New coordination polymers based on two metal-containing moieties Ru–Ag are synthesized: Na[RuCpX(PTA)-μ-(PTA)-1κP:2κ²N-AgX₂]_∞ (X = Cl (1), Br (2), I (3)). Characterization is performed by NMR, UV-visible and FT-IR spectroscopy, optical-electron microscopy, and elemental analyses (C, H, N, S). Light scattering is employed to characterize the colloidal particles growth by polymer self-assembling. These structures are stable over a broad range of pH and exhibit thermally-driven swelling, thus resembling a typical thermosensitive hydrogel. Full article

Bacterial cells do not have a nuclear membrane that encompasses and isolates the genetic material. In addition, they do not possess histone proteins, which are responsible for the first levels of genome condensation in eukaryotes. Instead, there is a number of more or less specific nucleoid-associated proteins that induce DNA bridging, wrapping and bending. Many of these proteins self-assemble into oligomers. The crowded environment of cells is also believed to contribute to DNA condensation due to excluded volume effects. Ribosomes are protein-RNA complexes found in large concentrations in the cytosol of cells. They are overall negatively charged and some DNA-binding proteins have been reported to also bind to ribosomes. Here the effect of protein self-association on DNA condensation and stability of DNA-protein complexes is explored using Monte Carlo simulations and a simple coarse-grained model. The DNA-binding proteins are described as positively charged dimers with the same linear charge density as the DNA, described using a bead and spring model. The crowding molecules are simply described as hard-spheres with varying charge density. It was found that applying a weak attractive potential between protein dimers leads to their association in the vicinity of the DNA (but not in its absence), which greatly enhances the condensation of the model DNA. The presence of neutral crowding agents does not affect the DNA conformation in the presence or absence of protein dimers. For weakly self-associating proteins, the presence of negatively charged crowding particles induces the dissociation of the DNA-protein complex due to the partition of the proteins between the DNA and the crowders. Protein dimers with stronger association potentials, on the other hand, stabilize the nucleoid, even in the presence of highly charged crowders. The interactions between protein dimers and crowding agents are not completely prevented and a few crowding molecules typically bind to the nucleoid. Full article

Multilayer films containing α- and β-casein and polypeptides, poly-L-lysine (PLL), and poly-L-arginine (PLArg) were formed by the layer-by-layer technique and Fourier Transform InfraRed spectroscopy with Attenuated Total Reflection (FTIR-ATR) and FTIR/Grazing Angle analyzed their infrared spectra. We investigated the changes of conformations of casein and polypeptides in the complexes formed during the build-up of the films. To elucidate the differences in the mechanism of complex formation leading to various growths of (PLL/casein)_n and (PLArg/casein)_n films, we performed the molecular dynamics simulations of the systems consisting of short PLL and PLArg chains and the representative peptide chains—casein fragments, which consists of several aminoacid sequences. The results of the simulation indicated the preferential formation of hydrogen bonds of poly-L-arginine with phosphoserine and glutamic acid residues of caseins. FTIR spectra confirmed those, which revealed greater conformational changes during the formation of casein complex with poly-L-arginine than with poly-L-lysine resulting from stronger interactions, which was also reflected in the bigger growth of (PLArg/casein)_n films with the number of deposited layers. Full article

Stratum corneum (SC), the outermost layer of human skin, acts as an intelligent physicochemical interface between the inside and the outside of our body. To make clear the relationship between structure and physical barrier properties of SC, we developed a method that enables us to simultaneously acquire X-ray diffraction (XD) patterns and transepidermal water loss (TEWL) values using a spread SC sheet isolated from human skin. The synchrotron X-ray was incident on the SC sheet surface at an angle of 45° to avoid interference between the two kinds of measurements. Detailed comparison between XD and TEWL data suggested that the thermal behavior of water permeability is closely related to the thermal expansion of the lattice spacings of the hexagonal phases above 40 °C and to the existence ratio of the orthorhombic phase below 40 °C. Thus, the new method we developed can give useful information on the mechanism of water permeation in SC without ambiguity caused by separate measurements of structure and water permeability with different samples. Full article

