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This study focuses on finding direct evidence of oxidative degradation of chlorophenols. The aim of the study was distinguishing major and minor degradation products. Several chlorophenols with different numbers of chloride substituents (2‐chlorophenol, 2,4‐dichlorophenol, and 2,4,5‐trichlorophenol) were chosen for a thorough study. UV photolysis, Fenton, and photo‐Fenton processes were tested as advanced oxidative processes. Photo‐Fenton appeared to result in higher conversions of mono‐ and dichlorophenols. Conversions of trichlorophenol were comparable for all the processes under this study. Formic and acetic acids were shown to be the major products. Their formation was confirmed by 1H NMR spectroscopy. Other possible products are minor and are formed in negligible concentrations. The degradation methods can be considered harmless techniques of inactivating the chlorophenols, leading to the formation of products of low toxicity.

Schizophrenia is a prototypical network disorder with widespread brain-morphological alterations, yet it remains unclear whether these distributed alterations robustly reflect the underlying network layout. We tested whether large-scale structural alterations in schizophrenia relate to normative structural and functional connectome architecture, and systematically evaluated robustness and generalizability of these network-level alterations. Leveraging anatomical MRI scans from 2439 adults with schizophrenia and 2867 healthy controls from 26 ENIGMA sites and normative data from the Human Connectome Project (n= 207), we evaluated structural alterations of schizophrenia against two network susceptibility models: (i) hub vulnerability, which examines associations between regional network centrality and magnitude of disease-related alterations; (ii) epicenter mapping, which identifies regions whose typical connectivity profile most closely resembles the disease-related morphological alterations. To assess generalizability and specificity, we contextualized the influence of site, disease stages, and individual clinical factors and compared network associations of schizophrenia with that found in affective disorders. Our findings show schizophrenia-related cortical thinning is spatially associated with functional and structural hubs, suggesting that highly interconnected regions are more vulnerable to morphological alterations. Predominantly temporo-paralimbic and frontal regions emerged as epicenters with connectivity profiles linked to schizophrenia’s alteration patterns. Findings were robust across sites, disease stages, and related to individual symptoms. Moreover, transdiagnostic comparisons revealed overlapping epicenters in schizophrenia and bipolar, but not major depressive disorder, suggestive of a pathophysiological continuity within the schizophrenia-bipolar-spectrum. In sum, cortical alterations over the course of schizophrenia robustly follow brain network architecture, emphasizing marked hub susceptibility and temporo-frontal epicenters at both the level of the group and the individual. Subtle variations of epicenters across disease stages suggest interacting pathological processes, while associations with patient-specific symptoms support additional inter-individual variability of hub vulnerability and epicenters in schizophrenia. Our work outlines potential pathways to better understand macroscale structural alterations, and inter- individual variability in schizophrenia.

Machine learning approaches using structural magnetic resonance imaging (sMRI) can be informative for disease classification, although their ability to predict psychosis is largely unknown. We created a model with individuals at CHR who developed psychosis later (CHR-PS+) from healthy controls (HCs) that can differentiate each other. We also evaluated whether we could distinguish CHR-PS+ individuals from those who did not develop psychosis later (CHR-PS-) and those with uncertain follow-up status (CHR-UNK). T1-weighted structural brain MRI scans from 1165 individuals at CHR (CHR-PS+, n= 144; CHR-PS-, n= 793; and CHR-UNK, n= 228), and 1029 HCs, were obtained from 21 sites. We used ComBat to harmonize measures of subcortical volume, cortical thickness and surface area data and corrected for non-linear effects of age and sex using a general additive model. CHR-PS+ (n= 120) and HC (n= 799) data from 20 sites served as a training dataset, which we used to build a classifier. The remaining samples were used external validation datasets to evaluate classifier performance (test, independent confirmatory, and independent group [CHR-PS- and CHR-UNK] datasets). The accuracy of the classifier on the training and independent confirmatory datasets was 85% and 73% respectively. Regional cortical surface area measures-including those from the right superior frontal, right superior temporal, and bilateral insular cortices strongly contributed to classifying CHR-PS+ from HC. CHR-PS- and CHR-UNK individuals were more likely to be classified as HC compared to CHR-PS+ (classification rate to HC: CHR-PS+, 30%; CHR-PS-, 73%; CHR-UNK, 80%). We used multisite sMRI to train a classifier to predict psychosis onset in CHR individuals, and it showed promise predicting CHR-PS+ in an independent sample. The results suggest that when considering adolescent brain development, baseline MRI scans for CHR individuals may be helpful to identify their prognosis. Future prospective studies are required about whether the classifier could be actually helpful in the clinical settings.

