Solid state NMR spectroscopy as a precise tool for assigning the tautomeric form and proton position in the intramolecular bridges of o-hydroxy Schiff bases

Two analogous Schiff bases, (S,E)-2-((1-hydroxy-3-methyl-1,1-diphenylbutan-2-ylimino)methyl)phenol (1) and (S,Z)-2-hydroxy-6-((1-hydroxy-3-methyl-1,1-diphenylbutan-2-ylamino)methylene)cyclohexa-2,4-dienone (2), exist in the solid state as phenol-imine and keto-amine tautomers, respectively. Their crystal structures were solved using the X-ray diffraction method. Sample 1 forms orthorhombic crystals of space group P2(1)2(1)2(1), while 2 forms monoclinic crystals of space group P2(1). In each sample, one molecule is in the asymmetric unit of the crystal structure. One-dimensional and two-dimensional solid state NMR techniques were used for structure assignment and for inspection of the (13)C and (15)N δ(ii) of the chemical shift tensor (CST) values. NMR study indicates that the span (Ω = δ(11)-δ(33)) and the skew (κ = 3(δ(22)-δ(iso)/Ω) are extremely sensitive to change in the tautomeric form of the Schiff bases. Theoretical calculations of NMR shielding parameters for 1 and 2 and a model compound with reduced aliphatic residue were performed using the GIAO method with B3LYP functional and 6-311++g(d,p) basis sets. From comparative analysis of the experimental and theoretical parameters, it was concluded that the position of hydrogen in the intramolecular bridge has tremendous influence on (13)C and (15)N CST parameters. Inspection of Ω and κ parameters allowed for the establishment of the nature of the hydrogen bonding and the assignment of the equilibrium proton position in the intramolecular bridges in the solid state.     

Characterization of 1,3-alternate calix[4]arene-silica bonded stationary phases and their comparison to selected commercial columns by using principal component analysis

Twelve calix[4]arene stationary phases in 1,3-alternate conformation, synthesized in the authors’ laboratory, were characterized in terms of their surface coverage, hydrophobic selectivity, aromatic selectivity, shape selectivity, hydrogen bonding capacity and ion-exchange capacity. The set of tests commonly used for evaluation of commercially available stationary phases was applied to assess fundamental chromatographic properties of the calixarene phases. The new calixarene phases were compared to each other, to Caltrex and LiChrosorb C-18 columns. Principal component analysis has been used to provide comparison between 1,3-alternate calix[4]arene phases and commercially available phenyl, fluorophenyl and fluoroalkyl columns.     

The Crystal Structure of Fluphenazinium Dipicrate Dimethylsulphoxide Solvate

Abstract  

The title compound, C₂₂H₂₈F₃N₃OS²⁺ × 2(C₆H₂N₃O₇ ⁻) × (CH₃)₂SO—the picrate salt of the potent antipsychotic drug, fluphenazine—crystallizes in the triclinic P-1 space group with unit cell parameters a = 10.6333(12) ?, b = 11.9696(12) ?, c = 17.7036(15) ?, α = 103.265(9)°, β = 98.414(9)°, γ = 102.702(10)°. The ionic fragments: the fluphenazinium dictation, and two picrate anions, are joined by means of strong N–H···O and weak C–H···O hydrogen bonds into the chains of alternating cations and anions, expanding along [010] direction. Within the chain, the picrates interact by means of short π···π interactions: the mean distance between the planes is 3.366 ?; additional interaction of the same type between one of the picrates and the phenyl ring of the phenothiazine ring system additionally strengthen the pattern. The phenothiazine ring exists in a typical, “butterfly-like” conformation, with two terminal rings planar and the central ring in a slightly flattened boat form. This conformation results in the dihedral angle between the terminal rings of 41.76(5)°. The aliphatic chain which substitutes phenothiazine at N-position is not in an extended conformation, the torsion angles along this chain are 75.95(14)° and −163.96(10)°. The structure contains also the solvent—dimethylsulphoxide molecules, which are connected with the cation–anion structure by means of strong O–H···O hydrogen bonds.     

Epitaxial graphene perfection vs. SiC substrate quality

Polytype instability of SiC epitaxial films was the main focus of attention in the experiment performed since this factor has a decisive influence on graphene growth, which was the second stage of the experiment. Layers deposited in various initial C/Si ratios were analyzed.     

Enhancement of local superconductivity in ferromagnetic FeCrB metallic glass by Ar+ ion irradiation

We have reinforced local superconductivity in ferromagnetic Fe(67)Cr(18)B(15) metallic glasses by ion irradiation. Superconductivity in this medium appears due to the presence of large-scale layered clusters of metallic Fe-Cr phase, 150-230 ? in size, with a ferromagnetic (or superparamagnetic) Fe-rich core and nonmagnetic Cr-rich superconducting shell. Here we show that due to the intensification of concentration phase separation in the Fe-Cr clusters under ion (Ar(+)) irradiation, the volume of the superconducting phase increases from the initial 0.4-0.5% up to 7-8%. After irradiation, the resistivity jump Δρ/ρ in the temperature range T=3.1-3.6 K increases ～14 times, reaching 19%, as compared to 1.36% for the initial sample. In the interval of T=3.1-3.6 K, the rate of resistance change reaches 79% K(-1) for the irradiated sample instead of 3.6% K(-1) for the initial sample. In the same temperature interval, the rate of magnetoresistance change increases from 3% K(-1) for the initial sample up to 70% K(-1) after irradiation.     

Unified encoding for hyper-heuristics with application to bioinformatics

This paper introduces a new approach to applying hyper-heuristic algorithms to solve combinatorial problems with less effort, taking into account the modelling and algorithm construction process. We propose a unified encoding of a solution and a set of low level heuristics which are domain-independent and which change the solution itself. This approach enables us to address NP-hard problems and generate good approximate solutions in a reasonable time without a large amount of additional work required to tailor search methodologies for the problem in hand. In particular, we focused on solving DNA sequencing by hybrydization with errors, which is known to be strongly NP-hard. The approach was extensively tested by solving multiple instances of well-known combinatorial problems and compared with results generated by meta heuristics that have been tailored for specific problem domains.     

Synthesis of β-amino-α-trifluoromethyl alcohols and their applications in organic synthesis

A comprehensive overview on methods applied for syntheses of β-amino-α-trifluoromethyl alcohols, including stereocontrolled variants, is presented. In addition, reported cases of the exploration of β-amino-α-trifluoromethyl alcohols for the preparation of trifluoromethylated peptidomimetics and other biologically active, fluorinated compounds are discussed. Attractive opportunities for their applications as organocatalysts are also presented.     

Structure and atropisomerisation of new diastereomeric gossypol Schiff bases with (R)-(+)-2-amino-3-benzyloxy-1-propanol studied by NMR,ECD and DFT methods

Gossypol Schiff base with (R)-(+)-2-amino-3-benzyloxy-1-propanol 1 was synthesised and resolved by HPLC method into diastereomers to study their atropisomerisation process. The spectroscopic analysis performed by one- and two-dimensional NMR, UV–vis and FT-IR methods indicated that the compound exists in solution as an enamine-oxo tautomer. The ECD measurements and TD-DFT calculations allowed us to unambiguously determine the configuration about the axially chiral biaryl moiety of 1. The conditions of the atropisomerisation processes of diastereopure gossypol Schiff bases (S_AX,R)-1 and (R_AX,R)-1 were determined on the basis of ECD and NMR measurements. Exposure of the diastereomers of 1 to sunlight and to the light at λ = 254 nm significantly accelerated the atropisomerisation when compared to its rate in the dark.