Srinivas Janaswamy

Three-dimensional structure of the sodium salt of iota-carrageenan.

The three-dimensional structure of the sodium salt of iota-carrageenan has been determined by using X-ray diffraction data collected from its polycrystalline and oriented fibers. The molecule forms a half-staggered, parallel, threefold, right-handed double helix that is stabilized by interchain hydrogen bonds from 2- and 6-hydroxyl groups in the galactosyl units. Three helices are organized in a trigonal unit cell, of dimensions a=24.02 and c=12.93 A, with a lateral separation of 13.9 A for each pair. Both 2- and 4-sulfate groups are essential in helix-helix interactions that are mediated only by sodium ions and water molecules.

Effect of calcium ions on the organization of iota-carrageenan helices: an X-ray investigation

X-ray fiber diffraction analysis confirms that calcium iota-carrageenan forms a threefold, right-handed, half-staggered, parallel, double helix of pitch 26.42 A stabilized by interchain hydrogen bonds. According to the detailed structural results, three helices are packed in a trigonal unit cell (a=23.61 and c=13.21 A). Strong interactions between the sulfate groups of neighboring helices, mediated by calcium ions and water molecules, are responsible for stabilizing the three-dimensional structure.

Structural analysis of BaMg1/3(Ta, Nb)2/3O3 ceramics

X-ray structure analysis of BaMg1/3(Ta,Nbx)2/3O3 ceramics revealed that BaMg1/3Ta2/3O3 (BMT) has an ordered trigonal phase as well as a disordered cubic phase depending on the preparation temperature. Complete ordered phase for BaMg1/3Nb2/3O3 (BMN) has not been observed. The ordering of Mg, Ta and Nb cations has dependence on the size, charge difference and calcination temperature.

Morphology of Western larch arabinogalactan.

A molecular modeling study has revealed that (1 --> 3)-beta-D-galactan can not only adopt a triple helical structure similar to that of the corresponding glucan but can also accommodate a highly flexible beta-D-Gal-(1 --> 6)-beta-D-Gal disaccharide moiety as a side group 6-linked to every galactosyl unit in the main chain. The resulting triple helix, applicable to Western larch arabinogalactan, can assume quite different morphologies since the side group has access to several allowed conformational states. Some of the preferred modes of association between these helices have been visualized using preliminary X-ray fiber diffraction data.

Effects of ripening temperature on starch structure and gelatinization, pasting, and cooking properties in rice (Oryza sativa).

The effect of ripening temperature on rice (Oryza sativa) grain quality was evaluated by assessing starch structure and gelatinization, pasting, and cooking properties. As the ripening temperature increased, the amylose content and number of short amylopectin chains decreased, whereas intermediate amylopectin chains increased, resulting in higher gelatinization temperatures and enthalpy in the starch. These results suggested that an increase in cooking temperature and time would be required for rice grown at higher temperatures. A high ripening temperature increased the peak, trough, and final viscosities and decreased the setback due to the reduction in amylose and the increase in long amylopectin chains. With regard to starch crystallinity and amylopectin molecular structure, the highest branches and compactness were observed at 28/20 °C. Rice that was grown at temperatures above 28/20 °C showed a deterioration of cooking quality and a tendency toward decreased palatability in sensory tests.

Influence of glucan structure on the swelling and leaching properties of starch microparticles.

Microparticles were made by a water-in-oil emulsion technique from acid-hydrolyzed and debranched normal, waxy and high-amylose corn starches. The starches prepared had a weight-average molecular weight (Mw) ranging 3.6 × 10(7)-2.5 × 10(4), a polydispersity ranging 1.16-9.16, an apparent amylose content ranging 2.84-100%. These microparticles exhibited crystallinity ranging 4.41-22.84%, swelling power ranging 2.45-7.84 and percentage of leaching ranging 1.72-74.91%. Swelling power in water (R(2)=0.86) and percentage of leaching in water (R(2)=0.89) were modeled by a response surface method, using the following parameters: Mw, polydispersity, apparent amylose content and crystallinity of starch in microparticles. Overall, this study showed the key parameters for controlling the behavior of starch microparticles were related to the cohesiveness of the three-dimensional network, particularly through the retrogradation of starch polymers, the formation of crystallites and junctions zones. Such microparticles could be used for designing economical and biocompatible delivery systems of compounds for food, drug, or other applications.

