Modulation of Molecular Structure and Mechanical Properties of κ-Carrageenan-Gelatin Hydrogel with Multi-Walled Carbon Nanotubes.

Hydrogels, three-dimensional hydrophilic water-insoluble polymer networks having mechanical properties inherent for solids, have attracted continuous research attention over a long time period. Here, we studied the structure and properties of hydrogel based on gelatin, κ-carrageenan and CNTs using the combination of SAXS, PXRD, AFM microscopy, SEM and rheology methods. We have shown that the integration of polysaccharide and protein in the composite hydrogel leads to suppression of their individual structural features and homogenization of two macromolecular components into a single structural formation. According to obtained SAXS results, we observed the supramolecular complex, which includes both polysaccharide and protein components associated with each other. It was determined that hydrogel structure formed in the initial solution state (dispersion) retains hydrogel supramolecular structure under its cooling up to gel state. The sizes of dense cores of these polyelectrolyte complexes (PEC) slightly decrease in the gel state in comparison with PEC water dispersion. The introduction of CNTs to hydrogel does not principally change the type of supramolecular structure and common structural tendencies observed for dispersion and gel states of the system. It was shown that carbon nanotubes embedded in hydrogel act as the supplementary template for formation of the three-dimensional net, giving additional mechanical strengthening to the studied system.

Engineering nanocolumnar defect configurations for optimized vortex pinning in high temperature superconducting nanocomposite wires.

We report microstructural design via control of BaZrO3 (BZO) defect density in high temperature superconducting (HTS) wires based on epitaxial YBa2Cu3O7-δ (YBCO) films to achieve the highest critical current density, Jc, at different fields, H. We find the occurrence of Jc(H) cross-over between the films with 1-4 vol% BZO, indicating that optimal BZO doping is strongly field-dependent. The matching fields, Bφ, estimated by the number density of BZO nanocolumns are matched to the field ranges for which 1-4 vol% BZO-doped films exhibit the highest Jc(H). With incorporation of BZO defects with the controlled density, we fabricate 4-µm-thick single layer, YBCO + BZO nanocomposite film having the critical current (Ic) of ~1000 A cm(-1) at 77 K, self-field and the record minimum Ic, Ic(min), of 455 A cm(-1) at 65 K and 3 T for all field angles. This Ic(min) is the largest value ever reported from HTS films fabricated on metallic templates.

Supramolecular systems based on novel mono- and dicationic pyrimidinic amphiphiles and oligonucleotides: a self-organization and complexation study.

Novel mono- and dicationic pyrimidinic surfactants are synthesized and their aggregation behavior is studied by methods of tensiometry and nuclear magnetic resonance (NMR) self-diffusion. To estimate their potentiality as gene delivery agents, the complexation with oligonucleotides (ONus) is explored by dynamic light scattering (DLS) and zeta-potential titration methods and ethidium bromide exclusion experiments. Bola-type pyrimidinic amphiphile (BPM) demonstrates rather a weak affinity to ONus. Although it induces mixed associations with ONus, only slight charge compensation changes occur at a large excess of bola, with no recharging reached. Similarly, the ethydium bromide exclusion study reveals a slow increase in the binding capacity toward an ONu with an increment in BPM concentration. The monocationic pyrimidinic surfactant (MPM) and its gemini analogue (GPM-1) are ranked as intermediates in both their aggregative activity and complexing properties toward ONus. They both form mixed associates with ONus well below the critical micelle concentrations (cmcs) of 2 and 15 mM respectively. However, GPM-1 has a much lower isoelectric point at the molar ratio surfactant/ONu r~1 compared to r~3 for MPM. This probably indicates a larger electrostatic contribution to the ONu complexation in the case of GPM-1. The most hydrophobic pyrimidinic surfactant (GPM-2), bearing three alkyl tails, demonstrates enhanced aggregative activity and binding capacity toward ONus as compared to former pyrimidinic surfactants. Due to effective aggregative (low cmc of 0.04 mM) plus binding properties (fraction of bound ONu ß=0.76 at r=2.5), GPM-2 may be ranked as a promising agent for wider biological applications.

Interactions of ß-lactoglobulin with serotonin and arachidonyl serotonin.

