Fractional composition of partly hydrolysed polyvinyl acetate and its compatibility with hydroxypropyl methylcellulose in aqueous solutions

Fractionation of partly hydrolysed polyvinyl acetate (PVA) was performed by warming of its aqueous solutions. The following properties of the obtained fractions were determined: viscosity, molecular weight and molecular weight distribution, surface tension, and absorbance in the IR range. The blockiness of the polymer molecules, characterized by their behaviour towards iodine-containing systems such as I₂,-H₃BO₃ and I₂,-KI, was estimated. Fractionation of the aqueous solutions of PVA by warming is based mainly on the different internal molecular structure of the separated products, i.e. on the length of the vinyl acetate blocks in the PVA molecules and, to a lesser extent, on the degree of hydrolysis and the degree of polymerization. The more blocklike are the PVA molecules, the less compatible are the polymers in the PVA-hydroxypropyl methylcellulose (HPMC)-water system. At phase separation in this sytem the PVA molecules which are not compatible with HPMC are, in the first place, those of the highest blockiness.     

Radiation-Chemical Behavior of TBP in Hydrocarbon and Chlorohydrocarbon Diluents under Conditions of Reprocessing of Spent Fuel from Nuclear Power Plants

Experiments were performed for comparative assessment of the effect of ionizing radiation on the service characteristics of 30% TBP solutions in various diluents: hexachlorobutadiene (HCBD), mixtures of n-paraffins (RED diluent), and fraction of naphthenic hydrocarbons (RZh diluent). The following main parameters were chosen for comparative assessment of the quality of irradiated extractant solutions: composition and behavior of diluent radiolysis products, effect of diluents on the TBP radiolysis, and aggregative stability of emulsions in the main operations of the extraction cycle. The service life of the extraction mixtures was estimated from variation of the above parameters with the irradiation dose. Principles for choosing solvents with increased service life under irradiation were substantiated.     

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.     

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.     

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.     

Beyond-design-basis regimes of uranium stripping and of carbonate regeneration of the solvent

Beyond-design-basis regimes of centrifugal contactors for U stripping and of mixer–settlers for carbonate regeneration of the solvent, 30% TBP in Isopar M, were studied from the viewpoint of the influence of incomplete uranium stripping on the phase stability of the extraction system in the step of the carbonate scrubbing of the solvent. Dynamic relationship between these two operations was determined. A mathematical model of uranium stripping at stepwise–20% deviation from the nominal value was developed and verified; it was shown that the beyond-design-basis regime develops in such apparatuses within 4 h at the total trial time longer than 8 h. The mathematical relationships obtained were used in the development of software for calculating transient processes that occur when the stream parameters in the course of carbonate regeneration of the solvent change. The beyond-design-basis regime of the solvent regeneration was found to have two regions: region of stoichiometric excess of carbonate ions over uranyl ions with the risk of precipitation and region of excess of uranyl ions over carbonate ions with acidification of the unit and uranium breakthrough with the recycled solvent. The conditions of the tests performed correspond to the second region.     

Interaction of thorium and plutonium with pertechnetic acid in the course of extraction from nitric acid solutions with tributyl phosphate in diluent and its mathematical description

Databases on the coextraction of Th or Pu with Tc into 30% TBP in hydrocarbon diluent at 25°С are presented. The coextraction leads to mutual enhancement of the extraction of all the elements. The interactions in the system are described within the framework of a new approach to modeling, using the previously suggested and additional equations of concurrently occurring chemical reactions. The apparent equilibrium constants of these reactions are calculated.     

GPR55 Receptor Activation by the N-Acyl Dopamine Family Lipids Induces Apoptosis in Cancer Cells via the Nitric Oxide Synthase (nNOS) Over-Stimulation

GPR55 is a GPCR of the non-CB1/CB2 cannabinoid receptor family, which is activated by lysophosphatidylinositol (LPI) and stimulates the proliferation of cancer cells. Anandamide, a bioactive lipid endocannabinoid, acts as a biased agonist of GPR55 and induces cancer cell death, but is unstable and psychoactive. We hypothesized that other endocannabinoids and structurally similar compounds, which are more hydrolytically stable, could also induce cancer cell death via GPR55 activation. We chemically synthesized and tested a set of fatty acid amides and esters for cell death induction via GPR55 activation. The most active compounds appeared to be N-acyl dopamines, especially N-docosahexaenoyl dopamine (DHA-DA). Using a panel of cancer cell lines and a set of receptor and intracellular signal transduction machinery inhibitors together with cell viability, Ca²⁺, NO, ROS (reactive oxygen species) and gene expression measurement, we showed for the first time that for these compounds, the mechanism of cell death induction differed from that published for anandamide and included neuronal nitric oxide synthase (nNOS) overstimulation with concomitant oxidative stress induction. The combination of DHA-DA with LPI, which normally stimulates cancer proliferation and is increased in cancer setting, had an increased cytotoxicity for the cancer cells indicating a therapeutic potential.