Binding of aliphatic aldehydes by cornstarch polysaccharides

Binding by cryotextured cornstarch of individual aliphatic aldehydes (C6-C10; saturated or unsaturated) and their mixtures from aqueous solutions has been studied using capillary gas chromatography. The amount of compounds absorbed by the cryotextures depended linearly on the concentration of aldehydes in the original gel. The majority of the compounds under study were bound irreversibly. Aldehydes with low molecular weight were better absorbed by the cryotextures than by granules of intact cornstarch. Data of IR spectrocopy demonstrated that binding to cornstarch polysaccharides decreased the conformational mobility of odorants. The appearance of binding isotherms depended of the extent of aldehyde sorption, suggesting the involvement of multiple mechanisms of binding. The formation of supramolecular complexes through cooperative hydrophobic interactions between aldehydes and cornstarch polysaccharides was the preferential mechanism of the sorption.     

Binding of aromatic compounds to cornstarch polysaccharides

Sorption of aromatic compounds from aqueous solutions by cryotextures and suspensions of native cornstarches was studied by capillary gas chromatography. Acetophenone and benzyl alcohol were not sorbed by cryotropic-cornstarch gel and native-cornstarch suspension. A linear concentration dependence was found for aldehydes. Phenylethyl alcohol was characterized by a nonlinear concentration dependence. The presence of a benzene ring contributed to decreased binding (relative to the level characteristic of aliphatic compounds). The degree of binding depended considerably on the type of functional group in the aromatic compounds. Cryotextures were more potent than granules of native cornstarch in binding aromatic compounds.     

Binding of aromatic compounds to cornstarch polysaccharides

Sorption of aromatic compounds from aqueous solutions by cryotextures and suspensions of native cornstarches was studied by capillary gas chromatography. Acetophenone and benzyl alcohol were not sorbed by cryotropic-cornstarch gel and native-cornstarch suspension. A linear concentration dependence was found for aldehydes. Phenylethyl alcohol was characterized by a nonlinear concentration dependence. The presence of a benzene ring contributed to decreased binding (relative to the level characteristic of aliphatic compounds). The degree of binding depended considerably on the type of functional group in the aromatic compounds. Cryotextures were more potent than granules of native cornstarch in binding aromatic compounds.     

Binding of lactones by polysaccharides of corn and potato starches

Sorption of gamma- and delta-lactones from aqueous solutions by cryotropic gels of corn and potato starches was studied using capillary gas-liquid chromatography and Fourier transform infrared spectroscopy. The sorption patterns were similar for both types of starch. However, the sorption of lactones by potato starch was 5-10% lower than their sorption by cornstarch. The amount of substances bound by cryotextures of the starches depended linearly on their initial concentrations in gel. Increase in the length of the alkyl substituent improved sorption of lactones. It was shown that six-membered rings play a greater role in total lactone sorption than five-membered rings. The apparent constants and numbers of binding sites were estimated for compounds that reached the stage of saturation. The interaction between lactones and polysaccharides was accompanied by a decrease in their conformational lability and changes in the rheological characteristics of thermotropic and cryotropic starch gels.     

Sorption of components from a mixture of odorants by polysaccharides of starch, chitosan, and carrageenan

Sorption of components from a mixture of odorants in aqueous suspensions of native cornstarch, chitosan, and carrageenan was studied by the method of capillary gas-liquid chromatography. Binding was primarily effected via hydrophobic cooperative interactions. The amount of sorbed odorants depended linearly on their initial concentration in the suspension. The differences in sorption characteristics of starch and chitosan were related to the presence of amino groups in the latter compound, which contributed to increased binding of aldehydes via polar interactions. Sorption of odorants by the sulfated polysaccharide carrageenan largely depended on the structure of odorants and properties of their functional groups. Carrageenan was potent in binding aldehydes, ketones, and esters. Alcohols were less strongly bound to this compound. Sorption of lactones and guaiacol by carrageenan was the least significant.     

Sorption of components from a mixture of odorants by polysaccharides of starch, chitosan, and carrageenan

Sorption of components from a mixture of odorants in aqueous suspensions of native cornstarch, chitosan, and carrageenan was studied by the method of capillary gas-liquid chromatography. Binding was primarily effected via hydrophobic cooperative interactions. The amount of sorbed odorants depended linearly on their initial concentration in the suspension. The differences in sorption characteristics of starch and chitosan were related to the presence of amino groups in the latter polysaccharide, which contributed to an increased binding of aldehydes via polar interactions. Sorption of odorants by the sulfated polysaccharide carrageenan largely depended on the structure of odorants and properties of their functional groups. Carrageenan was potent in binding aldehydes, ketones, and esters. Alcohols were less strongly bound to this polysaccharide. Sorption of lactones and guaiacol by carrageenan was the least significant.     

