha-dehydroxylase activity. Eight healthy male subjects (age 20 to 27 yr) were used in a switchback design with or without 15 g citrus pectin added to a mixed low fiber diet. There were three successive 18-day periods preceded by a 4-day adjustment period. Half of the subjects followed a pectin-nonpectin-pectin protocol and the other half followed a nonpectin-pectin-nonpectin protocol. Fecal samples were collected throughout the study under anaerobic conditions. Compared to the control diet, mean fecal weight, percentage moisture, transit time, and fecal fat for both groups of subjects were not significantly different by analysis of variance when subjects were fed pectin diet. Mean beta-glucuronidase activity was increased (35%) when subjects were fed the pectin. Mean 7alpha-dehydroxylase activity showed no definite trend. Mean neutral steroid concentration was slightly decreased (8%) when the pectin diet was fed but total excretion was unchanged. End of period neutral steroid concentration was decreased 9% and total excretion was decreased 3.5%. Mean acid steroid concentration was not changed but total excretion was increased (11%) on the pectin diet. End of period acid steroid concentration and excretion was increased 6% on the pectin diet. This study shows that there were interrelationships between dietary pectin, neutral and acid steroid metabolism, and bacterial enzyme activity.

Adult↗

The effect of pectin on hepatic lipogenesis in the enterally-fed rat.

The fermentation of pectin by colonic bacteria produces short-chain fatty acids (SCFA) which are then absorbed by the host. The purpose of this study was to determine whether pectin, added to a chemically defined diet, would increase hepatic lipogenesis and whether this effect is mediated by intestinal bacteria. Eighteen Sprague-Dawley rats underwent placement of a feeding gastrostomy and a swivel apparatus. Postoperatively, rats were randomly assigned to one of three groups: 1) No Pectin received a fat-free chemically defined diet, 2) Pectin received the same diet with the addition of 1% (w/v) pectin, and 3) Neomycin received the same diet with 1% w/v pectin and neomycin (80 mg/kg of body weight daily). On the 5th postoperative d, all diets included 12.5% (v/v) deuterium as D2O. After the infusion of the labeled diets for 24 hr, the content and deuterium enrichment of liver palmitate, stearate and oleate were measured and the production rates calculated. The liver content and production rates of these fatty acids were higher in Pectin animals than in either the No Pectin or Neomycin animals. Since the effect of pectin on hepatic lipogenesis was reduced by the concomitant administration of the intestinal antibiotic neomycin, it appears that this effect depends on the bacterial fermentation of pectin. It is postulated that the SCFA produced during pectin fermentation promote lipogenesis via a direct stimulatory effect, in addition to being carbon donors.

Animals↗

Inhibition of spontaneous metastasis in a rat prostate cancer model by oral administration of modified citrus pectin.

BACKGROUND: Prostate cancer is the most common cancer diagnosed in U.S. men and remains incurable once it has metastasized. Many stages of the metastatic cascade involve cellular interactions mediated by cell surface components, such as carbohydrate-binding proteins, including galactoside-binding lectins (galectins). Modified citrus pectin (pH-modified), a soluble component of plant fiber derived from citrus fruit, has been shown to interfere with cell-cell interactions mediated by cell surface carbohydrate-binding galectin-3 molecules. PURPOSE: The aim of this study was to determine whether modified citrus pectin, a complex polysaccharide rich in galactosyl residues, could inhibit spontaneous metastasis of prostate adenocarcinoma cells in the rat. METHODS: The ability of modified citrus pectin to inhibit the adhesion of Dunning rat prostate cancer MAT-LyLu cells to rat endothelial cells was measured by 51Cr-labeling. Modified citrus pectin inhibition of MAT-LyLu cell anchorage-independent growth was measured by colony formation in agarose. The presence of galectin-3 in rat MAT-LyLu cells and human prostate carcinoma was demonstrated by immunoblotting and immunohistochemistry. One million MAT-LyLu cells were injected subcutaneously into the hind limb of male Copenhagen rats on day 0. Rats were given 0.0%, 0.01%, 0.1%, or 1.0% (wt/vol) modified citrus pectin continuously in their drinking water (from day 4 until necropsy on day 30). The number of MAT-LyLu tumor colonies in the lungs were counted. RESULTS: Compared with 15 or 16 control rats that had lung metastases on day 30, seven of 14 rats in the 0.1% and nine of 16 rats in the 1.0% modified citrus-pectin group had statistically significant (two-sided; P < .03 and P < .001, respectively) reductions in lung metastases. The lungs of the 1.0% modified citrus pectin-treated rats had significantly (two-sided; P < .05) fewer metastatic colonies than control groups (9 colonies +/- 4 [mean +/- SE] in the control group compared with 1 colony +/- 1 in the treated group). Modified citrus pectin had no effect on the growth of the primary tumors. In vitro, modified citrus pectin inhibited MAT-LyLu cell adhesion to rat endothelial cells in a time- and dose-dependent manner as well as their colony formation in semisolid medium. CONCLUSIONS: We present a novel therapy in which oral intake of modified citrus pectin acts as a potent inhibitor of spontaneous prostate carcinoma metastasis in the Copenhagen rat. IMPLICATIONS: Further investigations are warranted to determine the following: 1) the role of galectin-3 in normal and cancerous prostate tissues and 2) the ability of modified citrus pectin to inhibit human prostate metastasis in nude mice.

