Energetics of ß-lactoglobulin-flavor compounds interactions.

Interaction of bovine ß-lactoglobulin (BLG) with several flavor compounds (FC) (2-methylpyrazine, vanillin, 2-acetylpyridine, 2- and 3-acetylthiophene, methyl isoamyl ketone, heptanone, octanone, and nonanone) was studied by high-sensitivity differential scanning calorimetry. The denaturation temperature, enthalpy, and heat capacity increment were determined at different FC concentrations. It was found that the denaturation temperature and heat capacity increment do not depend on the FC concentration, while the denaturation enthalpy decreases linearly with the FC concentration. These thermodynamic effects disclose the preferential FC binding to the unfolded form of BLG. By the obtained calorimetric data, the free energies of FC binding vs. the FC concentrations were calculated. These dependences were shown to be linear. Their slope relates closely to the overall FC affinity for the unfolded BLG in terms of the Langmuir binding model. The overall BLG affinity for FC varies from 20 M-1 (2-methylpyrazine) up to 360 M-1(nonanone). The maximal stoichiometry of the BLG-FC complexes was roughly estimated as a ratio of the length of the unfolded BLG to the molecular length of FC. Using these estimates, the apparent BLG-FC binding constants were determined. They are in the range of 0.3-8.0 M-1 and correlated strictly with the FC lipophilicity descriptor (logP).

Chitosan polyplexes: Energetics of formation and conformational changes in DNA upon binding and release.

Energetics of chitosan (CS) polyplexes and conformational stability of bound DNA were studied at pH 5.0 by ITC and HS-DSC, respectively. The CS-DNA binding isotherm was well approximated by the McGhee-von Hippel model suggesting the binding mechanism to be a cooperative attachment of interacting CS ligands to the DNA matrix. Melting thermograms of polyplexes revealed the transformation of different conformational forms of bound DNA in dependence on the CS/DNA weight ratio rw. At 0

Changes in Structural and Thermodynamic Properties of Starch during Potato Tuber Dormancy.

The main reserve polysaccharide of plants-starch-is undoubtedly important for humans. One of the main sources of starch is the potato tuber, which is able to preserve starch for a long time during the so-called dormancy period. However, accumulated data show that this dormancy is only relative, which raises the question of the possibility of some kind of starch restructuring during dormancy periods. Here, the effect of long-term periods of tuber rest (at 2-4 °C) on main parameters of starches of potato tubers grown in vivo or in vitro were studied. Along with non-transgenic potatoes, Arabidopsis phytochrome B (AtPHYB) transformants were investigated. Distinct changes in starch micro and macro structures-an increase in proportion of amorphous lamellae and of large-sized and irregular-shaped granules, as well as shifts in thickness of the crystalline lamellae-were detected. The degree of such alterations, more pronounced in AtPHYB-transgenic tubers, increased with the longevity of tuber dormancy. By contrast, the polymorphic crystalline structure (B-type) of starch remained unchanged regardless of dormancy duration. Collectively, our data support the hypothesis that potato starch remains metabolically and structurally labile during the entire tuber life including the dormancy period. The revealed starch remodeling may be considered a process of tuber preadaptation to the upcoming sprouting stage.

Effect of Chitosan on the Activity of Water-Soluble and Hydrophobic Porphyrin Photosensitizers Solubilized by Amphiphilic Polymers.

In this work, we studied the photocatalytic activity of photosensitizers (PSs) of various natures solubilized with polyvinylpyrrolidone (PVP) and ternary block copolymer ethylene and propylene oxide Pluronic F127 (F127) in a model reaction of tryptophan photo-oxidation in water in the presence of chitosan (CT). Water-soluble compounds (dimegin and trisodium salt of chlorin e6 (Ce6)) and hydrophobic porphyrins (tetraphenylporphyrin (TPP) and its fluorine derivative (TPPF20)) were used as PSs. It was shown that the use of chitosan (Mw ~100 kDa) makes it possible to obtain a system whose activity is comparable to that of the photosensitizer-amphiphilic polymer systems. Thus, the previously observed drop in the photosensitizing activity of PS in the presence of a polysaccharide and amphiphilic polymers (AP) was absent in this case. At the same time, chitosan had practically no inhibitory effect on hydrophobic porphyrins solubilized by Pluronic F127.