Binding of Lactones by Polysaccharides of Corn and Potato Starches

Sorption of - and -lactones from aqueous solutions by cryotropic gels of corn and potato starches was studied using capillary gas–liquid chromatography and Fourier transform infrared spectroscopy. The sorption patterns were similar for both types of starch. However, the sorption of lactones by potato starch was 5–10% lower than their sorption by corn starch. The amount of substances bound by cryotextures of the starches depended linearly on their initial concentrations in the gel. An increase in the length of the alkyl substituent improved sorption of lactones. It was shown that six-membered rings play a greater role in total lactone sorption than five-membered rings. The apparent constants and numbers of binding sites were estimated for compounds that reached the stage of saturation. The interaction between lactones and polysaccharides was accompanied by a decrease in their conformational mobility and changes in the rheological characteristics of thermotropic and cryotropic starch gels.     

Effect of the Composition of Polysaccharides in Gelatinized Cornstarch on Alcohol Absorption

Sorption of alcohols in aqueous suspensions of gelatinized cornstarches with various contents of amylose was studied by capillary gas chromatography. Alcohol sorption depended primarily on the structure of alcohols, rather than on the composition of polysaccharides. No correlation was found between the efficiency of sorption and amylose content in starch. The amount of substances sorbed by starches depended linearly on their initial concentration in the gel. Normal and high-amylose starches sorbed alcohols to a similar degree. However, increasing the length of alkyl substituents improved sorption of alcohols. Amylopectin starch differed in high affinity for small molecules and low sensitivity to the structure and hydrophobicity of alcohols.     

Effect of the composition of polysaccharides in gelatinized cornstarch on alcohol absorption

Sorption of alcohols in aqueous suspensions of gelatinized cornstarches with various contents of amylose was studied by capillary gas chromatography. Alcohol sorption depended primarily on the structure of alcohols, but not on the composition of polysaccharides. No correlation was found between the efficiency of sorption and amylose content in starch. The amount of substances sorbed by starches depended linearly on their initial concentration in the gel. Normal and highly amylose starches sorbed alcohols to a similar degree. However, increasing the length of alkyl substituents improved sorption of alcohols. Amylopectin starch differed in high affinity for small molecules and low sensitivity to the structure and hydrophobicity of alcohols.     

Sorption of components from a mixture of essential oils by cryotextured cornstarches

Sorption by cryotextured cornstarches of components of the aqueous phase of a mixture of essential oils was studied by capillary gas chromatography. The amount of cryotexture-sorbed substances depended linearly on their concentration in the initial gel. The sorption of components from the mixture by starch polysaccharides was mainly associated with hydrophobic cooperative interactions, which resulted in the formation of supramolecular structures and inclusion complexes. The structure of the compounds was a major factor determining the degree of sorption. Sorption of monoterpene carbohydrates was the most pronounced. We revealed a synergistic increase in the degree of sorption from the mixture as compared to binding of individual compounds.     

Sorption of Components from a Mixture of Essential Oils by Cryotextured Cornstarches

Sorption by cryotextured cornstarches of components of the aqueous phase of a mixture of essential oils was studied by capillary gas chromatography. The amount of cryotexture-sorbed substances depended linearly on their concentration in the initial gel. The sorption of components from the mixture by starch polysaccharides was mainly associated with hydrophobic cooperative interactions, which resulted in the formation of supramolecular structures and inclusion complexes. The structure of the compounds was a major factor determining the degree of sorption. Sorption of monoterpene hydrocarbons was the most pronounced. We revealed a synergistic increase in the degree of sorption from the mixture as compared to binding of individual compounds.__________Translated from Prikladnaya Biokhimiya i Mikrobiologiya, Vol. 41, No. 4, 2005, pp. 463–469.Original Russian Text Copyright © 2005 by Terenina, Misharina.     

Factors affecting aluminium sorption by calcium pectate

Extracellular processes, particularly the adsorption of aluminium (Al) by pectate in the cell wall, have been proposed as important in the expression of Al toxicity to plant roots. In vitro studies were conducted on the effects of Al concentration (generally ≤ 32 μM), calcium (Ca) concentration (0.05 to 10 mM) and pH (3.2 to 5.4) on Al sorption by Ca pectate. There was a rapid reaction between Al and Ca pectate, there being no difference in Al remaining in solution after reaction times of 1 to 16 min, and only a slight decrease after 24 h. Increased Al concentration in solution increased linearly the sorption of Al by Ca pectate, with 70 to 84% of the Al originally in solution sorbed with ≤32 μM Al. In contrast, Al sorption decreased with increased Ca concentration in solution, and as pH decreased from 5.4 to 3.2. Only ≤30% of the sorbed Al was desorbed after 1 h by 1 mM CaCl₂, 10 mM CaCl₂ or 1 mM HCl. The amount of Al desorbed increased with a desorption period of 5 h, particularly with 1 mM HCl. These studies suggest that Al sorbed by Ca pectate in root cell walls is in equilibrium with Al in solution, and that Al toxicity is associated with the strong binding between Al and Ca pectate external to the cytoplasm.     

