Study of migration of active components of phosphorescent oxygen sensors for food packaging applications

A study of migration of the active components of oxygen sensors into food is presented. Six types of sensors, based on different oxygen sensitive dyes (two metalloporphyrins and one ruthenium dye), polymers (polystyrene and polysulfone) and support materials, were exposed to a number of standard ‘food simulants’ recommended by FDA/EU guidelines and then assayed for migration or sensor components and changes in oxygen calibration. Both metalloporphyrin sensor dyes leached only in olive oil and in 95% ethanol (used as a positive control), at maximum levels of 19.22 μg/dm² for PtOEPK and 113.96 μg/dm² for PtTFPP. The RuDPP dye showed maximum leaching in 95% ethanol (25.19 μg/dm²) while also migrating in an acidic aqueous simulant. Planar supports such as polyester tended to enhance the stability of the sensor. Migration of the styrene monomer from the polystyrene encapsulation medium was concluded to be low enough to be insignificant. Migration of sensor components was shown to correlate with the changes in sensor response to oxygen. Based on these results, sensor combinations were ranked on the basis of their resistance to leaching and their general stability, safety and suitability for use on a large scale in packaged foods and related food applications was proven.     

Macroporous poly(methyl methacrylate) produced by phase separation during polymerisation in solution

Polymethyl methacrylate (PMMA) sponges were obtained by polymerization in a solution with monomer/ethanol ratios up to 20:80. The material obtained after the elimination of the solvent present a homogeneous distribution of dispersed pores up to a monomer/ethanol ratio lower than 40:60. For higher ethanol contents in the reacting mixture, the morphology of the sponge corresponds to a network of PMMA microparticles, leaving large empty spaces leading to highly porous structure. The monomer/ethanol ratio during polymerization has a large influence on the porosity, thermal, and mechanical properties of the material and, for large solvent contents, on the size of the polymer microparticles.     

Haplotyping by capillary electrophoresis

The investigation of the genetic background and phenotype structures of complex diseases, such as cardiovascular or psychiatric disorders and tumors, is one of the most scrutinized fields of the post genomic era. Besides the multiplex analysis of genetic markers and polymorphisms throughout the whole genome, more and more attention is focused on the interaction between the etiological factors of these traits. Haplotype determination, rather than multiplex genotyping seems to be one of the first building blocks of this endeavor. This review focuses on the importance and theoretical background of haplotyping, and summarizes the recent examples of novel and emerging haplotyping techniques by capillary gel electrophoresis based DNA fragment analysis, a powerful tool for the examination of the inheritance of complex traits.     

Modified determination of dihydrostreptomycin in kidney, muscle and milk by HPLC.

A method is presented for the determination of dihydrostreptomycin in milk, muscle and kidney by reversed-phase ion-pair high-performance liquid chromatography and post-column derivatisation with beta-naphthoquinone-4-sulfonate prior to fluorescence detection. The new sample work-up procedures include acid precipitation of proteins and, in the case of muscle and kidney, removal of fats by solvent extraction followed by solid phase extraction on a cation exchanger. The fluorescence response was linear from 25 to 2000 micrograms l-1 of injected analyte. The detection limits were 10 micrograms kg-1 for milk and 15 micrograms kg-1 for muscle and kidney and the analyte recoveries were on average 93% for milk, 70% for kidney and 75% for muscle.     

Development of reactive thiol-modified monolithic capillaries and in-column surface functionalization by radical addition of a chromatographic ligand for capillary electrochromatography

Reactive thiol-modified capillary columns for capillary electrochromatography (CEC) were developed by transforming the pendent 2,3-epoxypropyl groups of poly(glycidyl methacrylate-co-ethylene dimethacrylate) (poly(GMA-co-EDMA)) monoliths into 3-mercapto-2-hydroxy-propyl residues by a nucleophilic substitution reaction, employing sodium-hydrogen sulfide as nucleophilic reagent. Conditions for this modification reaction were systematically optimized with respect to different parameters, such as reaction temperature, pH-value, reaction time, type and concentration of organic modifier, and concentration of the sodium-hydrogen sulfide solution. The amount of thiol groups that was generated on the monolith surface was determined directly in the capillaries by a disulfide-exchange reaction employing 2,2'-dipyridyl disulfide (DPDS). This reaction in the capillary liberates pyridine-2-thione in equimolar amount to the surface sulfhydryls, which was collected into a vial and determined photometrically at 343 nm by RP-HPLC. About 17% of the total lateral epoxide moieties of the monolithic substrate could be transformed to reactive sulfhydryl groups, which corresponds to about 0.7 mmol g(-1) monolithic polymer, with a column-to-column repeatability of 3.2% R.S.D. The reactive thiol groups can be utilized to attach any chromatographic ligand with appropriate anchor in a second step, e.g. by radical addition, graft polymerization, nucleophilic substitution, disulfide formation or Michael addition reaction. To demonstrate the feasibility of the concept, we chose an anion exchange type chromatographic ligand based on a quinine derivative, O-9-tert-butylcarbamoylquinine (t-BuCQN) which was attached to the monolith in a radical addition reaction, for a further in-column surface functionalisation. About 78% of the sulfhydryl groups were derivatized with t-BuCQN as determined from differential DPDS assays before and after the selector immobilization reaction. The applicability of these surface-functionalised monolithic capillary columns could be shown by an electrochromatographic separation of the enantiomers of N-3,5-dinitrobenzoyl-leucine, which performed fairly well compared to an analogous capillary that was fabricated by an in situ copolymerization approach.     

The contribution of the pressure drop to analyte retention in coupled column supercritical fluid chromatography of lipids

Summary This paper reports the qualitative and quantitative effects of the column pressure drop on the retention of lipid components in a serially coupled capillary column SFC system. The contribution of the pressure drop consists of two components, the density effect and the flow effect. The magnitude of the flow effect,i. e. the change in retention which results from changes in the flow-rate when column pressures are changed, is determined by the difference in single column analyte k values. The effect will be positive compared with the uncorrected retention values when the column with largest k value is closest to the injector. With the columns in reversed order, the effect will be negative. The contribution from the density effect always resulted in larger coupled column k values and was in most instances of more significance than the flow effect component. Values calculated with and without pressure drop correction have been compared and it has been shown that for most of the eighteen model lipid compounds investigated, the deviations from the experimental retention factors were smaller when pressure drop corrections were made.     

Rh complexes of 1-(2,4,6-triisopropylphenyl-)3-methyl-1H-phosphole: preparation and use as catalysts in the hydroformylation of styrene

In the series of 1-(2,4,6-trialkylphenyl-)3-methyl-1H-phospholes (1a–c) that are to a certain extent of aromaticity, only the isopropyl substituted one (1a) entered into reaction with dimeric (pentamethylcyclopentadienyl)rhodium dichloride to afford Rh(III) complex (2a) in a reversible manner. After a careful workup, (2a) could be prepared and characterized whose stereostructure was elucidated by B3LYP/3–21G*, B3LYP/6–31G* and LANL2DZ calculations. Complex (2a) as a preformed catalyst, as well as the Rh(acac)(CO)₂ + 2(1a) in situ catalytic system were useful in the hydroformylation of styrene and gave the branched aldehyde in regioselectivities of 65–96%.     

A comparative study of several HPLC methods for determining free amino acid profiles in honey

A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results.     

Adducts of Rh2[MTPA]4 with some phosphine chalcogenides: nature of binding and ligand exchange

Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.