Adenocarcinoma↗

Effect of dietary cereal grain, citrus pectin, and guar gum on liver fat in laying hens and young chicks.

One laying hen and three chick experiments were conducted to study the effect of cereal grains, citrus pectin, and guar gum on liver fat of chicks and hens and on serum cholesterol of chicks. Feeding of wheat, rye, or 2% pectin in place of corn reduced liver fat content. The decrease in liver fat of hens fed wheat or rye was larger than that of those fed 2% pectin (P less than .05). The smallest amount of liver fat was found in livers of hens fed the rye diet. Wheat or pectin did not affect egg production of egg weight, but rye caused a significant decline in egg production in comparison with other treatments. Addition of 4% pectin or 2% guar gum to the corn control diet lowered liver fat, serum cholesterol (P less than .05), and body weight in chicks (P less than .05). Penicillin added to the diets containing 2% guar gum gave an increase in body weight (P less than .05) but had no effect on body weight of chicks fed diets containing 4% pectin. In contrast, pectinase prevented growth depression by pectin and guar gum. Pectinase also increased liver fat and serum cholesterol of birds fed the diet containing pectin or guar gum. When the corn control diet was pair-fed to the pectin diet, growth of the pair-fed chicks was better than that of the pectin-fed birds but was lower than that of birds fed the control diet ad libitium. Pectin-fed birds again had lower liver fat the serum cholesterol than the control birds. The reduced feed intake of chicks pair-fed the corn control diet had no effect on liver fat content.

Adipose Tissue↗

Effect of pectin on gastric emptying and gastroduodenal motility in normal subjects.

The effects of pectin ingestion on gastric emptying, gastroduodenal motility, and plasma levels of glucose, insulin, and glucagon were studied. Initial studies demonstrated that 15 g of pectin was the optimal dose. Subsequently 6 healthy male volunteers were studied on 4 separate days at random. On day 1, gastric emptying of a liquid and a solid meal was assessed by radioisotope technique using 99mTc-dithiopropylthiomine. On day 2, the gastric emptying study was repeated with the addition of pectin to each meal. Plasma levels of glucose, insulin, and glucagon also were determined during these 2 days. On day 3, the effects of liquid and solid meals on gastroduodenal motility were assessed by means of a perfused catheter system. On day 4, the motility study was repeated with the addition of pectin to each meal. Pectin supplementation caused a significant prolongation of gastric emptying half-time of both liquid and solid meals (p less than 0.05). The addition of pectin, however, did not have any significant effect on gastroduodenal motility other than increasing the duodenal motility index 10 min after the liquid meal. The addition of pectin to the liquid meal lowered plasma levels of insulin at 15, 30, and 45 min, and glucagon levels 15 min after the meal. No effect was noted on blood sugar levels. On the other hand, the addition of pectin to the solid meal had no effect on plasma levels of glucose, insulin, and glucagon. We conclude that pectin supplementation delays gastric emptying of both liquid and solid meals in normal human subjects without causing notable changes in gastroduodenal motility or significant variations in pancreatic hormone plasma levels. The pectin effect on gastric emptying may be caused solely by increasing the viscosity of the meals.