Volatile compounds from triticum aestivum

Volatile compounds were isolated from aerial parts (foliage and culms) of wheat plants by reduced pressure steam distillation-extraction and identified by gas chromatography-mass spectrometry and co-chromatography with authentic compounds. Infrared spectra were also obtained on some constituents. Compounds identified included nonanal and related unsaturated C₉ aldehydes and alcohols as major components and some additional aldehydes, alcohols and a ketone.     

Pesticide desorption from soils facilitated by dissolved organic matter coming from composts: experimental data and modelling approach

Dissolved organic matter (DOM) interaction with pesticides was examined studying the ability of DOM to desorb 8 pesticides previously sorbed to soil. DOM was originating from municipal waste composts at two maturity degrees, recovered at 20°C and by hot-pressurised subcritical water. Pesticide desorption depended on their previous sorption on soil. When sorption was low (K_OC ≤ 50, sulcotrione, metalaxyl), water was more efficient than DOM for desorption. On the contrary, when sorption was high (K_OC ≥ 2000, trifluraline), little effect of DOM was observed. For the moderately sorbed pesticides, DOM favoured pesticide desorption compared to water. For the lowest sorbed pesticides (K_OC ≤ 100), hysteresis was increased with larger proportions of DOM extracted with subcritical-water. Dissolved organic matter extracted from fresh-immature compost had larger capacity to mobilize the sorbed pesticides than the DOM from the mature compost. The pesticide desorption resulted from the positive and competitive interactions between pesticide, DOM and soil surfaces. These interactions were modelled considering separate partitioning coefficients. A general equation allowed the deduction of specific coefficients describing interactions in solution between pesticides and the non-sorbed fraction of DOM remaining in solution. This fraction was supposed to contain the most hydrophilic fraction of DOM and was able to interact with the most polar pesticide (amitrol). When pesticide hydrophobicity increased, the partitioning between pesticide and DOM decreased. Modelling the three-phase system (liquid, DOM and solid phases) pointed out that the solid phase played the most important role on pesticide behaviour through the sorption process of DOM and pesticides.     

Biosorption of scandium and yttrium from solutions

Summary The usage of biosorbents allows separation of scandium and yttrium from each other and from Fe, Al, Ti, Si, and Ca in hydrometallurgical processing of ores and wastes. It was shown that sorption of scandium and yttrium increased with the increase in pH of solution. Initial rate of scandium sorption depended on the biomass type; however 85–98% of scandium was sorbed within 10–30 min with most biomass types tested. The presence of aluminum, iron (III), and titanium in the solution inhibited sorption of scandium and particularly yttrium. After four cycles of sorption, 98.8% of scandium and 87% of yttrium was extracted from red mud leach solution by the biomass of Saccharomyces cerevisiae and Aspergillus terreus, respectively. Selectivity of the process of scandium and yttrium recovery could be achieved during sorption and also desorption, when solubilization of sorbed associated elements was inhibited by high pH values.     

Conversion of Some Saturated Fatty Acids,Aldehydes, and Alcohols into γ- and δ-Lactones

A series or γ- and δ-lactones could be found in the thermal oxidative products of normal saturated acids, aldehydes, and alcohols (C₉, C₁₀, and C₁₂, respectively) heated at 180°C in the presence of 0.1% KMnO₄. Their lactones were identified by gas chromatography, infrared spectroscopy, and mass spectroscopy. And they could be detected also in the volatile compounds occurred by heating of C₁₀ acid, aldehyde, and alcohol mixed with pork fat. So it was expected that lactones in meat fat flavor described in the earlier papers could be secondary products converted from saturated acids, aldehydes, and alcohols formed by oxidative degradation of meat fats. This process was presumed to be one of the mechanisms of the lactone formation.

It was discussed that lactones might be derived through mono or dihydroperoxides of acids, aldehydes, and alcohols.     

