Synthesis and Reactions of Medium-Ring Silyl Ethers

Olefin metathesis is a reaction that creates new carbon-carbon double bonds by rearranging two alkenes. The reaction has undergone significant development since its discovery in the 1950s, from first reports to new catalysts and industrial uses, culminating in the 2005 Nobel Prize in chemistry. Grubbs ruthenium-based catalysts are widely used for such reactions, including ring closing metathesis (RCM) that involves the rearrangement of two alkenes on a single molecule to form a ring. During the course of investigating RCM reactions to produce eight-membered ring silyl ethers, we observed double bond isomerization when using the second-generation Grubbs catalyst and the Hoveyda-Grubbs catalyst but not the first-generation Grubbs catalyst. Isomerization during metathesis reactions can be problematic, giving undesired products and signaling catalyst degradation. If controllable, however, tandem metathesis/isomerization can be of value to make compounds that would otherwise be difficult to prepare. For this reason, the RCM/isomerization we observed was studied in detail. The impact of temperature, solvent, time, and additives on the distribution of isomerized and non-isomerized products were investigated. By monitoring the reaction via nuclear magnetic resonance (NMR) at different reaction times, we were able to conclude that ring closure generally occurs first, followed by isomerization of the double bond in the ring. For systems where a single isomerization event results in formation of a silyl enol ether, this was the major product obtained (which we explain as being driven by thermodynamics). However, the direction of isomerization when using the Grubbs second-generation catalyst was not entirely selective, giving a mixture of regioisomers representing both kinetic and thermodynamic products. This thesis describes investigations aimed at understanding what drives the isomerization (e.g. the catalyst species responsible, substrate structure considerations, reaction conditions) and whether we can control the direction of isomerization

Язык, речь, личность в зеркале психолингвистики

В издании раскрываются вопросы психологии языка, речи и личности. Исследуются проблемы переводческих универсалий. Особое внимание уделяется сравнительно новым научным понятиям и категориям: языковая личность, языковая картина мира, чувство языка, речевой опыт. Для научных работников, аспирантов, студентов и всех, кто интересуется вопросами психологических особенностей речевой деятельности.СОДЕРЖАНИЕ Предисловие 4; Часть 1. Язык и мир. Речь и личность 6; Засекина Л. В. Интеллект личности в зеркале психолингвистики 6; Засекин С. В. Язык в зеркале перевода: психолингвистическое исследование переводческих универсалий 25; Лавриненко А. Л. Когнитивно-мотивационные особенности языковой личности 53; Орап М. О. Психология речевого опыта личности 73; Савченко Е. В. Нарративный подход в исследовании индивидуального опыта на личностном уровне 94; Фомина Н. А. Соотношение различных свойств языковой личности и особенностей ее речевой деятельности 126; Часть 2. Психология языка, речи и речевой деятельности личности 148; Белык Т. Н. Психологические особености речевого имиджа личности 148; Дячук Н. В. Творческий потенциал будущего переводчика художественных текстов в его профессиональной деятельности 162; Крупыч С. О. Психологические проявления личности в речевой деятельности 176; Тарасюк И. В. Психологические основы речевой адаптации детей мигрантов 198; Шишкина К. Ю. Информационная безопасность личности в контексте психолингвистики 216; Часть 3. Психолингвистические исследования речи личности: норма-аномалия-патология 223; Василюк О. П. Психолингвистические средства реорганизации травматической памяти личности 223; Соловей О. А. Речевая деятельность детей с синдромом дефицита внимания и гиперактивности 244; Тригуб Г. В. Психологические основы овладения иностранным языком младшими школьниками с ведущей левой рукой 268; Об авторах 288

