Radiation-induced stable radicals in calcium phosphates: Results of multifrequency epr, ednmr, eseem, and endor studies

This article presents the results of a study of radiation-induced defects in various synthetic calcium phosphate (CP) powder materials (hydroxyapatite—HA and octacalcium phosphate—OCP) by electron paramagnetic resonance (EPR) spectroscopy at the X, Q, and W-bands (9, 34, 95 GHz for the microwave frequencies, respectively). Currently, CP materials are widely used in orthopedics and dentistry owing to their high biocompatibility and physico-chemical similarity with human hard tissue. It is shown that in addition to the classical EPR techniques, other experimental approaches such as ELDOR-detected NMR (EDNMR), electron spin echo envelope modulation (ESEEM), and electronnuclear double resonance (ENDOR) can be used to analyze the electron–nuclear interactions of CP powders. We demonstrated that the value and angular dependence of the quadrupole interaction for14 N nuclei of a nitrate radical can be determined by the EDNMR method at room temperature. The ESEEM technique has allowed for a rapid analysis of the nuclear environment and estimation of the structural positions of radiation-induced centers in various crystal matrices. ENDOR spectra can provide information about the distribution of the nitrate radicals in the OCP structure. © 2021 by the authors. Licensee MDPI, Basel, Switzerland. Published under the CC BY 4.0 license.Authors would like to thank the Russian Foundation for Basic Research, project no. 18-29-11086. Institute of Solid State Physics, University of Latvia as the Center of Excellence received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01–2016-2017- TeamingPhase2 under grant agreement No. 739508, project CAMART2

Isothermal Kinetics of Epoxyphosphazene Cure

The influence of epoxycyclophosphazene modifier on the process of epoxy-amine curing was studied by differential scanning calorimetry (DSC). The study revealed that the curing process of epoxyphosphazene binders with 4′4′diaminodiphenylsulfone (DDS) provides more complete curing of the formulations in comparison with ones applying low molecular-weight polyamide curing agent (L-20). The isothermal kinetics of curing was described by means of model fitting and the isoconversional approach (Friedman method). Accurate n-order approximation was obtained for all systems under study. In particular, the 2-order equation fits well with the main part of curing excluding high degrees of conversion. The process of curing could be distinguished into three zones. The transition from zone 2 to zone 3 correlates with gelation. According to the isoconversional analysis by Friedman method, the diffusion-controlled mechanism is found at final stage of curing

Benzoxazine Monomers and Polymers Based on 3,3′-Dichloro-4,4′-Diaminodiphenylmethane: Synthesis and Characterization

To reveal the effect of chlorine substituents in the ring of aromatic amine on the synthesis process of benzoxazine monomer and on its polymerization ability, as well as to develop a fire-resistant material, a previously unreported benzoxazine monomer based on 3,3′-dichloro-4,4′-diaminodiphenylmethane was obtained in toluene and mixture toluene/isopropanol. The resulting benzoxazine monomers were thermally cured for 2 h at 180 °C, 4 h at 200 °C, 2 h at 220 °C. A comparison between the rheological, thermal and fire-resistant properties of the benzoxazines based on 3,3′-dichloro-4,4′-diaminodiphenylmethane and, for reference, 4,4′-diaminodimethylmethane was made. The effect of the reaction medium on the structure of the oligomeric fraction and the overall yield of the main product were studied and the toluene/ethanol mixture was found to provide the best conditions; however, in contrast to most known diamine-based benzoxazines, synthesis in the pure toluene is also possible. The synthesized monomers can be used as thermo- and fire-resistant binders for polymer composite materials, as well as hardeners for epoxy resins. Chlorine-containing polybenzoxazines require more severe conditions for polymerization but have better fire resistance

Synthesis and Application of Arylaminophosphazene as a Flame Retardant and Catalyst for the Polymerization of Benzoxazines

A novel type of phosphazene containing an additive that acts both as a catalyst and as a flame retardant for benzoxazine binders is presented in this study. The synthesis of a derivative of hexachlorocyclotriphosphazene (HCP) and meta-toluidine was carried out in the medium of the latter, which made it possible to achieve the complete substitution of chlorine atoms in the initial HCP. Thermal and flammability characteristics of modified compositions were investigated. The modifier catalyzes the process of curing and shifts the beginning of reaction from 222.0 °C for pure benzoxazine to 205.9 °C for composition with 10 phr of modifier. The additive decreases the glass transition temperature of compositions. Achievement of the highest category of flame resistance (V-0 in accordance with UL-94) is ensured both by increasing the content of phenyl residues in the composition and by the synergistic effect of phosphorus and nitrogen. A brief study of the curing kinetics disclosed the complex nature of the reaction. An accurate two-step model is obtained using the extended Prout–Tompkins equation for both steps

The Immunogenicity in Mice of HCV Core Delivered as DNA Is Modulated by Its Capacity to Induce Oxidative Stress and Oxidative Stress Response

HCV core is an attractive HCV vaccine target, however, clinical or preclinical trials of core-based vaccines showed little success. We aimed to delineate what restricts its immunogenicity and improve immunogenic performance in mice. We designed plasmids encoding full-length HCV 1b core and its variants truncated after amino acids (aa) 60, 98, 152, 173, or up to aa 36 using virus-derived or synthetic polynucleotides (core191/60/98/152/173/36_191v or core152s DNA, respectively). We assessed their level of expression, route of degradation, ability to trigger the production of reactive oxygen species/ROS, and to activate the components of the Nrf2/ARE antioxidant defense pathway heme oxygenase 1/HO-1 and NAD(P)H: quinone oxidoreductase/Nqo-1. All core variants with the intact N-terminus induced production of ROS, and up-regulated expression of HO-1 and Nqo-1. The capacity of core variants to induce ROS and up-regulate HO-1 and Nqo-1 expression predetermined their immunogenicity in DNA-immunized BALB/c and C57BL/6 mice. The most immunogenic was core 152s, expressed at a modest level and inducing moderate oxidative stress and oxidative stress response. Thus, immunogenicity of HCV core is shaped by its ability to induce ROS and oxidative stress response. These considerations are important in understanding the mechanisms of viral suppression of cellular immune response and in HCV vaccine design