Biosorption of inorganic and methyl mercury by a biosorbent from Aspergillus niger

A biosorbent prepared by alkaline extraction of Aspergillus niger biomass was evaluated for its potential to remove mercury species – inorganic (Hg²⁺) and methyl mercury (CH₃Hg⁺) – from aqueous solutions. Batch experiments were carried out to determine the pH and time profile of sorption for both species in the pH range 2–7. The Hg²⁺ exhibited more rapid sorption and higher capacity than the CH₃Hg⁺. Further, removal of both mercury species from spiked ground water samples was efficient and not influenced by other ions. Sorption studies with esterified biosorbent indicated loss of binding of both mercury species (>80%), which was regained when the ester groups were removed by alkaline hydrolysis, suggesting the involvement of carboxyl groups in binding. Further, no interconversion of sorbed species occurred on the biomass. The biosorbent was reusable up to six cycles without serious loss of binding capacity. Our results suggest that the biosorbent from Aspergillus niger can be used for removal of mercury and methyl mercury ions from polluted aqueous effluents.     

Absence of long chain aldehydes in the wax of the Glossy II mutant of maize

Wax from the glll mutant of maize lacks aldehydes, which constitute 20 % in the normal genotype. The absence of aldehydes is not associated with a block in the synthesis of alcohols. Moreover in contrast to the wild type, glll wax is characterized by a higher content of C₁₆ and C₁₈ free acids, with a clear defect in the synthesis of C₂₄, C₂₆ and C₂₈ homologues. The results from this study are taken as evidence that the wild type elongation-decarboxylation I (EDI) pathway, leading to the synthesis of all the wax classes of compounds except esters, may be split into an early (EDIa) and a late (EDIb) group of reactions. Mutant glll is apparently defective at the EDIa, governing the synthesis of C₂₄–C₂₈ fatty acyl chains.     

Model of the regulation of activity of immobilized enzymes (amylases) in soil

The preservation of activity of extracellular enzymes in soil is presently associated with their immobilization on organic or inorganic carriers. Enzyme immobilization results, however, in a significant decrease in enzymatic activity. In the present work, the mechanism responsible for promotion of the catalytic activity was revealed, as well as the favorable effect of low-molecular alkylhydrozybenzenes of the class of alkylresorcinols, which are common in soil organic matter, on stability of immobilized enzymes (exemplified by amylases) by their post-translational modification. Optimal conditions (enzyme to sorbent ratio, pH optimum, CaCl₂ concentration, and sorption time) for amylase sorption on a biological sorbent (yeast cell walls) were determined and decreased activity of the immobilized enzyme compared to its dissolved state was confirmed. Alkylresorcinols (C₇AHB) at concentrations of 1.6 to 80 mM were found to cause an increase of amylase activity both in the case of already sorbed enzymes (by 30%) and in the case of a free dissolved enzyme with its subsequent immobilization (by 50–60%). In both cases, the optimal C₇AHB concentration was 16 mM. Amylase stability was determined for C7AHB-modified and unmodified enzymes immobilized on the biological sorbent after two cycles of freezing (–20°C) and thawing (4°C). Inverse dependence was revealed between increasing stability of C₇AHB-modified enzymes and an increase in their activity, as well as higher stability of immobilized modified amylases than of the dissolved modified enzyme. Investigation of the effect of C₇HOB-modification in the preservation of activity in immobilized amylases after four freeze–thaw cycles revealed: (1) better preservation of activity by the modified immobilized enzymes compared to immobilized ones; (2) differences in the dynamics of activity loss within compared pairs, with activity of immobilized amylases decreasing after the second cycle to a lower level (42%) than activity of the modified immobilized enzymes after the fourth cycle (48%). These results demonstrate that in the preservation of activity of extracellular enzymes in soil both stabilization mechanisms are of importance: immobilization on organic carriers and modification of the enzyme conformation by low-molecular compounds with the functions of chemical chaperones.     

Fatty acids and aldehydes of brain phospholipids during fetal and infant development in man

Abstract— Brains of human fetuses III, V, VI, VII months) newborn and infants (3, 7 and 13 months old) were investigated and the contents of total lipid, neutral- and phospholipid fractions were estimated. Fatty acids as well as fatty aldehydes of the phosphatides were analysed by gas chromatography. The results showed, that during this period of development the C₁₆-compounds in the fatty acid and aldehyde fractions decrease, while the total C₁₈-derivatives increase. However, the C₁₈-monoenoic fatty acids decrease from the third fetal month until birth and increase during myelination. The same pattern was found for the C₁₈-monoenoic aldehydes. The amounts of C₂₀- and C₂₂-polyenoic fatty acids were relatively constant. Only trace amounts of aldehydes with chain lengths other than C₁₆- and C₁₈-saturated and C₁₈-monoenoic comnniinds were found.