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Introduction: Immune checkpoint inhibitors are highly effective in treating various cancers. We analyzed the significance of the KRAS/STK11co-mutation in relation to the efficacy of immune checkpoint inhibitors in pan-cancer patient cohort.Methods: We analyzed data from open-access research: MSK-IMPACT (molecular profiling data from patients receiving systemic antitumor therapy) and MSK-TMB (molecular profiling data from patients receiving immune checkpoint inhibitors). In both studies, high throughput sequencing was used for molecular profiling.Results: A total of 10,336 patients receiving antitumor therapy (MSK-IMPACT study) and 1661 patients receiving immune checkpoint inhibitors (MSK-TMB study) were included in the analysis. Co-mutation STK11/KRASwas found in 156 (1.5%) and 46 (2.8%) patients in the two studies, respectively. Most patients with the STK11/KRASco-mutation had non-small cell lung cancer (83% and 85% in the two studies, respectively). Among non-small cell lung cancer patients, the STK11mutation was associated with a worse outcome for patients receiving systemic antitumor therapy, but not immune checkpoint inhibition therapy (HR for OS 1.90 [95% CI 1.36-2.65] and 1.44 [95% CI 0.88-2.37]). Co-mutation STK11/KRASwas also not associated with patient outcome in any of the studies (HR for OS 0.93 [95% CI 0.56-1.52] and 1.09 [95% CI 0.54-2.19]). High tumor mutational burden was associated with better outcome in the cohort of patients receiving immune checkpoint inhibitors. An analogous analysis among patients in the pan-cancer cohort (excluding patients with non-small cell lung cancer) showed STK11mutations and high tumor mutational burden have a predictive role for the efficacy of immune checkpoint inhibitors, but not STK11/KRASco-mutation.Conclusions: Co-mutation STK11/KRASis common among patients with non-small cell lung cancer and is not an independent predictive marker for the efficacy of immune checkpoint inhibitors. Further studies are required to clarify the role of STK11mutations in immune checkpoint inhibitor treatment response.

Densities of dilute solutions of urea (U) in tert-butylamine (t-BuNH2) with molalities being up to ∼0.023 mol·kg–1were measured at T= 278.15, 283.15, 288.15, 293.15, 298.15, and 303.15 K and p= 99.6 kPa. All experiments were carried out using a sealed U-tube vibrating densimeter. The total uncertainty in the density measurements did not exceed 0.03 kg·m–3. The standard (apparent at infinite dilution) molar volumes and expansibilities of U as a solute in t-BuNH2were computed. Similar to infinitely dilute solutions of U in methanol (MeOH) and tert-butanol (t-BuOH), the phenomenon of the so-called “negative partial molar expansibility” or “partial molar isobaric compaction of a solute” was found in the studied binary system. The mixed structural aggregate or “solvation complex” formed by a U molecule in the t-BuNH2medium becomes increasingly compact as the temperature rises because the solute-to-solvent affinity more and more noticeably prevails over the affinity of the solvent molecules for each other. In doing so, the stronger heterocomponent H-bonding leads to the marked increase in the compactness of solvation complexes formed in U solutions going from t-BuOH to t-BuNH2.

Formation of a droplet around a spherical solid particle in supersaturated vapor is considered. The number and stability of equilibrium solutions in a closed small system are studied in the canonical ensemble in comparison to an open system in the grand canonical ensemble. Depending on the system’s parameters, two modes exist in the canonical ensemble: the first one with only one solution and the second one with three solutions; the presence of the third solution is due to confinement. The analysis is conducted first on a macroscopic thermodynamic level of description, and then the results are supported by studies within two versions of classical density functional theory: the square-gradient approximation with the Carnahan–Starling equation of state for hard spheres on a completely wettable particle and the random-phase approximation with the fundamental measure theory on a poorly wettable particle. In the latter case, a solution breaking the spherical symmetry is observed at a small total number of molecules.

