Water‐Soluble Polymeric Carbon Nitride Colloidal Nanoparticles for Highly Selective Quasi‐Homogeneous Photocatalysis

Heptazine‐based polymeric carbon nitrides (PCN) are promising photocatalysts for light‐driven redox transformations. However, their activity is hampered by low surface area resulting in low concentration of accessible active sites. Herein, we report a bottom‐up preparation of PCN nanoparticles with a narrow size distribution (ca. 10±3 nm), which are fully soluble in water showing no gelation or precipitation over several months. They allow photocatalysis to be carried out under quasi‐homogeneous conditions. The superior performance of water‐soluble PCN, compared to conventional solid PCN, is shown in photocatalytic H₂O₂ production via reduction of oxygen accompanied by highly selective photooxidation of 4‐methoxybenzyl alcohol and benzyl alcohol or lignocellulose‐derived feedstock (ethanol, glycerol, glucose). The dissolved photocatalyst can be easily recovered and re‐dissolved by simple modulation of the ionic strength of the medium, without any loss of activity and selectivity.     

Fuzzy equational logic

Presented is a completeness theorem for fuzzy equational logic with truth values in a complete residuated lattice: Given a fuzzy set Σ of identities and an identity p≈q, the degree to which p≈q syntactically follows (is provable) from Σ equals the degree to which p≈q semantically follows from Σ. Pavelka style generalization of well-known Birkhoff's theorem is therefore established. Received: 15 March 2000 / Revised version: 20 September 2000 Published online: 12 December 2001     

Capillary electrophoresis of boron cluster compounds in aqueous and nonaqueous solvents

The electrophoretic properties of boron cluster compounds were determined in water, methanol and ACN as solvents of the BGE and discussed based on the principles of ion migration. Two types of boron cluster compounds were investigated. One type consisted of derivatives of the nido-7,8-dicarbaundecaborate cluster, the other types are derivatized cobalt bis(dicarbollide) ions (COSANs) whose central cobalt atom is sandwiched by two 7,8-dicarbaundecaborate clusters. The BGE in all solvents was acetate/acetic acid buffer with pH 4.75 in water, 9.7 in methanol and 22.3 in ACN, respectively, at different ionic strength between 5 and 30 mM. The dependence of the mobility on ionic strength could not be explained by the theory of Debye, Hückel and Onsager, but good agreement was found upon considering an ion size parameter. Limiting mobilities were derived by curve fitting, and by the aid of the solvent viscosities the hydrodynamic radii of the analyte anions were calculated. They are between 0.25 and 0.48 nm, and were nearly independent of the solvent. Electrophoresis of the analytes in a BGE consisting of 6 mM perchloric acid in ACN allows the conclusion that the present boron cluster compounds behave as stronger acids than perchloric acid.     

Alkyl glycosides as potential anti-<Emphasis Type="Italic">Candida albicans</Emphasis> growth agents

Candida infections are becoming increasingly prevalent and many clinical isolates are resistant to common azole derivatives treatment. Accordingly, the capacity of a series of 19 alkyl glycosides, mainly mannosides and glucosides but also a cellobioside with aglycone chain-length from C-6 to C-20, to inhibit the growth of laboratory and clinically isolated strains of Candida albicans, was investigated. The study showed that only glycosides with the C-10 and C-12 aglycones were effective growth inhibitors of both types of Candida, strains, whose metabolic activity was also significantly reduced as revealed by an XTT assay.     

Water-Soluble Polymeric Carbon Nitride Colloidal Nanoparticles for Highly Selective Quasi-Homogeneous Photocatalysis

Heptazine-based polymeric carbon nitrides (PCN) are promising photocatalysts for light-driven redox transformations. However, their activity is hampered by low surface area resulting in low concentration of accessible active sites. Herein, we report a bottom-up preparation of PCN nanoparticles with a narrow size distribution (ca. 10±3 nm), which are fully soluble in water showing no gelation or precipitation over several months. They allow photocatalysis to be carried out under quasi-homogeneous conditions. The superior performance of water-soluble PCN, compared to conventional solid PCN, is shown in photocatalytic H₂O₂ production via reduction of oxygen accompanied by highly selective photooxidation of 4-methoxybenzyl alcohol and benzyl alcohol or lignocellulose-derived feedstock (ethanol, glycerol, glucose). The dissolved photocatalyst can be easily recovered and re-dissolved by simple modulation of the ionic strength of the medium, without any loss of activity and selectivity.     

Exploration of the electrophoretic behaviour of borane cluster anions and of the capability of capillary electrophoresis to separate them chirally

Mobilities of investigated boron cluster compounds in 3-(N-morpholino)propanesulfonic and phosphate buffers adjusted to pH 7 either with sodium hydroxide or with tris(hydroxymethyl)aminomethane depend on both buffer ions. The zone width and zone asymmetry, which are usually markedly higher than those of organic or common inorganic ions of comparable size, depend on the type of the borane cluster anion. Unusual shapes of zones of two investigated compounds have been found in tris phosphate buffer. Acetonitrile was superior to methanol as an organic additive to separation systems from the viewpoint of the zone symmetry and separation speed. Narrow trigonal zones, typical of organic ions non-interacting with the capillary wall, have been observed for some bridged sandwich cobalt complexes in run buffers with the addition of acetonitrile. The interaction of borane cluster anions with beta-cyclodextrin cavity is excessively strong in purely aqueous solutions. Methanol and acetonitrile, which generally weaken the interaction, sometimes affect the separation enantioselectivity of various compounds in different ways in addition to the weakening effect. Chiral discrimination was reached for all ten investigated anions, which belong to four different structural types of cluster boranes. Stability constants estimated for some analyte-beta-cyclodextrin complexes range between 100 and 1800 l/mol in acceptable separations. The relative difference of the constants was from 3 to 20%.     

