Asymmetric Synthesis of Functionalized α-Amino Acid Derivatives via the γ-Pyrone Carbaldimine-Based Organocatalytic Mannich Reaction.

A powerful synthetic strategy for the asymmetric synthesis of enantiomerically enriched γ-functionalized α-amino acid derivatives based on the highly stereoselective proline-catalyzed Mannich-type reaction of pre-prepared or -generated γ-pyrone-derived aldimines with carbonyl compounds and subsequent transformations of multifunctional reaction products has been developed. A significant positive nonlinear effect was detected for the key organocatalytic reaction. The developed strategy was applied for facile gram-scale preparation of ()-γ-oxonorvaline, used for site-specific modification of proteins, and both enantiomers of amycolatolide A recently isolated from the lichen-derived actinomycete sp.

Concise enantioselective synthesis of non-proteinogenic α-aminoacids an organocatalytic Mannich-type reaction.

A bifunctional tertiary amine-squaramide-catalyzed enantioselective Mannich-type addition of available allomaltol to -protected aldimines was developed. The resulted adducts were readily transformed into non-proteinogenic α-amino acids and their derivatives were not easily accessible by other methods oxidative fragmentation, esterification, amidation and deprotection reactions. The absolute ()-configuration of the thus obtained α-amino acids was established by comparison of the -Ts-PheGly optical rotation sign with the reported data.

Obtainment and Characterization of Metal-Coated Polyethylene Granules as a Basis for the Development of Heat Storage Systems.

The research studied the feasibility of using copper-coated polyethylene granules as a basis for creating efficient heat storage systems. A technology for imparting catalytic properties to a polymer surface by the joint processing of polymer granules and an activator metal in a ball mill with their subsequent metallization in a chemical reducing solution is proposed. The efficiency of copper-coating a polyethylene surface is shown to be largely determined by the activation stage and the assumption regarding the mechanism of interaction of the activator metal with the polymer surface is made.

The effect of resource-saving tillage technologies on the mobility, distribution and migration of trace elements in soil.

The influence of agricultural tillage technologies on the accumulation and distribution of trace elements in the soil is poorly studied. At the same time, intensive agriculture requires large amounts of fertilizers, growth stimulators, pesticides, and other substances, which can effect the ecological safety of the plant products and soil. This paper represents studying the effect of various agricultural techniques (including resource-saving technologies) on the mobility and profile distribution of Pb, Zn, and Cu in Haplic Chernozem.

Anti-inflammatory and antidiabetic effects of grape-derived stilbene concentrate in the experimental metabolic syndrome.

Aims: This study aimed to investigate the carbohydrate and lipid dynamics, associated inflammation markers and the effectiveness of a grape-derived stilbene concentrate (GDSC) treatment in experimental metabolic syndrome (MetS).

Methods: The study was carried out on 40 male 12-weeks of age Wistar rats. The MetS was induced using the fructose model (feeding with 60%-solid fructose diet for 24 weeks).

2-Nitroallyl carbonate-based green bifunctional reagents for catalytic asymmetric annulation reactions.

2-Nitroallylic carbonates, a new class of "green" 1,3-bielectrophilic reagents for organic synthesis and catalysis, have been prepared. The bifunctional tertiary amine-catalyzed asymmetric [3 + 3] annulations of cyclic enols with these reagents occur much faster than corresponding reactions with 2-nitroallylic esters and produce no acidic by-products poisoning the catalyst. Furthermore, 2-nitroallylic carbonates enable highly enantioselective one-pot synthesis of a variety of fused dihydropyrane derivatives from available precursors bearing pharmacophoric fragments.

Risk of Recurrent Pregnancy Loss in the Ukrainian Population Using a Combined Effect of Genetic Variants: A Case-Control Study.

We assessed the predictive ability of a combined genetic variant panel for the risk of recurrent pregnancy loss (RPL) through a case-control study. Our study sample was from Ukraine and included 114 cases with idiopathic RPL and 106 controls without any pregnancy losses/complications and with at least one healthy child. We genotyped variants within 12 genetic loci reflecting the main biological pathways involved in pregnancy maintenance: blood coagulation (, , , ), hormonal regulation (, ), endometrium and placental function (, ), folate metabolism () and inflammatory response (, , ).

Nitrogen state of Haplic Chernozem of the European part of Southern Russia in the implementation of resource-saving technologies.

Background: The prolonged use of traditional moldboard ploughing often results in soil degradation and, ultimately, has an impact on national food security. Therefore, the implementation of resource-saving technologies (minimal and No-till) is a promising approach in the development of agriculture, especially in drought regions. The present study reports the results of long-term research on the effect of various tillage methods (moldboard ploughing, minimal tillage and No-till technique) on the nitrogen content of Haplic Chernozem of the European part of Southern Russia.

Utilization of Polypropylene in the Production of Metal-Filled Polymer Composites: Development and Characteristics.

