Synthesis and Photophysical Properties of Novel Meta-Conjugated Organic Molecules with 1,3,5-Benzene Branching Units.

The synthesis and photophysical investigation of three novel meta-conjugated molecules based on 3,1,2-benzothiadiazole and thiophene-2,5-diyl derivatives linked through 1,3,5-benzene branching units are described. Each of them is a symmetrical molecule with two branching units, four identical lateral thiophene-containing fragments, and one central benzothiadiazole-containing fragment. To study the effect of the chemical structure on their photophysical properties, the molecules with different linearly conjugated lateral and central fragments due to incorporation of additional thiophene rings were synthesized and compared.

The Sphingolipid Asset Is Altered in the Nigrostriatal System of Mice Models of Parkinson's Disease.

Parkinson's disease (PD) is a neurodegenerative disease incurable due to late diagnosis and treatment. Therefore, one of the priorities of neurology is to study the mechanisms of PD pathogenesis at the preclinical and early clinical stages. Given the important role of sphingolipids in the pathogenesis of neurodegenerative diseases, we aimed to analyze the gene expression of key sphingolipid metabolism enzymes (ASAH1, ASAH2, CERS1, CERS3, CERS5, GBA1, SMPD1, SMPD2, UGCG) and the content of 32 sphingolipids (subspecies of ceramides, sphingomyelins, monohexosylceramides and sphinganine, sphingosine, and sphingosine-1-phosphate) in the nigrostriatal system in 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) mouse models of the preclinical and clinical stages of PD.

Mono- and Diamination of 4,6-Dichloropyrimidine, 2,6-Dichloropyrazine and 1,3-Dichloroisoquinoline with Adamantane-Containing Amines.

-heteroaryl substituted adamantane-containing amines are of substantial interest for their perspective antiviral and psychotherapeutic activities. Chlorine atom at alpha-position of -heterocycles has been substituted by the amino group using convenient nucleophilic substitution reactions with a series of adamantylalkylamines. The prototropic equilibrium in these compounds was studied using NMR spectroscopy.

[Development of early diagnosis of Parkinson's disease based on the search for biomarkers such as premotor symptoms and changes in blood].

Objective: To determine changes in the chemical composition of blood plasma in subjects at risk of Parkinson's disease (PD) at the prodromal stage compared with age control.

Material And Methods: Subjects at risk were selected for the presence of characteristic premotor symptoms, including impairments of sleep, olfaction and constipation.The risk group included 12 people, the control group - 8 people.

Synthesis and Evaluation of the ()-BINAM Derivatives as Fluorescent Enantioselective Detectors.

Pd(0)-catalyzed amination was employed for the synthesis of a new family of ()-1,1'-bianaphthalene-2,2'-diamine derivatives possessing additional chiral and fluorophore substituents. The compounds thus obtained were tested as potential detectors of seven amino alcohols, and some of them were found to be able to recognize individual enantiomers of certain amino alcohols by specific changes of their emission spectra in the presence of these analytes. A pronounced dependence of the detecting abilities on the nature of the substituents in the ()-BINAM derivatives was observed.

Cu(I)- and Pd(0)-Catalyzed Arylation of Oxadiamines with Fluorinated Halogenobenzenes: Comparison of Efficiency.

The comparison of the possibilities of Pd- and Cu-catalyzed amination reactions using fluorine-containing aryl bromides and iodides with oxadiamines to produce their -diaryl derivatives was carried out. The dependence of the reactivity of the aryl halides on the nature of the substituents and halogen atoms as well as on the structure of oxadiamines was investigated. It was found that the copper-catalyzed reactions were somewhat comparable with the palladium-mediated processes in the majority of cases, especially in the reactions with -fluorine- and -(trifluoromethyl)-substituted aryl halides, although the necessity to use aryl iodides in the Cu(I)-catalyzed amination was obvious.

Changes in the Metabolism of Sphingoid Bases in the Brain and Spinal Cord of Transgenic FUS(1-359) Mice, a Model of Amyotrophic Lateral Sclerosis.

