N‐Alkylacylamides in Thin Films Display Infrared Spectra of 310‐, α‐, and π‐Helices with Visible Static and Dynamic Growth Phases

A peptide model is a physical system containing a CONH group, the simplest being HCONHCH₃, N‐methylformamide (NMF). We have discovered that NMF and N‐methylacetamide (NMA), which form hydrogen‐bonded oligomers in thin films on a planar AgX fiber, display infrared (IR) spectra with peaks like those of polypeptide helices. Structures can be assigned by their amide I maxima near 1672 (3₁₀), 1655 (3₁₀), 1653 (α), 1655 (π), and 1635 cm^?1 (π), which are the first IR data for the π‐helix. Sharp peaks are an outcome of immobilization of polar species on the polar surface of silver halides. We report the first use of expanded thin‐film IR spectroscopy, in which plots of every spectrum over the amide I–II range show pauses or slow stages in the increase or decrease of absorption. These are identified as static phases followed by dynamic phases, with the incremental gain or loss of a helix turn. A general theory can be stated for such processes. Density functional calculations show that the NMA α‐helix pentamer (crystal structure geometry) is transformed into a π‐helix‐like form. For the first time, an entire sequence (3₁₀‐helix, α‐helix, π‐helix, quasiplanar species) of spectra has been recorded for NMA.     

Synthesis,antiradical, and antimicrobial activities of new pteridine-2,4,7-trione derivatives

The synthesis of 6-(2-hydroxy-2-aryl (heteryl)ethyl)-1-methylpteridine-2,4,7(1H,3H,8H)-triones by the reduction of the corresponding ketones and the peculiarities of conversion of the synthesized alcohols to (E)-1-methyl-6-(2-aryl (heteryl)ethenyl)pteridine-2,4,7(1H,3H,8H)-triones was reported. The mechanism of monomolecular elimination that occurred in the presence of hydrogen halides was discussed, namely, the competitive formation of an energy-efficient conjugated system by deprotonation of a stable benzyl-type carbocation. Alternative synthesis methods of pteridine-2,4,7(1H,3H,8H)-triones were developed. Abovementioned approach involved [4+2]-cyclocondensation of 1-methyl-5,6-diaminouracil to 2-oxo-4-R-but-3-enoic acids and Knoevenagel condensation of 1,6-dimethylpteridine-2,4,7(1H,3H,8H)-trione with aromatic aldehydes. The antiradical, antimicrobial, and antifungal activities were studied for the synthesized compounds.     

Synthesis of Supported Heterogeneous Catalysts by Laser Ablation of Metallic Palladium in Supercritical Carbon Dioxide Medium

To obtain a supported heterogeneous catalyst, laser ablation of metallic palladium in supercritical carbon dioxide was performed in the presence of a carrier, microparticles of γ-alumina. The influence of the ablation process conditions—including supercritical fluid density, ablation, mixing time of the mixture, and laser wavelength—on the completeness and efficiency of the deposition of palladium particles on the surface of the carrier was studied. The obtained composites were investigated by scanning and transmission electron microscopy using energy dispersive spectroscopy. We found that palladium particles were nanosized and had a narrow size distribution (2–8 nm). The synthesized composites revealed high activity as catalysts in the liquid-phase hydrogenation of diphenylacetylene.     

Biological properties of two enantiomorphic forms of N‐(2,6‐dimethylphenyl)‐4‐hydroxy‐2,2‐dioxo‐1H‐2λ6,1‐benzothiazine‐3‐carboxamide,a structural analogue of piroxicam

The title benzothiazine‐3‐carboxamide, C₁₇H₁₆N₂O₄S, crystallized in two enantiomorphic crystal forms with the space groups P3₂ and P3₁ despite the absence of a classic stereogenic atom. The molecular structures are mirror images of each other. Only one sulfonyl O atom takes part in intramolecular hydrogen bonding as a proton acceptor and this atom is different in the two enantiomorphic structures. As a result, the S atom becomes a pseudo‐stereogenic centre. This fact is worth taking into account due to the different biological activities of the enantiomorphic forms. One form possesses a high analgesic activity, while the other form revealed a high anti‐inflammatory activity.     

Protein and Peptide Substances in the Treatment of Respiratory Syncytial Infection: Current State

Respiratory syncytial virus infection (RSVI) is an acute medical and social problem in many countries globally. Infection is most dangerous for infants under one year old and the elderly. Despite its epidemiological relevance, only two drugs are registered for clinical use against RSVI: ribavirin (approved in a limited number of countries due to side effects) and palivizumab (Synagis), which is intended only for the prevention, but not the treatment, of infection. Currently, various research groups are searching for new drugs against RSV, with three main areas of research: small molecules, polymeric drugs (proteins and peptides), and plant extracts. This review is devoted to currently developed protein and peptide anti-RSV drugs.     