Metal-filled composites based on polypropylene waste have been successfully obtained with an injection molding method of metalized polymer raw materials. Using the model polymer, the peculiarities of the formation of the copper layer in solutions of chemical metallization on the polypropylene surface were investigated and the main factors influencing this process were established. The main influence on the rate of reduction of copper in solutions of chemical metallization has the concentration of copper sulfate, sodium hydroxide, and EDTA-Na.

Conjugate Addition of Carbon Acids to β,γ-Unsaturated α-Keto Esters: Product Tautomerism and Applications for Asymmetric Synthesis of Benzo[]phenazin-5-ol Derivatives.

A correlation between the equilibrium ratio of tautomeric products generated by the asymmetric Michael reactions of cyclic carbon acids with β,γ-unsaturated α-keto esters and the chemical shift of the α-proton in starting nucleophilic substrates was revealed which makes equilibration predictable. New tetrahydropyran-fused benzo[]phenazins were enantioselectively (up to 99% ee) synthesized from β,γ-unsaturated α-keto esters and benzo[]phenazin-5-ol, a powerful anti-cancer agent sAJM589. Facile recyclability of catalyst in the catalytic reactions was demonstrated.

C-Symmetric Chiral Squaramide, Recyclable Organocatalyst for Asymmetric Michael Reactions.

A very simple and highly efficient C-symmetric tertiary amine-squaramide organocatalyst for asymmetric Michael reactions has been elaborated. In the presence of only 1 mol % of this catalyst, kojic acid derivatives and β-dicarbonyl compounds reacted with nitroolefins, affording the corresponding adducts in a nearly quantitative yield with an enantioselectivity up to 99% ee. The kojic acid-derived adducts could be efficiently produced under "green" conditions (in 96% EtOH or pure water).

Asymmetric Michael addition between kojic acid derivatives and unsaturated ketoesters promoted by C-symmetric organocatalysts.

An efficient sterically hindered C2-symmetric bifunctional tertiary amine-squaramide organocatalyst for the asymmetric Michael addition/hemiketalization domino reaction of kojic acid derivatives with β,γ-unsaturated α-ketoesters has been designed. Pharmacology-relevant functionalized 2,3,4,8-tetrahydropyrano[3,2-b]pyran derivatives were produced over the catalyst in as low as 1 mol% with up to 99% yield and 99% ee. The procedure is at least 30-fold scalable and the catalyst is readily reusable in the catalytic reaction via acid-base extraction.

Asymmetric synthesis of warfarin and its analogs catalyzed by C-symmetric squaramide-based primary diamines.

Novel C2-symmetric N,N'-bis(2-amino-1,2-diphenylethyl)squaramides with 1,2-di(pyridin-2-yl)ethane and 1,2-diphenylethane spacer groups were designed and applied as organocatalysts in asymmetric additions of 4-hydroxycoumarin and 4-hydroxy-6-methyl-2H-pyran-2-one to α,β-unsaturated ketones. Both enantiomers of the anticoagulant warfarin and its analogs were prepared in up to 96% yield and with 96% ee. Recyclability of the developed catalysts and synthetic utility of the prepared Michael adducts for asymmetric synthesis of potential chiral medications via acylation reactions were demonstrated.

Stereospecific diaza-Cope rearrangement as an efficient tool for the synthesis of DPEDA pyridine analogs and related C-symmetric organocatalysts.

A simple and efficient synthesis of enantiomerically pure (1S,2S)-1,2-di(pyridin-2-yl)- and (1R,2R)-1,2-di(pyridin-4-yl)-ethane-1,2-diamines from commercial picolinaldehyde or isonicotinaldehyde and 2,2'-((1S,2S)-1,2-diaminoethane-1,2-diyl)diphenol (HPEN) via a stereospecific diaza-Cope rearrangement has been developed. Diamine (R,R)-2b was readily converted to novel diastereomeric ionic group-supported bis-prolinamides (R,S)-1b and (R,R)-1b which appeared to be efficient organocatalysts of asymmetric cross-aldol reactions in aldehyde/aldehyde, ketone/ketone or ketone/aldehyde reagent systems under neat conditions to afford corresponding aldols in high yields and with up to 99% ee. Furthermore, catalyst (R,S)-1b could be reused over 15 times in the same or similar catalytic reactions exhibiting close to original activity and a high level of stereoinduction.

C-Symmetric pyrrolidine-derived squaramides as recyclable organocatalysts for asymmetric Michael reactions.

Novel C-symmetric N,N'-bis-[(pyrrolidin-2-yl)methyl-squaramide] TFA salts bearing (R,R)- or (S,S)-1,2-di(pyridin-2-yl)ethane spacer groups were synthesized and applied, in combination with TEA, as efficient organocatalysts for asymmetric reactions between cyclohexanone derivatives and β-nitrostyrenes to afford the corresponding Michael adducts in high yields with good to excellent enantioselectivity. The catalytic procedure is readily scalable and recyclable over four times without a negative impact on the selectivity of the reaction. Some of the prepared compounds are valuable precursors to useful bioactive molecules.

