Energetics of β-lactoglobulin-flavor compounds interactions.

Interaction of bovine β-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.

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.

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 β-glycerophosphate (GP) were investigated using ITC, DSC, and DLS.

Stimuli-sensitive cross-linked hydrogels as drug delivery systems: Impact of the drug on the responsiveness.

Responsiveness of drug delivery systems (DDS) against internal and external stimuli attracts wide interest as a mechanism that can provide both site-specific release at the target place and feedback regulated release rate. Biological environment is quite complex and the effects that the intricate medium may have on the effectiveness of the stimulus have received certain attention. Differently, the impact that the drug loaded may have itself on the responsiveness of the DDS has been underestimated.

Binding Energetics of Charged Amphiphilic Ligands to Thermoresponsive Biodegradable Poly(methoxyethylaminophosphazene) Hydrogels.

Changes in the affinity of the swollen and collapsed forms of a thermoresponsive polymer gel for targeted ligands can be directly estimated using a thermodynamic approach based on high-sensitivity differential scanning calorimetry (HS-DSC). For macromolecular ligands (proteins) bound to the gel, this method provides information on changes in their conformational stability, which is of crucial importance for the biological or pharmaceutical activity of the protein. We used HS-DSC for the study of interactions of two widely administrated drugs-gemfibrozil and ibuprofen-and two globular proteins-α-lactalbumin and BSA-with hydrogels of the cross-linked poly(methoxyethylaminophosphazene).

Cryostructuring of Polymeric Systems. 49. Unexpected "Kosmotropic-Like" Impact of Organic Chaotropes on Freeze⁻Thaw-Induced Gelation of PVA in DMSO.

Urea (URE) and guanidine hydrochloride (GHC) possessing strong chaotropic properties in aqueous media were added to DMSO solutions of poly(vinyl alcohol) (PVA) to be gelled via freeze⁻thaw processing. Unexpectedly, it turned out that in the case of the PVA cryotropic gel formation in DMSO medium, the URE and GHC additives caused the opposite effects to those observed in water, i.e.

Conformation-Dependent Affinity of Thermoresponsive Biodegradable Hydrogels for Multifunctional Ligands: A Differential Scanning Calorimetry Approach.

We investigated energetics of binding of multifunctional pyranine ligands to hydrogels of the cross-linked poly(methoxyethylaminophosphazene) (PMOEAP) from data on the thermotropic volume phase transition of the gels by means of high-sensitivity differential scanning calorimetry. Dependences of the transition temperature, enthalpy, and width on the concentration of pyranines were obtained, and the excess transition free energy as a function of the pyranine concentration was calculated. We found that the affinity of the gels for the pyranine ligands increased very significantly upon the gel collapse.

Salt-Induced Thermoresponsivity of Cross-Linked Polymethoxyethylaminophosphazene Hydrogels: Energetics of the Volume Phase Transition.

Biodegradable hydrogels of cross-linked polymethoxyethylaminophosphazenes (PMOEAPs) of various cross-linking density and apparent subchain hydrophobicity were investigated by high-sensitivity differential scanning calorimetry and equilibrium swelling measurements. The volume phase transition of the hydrogels was found to be induced by salts of weak polybasic acids. The transition parameters were determined depending on the pH, phosphate concentration, cross-linking density, and apparent hydrophobicity of the gels.

Binding affinity of thermoresponsive polyelectrolyte hydrogels for charged amphiphilic ligands. A DSC approach.

Controlled drug binding and release stand among top requirements postulated for targeted drug delivery systems of the new generations. "Smart" polymers and gels are highly suitable for the controlled delivery due to their structural sensitivity to minor environmental variations. The aim of this work was to study thermoresponsive polyanionic and polycationic hydrogels of N-isopropylacrylamide copolymers with acrylic acid and N-aminopropylmethacrylamide in terms of their interaction with two widely used drugs, propranolol and ibuprofen.

Ternary interpolyelectrolyte complexes insulin-poly(methylaminophosphazene)-dextran sulfate for oral delivery of insulin.

Ternary interpolyelectrolyte complexes of insulin with biodegradable synthetic cationic polymer, poly(methylaminophosphazene) hydrochloride (PMAP), and dextran sulfate (DS) were investigated by means of turbidimetry, dynamic light scattering, phase analysis, and high-sensitivity differential scanning calorimetry. Formation of ternary insoluble stoichiometric Insulin-PMAP-DS complexes was detected under conditions imitating the human gastric environment (pH 2, 0.15 M NaCl).

Polyplexes of poly(methylaminophosphazene): energetics of DNA melting.