The value of normative models in research and clinical practice relies on their robustness and a systematic comparison of different modelling algorithms and parameters; however, this has not been done to date. We aimed to identify the optimal approach for normative modelling of brain morphometric data through systematic empirical benchmarking, by quantifying the accuracy of different algorithms and identifying parameters that optimised model performance. We developed this framework with regional morphometric data from 37 407 healthy individuals (53% female and 47% male; aged 3–90 years) from 87 datasets from Europe, Australia, the USA, South Africa, and east Asia following a comparative evaluation of eight algorithms and multiple covariate combinations pertaining to image acquisition and quality, parcellation software versions, global neuroimaging measures, and longitudinal stability. The multivariate fractional polynomial regression (MFPR) emerged as the preferred algorithm, optimised with non-linear polynomials for age and linear effects of global measures as covariates. The MFPR models showed excellent accuracy across the lifespan and within distinct age-bins and longitudinal stability over a 2-year period. The performance of all MFPR models plateaued at sample sizes exceeding 3000 study participants. This model can inform about the biological and behavioural implications of deviations from typical age-related neuroanatomical changes and support future study designs. The model and scripts described here are freely available through CentileBrain.

BackgroundThe Tobacco Products Directive (2014/40/EU) partially harmonised the regulation of electronic cigarettes (e-cigarettes) in Europe, but individual countries maintain jurisdiction over bans on use in public places, domestic advertising, taxation and flavour regulations. Their association with youth e-cigarette use has not been examined.MethodsWe used the cross-sectional 2019 European School Survey Project on Alcohol and Other Drugs data from 32 countries with 98 758 students aged 15–16 years and the 2020 WHO’s assessment of the e-cigarette regulations. Multilevel logistic regression models on ever (vs never) and current (vs non-current) exclusive e-cigarette use, exclusive cigarette use and dual use by e-cigarette regulations’ composite score were adjusted for age, gender, parental education, perceived family’s financial well-being, perceived difficulty of obtaining cigarettes, country income level and general progress in tobacco control.ResultsOf the respondents, 13.3% had ever used cigarettes, 10.6% e-cigarettes and 27.3% both; 13.0% currently used cigarettes, 6.0% e-cigarettes and 6.4% both. Higher composite country score in the e-cigarette regulations was associated with lower current exclusive e-cigarette use (OR=0.78; 95% CI 0.65 to 0.94) and current dual use (OR=0.80; 95% CI 0.67 to 0.95). Youth perceiving more difficulties in obtaining cigarettes were less likely to use cigarettes, e-cigarettes and both ever and currently (OR from 0.80 (95% CI 0.76 to 0.85) to 0.94 (95% CI 0.92 to 0.96)).ConclusionsMore comprehensive e-cigarette regulations and enforcement of age-of-sale laws may be protective of e-cigarette and dual use among adolescents.

In this study, smart bioactive humic-polymer hydrogel transdermal materials based on gelatin and sodium alginate modified with humic acids have been developed and studied. A literature review was carried out and the prospects of using humic acids for a functional effect on the transdermal properties of a smart biologically active humic-polymer hydrogel have been proved. Based on the results of the experimental research of conditional viscosity and electrical conductivity, the chemical structures of the sodium alginate–gelatin systems modified with humic acids were proposed. The influence of the content of humic acids on the swelling degree and the moisture-lipid balance of the skin was studied. It was found that efficient processes for obtaining smart bioactive polymer-hydrogel transdermal materials based on gelatin and sodium alginate can be carried out at concentrations of humic acids from 2.5 to 7.5 wt.%. Modification of these hydrogels with humic acids causes the formation of structures with a higher degree of crosslinking due to more hydrogen bonds, as well as the formation of more agglomerates. As an example of the practical use of the obtained smart bioactive transdermal materials, their suitability for use in cosmetic patches was confirmed by the results of the study of swelling and moisture-lipid balance of the skin in the area around the eyes. The prospect for the use of smart biologically active humic-polymeric transdermal hydrogel materials based on gelatin and sodium alginate modified by humic acids in cosmetic patches have been shown.