[Not Available].

The aim of this study was to examine association between IFNL4 gene ss469415590 and treatment efficiency in group of Ukrainian PEG-interferon/ribavirin-treated chronic hepatitis C patients. Study group consisted of 92 unrelated hepatitis C virus genotype 1 mono-infected patients: case group - 29 patients with late or absent virological response; control group - 63 patients with sustained virological response. Study material was genomic DNA.

polymorphism as a predictor of chronic hepatitis C treatment efficiency in Ukrainian patients.

The aim of this study was to examine association between gene ss469415590 and treatment efficiency in group of Ukrainian PEG-interferon/ribavirin-treated chronic hepatitis C patients. Study group consisted of 92 unrelated hepatitis C virus genotype 1 mono-infected patients: case group-29 patients with late or absent virological response; control group-63 patients with sustained virological response. Study material was genomic DNA.

(1,2-Diaminoethane-1,2-diyl)bis(N-methylpyridinium) Salts as a Prospective Platform for Designing Recyclable Prolinamide-Based Organocatalysts.

A new efficient and highly recyclable organocatalyst has been developed for asymmetric cross-aldol reactions under neat conditions in ketone-ketone, ketone-aldehyde, and aldehyde-aldehyde systems. The catalyst features two prolinamide fragments and a C2-symmetrical (1,2-diaminoethane-1,2-diyl)bis(N-methylpyridinium) group. The catalyst retained high activity and excellent stereoselection over the operating period of more than 830 h (25 cycles).

ITPA gene variant may protect against anemia induced during pegylated interferon alfa and ribavirin combination treatment in Ukrainian patients with chronic hepatitis C.

The aim of this study was to clarify the association between the inosine triphosphate pyrophosphatase (ITPA) gene variants and PEG-IFNalpha/RBV combination treatment induced anemia in chronic hepatitis C (CHC) Ukrainian patients. The data were collected from 80 CHC patients with HCV genotype 1 infection. All study participants received standard doses of PEG-IFNalpha and RBV According to the Hb level changes patients were distributed into: case group--42 patients with combination treatment induced anemia, and control group--38 patients with no signs of anemia.

[Electrocardiotherapy using pericardoscopy].

The standard transvenous electrocardiostimulation (ECS) is currently used in many specialized hospitals. The authors offered and launched systematic application of simple but available technique of epymiocardiac ECS using pericardoscopy since middle of 80th. According to this principle, the authors developed some diversities of manipulation which are distinctive due to their availability, reliability and supersafety.

IL1beta, IL6 and IL8 gene polymorphisms involvement in recurrent corneal erosion in patients with hereditary stromal corneal dystrophies.

TGFBI gene mutations cause corneal stromal dystrophies of autosomal dominant inheritance. The most frequent complication of stromal dystrophies is recurrent corneal erosion with varying degree of accompanying inflammation. IL-1beta, IL-6 and IL-8 are main cytokines involved in corneal erosion healing.

[ESR1 gene allelic polymorphism analysis in population of Ukraine].

In this study analysis of single nucleotide polymorhisms A351G, C397T and number of TA-repeats in ESR1 gene among 199 healthy volunteers from Ukraine was performed. Data concerning genotypes and particular alleles of polymorphic variants distribution were obtained. Possible mechanisms of these polymorphic variants role in ESR1 gene transcription and estrogen receptor expression changes are being discussed.

[Clinical genealogical and molecular genetic study of patients with mental retardation].

The results of clinical, genealogical, cytogenetic and molecular genetic studies of 113 patients from 96 families with different forms of mental retardation from Ukraine are presented. This study was held as part of the CHERISH project of the 7-th Framework Program. The aim of the project is to improve diagnostics of mental retardation in children in Eastern Europe and Central Asia through detailed analysis of known chromosomal and gene's aberrations and to find the new gene-candidates that cause mental retardation.

[Potentialities of non-invasive diagnosis of liver cirrhosis in children with the use of serological markers].

The study included 95 children with chronic hepatic disorders of different etiology. All of them underwent hepatic puncture biopsy for morphological studies and calculation of histological sclerosis index based on the Knoddel scale. Commercial enzyme immunoassay kits were used to measure hyaluronic acid (HA), type IV collagen (CIV), matrix metalloproteinase-1 (MMP-2), transforming growth factor-beta 1 (TGF), and leptin levels as non-invasive markers of fibrosis.

Allelic polymorphism of F2, F5 and MTHFR genes in population of Ukraine.

Analysis of F2, F5 and MTHFR genes SNPs allelic variants in population of Ukraine. Polymorphic variants were analyzed in 172 unrelated individuals using PCR followed by RFLP analysis. Following genotypes have been identified: GG (97%), GA (3%) for F2 gene G20210A SNP, GG (96.