Cocrystals “Divorce and Marriage”: When a Binary System Meets an Active Multifunctional Synthon in a Ball Mill

A well-defined and stable “AB” binary system in the presence of “C” a crystalline synthon ground in a ball mill undergoes selective transformation in the solid state according to the equation AB+C→AC+B. When the amount of C is increased two times then the equation AB+2C→AC+BC is valid. The other variants are more complex. The pathway BC+A is allowed and leads to the AC and B products. The pathway AC+B is not preferred, and no transformation is observed. These non-obvious correlations were observed for cocrystal of barbituric acid (BA):thiobarbituric acid (TBA) recently reported by Shemchuk et al. (Chem. Commun. 2016 , 52, 11815–11818) in the presence of 1-hydroxy-4,5-dimethyl-imidazole 3-oxide (HIMO). This synthon shows high affinity for the BA_0.5TBA_0.5 cocrystal as well for its individual components, BA and TBA. Single-quantum, double-quantum (SQ-DQ) 2D ¹H very fast MAS NMR with a spinning rate of 60 kHz was employed as a basic and most diagnostic tool for the study of cocrystals transformations. Analysis of the experimental data was supported by theoretical calculations, including computation of the stabilization energy, E^stab, defined as the energy difference between the energy of a co-crystal and the sum of the energies of particular components in the respective stoichiometric ratios. Two mechanisms of synthon replacement have been proposed. Pathway 1 assumes a concerted mechanism of substitution. In this approach, synthon attack is synchronized in time with the departure of one of the components of the binary system. Pathway 2 implies a non-concerted process, with an intermediate stage in which three separate components are present. Evidence suggesting a preference for Pathway 2 is shown.     

Backbone and side chain assignment strategies for multiply labeled membrane peptides and proteins in the solid state

We demonstrate that the SPECIFIC CP technique can be used to obtain heteronuclear correlation (HETCOR) spectra of peptide backbones with greater efficiency than conventional HETCOR methods. We show that similar design principles can be employed to achieve selective homonuclear polarization transfer mediated through dipolar or scalar couplings. Both approaches are demonstrated in a tripeptide with uniform 15N and 13C labeling, and with uniform 15N labeling and natural abundance 13C. In other applications, the high efficiency of the heteronuclear SPECIFIC CP transfer allows discrimination of single amide signals in the 248-residue membrane protein bacteriorhodopsin (bR). In particular, variations are detected in the ordering of the Ala81-Arg82 peptide bond among the photocycle intermediates of bR and SPECIFIC CP is used to correlate 15N and 13C signals from the three Val-Pro peptide bonds.     

Adsorption of urea on a polycrystalline copper electrode

The adsorption of urea on a polycrystalline copper electrode from 0.01 M NaClO₄ solution has been studied by impedance spectroscopy and radiometric method. The dependence of the surface concentration of urea on the electrode potential and the bulk concentration was determined. From radiometric data, it follows that the adsorption of urea on the copper electrode takes place in the entire range of studied potentials where no faradaic processes occur. In this range, the process of adsorption is practically reversible with respect to the potential and the bulk concentration of urea. The experimental data were described by the Langmuir and the virial isotherms and the Gibbs energy of adsorption were calculated. The data of the urea adsorption on different electrodes have been compared and the role of the kind of the metal on the adsorption process was discussed.     

Wavelength-dependent photochemistry of Diazo Meldrum's acid and its spirocyclic isomer,Diazirino Meldrum's acid: Wolff rearrangement versus isomerization

Photoreaction of diazo Meldrum's acid (1) shows a unique wavelength selectivity. At 254 nm it results in efficient (phi(254) = 0.34) Wolff rearrangement, while irradiation with 355 nm light leads to a completely different process, isomerization into corresponding cyclic alpha,alpha"-dicarbonyl diazirine 2 (phi(350) = 0.024). UV photolysis of diazirine 2 is accompanied by two competing processes: loss of nitrogen followed by the Wolff rearrangement and isomerization into diazo compound 1. Thermal decomposition of 1 leads to clean Wolff rearrangement, while heating of 2 causes quantitative conversion into diazo isomer 1.     

The effect of interaction between K(+) ions and gramicidin D on the lecithin membrane interfacial tension

The effect of the presence of gramicidin D in a lecithin membrane on its interfacial tension has been studied. The studies have been carried out at various forming solution compositions and at various potassium ion concentrations in the electrolyte solution. Potassium chloride was used as the electrolyte. The complex was formed between the gramicidin molecule and K(+) ion. The following parameters describing the complex were determined: the surface area occupied by GK(+) complex (A(GK(+))), the interfacial tension of the GK(+) membrane complex (gamma(GK+)), and the stability constant of the gramicidin-K(+) complex (K). These values are 156 A(2), 1.89 mN m(-1) and 0.033 m(3) mol(-1), respectively.     

