Учебный план УВО

This review sets out to understand the reactivity of diradicals and how that may differ from monoradicals. In the first part of the review, we delineate the electronic structure of a diradical with its two degenerate or nearly degenerate molecular orbitals, occupied by two electrons. A classification of diradicals based on whether or not the two SOMOs can be located on different sites of the molecule is useful in determining the ground state spin. Important is a delocalized to localized orbital transformation that interchanges "closed-shell" to "open-shell" descriptions. The resulting duality is useful in understanding the dual reactivity of singlet diradicals. In the second part of the review, we examine, with a consistent level of theory, activation energies of prototypical radical reactions (dimerization, hydrogen abstraction, and addition to ethylene) for representative organic diradicals and diradicaloids in their two lowest spin states. Differences and similarities in reactivity of diradicals vs monoradicals, based on either a localized or delocalized view, whichever is suitable, are then discussed. The last part of this review begins with an extensive, comparative, and critical survey of available measures of diradical character and ends with an analysis of the consequences of diradical character for selected diradicaloids

Symptom-based stratification of patients with primary Sjögren's syndrome: multi-dimensional characterisation of international observational cohorts and reanalyses of randomised clinical trials

Background Heterogeneity is a major obstacle to developing effective treatments for patients with primary Sjögren's syndrome. We aimed to develop a robust method for stratification, exploiting heterogeneity in patient-reported symptoms, and to relate these differences to pathobiology and therapeutic response. Methods We did hierarchical cluster analysis using five common symptoms associated with primary Sjögren's syndrome (pain, fatigue, dryness, anxiety, and depression), followed by multinomial logistic regression to identify subgroups in the UK Primary Sjögren's Syndrome Registry (UKPSSR). We assessed clinical and biological differences between these subgroups, including transcriptional differences in peripheral blood. Patients from two independent validation cohorts in Norway and France were used to confirm patient stratification. Data from two phase 3 clinical trials were similarly stratified to assess the differences between subgroups in treatment response to hydroxychloroquine and rituximab. Findings In the UKPSSR cohort (n=608), we identified four subgroups: Low symptom burden (LSB), high symptom burden (HSB), dryness dominant with fatigue (DDF), and pain dominant with fatigue (PDF). Significant differences in peripheral blood lymphocyte counts, anti-SSA and anti-SSB antibody positivity, as well as serum IgG, κ-free light chain, β2-microglobulin, and CXCL13 concentrations were observed between these subgroups, along with differentially expressed transcriptomic modules in peripheral blood. Similar findings were observed in the independent validation cohorts (n=396). Reanalysis of trial data stratifying patients into these subgroups suggested a treatment effect with hydroxychloroquine in the HSB subgroup and with rituximab in the DDF subgroup compared with placebo. Interpretation Stratification on the basis of patient-reported symptoms of patients with primary Sjögren's syndrome revealed distinct pathobiological endotypes with distinct responses to immunomodulatory treatments. Our data have important implications for clinical management, trial design, and therapeutic development. Similar stratification approaches might be useful for patients with other chronic immune-mediated diseases. Funding UK Medical Research Council, British Sjogren's Syndrome Association, French Ministry of Health, Arthritis Research UK, Foundation for Research in Rheumatology

Sodium fast reactor safety and licensing research plan. Volume II.

Expert panels comprised of subject matter experts identified at the U.S. National Laboratories (SNL, ANL, INL, ORNL, LBL, and BNL), universities (University of Wisconsin and Ohio State University), international agencies (IRSN, CEA, JAEA, KAERI, and JRC-IE) and private consultation companies (Radiation Effects Consulting) were assembled to perform a gap analysis for sodium fast reactor licensing. Expert-opinion elicitation was performed to qualitatively assess the current state of sodium fast reactor technologies. Five independent gap analyses were performed resulting in the following topical reports: (1) Accident Initiators and Sequences (i.e., Initiators/Sequences Technology Gap Analysis), (2) Sodium Technology Phenomena (i.e., Advanced Burner Reactor Sodium Technology Gap Analysis), (3) Fuels and Materials (i.e., Sodium Fast Reactor Fuels and Materials: Research Needs), (4) Source Term Characterization (i.e., Advanced Sodium Fast Reactor Accident Source Terms: Research Needs), and (5) Computer Codes and Models (i.e., Sodium Fast Reactor Gaps Analysis of Computer Codes and Models for Accident Analysis and Reactor Safety). Volume II of the Sodium Research Plan consolidates the five gap analysis reports produced by each expert panel, wherein the importance of the identified phenomena and necessities of further experimental research and code development were addressed. The findings from these five reports comprised the basis for the analysis in Sodium Fast Reactor Research Plan Volume I

Découverte d’une nécropole du huitième siècle av. J.-C. à Carthage Bir Massouda. Rapport préliminaire sur les fouilles de l’Institut National du Patrimoine (Tunis) et l’Université de Gand

A