Alginate is a promising biocompatible and biodegradable polymer for production of nanofibers for drug delivery and tissue engineering. However, alginate is difficult to electrospin due to its polyelectrolyte nature. The aim was to improve the ‘electrospinability’ of alginate with addition of exceptionally high molecular weight poly(ethylene oxide) (PEO) as a co-polymer. The compositions of the polymer-blend solutions for electrospinning were varied for PEO molecular weight, total (alginate plus PEO) polymer concentration, and PEO proportion in the dry alginate–PEO polymer mix used. These were tested for rheology (viscosity, complex viscosity, storage and loss moduli) and conductivity, and the electrospun nanofibers were characterized by scanning electron microscopy. One-parameter-at-a-time approach and response surface methodology (RSM) were used to optimize the polymer-blend solution composition to obtain defined nanofibers. Both approaches revealed that the major influence on nanofiber formation and diameter were total polymer concentration and PEO proportion. These polymer-blend solutions of appropriate conductivity and viscosity enabled fine-tuning of nanofiber diameter. PEO molecular weight of 2–4 million Da greatly improved the electrospinnability of alginate, producing nanofibers with >85% alginate. This study shows that RSM can be used to design nanofibers with optimal alginate and co-polymer contents to provide efficient scaffold material for regenerative medicine. Full article

The formation of nanoparticles of two poly(methacrylic acid) (PMA) isomers, atactic (aPMA) and isotactic (iPMA), was investigated in aqueous solutions in the presence of mono- (Na⁺) and multivalent cations (Mg²⁺ and La³⁺). Using dynamic (DLS) and static light scattering (SLS), we show that PMA nanoparticles have characteristics of microgel-like particles with a denser core and a swollen corona. iPMA aggregates are stable at a much higher degree of neutralization (α_N) than the aPMA ones, indicating a much stronger association between iPMA chains. This is explained by proposing segregation of ionized and unionized carboxyl groups within the iPMA aggregates and subsequent cooperative hydrogen-bonding between COOH groups. The calculated shape parameter (ρ) suggests different behavior of both isomers in the presence of Mg²⁺ ions on one hand and Na⁺ and La³⁺ on the other. The microgel-like particles formed in the presence of Mg²⁺ ions have a more even mass distribution (possibly a no core-shell structure) in comparison with those in the presence of Na⁺ and La³⁺ ions. Differences between the aggregate structures in the presence of different ions are reflected also in calorimetric experiments and supported by pH and fluorimetric measurements. Reasons for different behavior in the presence of Mg²⁺ ions lie in specific properties of this cation, in particular in its strong hydration and preference towards monodentate binding to carboxylate groups. Full article

We investigated magnetic-field-induced modifications of the surface roughness of magnetoactive elastomers (MAEs) with four material compositions incorporating two concentrations of ferromagnetic microparticles (70 wt% and 80 wt%) and exhibiting two shear storage moduli of the resulting composite material (about 10 kPa and 30 kPa). The analysis was primarily based on spread optical reflection measurements. The surfaces of all four materials were found to be very smooth in the absence of magnetic field (RMS roughness below 50 nm). A maximal field-induced roughness modification (approximately 1 μm/T) was observed for the softer material with the lower filler concentration, and a minimal modification (less than 50 nm/T) was observed for the harder material with the higher filler concentration. All four materials showed a significant decrease in the total optical reflectivity with an increasing magnetic field as well. This effect is attributed to the existence of a distinct surface layer that is depleted of microparticles in the absence of a magnetic field but becomes filled with particles in the presence of the field. We analyzed the temporal response of the reflective properties to the switching on and off of the magnetic field and found switching-on response times of around 0.1 s and switching-off response times in the range of 0.3–0.6 s. These observations provide new insight into the magnetic-field-induced surface restructuring of MAEs and may be useful for the development of magnetically reconfigurable elastomeric optical surfaces. Full article