Biodegradable thermoresponsive oligochitosan nanoparticles: Mechanisms of phase transition and drug binding-release.

Oligochitosan, a low molecular weight derivative of the cationic biopolymer, chitosan, currently shows a great potential of application as a biodegradable non-toxic stimuli-sensitive drug carrier. This paper aimed to elucidate the thermoresponsive potential of oligochitosan and the temperature-controlled drug binding and release to shed light on oligochitosan potential in stimuli-responsive drug delivery. Mechanisms of thermoresponsive behavior of oligochitosan induced by ß-glycerophosphate (GP) were investigated using ITC, DSC, and DLS. Upon heating, the aqueous oligochitosan solution underwent a cooperative transition of the microphase separation type resulting in the formation of stable nano-sized particles. Energetics of the GP-oligochitosan interaction (evaluated by ITC) revealed a positive enthalpy of the GP binding to oligochitosan, which pointed to a notable contribution of dehydration and the related rearrangement of the polysaccharide hydration shell. Energetics of the thermal phase transition of oligochitosan was investigated by DSC upon variation of the solvent dielectric constant and GP concentration. The dependences of the transition parameters on these variables were determined and used for the analysis of the oligochitosan thermoresponsivity mechanism. The binding of ibuprofen to the thermotropic oligochitosan nanogel particles and its release from them were evaluated under near-physiological conditions. Relevantly, the oligochitosan nanoparticles surpassed some reference macromolecular adsorbers by the affinity for the drug and by the delayed release kinetics.

Biopolymer nanovehicles for essential polyunsaturated fatty acids: Structure-functionality relationships.

Design of stimuli-sensitive (i.e., smart) nano-sized delivery systems for nutraceuticals, having both a nutritional and pharmaceutical value, is very important for the formulation of novel functional food. Omega-3 and omega-6 polyunsaturated fatty acids (PUFAs) are among the most needed nutraceuticals for the maintenance of good health. It is medically proven that in order to get the best effect on the human health the weight ratio of ω-6/ω-3 PUFAs should be within the range between 1/1 and 5/1. Thus, our work was focused on the molecular design of the delivery systems based on the nano-sized complexes formed between covalent conjugate (sodium caseinate+maltodextrin (a dextrose equivalent=2)) and the combinations of polyunsaturated lipids, which are mutually complementary in the ω-6 and ω-3 PUFAs content: α-linolenic (ALA)+linoleic (LA) acids; liposomes of soy phosphatidylcholine (PC)+ALA; and micelles of soy lysophosphatidylcholine (LPC)+ALA. For such complex particles the high extent (>95%) of encapsulation of these all combinations of lipids by the conjugate was found along with both the high protection of the lipids against oxidation and their high solubility in an aqueous medium. To gain a better insight into such functionality of the complex particles a number of their structural (the weight-averaged molar weight, Mw; the radius of gyration, RG; the hydrodynamic radius, Rh; the architecture; the volume; the density; the ζ-potential; the microviscosity of both the bilayers of PC liposomes and LPC micelles), and thermodynamic (the osmotic second virial coefficient, A2, reflecting the nature and intensity of both the complex-complex and complex-solvent pair interactions) parameters were measured by a combination of such basic physico-chemical methods as static and dynamic multiangle laser light scattering, particle electrophoresis, atomic-force microscopy and electron spin resonance spectroscopy.

Thermodynamic and structural properties of tuber starches from transgenic potato plants grown in vitro and in vivo.

Potato plants harboring Phytochrome B (PHYB) gene from Arabidopsis thaliana or rol genes from Agrobacterium rhizogenes were used to study the effect of transgene expression on structure and properties of starch in tubers. Thermodynamic characteristics of starch (melting temperature, enthalpy of melting, thickness of crystalline lamellae) were shown to be variable depending on the transgene expression and plant culturing mode: in vitro or in soil. The expression of rolB or rolC genes in in vitro cultured plants evoked opposite effects on starch melting temperature and crystalline lamellae thickness. AtPHYB or rolB expression in the soil-grown potato led to the formation of more defective or more ordered starch structures, respectively, in comparison with starches of the same lines grown in vitro. On the whole, our study revealed genotype-dependent differences between starches extracted from tubers of in vitro or in vivo grown plants.