STUDY OF THE PROPERTIES OF MARSHMALLOW WITH THE SUDANESE ROSE AND BLACK CHOKEBERRY DYES UPON STORAGE

Creation of marshmallow with natural dyes is impossible without investigation of properties of products and estimation of its quality. Our objects of investigation were organoleptic, physico-chemical and antioxidant properties of the products at storage for 30 days. The six of marshmallow samples were the objects of our research. They differed in the type of structuring agent - gelatin or gelatin with solubilized substances and the type of dye – water or water-alcohol extract of cryopowder from Sudanese rose or water-alcohol extract of cryopowder from вlack chokeberry.Necessary indexes of quality are supplied for the new types of marshmallow with natural dyes. Moisture content (19.0 ... 21.5 %), total acidity (3.5 °Brix), density (0.51 ... 0.67 g/cm3), reducing substances content (not more than 13.6 %) were determined by standard methods. Use of natural anthocyanin dyes let us to increase antioxidant properties of the ready product. Value of antioxidant capacity of the new samples, determined with use of galvanostatic coulometry method, is in 2 ... 2.5 times more than the same results for samples, made without the dyes.It was established that short time storage (up to 2 days) of marshmallow with natural anthocyanin dyes at temperature (15...18)°С and relative air humidity 60...75 % is possible without packing materials. Storage of the products in hermetically polyethylene wrap and cardboard box provides high indexes of quality, stability of colour in long time (up to 30 days). It was shown that antioxidant properties of marshmallow with water-alcohol extracts of cryopowder from Sudanese rose and black chokeberry remain stable.The new developed types of marshmallow with natural anthocyanin dyes makes wide market of confectionery and can be used for correction of feeding of a man

A Study of Properties of Marshmallow with Natural Anthocyanin Dyes During Storage

An actual problem of the development of marshmallow with natural anthocyanin dyes was solved. The object of the investigation was organoleptic, physicochemical, antioxidant properties of the products during storage for 30 days. The subject of the investigation was 6 samples of marshmallow. They differed in the type of a structuring agent gelatin or gelatin with solubilized substances and the type of a dye a water or water-alcohol extract of Sudanese rose сryopowder or water-alcohol extract of black chokeberry сryopowder.For the new types of marshmallow with natural anthocyanin dyes, the quality indexes necessary for the product were provided. Moisture content is within 19.0...21.5 %, density is 0.51...0.67 gcm3, reducing substances content does not exceed 13.6 %, total acidity is 3.5 degrees.The use of natural anthocyanin dyes allows increasing the antioxidant properties of the finished product. The value of the antioxidant capacity for all of the developed samples is 2...2.5 times more than that of the samples, made without the dyes.It was found that short-term (up to 2 days) storage of marshmallow with natural anthocyanin dyes at a temperature of (15...18)°C and relative air humidity of 60…75 % is possible without packaging.Storage of the products hermetically packed in polyethylene wrap and a cardboard box provides high indexes of quality, preservation of colour intensity within a long time (up to 30 days). It was shown that antioxidant properties of marshmallow with water-alcohol extract of Sudanese rose and black chokeberry сryopowders remain stable and do not depend on the type of packaging.The developed new types of marshmallow with natural anthocyanin dyes expand the range of confectionery and can be used for correction of the human die

SARS-CoV-2 evolution in a patient with secondary B-cell immunodeficiency: A clinical case

The article highlights the course of long-term SARS-CoV-2 infection in a patient with a secondary immunodeficiency developed with B-cell-depleting therapy of the underlying disease. Analysis of the intrapatient virus evolution revealed an inpatient S:G75A mutation that alters the 72GTNGTKR78 motif of the S-protein, with a possible role in binding to alternative cellular receptors. Therapy with a ready-made COVID-19-globulin preparation (native human immunoglobulin G (IgG) derived from the plasma of convalescent COVID-19-patients) resulted in rapid improvement of the patient’s condition, fast, and stable elimination of the virus, and passive immunization of the patient for at least 30 days. The results suggest the use of products containing neutralizing antibodies opens new prospects for treatment algorithms for patients with persistent coronavirus infection, as well as for passive immunization schemes for patients with a presumably reduced specific response to vaccination