An oncological-ophthalmological complex of proton-beam therapy based on the C-80 cyclotron is being created at Konstantinov St. Petersburg Institute of Nuclear Physics, National Research Center “Kurchatov Institute.” An analysis of publications devoted to the issues of quality control of specialized systems with a fixed proton beam direction in the horizontal plane for solving the problems of proton-beam therapy for patients with oncological-ophthalmological diseases is carried out. The analysis shows that since there are fewer than twenty such centers in the world, data on the frequency and content of quality-control tests for such installations is extremely contradictory. Quality-control tests based on the AAPM TG 224 protocol, supplemented by tests specific to proton oncology-ophthalmology, are presented. The levels of permissible deviations for various tests are developed on the basis of published data and technical-design data. These parameters will be included in the specialized software being created for quality control, which will allow data to be obtained on various parameters of all subsystems of the complex.

Prevention of cardiovascular disease (CVD) remains one of the largest public health challenges of our time. Identifying individuals at increased cardiovascular risk at an asymptomatic, sub-clinical stage is of paramount importance for minimizing disease progression as well as the substantial health and economic burden associated with overt CVD. Vascular ageing (VA) involves the deterioration in vascular structure and function over time and ultimately leads to damage in the heart, brain, kidney, and other organs. Vascular ageing encompasses the cumulative effect of all cardiovascular risk factors on the arterial wall over the life course and thus may help identify those at elevated cardiovascular risk, early in disease development. Although the concept of VA is gaining interest clinically, it is seldom measured in routine clinical practice due to lack of consensus on how to characterize VA as physiological vs. pathological and various practical issues. In this state-of-the-art review and as a network of scientists, clinicians, engineers, and industry partners with expertise in VA, we address six questions related to VA in an attempt to increase knowledge among the broader medical community and move the routine measurement of VA a little closer from bench towards bedside.

AbstractThe treatment of coronavirus COVID-19, like other viral diseases, is currently underdeveloped. This fact necessitates the search for new drugs and treatment methods that will effectively disrupt the life cycle of the virus. A big problem in the therapy of viral diseases is the ability of viruses to evade the host's immune response. We suppose that the search for drugs that can change the evasiveness of the virus from the immune response of the host is a very promising strategy, as it can help the body to cope with the infection. Protein SARS-CoV-2 ORF8 is one of the key proteins that can suppress antiviral immunity. This paper considers the available information on the structure and functioning of ORF8, as well as the results of molecular docking of ORF8 to a wide range of tetrapyrrole macroheterocyclic compounds capable of generating reactive oxygen species upon photoirradiation. This principle of photoinactivation of biosubstrates underlies the methods of photodynamic therapy of cancer. Application of photoinactivation of drug-resistant forms of bacteria and some viruses can be useful in the fight against COVID-19 and other viral infections. In this work, the structure of ORF8 complexes with macrocyclic compounds is considered in detail, the dependence of their binding affinity on the nature of macrocycles and the nature of peripheral substituents is analyzed and spectral studies of the binding of ORF8 to chlorin is performed. This paper is a part of a large project to investigate the possibility of using macrocyclic compounds for the treatment of viral diseases.Communicated by Ramaswamy H. Sarma

The chemical composition, distribution, and abundance of physiological groups of bacteria in thermal waters and microbial mats formed in the Nachikinsky, Malkinsky, and Verkhne-Paratunsky springs were studied. The degree of accumulation of microelements and formation of minerals by microbial mats of Kamchatka’s thermal springs was also analyzed. The study shows that the waters are characterized by different chemical composition, temperature, and pH content. The thermal waters under study show a low composition and numbers of functional groups of bacteria with the predominance of thionic bacteria. Prevalence of saprophytic, thionic, sulfate-reducing, manganese-oxidizing, ammonifying and nitrifying microorganisms in microbial mats was registered. The relevance of formed microbial mats in the concentration of many heavy metals, alkaline and alkaline earth elements was shown. Thus, cobalt, vanadium, arsenic (Nachikinsky), beryllium, cobalt (Malkinsky), cobalt and scandium (Verkhne-Paratunsky) were most concentrated in microbial mats of Kamchatka’s hydrotherms. All studied microbial communities show the lowest accumulation of Li (1.17-2.22), Sr (2.11-2.79), Rb (2.61-3.12), Cs (2.88-2.98) and As (1.98-2.58). The formation of minerals was found in algo-bacterial mats: quartz, plagioclase, anorthite, calcite, and magnetite.