Adult↗

Possible mechanisms through which dietary pectin influences fibrin network architecture in hypercholesterolaemic subjects.

It is suspected that not only fibrinogen concentration but also the quality of fibrin networks may contribute to cardiovascular risk. Evidence is accumulating that a "prudent" diet may protect against diseases associated with raised clotting factors. The effect of diet on fibrinogen is, however, still controversial. In a previous study performed in our laboratory, it was shown that dietary pectin influences fibrin network architecture in hypercholesterolaemic men without causing any changes in fibrinogen concentration. To elucidate the possible mechanisms, it was necessary to study the possibility that pectin may itself have indirect effects on fibrin network architecture. Pectin is fermented in the gastrointestinal tract to acetate, propionate, and butyrate. In humans, only acetate reaches the circulation beyond the liver. This investigation primarily examined the possibility that pectin may, through acetate, influence fibrin network architecture in vivo. The effects of pectin and acetate supplementation in hypercholesterolaemic subjects were compared. Furthermore, this study also aimed at describing the possible in vitro effects of acetate on fibrin network architecture. Two groups of 10 male hyperlipidaemic volunteers each received a pectin (15 g/day) or acetate (6.8 g/day) supplement for 4 weeks. Acetate supplementation did not cause a significant change in plasma fibrinogen levels. As in the pectin group, significant differences were found in the characteristics of fibrin networks developed in plasma after 4 weeks of acetate supplementation. Fibrin networks were more permeable (from 213+/-76 to 307+/-81 x 10(11) cm2), had lower tensile strength (from 23+/-3 to 32+/-9% compaction), and were more lyseable (from 252+/-11 to 130+/-15 minutes). These results strongly suggest that the effect of pectin on network architecture could partially be mediated by acetate. Progressive amounts of acetate were used in vitro to investigate the possibility that acetate may be directly responsible for changes that occurred in fibrin network architecture in the plasma medium. Results indicated that acetate influenced fibrin network architecture directly. From the results, it seems highly possible that acetate may be responsible in part for the beneficial effects of pectin supplementation in vivo. It is evident that pectin or acetate supplementation can be useful during the treatment or prevention of some clinical manifestations, especially those associated with raised total cholesterol and possibly also plasma fibrinogen.

Adult↗

Effects of pectin-induced passive linkage of gastric H+ on the gastric acid secretion on the development of ethanol- and salicylate-induced gastric mucosal lesions in rats.

The aim of this study was to evaluate the effects of intragastrically given pectin-induced physicochemical properties and actions on active gastric acid secretion and on the development of ethanol- and aspirin-induced gastric mucosal lesions. The observations were carried out on CFY-strain rats, fasted for 24 h before the experiments with water ad libitum. The observations were carried out in two experimental series. A) The gastric mucosal lesions were produced by intragastrically given 96% ethanol or aspirin prepared with 0.2 M HCl. Different doses of pectin (100, 50 and 25 mg x kg(-1), respectively) were administered intragastrically 30 min before giving necrotizing agents. The number of gastric lesions was noted 1 h after the administration, while the severity of gastric mucosal lesions was scored by semi-quantitative scale. B) The effects of pectin were studied on the volume and H+ secretion of the stomach in 4-h pylorus-ligated rats. It has been found that: 1) the gastric mucosal lesions could be produced in 100% of rats by the application of both necrotizing agents. 2) Pectin in doses of 50-100 mg x kg(-1) increased the number of gastric mucosal lesions in both models, while no increase was produced by the application of 25-mg x kg(-1) dose. 3) The severity of mucosal lesions increased significantly after the administration of all doses of pectin. 4) The pectin-induced increase of gastric lesions (number) showed a dose-response effect. 5) The pectin produced a significant increase in the volume of gastric secretion and gastric H+ secretion. It has been concluded that: a) pectin-induced physicochemical changes are able to enhance the aggression to gastric mucosa produced by ethanol and aspirin; b) a positive correlation exists between the linkage of H+ to pectin and significant active metabolic response in the rat stomach; c) pectin alone stimulates the active metabolic process of the gastric H+ secretion.

