RESUMEN

A comprehensive study was performed on the supramolecular ordering and optical properties of thin nanostructured glycerohydrogel sol-gel plates based on chitosan L- and D-aspartate and their individual components in the X-ray, UV, visible, and IR ranges. Our comparative analysis of chiroptical characteristics, optical collimated transmittance, the average cosine of the scattering angle, microrelief and surface asymmetry, and the level of structuring shows a significant influence of the wavelength range of electromagnetic radiation and the enantiomeric form of aspartic acid on the functional characteristics of the sol-gel materials. At the macrolevel of the supramolecular organization, a complex topography of the surface layer and a dense amorphous-crystalline ordering of polymeric substances were revealed, while at the nanolevel, there were two forms of voluminous scattering domains: nanospheres with diameters of 60-120 nm (L-) and 45-55 nm (D-), anisometric particles of lengths within ~100-160 (L-) and ~85-125 nm (D-), and widths within ~10-20 (L-) and ~20-30 nm (D-). The effect of optical clearing on glass coated with a thin layer of chitosan L-(D-)aspartate in the near-UV region was discovered (observed for the first time for chitosan-based materials). The resulting nanocomposite shape-stable glycerohydrogels seem promising for sensorics and photonics.

RESUMEN

Complex dynamical systems may exhibit multiple steady states, including time-periodic limit cycles, where the final trajectory depends on initial conditions. With tuning of parameters, limit cycles can proliferate or merge at an exceptional point. Here we ask how dynamics in the vicinity of such a bifurcation are influenced by noise. A pitchfork bifurcation can be used to induce bifurcation behavior. We model a limit cycle with the normal form of the Hopf oscillator, couple it to the pitchfork, and investigate the resulting dynamical system in the presence of noise. We show that the generating functional for the averages of the dynamical variables factorizes between the pitchfork and the oscillator. The statistical properties of the pitchfork in the presence of noise in its various regimes are investigated and a scaling theory is developed for the correlation and response functions, including a possible symmetry-breaking field. The analysis is done by perturbative calculations as well as numerical means. Finally, observables illustrating the coupling of a system with a limit cycle to a pitchfork are discussed and the phase-phase correlations are shown to exhibit nondiffusive behavior with universal scaling.

RESUMEN

The influence of l- and d-ascorbic acid diastereomers on the structure, supramolecular ordering, energy, sorption and biological properties of heterochiral (D-L) and homochiral (D-D) salt complexes of chitosan (d-glucan)-acid was studied. The thermal effect of dissolving chitosan in l-ascorbic acid and the protonation degree of (D-L)-salts were lower than those in the medium of the d-isomer. Homochiral (D-D) salts, in contrast to heterochiral (D-L) ones, are distinguished by a more developed system of intermolecular and intramolecular contacts, a more ordered and equilibrium supramolecular organization of macrochains, a higher crystallinity degree, and a smaller amount of crystallization water. The sorption isotherms of chiral salts were approximated by the thermal equation of sorption and the superposition of the Langmuir and Flory-Huggins isotherms. Significant differences were found in the limiting value and energy of sorption, the constant of adsorption equilibrium, the limiting sorption capacity of the localized mode of water, and the Gibbs mixing energy. Biotesting on non-vascular (Scenedesmus quadricauda) and vascular eukaryotes (Linum usitatissimum) revealed the growth-stimulating effect of the D-D salts. The obtained results confirm our hypothesis of the homochiral salt complexes d-glucan-d-ascorbic acid best corresponding to the principles of the functional organization of biological objects.

Asunto(s)

Quitosano , Quitosano/química , Sales (Química) , Ácido Ascórbico , Adsorción , Glucanos , Agua/química , Cinética , Concentración de Iones de Hidrógeno

RESUMEN

For the first time, anisotropic hydrogel material with a highly oriented structure was obtained by the chemical reaction of polymer-analogous transformation of chitosan glycolate-chitosan base using triethanolamine (TEA) as a neutralizing reagent. Tangential bands or concentric rings, depending on the reaction conditions, represent the structural anisotropy of the hydrogel. The formation kinetics and the ratio of the positions of these periodic structures are described by the Liesegang regularities. Detailed information about the bands is given (formation time, coordinate, width, height, and formation rate). The supramolecular ordering anisotropy of the resulting material was evaluated both by the number of Liesegang bands (up to 16) and by the average values of the TEA diffusion coefficient ((15-153) × 10-10 and (4-33) × 10-10 m2/s), corresponding to the initial and final phase of the experiment, respectively. The minimum chitosan concentration required to form a spatial gel network and, accordingly, a layered anisotropic structure was estimated as 1.5 g/dL. Morphological features of the structural anisotropic ordering of chitosan Liesegang structures are visualized by scanning electron microscopy. The hemocompatibility of the material obtained was tested, and its high sorption-desorption properties were evaluated using the example of loading-release of cholecalciferol (loading degree ~35-45%, 100% desorption within 25-28 h), which was observed for a hydrophobic substance inside a chitosan-based material for the first time.