Abstract—: The paper examines the impact of innovations on the socioeconomic development of the oil and gas regions of Russia. It applies a cross-methodical approach, including cluster analysis, panel data analysis and cognitive modeling. Each method performs its function in the research process: cluster analysis—multifactorial systematics of regions, analysis of panel data—obtaining quantitative estimates of the impact of resource and innovation factors on GRP, and cognitive modeling—building scenario forecasts for the socioeconomic development of an oil and gas region. As a result, the features of the interaction between the oil and gas sector and the sphere of innovation activity were revealed, and the nature of their influence on the growth of the economy of the regions of the Russian Federation was determined.

Abstract: Hybrid organic-inorganic membranes based on tetraethoxysilane and orthophosphoric acid-doped copolymers of 4-vinylpyridine (4-VP) and 2-hydroxyethyl methacrylate (HEMA) have been formed by the sol-gel synthesis method. The membranes are characterized by high values of exchange capacity and proton conductivity. An increase in the proton conductivity of hybrid organo-inorganic membranes compared to the initial copolymer can be associated with the generation of crystallization water during the formation of a silicon dioxide fragment, which follows from quantum-chemical modeling of the local structure of the membrane. The latter includes an organic part from the copolymerization product of 4-VP with HEMA (44 atoms) and an inorganic part of 27 atoms, repeating the structure of the silicon dioxide block.

Schizophrenia (SZ) is associated with an increased risk of life-long cognitive impairments, age-related chronic disease, and premature mortality. We investigated evidence for advanced brain ageing in adult SZ patients, and whether this was associated with clinical characteristics in a prospective meta-analytic study conducted by the ENIGMA Schizophrenia Working Group. The study included data from 26 cohorts worldwide, with a total of 2803 SZ patients (mean age 34.2 years; range 18–72 years; 67% male) and 2598 healthy controls (mean age 33.8 years, range 18–73 years, 55% male). Brain-predicted age was individually estimated using a model trained on independent data based on 68 measures of cortical thickness and surface area, 7 subcortical volumes, lateral ventricular volumes and total intracranial volume, all derived from T1-weighted brain magnetic resonance imaging (MRI) scans. Deviations from a healthy brain ageing trajectory were assessed by the difference between brain-predicted age and chronological age (brain-predicted age difference [brain-PAD]). On average, SZ patients showed a higher brain-PAD of +3.55 years (95% CI: 2.91, 4.19; I2= 57.53%) compared to controls, after adjusting for age, sex and site (Cohen’s d= 0.48). Among SZ patients, brain-PAD was not associated with specific clinical characteristics (age of onset, duration of illness, symptom severity, or antipsychotic use and dose). This large-scale collaborative study suggests advanced structural brain ageing in SZ. Longitudinal studies of SZ and a range of mental and somatic health outcomes will help to further evaluate the clinical implications of increased brain-PAD and its ability to be influenced by interventions.

The most promising direction in alternative energy is hydrogen energy, using hydrogen as a secondary energy carrier. A key component in hydrogen energy is a fuel cell, especially on solid polymer membranes. Increasing the efficiency, reducing the cost and increasing the service life of such elements is the primary task of this direction. These tasks need to be solved from two sides: by improving the parameters of platinum catalysts in electrochemical reactions of energy sources, as well as by improving the qualities of the membrane. The aim of the work is to synthesize and study composites with palladium and platinum nanoparticles in hydrogen-oxygen fuel cells.

This work is devoted to the development and research of functional and physico-chemical parameters of electrodes based on nanocomposite metals for water electrolysis. As a functional matrix support the nickel foam was chosen. The synthesis of bimetallic nanoparticles of nickel-platinum with further application to nickel foam was carried out. Particle sizes were investigated by electron microscopy methods. Resource tests of electrolysis cells constructed on the basis of the obtained electrodes were carried out.

