Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems

The study of the L- and D-amino acid properties in proteins and peptides has attracted considerable attention in recent years, as the replacement of even one L-amino acid by its D-analogue due to aging of the body is resulted in a number of pathological conditions, including Alzheimer’s and Parkinson’s diseases. A recent trend is using short model systems to study the peculiarities of proteins with D-amino acids. In this report, the comparison of the excited states quenching of L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (R)- and (S)-ketoprofen (KP-Trp) was carried out by photochemically induced dynamic nuclear polarization (CIDNP) and fluorescence spectroscopy. Quenching of the Trp excited states, which occurs via two mechanisms: prevailing resonance energy transfer (RET) and electron transfer (ET), indeed demonstrates some peculiarities for all three studied configurations of the dyad: (R,S)-, (S,R)-, and (S,S)-. Thus, the ET efficiency is identical for (S,R)- and (R,S)-enantiomers, while RET differs by 1.6 times. For (S,S)-, the CIDNP coefficient is almost an order of magnitude greater than for (R,S)- and (S,R)-. To understand the source of this difference, hyperpolarization of (S,S)-and (R,S)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation.     

The influence of poly(3,4-ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion-117 membranes

Nafion-117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion-exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion-117 membranes by PEDOT and hot-pressing of hydrogen-oxygen membrane-electrode assemblies (MEAs) on the performance of proton-exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5-fold: from 510 (for a pristine Nafion-117 membrane) to 810 mW cm⁻² (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm⁻², respectively.     

Reinforcing thermosets using crystalline desoxyanisoin structures

This article presents results on the potential of using crystalline flame retardants for thermoset reinforcement. The approach involves introducing reinforcement in thermosetting polymers through low molecular weight crystallizable additives. Thermally induced phase separation (TIPS) and crystallization of desoxyanisoin in diglycidylether of bisphenol‐A (DGEBA) epoxy monomer were investigated. Small angle light scattering and polarized optical microscopy were utilized to monitor phase separation and the crystallization of desoxyanisoin in DGEBA at different concentrations. Reaction induced phase separation (RIPS) with polyetheramine was carried out under isothermal and temperature gradient curing conditions. Altering the cure schedule resulted in a rich range of morphologies due to the competition between TIPS and RIPS. During isothermal cure, straight fiber‐like anisotropic crystals on a centimeter length scale developed. In contrast, thermal gradients frustrated the crystal growth and resulted in complex and rich morphologies. Desoxyanisoin provided marginal epoxy thermoset reinforcement at 10 vol %. However, the additive did not increase the thermoset flammability retardancy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39853.     

CHID1 Is a Novel Prognostic Marker of Non-Small Cell Lung Cancer

There is an urgent need for identification of new prognostic markers and therapeutic targets for non-small cell lung cancer (NSCLC). In this study, we evaluated immune cells markers in 100 NSCLC specimens. Immunohistochemical analysis revealed no prognostic value for the markers studied, except CD163 and CD206. At the same time, macrophage markers iNOS and CHID1 were found to be expressed in tumor cells and associated with prognosis. We showed that high iNOS expression is a marker of favorable prognosis for squamous cell lung carcinoma (SCC), and NSCLC in general. Similarly, high CHID1 expression is a marker of good prognosis in adenocarcinoma and in NSCLC in general. Analysis of prognostic significance of a high CHID1/iNOS expression combination showed favorable prognosis with 20 months overall survival of patients from the low CHID1/iNOS expression group. For the first time, we demonstrated that CHID1 can be expressed by NSCLC cells and its high expression is a marker of good prognosis for adenocarcinoma and NSCLC in general. At the same time, high expression of iNOS in tumor cells is a marker of good prognosis in SCC. When used in combination, CHID1 and iNOS show a very good prognostic capacity for NSCLC. We suggest that in the case of lung cancer, tumor-associated macrophages are likely ineffective as a therapeutic target. At the same time, macrophage markers expressed by tumor cells may be considered as targets for anti-tumor therapy or, as in the case of CHID1, as potential anti-tumor agents.     

Nanomaterials for Heterogeneous Combustion

Nanophase materials and nanocomposites, characterized by an ultra fine grain size (less than 100 nm) have attracted wide spread interest in recent years by virtue of their unusual mechanical, electrical, optical, magnetic, and energetic properties. Studies have shown that the thermal behavior of nano‐scaled materials is quite different from micron‐sized powders. Nanosized metallic and explosive powders have been used as solid propellant and explosive mixtures to increase efficiency. At the same time recent studies reveal that the presence of nanosized metals in propellants does not necessary translate into an increased burning rate and burning temperature. The reasons of this effect are far from being clear. This paper presents a new approach to the production of nanocomposites of some energetic materials – ammonium nitrite, cyclotrimethylene trinitramine (RDX), and aluminum – by the vacuum co‐deposition technique. The thermal behavior of the synthesized nanopowder and nanocomposites is investigated. A substantial difference in burning rate of RDX nanopowder has been found in comparison to micron‐sized material. Experimental results allow investigating the effects of nanosized materials on the combustion characteristics.     

Hemi- and Homozygous Loss-of-Function Mutations in DSG2 (Desmoglein-2) Cause Recessive Arrhythmogenic Cardiomyopathy with an Early Onset

About 50% of patients with arrhythmogenic cardiomyopathy (ACM) carry a pathogenic or likely pathogenic mutation in the desmosomal genes. However, there is a significant number of patients without positive familial anamnesis. Therefore, the molecular reasons for ACM in these patients are frequently unknown and a genetic contribution might be underestimated. Here, we used a next-generation sequencing (NGS) approach and in addition single nucleotide polymor-phism (SNP) arrays for the genetic analysis of two independent index patients without familial medical history. Of note, this genetic strategy revealed a homozygous splice site mutation (DSG2–c.378+1G>T) in the first patient and a nonsense mutation (DSG2–p.L772X) in combination with a large deletion in DSG2 in the second one. In conclusion, a recessive inheritance pattern is likely for both cases, which might contribute to the hidden medical history in both families. This is the first report about these novel loss-of-function mutations in DSG2 that have not been previously identi-fied. Therefore, we suggest performing deep genetic analyses using NGS in combination with SNP arrays also for ACM index patients without obvious familial medical history. In the future, this finding might has relevance for the genetic counseling of similar cases.     

Modified track membranes with antibacterial properties

Microbiological contamination of polymeric membranes in the process of their exploitation is an essential problem of membrane technology. It results in the increase of manufacturing costs, destruction of membranes, operating life reduction and secondary contamination of water by the metabolism products of microorganisms. For the purpose of reduction of membrane biofouling and biodegradation investigation of adsorption of the guanidine containing oligomers on the surface of PET track membranes was conducted and their influence on the selectivity and antibacterial properties of the membranes was investigated. It was established that modified membranes have substantially higher resistance to biofouling.