The aim of this study was to evaluate changes in the content of sphingoid bases - sphingosine (SPH), sphinganine, and sphingosine-1-phosphate (SPH-1-P) - and in expression of genes encoding enzymes involved in their metabolism in the brain structures (hippocampus, cortex, and cerebellum) and spinal cord of transgenic FUS(1-359) mice. FUS(1-359) mice are characterized by motor impairments and can be used as a model of amyotrophic lateral sclerosis (ALS). Lipids from the mouse brain structures and spinal cord after 2, 3, and 4 months of disease development were analyzed by chromatography/mass spectrometry, while changes in the expression of the SPHK1, SPHK2, SGPP2, SGPL1, ASAH1, and ASAH2 genes were assayed using RNA sequencing.

Cu(I)-catalyzed N,N'-diarylation of natural diamines and polyamines with aryl iodides.

The Cu(I)-catalyzed N,N'-diarylation of natural diamines and polyamines such as putrescine, cadaverine, spermine, spermidine and their homologues is described. Aryl iodides bearing electron-donating and electron-withdrawing groups have been employed in the study. The CuI/2-(isobutyryl)cyclohexanone/DMF catalytic system has found to be more efficient in the diarylation of diamines and spermine while the CuI/L-proline/EtCN system proved to be preferable for the diarylation of other tri- and tetraamines like spermidine, norspermidine and norspermine.

Palladium-catalyzed amination of dichloroquinolines with adamantane-containing amines.

Pd-catalyzed amination of isomeric 2,6-, 2,8-, 4,8- and 4,7-dichloroquinolines was studied using adamantane-containing amines in which substituents at the nitrogen atom differ in bulkiness. The selectivity of the amination of 2,6-dichloroquinoline was very low, substantially better results were obtained with 2,8-dichloroquinoline, and 4,8- and 4,7-dichloroquinolines provided the best yields of the amination products. Diamination of 4,8- and 4,7-dichloroquinolines was carried out with two amines which differ strongly in the bulkiness of the alkyl group.

The first solid phase synthesis of pincer palladium complexes.

Both dimeric μ-chlorine bridged and monomeric bidentate Pd(II) complexes with SCN hybrid pincer-type ligands, bearing thiophosphoryl group and imine moiety of the benzothiazole ring as coordination arms, formed in the reaction with (PhCN)(2)PdCl(2) under kinetic control (20 °C, dichloromethane solution) were readily converted into the corresponding SCN pincer complexes via solid phase synthesis (neat, 200 °C, 15 min). The synthesis of pincer complexes can be performed also by heating (200 °C, 5 min) of a homogeneous mixture of the initial reactants, namely, the ligand and (PhCN)(2)PdCl(2), obtained by manual grinding in a mortar. The efficacy of solid phase approaches is comparable with the analogous synthesis in solutions under severe conditions.

Cyclization of 2-acyl- and 2-thioacylaminobenzylcyclopropanes in the gas phase and solution.

Mass spectrometry proved itself to be a powerful tool to predict the directions and yields of mono- molecular reactions of organic compounds. Electron ionization (EI) and electrospray ionization (ESI) were used to study possible transformations of N-(ortho-cyclopropylmethylphenyl)arylamides I and N-(ortho- cyclopropylmethylphenyl)arylthioamides II as well as their para-isomers III and IV in a mass spectrometer and to predict directions and yields of their acid catalyzed cyclization reactions. Several five-eight-membered heterocycles were proposed as possible products of intramolecular transformations of compounds I and II.

Synthesis and structural characterization of cis- and trans-fused 4a,5,6,7,8,8a-hexahydro-2H,4H-1,3-benzodithiines and their 2-methyl and 2,2-dimethyl derivatives.

Both cis- and trans-fused 4a,5,6,7,8,8a-hexahydro-2H,4H-1,3-benzodithiine together with their 2-methyl and 2,2-dimethyl derivatives were prepared as racemates from the appropriate dithiols obtained via multistep syntheses. The products were characterized by (1)H and (13)C NMR, mass spectrometry, and for two of the cis-fused compounds by X-ray diffraction. (1)H,(1)H vicinal coupling constants indicated that all compounds attain chair-chair conformations as their predominant conformations.