Density functional calculation of the 2D potential surface and deuterium isotope effect on 13C chemical shifts in picolinic acid N-oxide. Comparison with experiment

2D free energy surfaces V = V(rOH, rO...O) for the intramolecular H-bond in the title compound were calculated by the DFT method and used in the calculation of primary and secondary chemical shifts of the compound dissolved in chloroform and acetonitrile. Solvent effects were accounted for by the SCRF/PCM method. The corresponding two-dimensional chemical shift surfaces with included solvent reaction field were obtained using the Continuous Set of Gauge Transformations approach at the B3LYP/6-311+G(2d,2p) level of theory. The chemical shifts were estimated as quantum averages along the two internal coordinates in the hydrogen bond and along several vibrational levels according to the Boltzmann distribution at room temperature. Fairly good agreement between the experimental and calculated isotope effects was obtained. 1D and 2D NMR spectra of solutions of picolinic acid N-oxide and its deuterated analogue were recorded and assigned.     

New imide 5-HT1A receptor ligands - modification of terminal fragment geometry

Two sets of new o-methoxyphenylpiperazine (MPP; series a) and 1,2,3,4-tetrahydroisoquinoline (THIQ; series b) derivatives, containing various imide moieties derived from NAN190, were synthesized and evaluated in vitro for their ability to bind to the serotonin 5-HT(1A) and 5-HT(2A) receptors. All new derivatives from series a demonstrated high 5-HT(1A) affinities, whereas THIQ analogues were much less active. With respect to 5-HT(2A) receptors, three MPP derivatives presented moderate activity but the rest of the investigated compounds were practically inactive. The influence of changes in terminus geometry on 5-HT(1A) receptor affinity was analyzed in regard to model compounds NAN190and MM199.     

Synthesis of N‐[(tert‐Butoxy)carbonyl]‐3‐(9,10‐dihydro‐9‐oxoacridin‐2‐yl)‐L‐alanine,a New Fluorescent Amino Acid Derivative

A simple synthesis of a new, highly fluorescent amino acid and of its protected derivative useful in peptide studies is described. The obtained derivative, N‐[(tert‐butoxy)carbonyl]‐3‐(9,10‐dihydro‐9‐oxoacridin‐2‐yl)‐L ‐alanine ( 6 ), shows intense long‐wave absorption (above 360 nm) and emission (above 400 nm). The quantum yield of fluorescence of the investigated compound is very high, so it can serve as a sensitive analytical probe useful, e.g., in analysis of peptide conformations.     

Microalgae as a Potential Functional Ingredient: Evaluation of the Phytochemical Profile,Antioxidant Activity and In-Vitro Enzymatic Inhibitory Effect of Different Species

The functional food market has been in a state of constant expansion due to the increasing awareness of the impact of the diet on human health. In the search for new natural resources that could act as a functional ingredient for the food industry, microalgae represent a promising alternative, considering their high nutritional value and biosynthesis of numerous bioactive compounds with reported biological properties. In the present work, the phytochemical profile, antioxidant activity, and enzymatic inhibitory effect aiming at different metabolic disorders (Alzheimer’s disease, Type 2 diabetes, and obesity) were evaluated for the species Porphyridium purpureum, Chlorella vulgaris, Arthorspira platensis, and Nannochloropsis oculata. All the species presented bioactive diversity and important antioxidant activity, demonstrating the potential to be used as functional ingredients. Particularly, P. purpureum and N. oculata exhibited higher carotenoid and polyphenol content, which was reflected in their superior biological effects. Moreover, the species P. purpureum exhibited remarkable enzymatic inhibition for all the analyses.     

Modern Methods of Pre-Treatment of Plant Material for the Extraction of Bioactive Compounds

In this review, recent advances in the methods of pre-treatment of plant material for the extraction of secondary metabolites with high biological activity are presented. The correct preparation of the material for extraction is as important as the selection of the extraction method. This step should prevent the degradation of bioactive compounds as well as the development of fungi and bacteria. Currently, the methods of preparation are expected to modify the particles of the plant material in such a way that will contribute to the release of bioactive compounds loosely bonded to cell wall polymers. This review presents a wide range of methods of preparing plant material, including drying, freeze-drying, convection drying, microwave vacuum drying, enzymatic processes, and fermentation. The influence of the particular methods on the structure of plant material particles, the level of preserved bioactive compounds, and the possibility of their release during the extraction were highlighted. The plant material pre-treatment techniques used were discussed with respect to the amount of compounds released during extraction as well their application in various industries interested in products with a high content of biologically active compounds, such as the pharmaceutical, cosmetics, and food industries.