Experimental and theoretical study of the mechanism and rate constants of the sequential 5- spirocyclization involving vinyl, aryl and -alkoxyaminyl radicals.

In this research the sequential generation and cyclization of -alkoxyaminyl radicals to produce 1-azaspiro[4.4]nonane, a prominent scaffold in organic and medicinal chemistry, was studied. Competition experiments in benzene at 80 °C with brominated oxime ethers using BuSnH as chain transfer and AIBN as the initiator generated vinyl or aryl radicals which were captured by oxime ethers, allowing approximate 5- cyclization constants at 4.

Structural parameters and physicochemical data from quantum chemical calculations of the peroxyacyl nitrate derivatives RC(O)ONO.

This article present the structural parameters and physicochemical data (Σ , and ) of the methoxyformyl peroxynitrate CHOC(O)ONO (MoPAN), peroxypropionyl nitrate CHCHC(O)ONO (PPN), peroxyacryloyl nitrate CHCHC(O)ONO (APAN), peroxy--butyryl nitrate CH(CH)C(O)ONO (PnBN), peroxycrotonyl nitrate CH(CH=CH)C(O)ONO (CPAN), peroxyisobutyryl nitrate (CH)CHC(O)ONO (PiBN), peroxymethacryloyl nitrate CH=C(CH)C(O)ONO (MPAN) and peroxy--valeryl nitrate CH(CH)C(O)ONO (PnVN) peroxyacyl nitrate derivatives. The equilibrium structures have been performed using the B3LYP and M06-2X functionals combined with the 6-311++G() basis set. The physicochemical data were calculated using several G methods, G3B3, G3MP2B3, G4 and G4MP2.

Screening for Interacting Proteins with Peptide Biomarker of Blood-Brain Barrier Alteration under Inflammatory Conditions.

Neurodegenerative diseases are characterized by increased permeability of the blood-brain barrier (BBB) due to alterations in cellular and structural components of the neurovascular unit, particularly in association with neuroinflammation. A previous screening study of peptide ligands to identify molecular alterations of the BBB in neuroinflammation by phage-display, revealed that phage clone 88 presented specific binding affinity to endothelial cells under inflammatory conditions in vivo and in vitro. Here, we aimed to identify the possible target receptor of the peptide ligand 88 expressed under inflammatory conditions.

Crystal structure, spectroscopic characterization and Hirshfeld surface analysis of aqua-dichlorido-{-[(pyridin-2-yl)methyl-idene]aniline}copper(II) monohydrate.

The reaction of -phenyl-1-(pyridin-2-yl)methanimine with copper chloride dihydrate produced the title neutral complex, [CuCl(CHN)(HO)]·HO. The Cu ion is five-coordinated in a distorted square-pyramidal geometry, in which the two N atoms of the bidentate Schiff base, as well as one chloro and a water mol-ecule, form the irregular base of the pyramidal structure. Meanwhile, the apical chloride ligand inter-acts through a strong hydrogen bond with a water mol-ecule of crystallization.

Carbon monoxide release properties and molecular structures of phenylthiolatomanganese(I) carbonyl complexes of the type [(OC)4Mn(μ-S-aryl)]2.

Several phenylthiolatomanganese carbonyl complexes of the type [(OC)4Mn(μ-SR)]2 (R = Ph (), C6H4-4-CH3 (), C6H4-4-CF3 (), C6H4-4-F (), C6H4-4-Cl (), C6H4-4-OMe (), C6F5 (), and CH2C6H4-4-Cl ()) have been prepared via the reaction of Mn2(CO)10 with diaryldisulfane or via the reaction of [(OC)5MnBr] with arylthiols. These complexes lose two carbon monoxide molecules quite easily yielding tetranuclear [(OC)3Mn(μ3-SR)]4 (). Derivatives with fluoro-substituted aryl groups commonly form mixtures of dinuclear and tetranuclear which can quantitatively be converted to by heating of the corresponding reaction mixtures.