Animals↗

Interchain heterogeneity of enzymatically deesterified lime pectins.

Two series of pectins with different levels and patterns of methyl esterification were produced by treatment of a very highly methylated lime pectin with a fungus- or plant-pectin methylesterase. The interchain distribution of free carboxyl groups was investigated by size exclusion and ion exchange chromatography. "Homogeneous" populations with respect to molar mass or charge density were thereby obtained, and their composition, molar mass, and calcium binding properties were investigated. The composition varies from one size exclusion chromatography fraction to another, the highest molar mass fraction being richer in rhamnogalacturonic sequences and exhibiting a slightly higher degree of methylation (DM). Separation of pectins by ion exchange chromatography revealed a narrow charge density distribution for pectins deesterified by fungus-pectin methylesterase, in agreement with a multichain mechanism. Conversely, pectins deesterified by plant-pectin methylesterase exhibited a very large charge density distribution suggesting a processive mechanism. The interchain polydispersity with regard to DM was however shown to have no impact on calcium binding properties of the different fractions. The progressive dimerization through calcium ions with decreasing DM of pectins deesterified by plant-pectin methylesterase seems to be the result of a peculiar intrachain pattern of methyl esterification that can be attributed to a multiple attack mechanism.

Carbohydrates↗

Nanostructure of native pectin sugar acid gels visualized by atomic force microscopy.

Height and phase shift images of high methoxyl sugar acid gels (HMSAG) of pectin were obtained by atomic force microscopy in the tapping mode. Images revealed that pores in these gels were fluid and flattened out when measured as a function of time. These images revealed for the first time the structure of adsorbed sugar on pectin in the hydrated native gels and how the pectin framework is organized within these gels. Segmentation of images revealed that the underlying pectin framework contained combinations of rods, segmented rods, and kinked rods connected end to end and laterally. The open network of strands was similar to pectin aggregates from 5 mM NaCl solution imaged earlier by electron microscopy (Fishman et al., Arch. Biochem. Biophys. 1992, 294, 253). Area measurements revealed that the ratio of bound sugar to pectin was in excess of 100 to 1 (w/w). Furthermore, images indicated relatively small differences in the organization of native commercial citrus pectin, orange albedo pectin, and lime albedo pectin gels at optimal pH as determined in this study. The findings are consistent with earlier gel strength measurements of these gels. In addition, values of gel strength were consistent with values of molar mass and viscosity of the constituent pectins in that they increased in the same order. Finally, we demonstrated the advantage of simultaneous visualization of height and phase shift images for observing and quantitating the nanostructure of relatively soft gels which are fully hydrated with a buffer.

Citrus aurantiifolia↗

Enzymatic modification of pectin to increase its calcium sensitivity while preserving its molecular weight.

A commercial high-methoxy citrus pectin was treated with a purified salt-independent pectin methylesterase (PME) isozyme isolated from Valencia orange peel to prepare a series of deesterified pectins. A series of alkali-deesterified pectins was also prepared at pH 10 under conditions permitting beta-elimination. Analysis of these pectins using high-performance size exclusion chromatography (HPSEC) with on-line multiangle laser light-scattering, differential viscometer, and refractive index (RI) detectors revealed no reduction in weight-average molecular weight (M(w); 150000) in the PME-treated pectin series, whereas a 16% reduction in intrinsic viscosity (IV) occurred below a degree of esterification (DE) of 47%. In contrast, alkali deesterification rapidly reduced both M(w) and IV to less than half of that observed for untreated pectin. PME treatment of a non-calcium-sensitive citrus pectin introduced calcium sensitivity with only a 6% reduction in the DE. Triad blocks of unesterified galacturonic acid were observed in (1)H nuclear magnetic resonance spectra of this calcium-sensitive pectin (CSP). These results demonstrate that the orange salt-independent PME isozyme utilizes a blockwise mode of action. This is the first report of the preparation of a CSP by PME treatment without significant loss of the pectin's M(w) due to depolymerization.

Calcium↗