Encapsulation altered starch digestion: Toward developing starch-based delivery systems

Starch is an abundant biomaterial that forms a vital energy source for humans. Altering its digestion, e.g. increasing the proportions of slowly digestible starch (SDS) and resistant starch (RS), would revolutionize starch utility in addressing a number of health issues related to glucose absorption, glycemic index and colon health. The research reported in this article is based on my hypothesis that water channels present in the B-type starch crystalline matrix, particularly in tuber starches, can embed guest molecules such as nutraceuticals, drugs, flavor compounds and vitamins leading to altered starch digestion. Toward this goal, potato starch has been chosen as the model tuber starch, and ibuprofen, benzocaine, sulfapyridine, curcumin, thymol and ascorbic acid as model guest molecules. X-ray powder diffraction and FT-IR analyses clearly suggest the incorporation of guest molecules in the water channels of potato starch. Furthermore, the in vitro digestion profiles of complexes are intriguing with major variations occurring after 60 min of starch digestion and finally at 120 min. These changes are concomitantly reflected in the SDS and RS amounts, with about 24% decrease in SDS for benzocaine complex and 6% increase in RS for ibuprofen complex, attesting the ability of guest molecule encapsulation in modulating the digestion properties of potato starch. Overall, this research provides an elegant opportunity for the design and development of novel starch-based stable carriers that not only bestow tailored glucose release rates but could also transport health promoting and disease preventing compounds.

Organized polysaccharide fibers as stable drug carriers

Many challenges arise during the development of new drug carrier systems, and paramount among them are safety, solubility and controlled release requirements. Although synthetic polymers are effective, the possibility of side effects imposes restrictions on their acceptable use and dose limits. Thus, a new drug carrier system that is safe to handle and free from side effects is very much in need and food grade polysaccharides stand tall as worthy alternatives. Herein, we demonstrate for the first time the feasibility of sodium iota-carrageenan fibers and their distinctive water pockets to embed and release a wide variety of drug molecules. Structural analysis has revealed the existence of crystalline network in the fibers even after encapsulating the drug molecules, and iota-carrageenan maintains its characteristic and reproducible double helical structure suggesting that the composites thus produced are reminiscent of cocrystals. The melting properties of iota-carrageenan:drug complexes are distinctly different from those of either drug or iota-carrageenan fiber. The encapsulated drugs are released in a sustained manner from the fiber matrix. Overall, our research provides an elegant opportunity for developing effective drug carriers with stable network toward enhancing and/or controlling bioavailability and extending shelf-life of drug molecules using GRAS excipients, food polysaccharides, that are inexpensive and non-toxic.

Impact of urea on the three-dimensional structure, viscoelastic and thermal behavior of iota-carrageenan.

Urea breaks hydrogen bonds among biopolymers leading to structural destabilization. In the case of hydrocolloids urea addition is thought to impact gelation. Detailed information about its pertinent role on influencing the structure-function relationships of hydrocolloids is still elusive, however. The present investigation is aimed at delineating hydrocolloids structural behavior in the presence of urea employing iota-carrageenan as a model system. X-ray fiber diffraction, rheological and thermal properties of two iota-carrageenan solutions with weight concentrations 4.5 and 6.0% (w/w) at two urea molar concentrations (0.5 and 2.0 M) with and without heat treatments have been analyzed. X-ray results suggest that the canonical double helical structural arrangement of iota-carrageenan is maintained even after urea addition. However, improved crystallinity, ordering and altered unit cell dimensions especially with heat treatments of the binary mixtures indicate the promotion of favorable interactions among carrageenan helices in the presence of urea. Increased elastic modulus and onset temperature of melting endotherm with the heat treatment compared to cold addition further attests the X-ray observations of enhanced structural ordering. Overall, results suggest that urea molecules synergistically aid iota-carrageenan interactions and stabilize structure of junction zones. Our findings are deemed to be helpful in the design and development of novel non-food applications of hydrocolloids.

Polysaccharide Modification through Green Technology: Role of Endodextranase in Improving the Physicochemical Properties of (1→3)(1→6)-α-D-Glucan.

The structure and properties of bioengineered (1→3)(1→6)-α-D-glucan subjected to endodextranase treatment were investigated. Upon enzyme treatment, OD220 and Mw decreased substantially during the first 60 min and thereafter slowed as the modification progressed. Compared to the native glucan, the modified sample solution had a lighter opalescent, bluish-white color. The morphological analysis revealed that bioengineered glucan produced quite a few small particles after hydrolysis. The molecular weight distribution curve gradually shifted to the low Mw region with a significant broadening distribution, and the chain hydrolysis reaction followed a combination of zeroth- and first-order processes. The NMR results showed some specific α-1,6 linkages of glucan chains were cleaved with enzyme treatment. The viscosity of modified glucan solution was markedly reduced, and the Newtonian plateaus were also observed at high shear rates (10-100 1/s). The above results suggested that the modified (1→3)(1→6)-α-D-glucan showed a tailor-made solution character similar to that of arabic gum and would be used as a novel food gum substitute in the design of artificial carbohydrate-based foods.