A full 3D numerical model of the industrial electrostatic coating process for moving targets

In this paper, a full three dimensional FLUENT numerical model of the electrostatic coating process as used in the automotive industry is presented and selected parametric studies on the numerical model have been conducted. The model incorporates a moving mesh capability in order to simulate movements of the target. The target follows piecewise linear motion and the entire area of the target has been coated in multiple passes. All the dominant mechanical and electrical phenomena were taken into account and cases with both neutral and charged particles were examined. It was confirmed that the transfer efficiency increases when the electrical forces are present in the model and that the coating uniformity improves with the movement of the target. The deposition pattern corresponds to the motion of the target and gradually builds up in a cumulative manner. Due to the aggregation effect associated with the target movement, the deposition uniformity is dramatically improved.     

Insights into base-free OsO4-catalyzed aminohydroxylations employing chiral ligands

Attempts to perform the OsO₄-catalyzed enantioselective base-free aminohydroxylation of β,β-disubstituted enoates are described. Low yields and racemic products were obtained in the presence of standard chiral ligands, suggesting the occurrence of a “Second Cycle” process due to slow hydrolysis of the amino alcohol product from the Os metal center. Support for this hypothesis was provided by the slightly improved enantioselectivity (60:40 er) obtained with an amino alcohol ligand. Based on density functional theory calculations, it is proposed that the lack of significant enantioselectivity is due to a low-energy (3 + 2) oxo/imido cycloaddition transition state without the chiral ligand in the Second Cycle that outcompetes protonolysis in the First Cycle.     

A method of test for residual isophorone diisocyanate trimer in new polyester-polyurethane coatings on light metal packaging using liquid chromatography with tandem mass spectrometric detection

A method of test for residual isophorone diisocyanate (IPDI) trimer in experimental formulation polyester-polyurethane (PEPU) thermoset coatings on metal food packaging is described. The method involves extraction of coated panels using acetonitrile containing dibutylamine for concurrent derivatisation, and then high performance liquid chromatography with electrospray ionisation tandem mass spectrometric detection (LC-MS/MS). Single laboratory validation was carried out using three different experimental PEPU-based coatings. The calibrations were linear, the analytical recovery was good, no interferences were seen, and substance identification criteria were met. The detection limit of the method is around 0.02 micro g/100 cm(2) of coating, which for a typical sized can and assuming complete migration of any residual IPDI trimer, corresponds to about 0.2 micro g/kg food or beverage. Separate studies indicated that, even if migration occurred at such low levels, the IPDI trimer would not be expected to persist in canned aqueous or fatty foodstuffs as it would hydrolyse to the corresponding aliphatic amine or react with food components to destroy the isocyanate moiety. The method of test developed here for residual IPDI trimer in thermoset polyester-polyurethane coatings should prove to be a valuable tool for investigating the cure kinetics of these novel coatings and help to guide the development of enhanced formulations.     

Surface science aspects of supramolecular conformation in elastin‐like polypeptides

Polypeptides can form helical fibres in aqueous media: potentially useful for the production of biocompatible fabric and yarns. A previous work has shown that fibre formation occurs readily with elastin‐like polypeptides constructed from hydrophobic amino acids, such as valine, glycine and leucine. However, elastin‐like polypeptides, when suspended in methyl alcohol, are observed to form globules and ‘string of bead’ structures. Thus, it seems probable that the interface energy is important. Interface energy is minimised by the formation of bonds extending from one phase to the other: a phenomenon that is central to adhesion science. We have looked for evidence of such bonding using XPS to study structures formed by poly(ValGlyGlyLeuGly). The structures formed were first characterised by atomic force microscopy. Differences were found between structures and spectra formed in either water or methanol. No evidence for the presence of unique bonds characterising the interface was found, but evidence was found for the influence of a water environment on the internal structure, suggesting that it is the increase in intermolecular bonding opportunities associated with the influence of water on the growth of fibres that is the thermodynamic driver for the observed transformation into fibre deposits. Copyright © 2011 John Wiley & Sons, Ltd.     

Syntheses of thiopyrone and pyrone derivatives by photocyclization reaction of 3‐aryl‐2‐( Benzothien‐3‐yl)propenoic acids

Naphtho[1,2‐b][1]benzothiophene‐6‐carboxylic acids, 6H‐benzo[b]naphtho[2,3‐d]thiopyran‐6‐ones and 6H‐benzo[b]naphtho[2,3‐d]pyran‐6‐ones were synthesized in one step by the photocyclization reaction of 3‐aryl‐2‐([1]benzothien‐3‐yl)propenoic acids. The photocyclization reaction did not occur when the 3‐aryl group contained the electron‐withdrawing nitro group. The assignment of the ¹H and ¹³C nmr spectra of 6H‐benzo[b]naphtho[2,3‐d]thiopyran‐6‐one and 6H‐benzo[b]naphtho[2,3‐d]pyran‐6‐one by two‐dimensional nmr methods is described. The difference between the chemical shift values of H12 for these two compounds is attributed to different molecular geometries.     

Total assignment of the proton NMR spectrum of dinaphtho[1,2-B:2′,3′-d]thiophene

Recently, there has been some question regarding the ¹H-nmr spectrum of dinaphtho[1,2-b-2′,3′-d]-thiophene. A recent study has reported differences in some of the proton resonance positions from results of earlier work. We report the total assignment of the ¹H-nmr spectrum of the title compound using a combination of ¹H-COSY and one dimensional NOE-difference spectroscopy (NOEDS).     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 16. [1]benzothieno[2′,3′:4,5]thieno[2,3-c]quinoline and [1]benzothieno[2′,3′:4,5]thieno[2,3-c]naphtho[1,2-f]quinoline

The synthesis of two previously unknown polycyclic heterocyclic ring systems via photocyclization is described. The unequivocal assignment of their proton and carbon spectra was achieved by utilizing two-dimensional nmr techniques.     

Application of capillary electrophoresis in migration studies of food contact materials – part 1: Substituted phenolic additives

A method has been developed to determine 11 phenolic antioxidants in the food simulants distilled water, 3% acetie acid, and 15% ethanol, using; micellar capillary electrophoresis (MCE). All the phenols could he analyzed within 35 min. The analytical recovery from spiked simulants was 80 to 119% except for 2,6-di-tert-butyl-4hydroxytoluenc (BHT) and octyl gallate, which could not be recovered from 3% acetic acid simulant. Calibration graph correlation coefficients for the 11 phenols were 0.982 to 0.999. Limits of detection (LoDs) were from 2.8 to 8.6 mg/L. These LoDs are well below European Union migration limits for these substances. It is concluded therefore that MCE offers a rapid and reliable analysis for the control of migration from plastics intended for food contact which employ these phenols as antioxidants.