Structural Rearrangements of Polylactide/Natural Rubber Composites during Hydro- and Biotic Degradation.

In the work, the impact of the biological medium and water on structural rearrangements in pure polylactide and polylactide/natural rubber film composites was studied. Polylactide/natural rubber films with a rubber content of 5, 10, and 15 wt.% were obtained by the solution method. Biotic degradation was carried out according to the Sturm method at a temperature of 22 ± 2 °C. Hydrolytic degradation was studied at the same temperature in distilled water. The structural characteristics were controlled by thermophysical, optical, spectral, and diffraction methods. Optical microscopy revealed the surface erosion of all samples after exposure to microbiota and water. Differential scanning calorimetry showed a decrease in the degree of crystallinity of polylactide by 2-4% after the Sturm test, and a tendency to an increase in the degree of crystallinity after the action of water was noted. Changes in the chemical structure were shown in the spectra recorded by infrared spectroscopy. Due to degradation, significant changes in the intensities of the bands in the regions of 3500-2900 and 1700-1500 cm-1 were shown. The X-ray diffraction method established differences in diffraction patterns in very defective and less damaged regions of polylactide composites. It was determined that pure polylactide hydrolyzed more readily under the action of distilled water than polylactide/natural rubber composites. Film composites were more rapidly subjected to biotic degradation. The degree of biodegradation of polylactide/natural rubber composites increased with the rise in the content of natural rubber in the compositions.

Thermo-Oxidative Destruction and Biodegradation of Nanomaterials from Composites of Poly(3-hydroxybutyrate) and Chitosan.

A complex of structure-sensitive methods of morphology analysis was applied to study film materials obtained from blends of poly(3-hydroxybutyrate) (PHB) and chitosan (CHT) by pouring from a solution, and nonwoven fibrous materials obtained by the method of electrospinning (ES). It was found that with the addition of CHT to PHB, a heterophase system with a nonequilibrium stressed structure at the interface was formed. This system, if undergone accelerated oxidation and hydrolysis, contributed to the intensification of the growth of microorganisms. On the other hand, the antimicrobial properties of CHT led to inhibition of the biodegradation process. Nonwoven nanofiber materials, since having a large specific surface area of contact with an aggressive agent, demonstrated an increased ability to be thermo-oxidative and for biological degradation in comparison with film materials.

Relation between molecular electronic structure and nuclear spin-induced circular dichroism.

The recently theoretically described nuclear spin-induced circular dichroism (NSCD) is a promising method for the optical detection of nuclear magnetization. NSCD involves both optical excitations of the molecule and hyperfine interactions and, thus, it offers a means to realize a spectroscopy with spatially localized, high-resolution information. To survey the factors relating the molecular and electronic structure to the NSCD signal, we theoretically investigate NSCD of twenty structures of the four most common nucleic acid bases (adenine, guanine, thymine, cytosine). The NSCD signal correlates with the spatial distribution of the excited states and couplings between them, reflecting changes in molecular structure and conformation. This constitutes a marked difference to the nuclear magnetic resonance (NMR) chemical shift, which only reflects the local molecular structure in the ground electronic state. The calculated NSCD spectra are rationalized by means of changes in the electronic density and by a sum-over-states approach, which allows to identify the contributions of the individual excited states. Two separate contributions to NSCD are identified and their physical origins and relative magnitudes are discussed. The results underline NSCD spectroscopy as a plausible tool with a power for the identification of not only different molecules, but their specific structures as well.

Coupled-cluster and density functional theory studies of the electronic 0-0 transitions of the DNA bases.

The 0-0 transitions of the electronic excitation spectra of the lowest tautomers of the four nucleotide (DNA) bases have been studied using linear-response approximate coupled-cluster singles and doubles (CC2) calculations. Excitation energies have also been calculated at the linear-response time-dependent density functional theory (TDDFT) level using the B3LYP functional. Large basis sets have been employed for ensuring that the obtained excitation energies are close to the basis-set limit. Zero-point vibrational energy corrections have been calculated at the B3LYP and CC2 levels for the ground and excited states rendering direct comparisons with high-precision spectroscopy measurements feasible. The obtained excitation energies for the 0-0 transitions of the first excited states of guanine tautomers are in good agreement with experimental values confirming the experimental assignment of the energetic order of the tautomers of the DNA bases. For the experimentally detected guanine tautomers, the first excited state corresponds to a π→π* transition, whereas for the tautomers of adenine, thymine, and the lowest tautomer of cytosine the transition to the first excited state has n →π* character. The calculations suggest that the 0-0 transitions of adenine, thymine, and cytosine are not observed in the absorption spectrum due to the weak oscillator strength of the formally symmetry-forbidden transitions, while 0-0 transitions of thymine have been detected in fluorescence excitation spectra.