Catalytic Activity of Amines Hydrochlorides,Intramolecular Catalysis and Stereoselectivity of Phosphorylation of Hydroxylcontaining Nucleophiles with P(III)-N-Ethylanilines

Abstract

The effect of acid-base properties of amines hydrochlorides (AH) on their catalytic activity in methanolysis of P(III)-N-ethylaniline has been studied. The analysis of Bronsted correlation equation was indicative of general acid catalysis and it was thus confirmed, that general regularities had place during alcoholysis of P(III)-amines under catalysis with AH. In addition, the increasing of alcohol polarity leads to the increasing of proton transfer degree (α) from acid catalysts to phospho(III)amine substrate and to the increasing of the positive charge at the phosphorus in the transition state. Besides, the comparison of α values indicates that in more polar methanol (in comparison with tbutanol) the catalysis is more sensitive to the acidity change of used catalysts.     

Acylative kinetic resolution of racemic amines using N-phthaloyl-(S)-amino acyl chlorides

A comparative study of the kinetic resolution of racemic 2-methyl-1,2,3,4-tetrahydroquinoline and 2,3-dihydro-3-methyl-4H-1,4-benzoxazine using N-phthaloyl-(S)-amino acyl chlorides as chiral acylating agents is described. Temperature and solvent effects on the stereochemical features have been examined. It has been found that N-phthaloyl-(S)-phenylalanyl and N-phthaloyl-(S)-2-phenylglycyl chlorides bearing aromatic substituents close to the stereogenic centre are more stereoselective acylating agents than N-phthaloyl-(S)-alanyl chloride. For the preparative kinetic resolution of racemic amines N-phthaloyl-(S)-phenylalanyl chloride proved to be the most appropriate chiral acylating agent.     

Novel ligands based on bromosubstituted hydroxycarbonyl [2.2]paracyclophane derivatives: synthesis and application in asymmetric catalysis

New planar-chiral hydroxycarbonyl [2.2]paracyclophane derivatives, 4-acetyl-13-bromo-5-hydroxy[2.2]paracyclophane (Br-АНРС, 63%) and 4-benzoyl-13-bromo-5-hydroxy[2.2]paracyclophane (Br-BHPC, 53%), were synthesized and reacted with the enantiomers of α-phenylethylamine to form corresponding Schiff bases, 12-bromo-4-hydroxy-5[1-(1-phenyl-ethylimino)-ethyl]-[2.2]paracyclophane and 12-bromo-4-hydroxy-5[1-(1-phenyl-ethylimino)-(phenyl)methylen-[2.2]paracyclophane. The diastereomers of the imines were resolved and their absolute configurations and consequently the corresponding configurations of the enantiomers of Br-АНРС were determined by X-ray diffraction. Enantiomerically pure Schiff bases were applied as ligands to form catalysts for the enantioselective addition reaction of diethylzinc with benzaldehyde where 1-phenylpropanol was obtained with 77–91% ee.     

Purification of the specific immunoglobulin G1 by immobilized metal ion affinity chromatography using nickel complexes of chelating porous and nonporous polymeric sorbents based on poly(methacrylic esters). Effect of polymer structure

Ni2+ complexes of the chelating nonporous and porous bead sorbents based on methacrylic esters crosslinked with ethylene dimethacrylate were used in isolation of the horseradish peroxidase-specific immunoglobulin IgG1 from the crude mouse ascitic fluid by immobilized metal ion affinity chromatography (IMAC). Iminodiacetic and aspartic acids were attached to porous poly(glycidyl methacrylate) beads differing in size, morphology and chemical composition. Ethylenediaminetriacetic acid and quinolin-8-ol chelating groups were attached mainly to the surface hydroxyl groups in nonporous poly(diethylene glycol methacrylate) beads through spacers. The latter sorbents exhibited better kinetic characteristics than the former but a very low IgG1 sorption capacity. In a single-step IMAC procedure, the best efficiency in the specific IgG1 purification was obtained with porous sorbents (recovery 92%, purity 73%). Differences in IMAC separations are discussed from the point of view of morphology of polymer beads as well as of the type and concentration of chelating ligands.     

Regioselective silylation of sugars through palladium nanoparticle-catalyzed silane alcoholysis

Palladium(0)-catalyzed silane alcoholysis was applied to sugars for the first time using tert-butyldimethylsilane (TBDMS-H) and Ph(3)SiH as the silanes. The catalyst is a colloidal solution of Pd(0) generated in situ from PdX(2) (X = Cl(-), OAc(-)) and TBDMS-H in N,N-dimethylacetamide. The colloid has been characterized by dynamic light scattering and transmission electron microscopy and consists of catalytically highly active nanoparticles of approximately 2 nm diameter. The silane alcoholysis reaction is an effective method for the regioselective silylation of methyl and phenyl glycosides and generates hydrogen gas as the only side product. For many of the sugar substrates investigated, the distribution of regioisomers obtained is complementary to that of the traditional R(3)SiCl/base (base = pyridine, imidazole) methodology and gives convenient access to the 3,6- rather than the 2,6-silylated pyranosides, obtained as the main product by the silyl chloride method. The method also allows a selective axial silylation of levoglucosan and 1,3,5-O-methylidene-myo-inositol. In an attempt to rationalize the observed regioselectivities, ab initio predictions (HF/3-21G) have been made on the relative energies of some of the silylated products. They suggest that the observed regioselectivities do not reflect a kinetic vs thermodynamic product distribution but are induced by the silylation agent employed. Models for the possible origin of the observed regioselectivity in both silylation methods (silane- and silyl chloride-based) are discussed.