Chromium(III)-isocinchomeronato and quinolinato complexes: kinetic studies in NaOH solutions and effect on 3T3 fibroblast proliferation

The aquation of chromium(III)-isocinchomeronato and quinolinato complexes, mer-[Cr(icaH)₃]⁰ and mer-[Cr(quinH)₃]⁰ (where icaH⁻ and quinH⁻ are N,O-bonded isocinchomeronic and quinolinic acid anion, respectively) was studied in NaOH solutions. The process leads to successive ligand liberation in the fully deprotonated species. The kinetics of the first ligand liberation were studied spectrophotometrically in the visible region. A mechanism is proposed in which the rate of the chelate-ring opening at the Cr–N bond is much faster than the rate of the Cr–O bond breaking. The rate-determining step is described by the rate law: k _obs1 = k _OH(1) + k _O Q ₂ [OH⁻], where k _OH(1) and k _O are rate constants of the first ligand liberation from the hydroxo- and oxo-forms of the intermediate, respectively, and Q ₂ is an equilibrium constant between these two protolytic forms. The first pseudo-first-order rate constants (k _obs1) were calculated using SPECFIT software for an A → B → C reaction pattern. The results are compared with those determined in acidic medium. Kinetics of the second and third ligand liberation were also studied and values of successive pseudo-first-order rate constants (k _obs2, k _obs3) are [OH⁻] independent. Effect of chromium(III)-quinolinato and isocinchomeronato complexes on 3T3 fibroblast proliferation was evaluated. Cytotoxicity of these complexes is low, suggesting they may be promising candidates as novel dietary supplements.     

Verteprofin conjugated to gold nanoparticles for fluorescent cellular bioimaging and X-ray mediated photodynamic therapy

Microchimica Acta - Photodynamic therapy (PDT) uses photosensitizers, light and molecular oxygen to generate cytotoxic reactive oxygen species. Its effectiveness is limited to <1 cm...     

Boronated (co)polystyrene: monomer reactivity ratios,thermal behavior and flammability

Chemical modification based on incorporation of flame retardants (FR) into the polymer backbone was used in order to reduce polystyrene flammability. Boronated styrenes such as 4‐vinylphenylboronic acid (StB(OH)₂) and 6‐methyl‐2‐(4‐vinylphenyl)‐1,3,6,2‐dioxazaborocane‐4,8‐dione (StBcyclo) were applied as reactive FR. Homo‐ and copolymers of boronated styrenes and styrene (St) were synthesized with different feed ratios using free radical polymerization. It yielded in series of (co)polymers with various amounts of StB(OH)₂ and StBcyclo (5–20% mol/mol of St). Copolymer compositions were determined by ¹H NMR. The relative reactivity ratios of system St‐StBcyclo were determined by applying the Jaacks method. Glass transition temperature and thermal stability of obtained (co)polymers were determined from DSC and TGA analysis, respectively. The pyrolysis combustion flow calorimeter was applied as a tool for assessing the flammability of the synthesized (co)polymers. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of the ionic liquid structure on thiophene solubility

Binary liquid-liquid equilibria for 10 systems containing an ionic liquid with thiophene were measured by dynamic method in the temperature range from 283 K to the boiling point of thiophene. The influence of ionic liquid structure on solubility of thiophene is discussed in comparison with results taken from the literature. The solubility of thiophene in all investigated ionic liquids is high - below 0.31 ionic liquid mole fraction.     

The determination of molybdenum in selected mushrooms by stripping voltammetry

The highly sensitive method of adsorptive stripping voltammetry (AdSV), with differential pulse steps, was performed at a mercury film electrode and has been applied here for the determination of trace molybdenum content in selected wild mushrooms. Fruiting body caps of 12 selected macrofungi species from Basidiomycetes have been investigated. Molybdenum content of investigated samples was determined in the range of 0.006 to 0.38 mg kg⁻¹ of dry matter. The highest value of molybdenum content was found in Leccinum rufum and the lowest in Lactarius deliciosus.     

Effect of time on the metal-support (Fe-MgO) interaction in CVD synthesis of single-walled carbon nanotubes

A study on the effect of the metal-support interaction by employing iron particles supported on magnesium oxide (MgO) nanopowder in an alcohol-CVD process for single-walled carbon nanotubes growth is presented. Upon the prolongation of the process time, three main observations were detected: (i) decrease of the mean nanotubes diameter, (ii) reduction of the diameter distribution by the factor of two, (iii) increase of relative purity of the samples.     

Towards the Nature of Active Sites in Polymerization of Cyclic Esters Initiated by Aluminium Alkoxides: First Structurally Authenticated Aluminium‐ε‐Caprolactone Complex

Summary: The isolation and structural characterization of a methylaluminium(bisphenoxide)‐ε‐caprolactone complex is reported. While the three‐coordinate methylaluminium complex was found not to catalyze the polymerization of ε‐caprolactone, its oxygenation led to the formation of an aluminium methoxide compound, which appeared to be a very good initiator. The relative propensity of the Al X bonds for monomer insertion in the initial step of polymerization is also discussed.

Structure of the methylaluminium(bisphenoxide)‐ε‐caprolactone complex reported here.     

Identification and expression analysis of genes encoding putative cellulose synthases (CesA) in the hybrid aspen, Populus tremula (L.) × P. tremuloides (Michx.)

Cellulose is synthesized in plant cell walls by large membrane-bound protein complexes proposed to contain several copies of the catalytic subunit of the cellulose synthase, CesA. Here we report identification of 10 distinct CesA genes within a database of 100,000 ESTs of the hybrid aspen, Populus tremula (L.) × P. tremuloides (Michx.). Expression analyses in normal wood undergoing xylogenesis and in tension wood indicate xylem specific expression of four putative CesA isoenzymes, PttCesA1, PttCesA3-1, PttCesA3-2 and PttCesA9. Both the protein sequences and the expression profiles of PttCesA3-1 and PttCesA3-2 are very similar, and they may thus represent redundant copies of an enzyme with essentially the same function. Further, one of the generally more constitutively expressed CesA genes, PttCesA2, seems to be activated on the opposite side of a tension wood induced stem, while PttCesA6 appears to be more specific for leaf tissues. The rest of the hybrid aspen CesA genes were found to be relatively evenly expressed over the poplar tissues hereby studied.     

The potential of autofluorescence spectroscopy to detect human urinary tract infection

Urinary tract infections (UTIs) are known to alter the normal urine composition which, in principle, can lead to changes in urine autofluorescence. This paper describes the study of human urine (normal and UTI) by using UV fluorescence excitation/emission matrices and synchronous spectra and proposes a method of diagnosing UTI without any sample preparation. The method is based on excitation in the shorter UV region (250-350 nm) which shows good discrimination between the normal urine and UTI samples. The synchronous scans with an offset of Δλ = 90 nm were also able to differentiate between normal urines and UTI samples. These differences were observed even though the two known major urine fluorophores, tryptophan and indoxyl sulfate were present in the normal urine and UTI samples in similar concentration as established by HPLC analysis. Although the identity of substances responsible for the altered autofluorescence in UTI is not established, our study shows that autofluorescence has the potential to differentiate between normal human urine samples and those with UTI.