Sensory cortices can be affected by stimuli of multiple modalities and are thus increasingly thought to be multisensory. For instance, primary visual cortex (V1) is influenced not only by images but also by sounds. Here we show that the activity evoked by sounds in V1, measured with Neuropixels probes, is stereotyped across neurons and even across mice. It is independent of projections from auditory cortex and resembles activity evoked in the hippocampal formation, which receives little direct auditory input. Its low-dimensional nature starkly contrasts the high-dimensional code that V1 uses to represent images. Furthermore, this sound-evoked activity can be precisely predicted by small body movements that are elicited by each sound and are stereotyped across trials and mice. Thus, neural activity that is apparently multisensory may simply arise from low-dimensional signals associated with internal state and behavior.

Nickel-aluminum layered double hydroxide with aluminum ions partially substituted by samarium ones was successfully synthesized via coprecipitation followed by hydrothermal treatment. X-ray diffraction data showed that the obtained sample is single-phase material with hydrotalcite-like structure. The presence of samarium in the sample was confirmed by elemental analysis. Electron microscopy demonstrated that the compound consists of very small plate-like particles with a shape similar to hexagonal. The study of thermal transformations of the material revealed that it decomposed upon heating above 300 °C with the formation of mixed oxide, and spinel-type oxide was formed while the heating temperature was increased up to 1000 °C. The rehydration ability of the sample was rather limited: no reconstruction of layered structure took place after mixed oxide was formed. The “memory effect” was observed only after heating the hydroxide at a temperature not higher than 300 °C. The thermal properties of samarium-containing samples resemble closely those of nickel-containing hydrotalcites.

Abstract: The aim of this work is to estimate changes in the functional state of the microvasculature and to study the peculiarities of the morphological parameters of skin by noninvasive research methods with different morphotypes of aging. The study involves 55 individuals aged 35–65 with involutional changes of the lower third of the face. Four morphotypes of aging are identified, depending on which patients are divided into the groups: the first group, 19 female patients with deformational type; second, 17 female patients with tired type; third, 8 female patients with fine-wrinkled type; and fourth, 11 female patients with mixed morphotype. Laser Doppler flowmetry and ultrasound examination of the skin (22 MHz) are used to study the state of the skin. Using the laser-Doppler-flowmetry method, significant changes are detected when comparing microcirculation indices and the ultrasound method for examination of the deformational and fine wrinkled types (p< 0.05). A predominantly atonic type of microcirculation is observed for the deformational and mixed types (9.42 ± 3.71 and 9.56 ± 2.31 perf. units, respectively); spasm type was observed for the fine-wrinkled morphotype (7.86 ± 1.6 perf. units); and for the tired morphotype, the microcirculation index was within the normal range (7.86 ± 1.6 perf. units). Data on skin ultrasound examination allows detection of the highest values of the thickness of the epidermis (125.94 ± 27.84 µm), dermis (1439 ± 118.11 µm), dermis density (12 ± 2.59 conv. units) in female patients with the deformational morphotype of aging as compared with the thickness of the epidermis (85 ± 22.01 µm), the thickness of the dermis (1130 ± 68.55 µm), and dermis density (7.87 ± 2.1 conv. units) with the fine-wrinkled morphotype of aging.

Abstract: The effect of atomic structural defects on the tribological properties of a system with structural superlubricity based on a graphene bilayer with twisted layers is studied using the density functional theory (DFT) method and the Kolmogorov–Crespi and Lebedev a semiempirical interatomic-interaction potentials. The amplitudes of corrugation the potential energy surface of the interlayer interaction and the barriers of relative motion of ideal graphene layers and layers with vacancies are estimated. Macroscopic ultralow friction is revealed for a graphene bilayer with ideal twisted layers. The DFT calculations show that the presence of vacancies in this graphene bilayer gives rise to a static friction force of 12–16 pN per vacancy. The adequacy of using semiempirical potentials of the interaction between graphene layers to study the tribological properties of a graphene bilayer with atomic structural defects is evaluated.