Современные подходы к ведению пациентов с крапивницей

The Union of Pediatricians of Russia together with the Russian Association of Allergologists and Clinical Immunologists and the Russian Society of Dermatovenerologists and Cosmetologists have developed new clinical guidelines for the urticaria in adults and children. Urticaria is a common disease; its various clinical variants are diagnosed in 15–25% of people in the global population, and a quarter of all cases belongs to chronic urticaria. The prevalence of acute urticaria is 20%, and 2.1–6.7% in child population, whereas acute urticaria is more common in children than in adults. The prevalence of chronic urticaria in adults in the general population is 0.7 and 1.4%, and 1.1% in children under 15 years of age, according to the systematic review and meta-analysis, respectively. This article covers features of epidemiology, etiology, and pathogenesis of the disease with particular focus on differential diagnostic search. Guidelines on treatment and step-by-step therapy scheme (both based on principles of evidencebased medicine) for pediatric patients were presented. Clarification on the analysis of the therapy efficacy and the degree of disease activity was given.Союзом педиатров России совместно с Российской ассоциацией аллергологов и иммунологов и Российским обществом дерматовенерологов и косметологов (РОДВК) разработаны новые клинические рекомендации для диагноза «крапивница» для взрослых и детей. Крапивница является распространенным заболеванием: различные ее клинические варианты диагностируются у 15–25% людей в популяции, при этом четверть случаев приходится на хроническую крапивницу. Распространенность острой крапивницы составляет 20%, среди детского населения — 2,1–6,7%, при этом острая крапивница у детей встречается чаще, чем у взрослых. По данным систематического обзора и мета-анализа, хроническая крапивница у взрослых в общей популяции составляет 0,7 и 1,4% соответственно, у детей до 15 лет — до 1,1%. В статье рассматриваются особенности эпидемиологии, этиологии и патогенеза заболевания, особое внимание уделено вопросам дифференциально-диагностического поиска. Для пациентов детского возраста приведены рекомендации по лечению согласно принципам доказательной медицины и предложена ступенчатая схема терапии. Дано четкое разъяснение к проведению анализа эффективности терапии и оценки степени активности заболевания

Urticaria exacerbations and adverse reactions in patients with chronic urticaria receiving COVID-19 vaccination:Results of the UCARE COVAC-CU study

Background: Concern about disease exacerbations and fear of reactions after coronavirus disease 2019 (COVID-19) vaccinations are common in chronic urticaria (CU) patients and may lead to vaccine hesitancy.Objective: We assessed the frequency and risk factors of CU exacerbation and adverse reactions in CU patients after COVID-19 vaccination. Methods: COVAC-CU is an international multicenter study of Urticaria Centers of Reference and Excellence (UCAREs) that retrospectively evaluated the effects of COVID-19 vaccination in CU patients aged ≥18 years and vaccinated with ≥1 dose of any COVID-19 vaccine. We evaluated CU exacerbations and severe allergic reactions as well as other adverse events associated with COVID-19 vaccinations and their association with various CU parameters. Results: Across 2769 COVID-19–vaccinated CU patients, most (90%) received at least 2 COVID-19 vaccine doses, and most patients received CU treatment and had well-controlled disease. The rate of COVID-19 vaccination–induced CU exacerbation was 9%. Of 223 patients with CU exacerbation after the first dose, 53.4% experienced recurrence of CU exacerbation after the second dose. CU exacerbation most often started &lt;48 hours after vaccination (59.2%), lasted for a few weeks or less (70%), and was treated mainly with antihistamines (70.3%). Factors that increased the risk for COVID-19 vaccination–induced CU exacerbation included female sex, disease duration shorter than 24 months, having chronic spontaneous versus inducible urticaria, receipt of adenovirus viral vector vaccine, having nonsteroidal anti-inflammatory drug/aspirin intolerance, and having concerns about getting vaccinated; receiving omalizumab treatment and Latino/Hispanic ethnicity lowered the risk. First-dose vaccine–related adverse effects, most commonly local reactions, fever, fatigue, and muscle pain, were reported by 43.5% of CU patients. Seven patients reported severe allergic reactions. Conclusions: COVID-19 vaccination leads to disease exacerbation in only a small number of CU patients and is generally well tolerated.</p