Experimental, Theoretical and Biological Activity Study on the Acyl-Substituted Benzo-18-crown-6, Dibenzo-18-crown-6 and Dibenzo-24-crown-8

Hexadecanoyl, dihexadecanoyl, dioctadecaneoyl, di-10-undecenoyl, and dicis-9-octadecenoyl derivatives of benzo[18]crown-6, dibenzo[18]crown-6 and dibenzo[24]-8 were synthesized by the condensation of carboxylic acids (palmitic, stearic, oleic and undecenoic acid) with benzo and dibenzo crown ethers in the presence of zinc chloride. The extraction equilibrium constants of such macrocyclic ethers with long side chains were estimated using chloroform/water and dichloromethane/water membranes transfer of Na-PAR (4-(2-pyridylazo)-resorcinol mono sodium monohydrate) with UV–Vis spectroscopy. It was found that they were in the range of 10.88–11.71 in dichloromethane and 8.04–11.77 in chloroform. These results actually show that the Na+ binding effect of macrocyclic ethers depends on the type and the length of side chains. The geometrical properties of the molecules were studied employing semi-empirical calculations by simulated annealing technique. The frontier molecular orbital energies and dipole moments were also examined. The biological activity results showed that the synthesized crown ethers have no activity against the studied microorganisms.     

Process control of apple winemaking by low-resolution gas-phase Fourier-transform infrared spectroscopy

Four apple wine fermentation processes have been observed by means of direct-inlet gas-phase FTIR spectroscopy. The apple juice concentrates were each fermented by two species of Saccharomyces cerevisiae starters, and the experiment was repeated. The development of the concentrations of 1-propanol, 4-methylpyridine, acetaldehyde, acetic acid, and ethyl acetate was monitored. Two different sampling methods were used--static headspace and direct injection of the must. The performance of the FTIR method is limited by the high ethanol concentration. It can be mathematically proven that the amount of sample can be selected so that any distortion due to ethanol is minimized. Headspace GC-MS was used for preliminary compound identification.     

FEATURES OF BIOECONOMICS MODELS FOR THE OPTIMAL MANAGEMENT OF A FISHERY EXPLOITED BY TWO DIFFERENT FLEETS

ABSTRACT. After the extension of the Exclusive Economic Zone, in 1977, to 200 miles, most fish stocks came under jurisdiction of the adjacent coastal states. This development opened prospects of effective management of the open sea fisheries. Coastal states have the right to plan out the operation of so-called by Clarke and Munro “distant water fishing nations” from their Exclusive Economic Zone. Under some arrangements, a foreign fleet is allowed to harvest the resource in the Exclusive Economic Zone area. Clarke and Munro, in [1987] and [1991], focus on the issue of optimum terms and conditions of access and, in doing so, built a multiobjective model. The main goal of the present work is the development of a more general model including more variables and parameters related to the presence of a domestic fleet as well as a distant water fishing nation. The main difficulty resides in sharing the harvesting between the two fleets. The study responds to the realistic problemof coastal states who own enough resource stocks to allow harvesting by several kinds of fleets. Two optimal scenarios are developed, in each of them a solution is given.     

Methyl α- -fructofuranoside: Synthesis and conversion into carboxylates

Methyl α- -fructofuranoside was synthesized by methylation of -fructose and subsequent isolation of the α-furanoside from the anomeric mixture. This fructofuranoside was used as a starting material for the syntheses of several carboxylates, applying glycolic oxidation, selective oxidation of the primary alcohol function at the C-6 position and carboxymethylation.     

Gold as intermolecular glue: a predicted planar triaurotriazine, C3Au3N3, isomer of gold cyanide

It is predicted that solid gold cyanide, AuCN, could have an alternative infinite trigonal-sheet crystal structure, of almost the same energy as the known hexagonally-packed infinite-chain structure.     

Feasibility of different mass spectrometric techniques and programs for automated metabolite profiling of tramadol in human urine

The purpose of the study was to determine the advantages of different mass spectrometric instruments and commercially available metabolite identification programs for metabolite profiling. Metabolism of tramadol hydrochloride and the excretion of it and its metabolites into human urine were used as a test case because the metabolism of tramadol is extensive and well known. Accurate mass measurements were carried out with a quadrupole time-of-flight mass spectrometer (Q-TOF) equipped with a LockSpray dual-electrospray ionization source. A triple quadrupole mass spectrometer (QqQ) was applied for full scan, product ion scan, precursor ion scan and neutral loss scan measurements and an ion trap instrument for full scan and product ion measurements. The performance of two metabolite identification programs was tested. The results showed that metabolite programs are time-saving tools but not yet capable of fully automated metabolite profiling. Detection of non-expected metabolites, especially at low concentrations in a complex matrix, is still almost impossible. With low-resolution instruments urine samples proved to be challenging even in a search for expected metabolites. Many false-positive hits were obtained with the automated searching and manual evaluation of the resulting data was required. False positives were avoided by using the higher mass accuracy Q-TOF. Automated programs were useful for constructing product ion methods, but the time-consuming interpretation of mass spectra was done manually. High-quality MS/MS spectra acquired on the QqQ instrument were used for confirmation of the tramadol metabolites. Although the ion trap instrument is of undisputable benefit in MS(n), the low mass cutoff of the ion trap made the identification of tramadol metabolites difficult. Some previously unreported metabolites of tramadol were found in the tramadol urine sample, and their identification was based solely on LC/MS and LC/MS/MS measurements.     

Porous Biodegradable Scaffold: Predetermined Porosity by Dissolution of Poly(ester‐anhydride) Fibers from Polyester Matrix

A novel selective leaching method for the porogenization of the biodegradable scaffolds was developed. Continuous, predetermined pore structure was prepared by dissolving fast eroding poly(ε‐caprolactone)‐based poly(ester‐anhydride) fibers from the photo‐crosslinked poly(ε‐caprolactone) matrix. The porogen fibers dissolved in the phosphate buffer (pH 7.4, 37 °C) within a week, resulting in the porosity that replicated exactly the single fiber dimensions and the overall arrangement of the fibers. The amount of the porosity, estimated with micro‐CT, corresponded with the initial amount of the fibers. The potential to include bioactive agents in the porogen fibers was demonstrated with the bioactive glass.

     

Precise half-life measurement of the 26Si ground state

The β-decay half-life of ²⁶Si was measured with a relative precision of 1.4·10^?3. The measurement yields a value of 2.2283(27) s which is in good agreement with previous measurements but has a precision that is better by a factor of 4. In the same experiment, we have also measured the non-analogue branching ratios and could determine the super-allowed one with a precision of 3%. The experiment was done at the Accelerator Laboratory of the University of Jyväskylä where we used the IGISOL technique with the JYFLTRAP facility to separate pure samples of ²⁶Si.