LC‐MS/MS method for the determination of haemanthamine in rat plasma,bile and urine and its application to a pilot pharmacokinetic study

Evidence gathered in various studies points to the fact that haemanthamine, an isoquinoline alkaloid, has multiple medicinally interesting characteristics, including antitumor, antileukemic, antioxidant, antiviral, anticonvulsant and antimalarial activity. This work presents, for the first time, a universal LC‐MS/MS method for analysis of haemanthamine in plasma, bile and urine which has been verified in a pilot pharmacokinetic experiment on rats. Chromatographic separation was performed on a pentafluorophenyl core–shell column in gradient elution mode with a mobile phase consisting of acetonitrile–methanol–ammonium formate buffer. A sample preparation based on liquid–liquid extraction with methyl tert‐butyl ether was employed with ambelline used as an internal standard. Quantification was performed using LC‐MS‐ESI(+) in Selected Reaction Monitoring mode. The method was validated according to the European Medicines Agency guideline in a concentration range of 0.1–10 μmol/L in plasma, bile and urine. The concentration–time profiles of haemanthamine in plasma, bile and urine after a single i.v. bolus of 10 mg/kg have been described for the first time. The presented study addresses the lack of information on haemanthamine pharmacokinetics and also introduces a new universal method of haemanthamine analysis in complex biological matrices. Copyright © 2015 John Wiley & Sons, Ltd.     

Silica-coated manganite and Mn-based ferrite nanoparticles: a comparative study focused on cytotoxicity

Magnetic oxide nanoparticles provide a fascinating tool for biological research and medicine, serving as contrast agents, magnetic carriers, and core materials of theranostic systems. Although the applications rely mostly on iron oxides, more complex oxides such as perovskite manganites may provide a much better magnetic performance. To assess the risk of their potential use, in vitro toxicity of manganite nanoparticles was thoroughly analysed and compared with another prospective system of Mn–Zn ferrite nanoparticles. Magnetic nanoparticles of La_0.63Sr_0.37MnO₃ manganite were prepared by two distinct methods, namely the molten salt synthesis and the traditional sol–gel route, whereas nanoparticles of Mn_0.61Zn_0.42Fe_1.97O₄ ferrite, selected as a comparative material, were synthesized by a new procedure under hydrothermal conditions. Magnetic cores were coated with silica and, moreover, several samples of manganite nanoparticles with different thicknesses of silica shell were prepared. The size-fractionated and purified products were analysed using transmission electron microscopy, dynamic light scattering, measurement of the zeta-potential dependence on pH, IR spectroscopy, and SQUID magnetometry. The silica-coated products with accurately determined concentration by atomic absorption spectroscopy were subjected to a robust evaluation of their cytotoxicity by four different methods, including detailed analysis of the concentration dependence of toxicity, analysis of apoptosis, and experiments on three different cell lines. The results, comparing two manganese-containing systems, clearly indicated superior properties of the Mn–Zn ferrite, whose silica-coated nanoparticles show very limited toxic effects and thus constitute a promising material for bioapplications.     

Synthesis of alpha-amino acids via asymmetric phase transfer-catalyzed alkylation of achiral nickel(II) complexes of glycine-derived Schiff bases

Achiral, diamagnetic Ni(II) complexes 1 and 3 have been synthesized from Ni(II) salts and the Schiff bases, generated from glycine and PBP (7) and PBA (11), respectively, in MeONa/MeOH solutions. The requisite carbonyl-derivatizing agents pyridine-2-carboxylic acid(2-benzoyl-phenyl)-amide 7 (PBP) and pyridine-2-carboxylic acid(2-formyl-phenyl)-amide 11 (PBA) were readily prepared from picolinic acid and o-aminobenzophenone or picolinic acid and methyl o-anthranilate, respectively. The structure of 1 was established by X-ray crystallography. Complexes 1 and 3 were found to undergo C-alkylation with alkyl halides under PTC conditions in the presence of beta-naphthol or benzyltriethylammonium bromide as catalysts to give mono- and bis-alkylated products, respectively. Decomposition of the complexes with aqueous HCl under mild conditions gave the required amino acids, and PBP and PBA were recovered. Alkylation of 1 with highly reactive alkyl halides, carried out under the PTC conditions in the presence of 10% mol of (S)- or (R)-2-hydroxy-2'-amino-1,1'-binaphthyl 31a (NOBIN) and/or its N-acyl derivatives and by (S)- or (R)-2-hydroxy-8'-amino-1,1'-binaphthyl 32a (iso-NOBIN) and its N-acyl derivatives, respectively, gave rise to alpha-amino acids with high enantioselectivities (90-98.5% ee) in good-to-excellent chemical yields at room temperature within several minutes. An unusually large positive nonlinear effect was observed in these reactions. The Michael addition of acrylic derivatives 37 to 1 was conducted under similar conditions with up to 96% ee. The (1)H NMR and IR spectra of a mixture of the sodium salt of NOBIN and 1 indicated formation of a complex between the two components. Implications of the association and self-association of NOBIN for the observed sense of asymmetric induction and nonlinear effects are discussed.