ß-Lactoglobulin (ß-LG) is a lipocalin, which is the major whey protein of cow's milk and the milk of other mammals. However, it is absent from human milk. The biological function of ß-LG is not clear, but its potential role in carrying fatty acids through the digestive tract has been suggested. ß-LG has been found in complexes with lipids such as butyric and oleic acids and has a high affinity for a wide variety of compounds. Serotonin (5-hydroxytryptamine, 5-HT), an important compound found in animals and plants, has various functions, including the regulation of mood, appetite, sleep, muscle contraction, and some cognitive functions such as memory and learning. In this study, the interaction of serotonin and one of its derivatives, arachidonyl serotonin (AA-5HT), with ß-LG was investigated using circular dichroism (CD) and fluorescence intensity measurements. These two ligands interact with ß-LG forming equimolar complexes. The binding constant for the serotonin/ß-LG interaction is between 105 and 106 M(-1) , whereas for the AA-5HT/ß-LG complex it is between 104 and 105 M(-1) as determined by measurements of either protein or ligand fluorescence. The observed binding affinities were higher in hydroethanolic media (25% EtOH). The interactions between serotonin/ß-LG and AA-5HT/ß-LG may compete with self-association (micellization) of both the ligand and the protein. According to far- and near-UV CD results, these ligands have no apparent influence on ß-LG secondary structure, however they partially destabilize its tertiary structure. Their binding by ß-LG may be one of the peripheral mechanisms of the regulation of the content of serotonin and its derivatives in the bowel of milk-fed animals.

Diameter dependence of the transport properties of antimony telluride nanowires.

We report measurements of electronic, thermoelectric, and galvanomagnetic properties of individual single crystal antimony telluride (Sb(2)Te(3)) nanowires with diameters in the range of 20-100 nm. Temperature-dependent resistivity and thermoelectric power (TEP) measurements indicate hole dominant diffusive thermoelectric generation with an enhancement of the TEP for smaller diameter wires up to 110 microV/K at T = 300 K. We measure the magnetoresistance in magnetic fields both parallel and perpendicular to the nanowire [110] axis, where strong anisotropic positive magnetoresistance behavior was observed.

Brownian dynamics simulation of substrate motion near active site of enzyme entrapped inside reverse micelle.

Brownian dynamics simulation has been applied to analyze the influence of the electrostatic field of a reverse micelle on the enzyme-substrate complex formation inside a micelle. The probability that the enzyme-substrate complex will form from serine protease (trypsin) and the specific hydrophilic cationic substrate Nalpha-benzoyl-L: -arginine ethyl ester has been studied within the framework of the encounter complex formation theory. It has been shown that surfactant charge, dipole moments created by charged surfactant molecules and counterions, and permittivity of the inner core of reverse micelles can all be used as regulatory parameters to alter the substrate orientation near the active site of the enzyme and to change the probability that the enzyme-substrate complex will form.

Engineering of caseins and modulation of their structures and interactions.

Beta-casein (beta-CN) is a milk protein widely used in food industries because of its mild emulsifying properties due to its amphiphilicity. However, the elements determining its micellization behavior in solution and interfacial behavior at the air-water interface are not well known. In order to study how the forced dimerisation influences functional properties of beta-CN, recombinant wild-type beta-CN was produced and distal cysteinylated forms of recombinant beta-CN were engineered. We show that 1) cysteinylated beta-CN formed mainly dimers bridged by disulfide bonds; 2) the process of dimerization adds to the micellization process with temperature and is poorly reversible; 3) covalent disulfide linkage forms at the air-water interface at a lower temperature than in bulk. In conclusion, the location of the cysteinylation in the C-terminus or N-terminus or both is of importance for the properties of beta-CN.

Thermoelectric and magnetothermoelectric transport measurements of graphene.

The conductance and thermoelectric power (TEP) of graphene is simultaneously measured using a microfabricated heater and thermometer electrodes. The sign of the TEP changes across the charge neutrality point as the majority carrier density switches from electron to hole. The gate dependent conductance and TEP exhibit a quantitative agreement with the semiclassical Mott relation. In the quantum Hall regime at a high magnetic field, quantized thermopower and Nernst signals are observed and are also in agreement with the generalized Mott relation, except for strong deviations near the charge neutrality point.

Correlation between superfluid density and T(C) of underdoped YBa2Cu3O6+x near the superconductor-insulator transition.

We report measurements of the ab-plane superfluid density n(s) (magnetic penetration depth lambda) of heavily underdoped films of YBa2Cu3O6+x, with T(C)'s from 6 to 50 K. We find the characteristic length for vortex unbinding transition equal to the film thickness, suggesting strongly coupled CuO2 layers. At the lowest dopings, T(C) is as much as 5 times larger than the upper limit set by the 2D Kosterlitz-Thouless-Berezinskii transition temperature calculated for individual CuO2 bilayers. Our main finding is that T(C) is not proportional to n(s)(0); instead, we find T(C) proportional to ns(1/2.3+/-0.4). This conflicts with a popular point of view that quasi-2D thermal phase fluctuations determine the transition temperature.