RESUMEN

CrAssphage is the most abundant human-associated virus and the founding member of a large group of bacteriophages, discovered in animal-associated and environmental metagenomes, that infect bacteria of the phylum Bacteroidetes. We analyze 4907 Circular Metagenome Assembled Genomes (cMAGs) of putative viruses from human gut microbiomes and identify nearly 600 genomes of crAss-like phages that account for nearly 87% of the DNA reads mapped to these cMAGs. Phylogenetic analysis of conserved genes demonstrates the monophyly of crAss-like phages, a putative virus order, and of 5 branches, potential families within that order, two of which have not been identified previously. The phage genomes in one of these families are almost twofold larger than the crAssphage genome (145-192 kilobases), with high density of self-splicing introns and inteins. Many crAss-like phages encode suppressor tRNAs that enable read-through of UGA or UAG stop-codons, mostly, in late phage genes. A distinct feature of the crAss-like phages is the recurrent switch of the phage DNA polymerase type between A and B families. Thus, comparative genomic analysis of the expanded assemblage of crAss-like phages reveals aspects of genome architecture and expression as well as phage biology that were not apparent from the previous work on phage genomics.

Asunto(s)

Bacteriófagos/genética , Microbioma Gastrointestinal/genética , Genoma Viral , Metagenoma , Codón/genética , Secuencia Conservada , ADN Polimerasa Dirigida por ADN/metabolismo , Humanos , Inteínas , Intrones/genética , Sistemas de Lectura Abierta/genética , Filogenia , Empalme del ARN/genética , Transcripción Genética , Viroma/genética

RESUMEN

This paper presents the results of our study of the diffusion front progression of OH- ions in the bulk of a flat layer of the salt chitosan form during the course of the chemical reaction of the polymer-analogous salt → base transformation, accompanied by the formation of a water-insoluble polymeric phase as a gel film with its structure of concentric rings or tangential bands. Using scanning electron microscopy and polarization microscopy, structural and morphological features of these periodic formations were visualized. Physicochemical parameters and spatiotemporal mass transfer characteristics were obtained. The process under study is shown to obey the classical laws of ion-exchange reactions, and the formation kinetics and the ratio of the positions of periodic structures are described by the laws characteristic of the Liesegang phenomenon. The average diffusion coefficients of hydroxide ions in the periodic formations calculated, considering the protonation degree of amino groups, were found to be no more than a decimal order of magnitude lower than those in an aqueous solution. This confirms the fact of swelling of the formed chitosan base and the existence of a gel film, in whose liquid phase diffusion occurs.

RESUMEN

The optical activity [α] of films of chitosan and chitosan acetate was studied. [α] depended on the orientation angle θ of the film sample around the light beam. The angular dependences [α] = f(θ) (indicatrices) were processed to extract the constant term [α]0and four harmonics ([α]i, Fourier's series) determined by structure elements with the corresponding symmetry: the amorphous (isotropic) phase of chitosan ([α]0), irregular-shaped structures ([α]1), rod-shaped ones in the film plane ([α]2), helical ones located perpendicular to the film surface ([α]3), and crystalline structures ([α]4). The contribution of individual supramolecular structures to the overall optical activity of chitosan was estimated: [α]2 and [α]4 predominated for the fresh chitosan acetate films, while [α]4 did for the chitosan ones. The results of the numerical decomposition of indicatrices are in satisfactory agreement with X-ray diffractometry data. The observed regularities predetermine prospects for obtaining stereoselective chiro-optic chitosan-based materials with novel functional properties.

RESUMEN

An algorithm is offered for finding the range within which cumulative particle size distribution functions can be located in consistency with experimental turbidimetric data at a number of wavelengths. It is based on linear programming and minimization techniques. Several tests were performed. The lower right-hand branch of the corridor was found to locate near the initial distribution function.