The interaction of DNA with a synthetic biocompatible and biodegradable cationic polymer, poly(methylaminophosphazene) hydrochloride (PMAP·HCl), was investigated by high-sensitivity differential scanning calorimetry under conditions of strong and weak electrostatic interactions of the macroions. Thermodynamic parameters of the DNA double-helix melting were determined as a function of pH and the PMAP·HCl/DNA weight ratio. PMAP·HCL was shown to reveal two functions with respect to DNA: the polyelectrolyte function and the donor-acceptor one.

Conformational energetics of interpolyelectrolyte complexation between ι-carrageenan and poly(methylaminophosphazene) measured by high-sensitivity differential scanning calorimetry.

The interaction of poly(methylaminophosphazene) hydrochloride (PMAP·HCl) of varying degrees of ionization (f) with the potassium salt of ι-carrageenan was studied by high-sensitivity differential scanning calorimetry at a KCl concentration of 0.15 M, which is included for the purpose of stabilizing the helix conformation of the polysaccharide up to 55 °C. The conditions of strong (pH 3.

Ionic and polyampholyte N-isopropylacrylamide-based hydrogels prepared in the presence of imprinting ligands: stimuli-responsiveness and adsorption/release properties.

The conformation of the imprinted pockets in stimulus-responsive networks can be notably altered when the stimulus causes a volume phase transition. Such a tunable affinity for the template molecule finds interesting applications in the biomedical and drug delivery fields. Nevertheless, the effect that the binding of the template causes on the stimuli-responsiveness of the network has barely been evaluated.

Binding energetics of lysozyme to copolymers of N-isopropylacrylamide with sodium sulfonated styrene.

Interpolyelectrolyte complexes of lysozyme with thermosensitive N-isopropylacrylamide-sodium sulfonated styrene copolymers of different charge density were investigated by high-sensitivity differential scanning calorimetry (HS-DSC) at pH 4.6-7.2 and low ionic strength.

Thermodynamic and kinetic stability of penicillin acylase from Escherichia coli.

Thermal denaturation of penicillin acylase (PA) from Escherichia coli has been studied by high-sensitivity differential scanning calorimetry as a function of heating rate, pH and urea concentration. It is shown to be irreversible and kinetically controlled. Upon decrease in the heating rate from 2 to 0.

Conformational changes in iota- and kappa-carrageenans induced by complex formation with bovine beta-casein.

The formation of electrostatic complexes between beta-casein and iota- and kappa-carrageenans is well-known. However, the molecular mechanism of the complexation has yet to be determined, particularly with respect to the conformational changes of the interacting macromolecules. High-sensitivity differential scanning calorimetry was used to study beta-casein/carrageenan mixtures at different pH values (3.

The structure of kappa/iota-hybrid carrageenans II. Coil-helix transition as a function of chain composition.

This paper describes the effect of the kappa/iota-ratio on the physical properties of kappa/iota-hybrid carrageenans (synonyms: kappa-2, kappa-2, weak kappa, weak gelling kappa). To this end, a series of kappa/iota-hybrid carrageenans ranging from almost homopolymeric kappa-carrageenan (98 mol-% kappa-units) to almost homopolymeric-carrageenan (99 mol-% iota-units) have been extracted from selected species of marine red algae (Rhodophyta). The kappa/iota-ratio of these kappa/iota-hybrids was determined by NMR spectroscopy.

Temperature-sensitive chitosan-poly(N-isopropylacrylamide) interpenetrated networks with enhanced loading capacity and controlled release properties.

Interpenetrated polymer networks (IPN) of poly(N-isopropylacrylamide) (PNIPA) and chitosan (two grades) were prepared by free radical polymerisation and cross-linking of PNIPA (700 mM) with bis(acrylamide) (20 mM) in chitosan solutions (1.5 wt.% in acetic acid), and subsequent immersion in glutaraldehyde solutions (0 to 0.

Coil-helix transition of iota-carrageenan as a function of chain regularity.

A series of iota-carrageenans containing different amounts of nu-carrageenan (0-23 monomer %) have been prepared from neutrally extracted carrageenan of Eucheuma denticulatum. nu-Carrageenan is the biochemical precursor of iota-carrageenan. The conformational order-disorder transition and rheological properties of these carrageenans were studied using optical rotation, rheometry, size exclusion chromatography coupled to multiangle laser light scattering, and high-sensitivity differential scanning calorimetry.

Thermodynamic stability of porcine beta-lactoglobulin. A structural relevance.

The proposed biological function of beta-lactoglobulins as transporting proteins assumes a binding ability for ligands and high stability under the acidic conditions of the stomach. This work shows that the conformational stability of nonruminant porcine beta-lactoglobulin (BLG) is not consistent with this hypothesis. Thermal denaturation of porcine BLG was studied by high-sensitivity differential scanning calorimetry within the pH range 2.