Hydrophilic Carotenoids: Surface Properties and Aggregation Behavior of the Potassium Salt of the Highly Unsaturated Diacid Norbixin

The oft‐claimed ‘good’ water solubility of the food color norbixin ( 3 ) could not be confirmed. In contrast, the potassium salt 5 of norbixin formed suitable dispersions. The surface and aggregation properties of salt 5 were investigated and compared with other naturally occurring and synthetic hydrophilic carotenoids (Table).     

Tackling an MCDM-problem with the help of some results from fuzzy set theory

The problem to be addressed and tackled in this paper arose as a byproduct from some efforts at solving problems involving multiple goals by linking linear and goal programming models. The critical issue was that some forms for interdependence among the goals could not be handled in the programming models. Here we will deal with a set of goals — with realistic counterparts in a Finnish plywood industry — in which a subset of the goals are (i) conflicting, another subset (ii) unilaterally supporting and a third subset (iii) mutually supporting. It is furthermore observed that the elements of a studied set of goals may be partly independent and partly interdependent, which makes the context a fullfledged MCDM-problem. It is tackled with a technique which is based on the theory of fuzzy sets, the conceptual framework for fuzzy decisions and the algorithms developed for fuzzy mathematical programming. The resulting fuzzy multiobjective programming model is simplified and tested with the help of a fairly complex numerical example.     

Analysis of permethrin isomers in composite diet samples by molecularly imprinted solid-phase extraction and isotope dilution gas chromatography–ion trap mass spectrometry

Determination of an individual's aggregate dietary ingestion of pesticides entails analysis of a difficult sample matrix. Permethrin-specific molecularly imprinted polymer (MIP) solid-phase extraction cartridges were developed for use as a sample preparation technique for a composite food matrix. Vortexing with acetonitrile and centrifugation were found to provide optimal extraction of the permethrin isomers from the composite foods. The acetonitrile (with 1% acetic acid) was mostly evaporated and the analytes reconstituted in 90:10 water/acetonitrile in preparation for molecularly imprinted solid-phase extraction. Permethrin elution was accomplished with acetonitrile and sample extracts were analyzed by isotope dilution gas chromatography–ion trap mass spectrometry. Quantitation of product ions provided definitive identification of the pesticide isomers. The final method parameters were tested with fortified composite food samples of varying fat content (1%, 5%, and 10%) and recoveries ranged from 99.3% to 126%. Vegetable samples with incurred pesticide levels were also analyzed with the given method and recoveries were acceptable (81.0–95.7%). Method detection limits were demonstrated in the low ppb range. Finally, the applicability of the MIP stationary phase to extract other pyrethroids, specifically cyfluthrin and cypermethrin, was also investigated.     

Reevaluation of the mechanism of the amination of aryl halides catalyzed by BINAP-ligated palladium complexes

Two previous mechanistic studies of the amination of aryl halides catalyzed by palladium complexes of 1,1'-binaphthalene-2,2'-diylbis(diphenylphosphine) (BINAP) are reexamined by the authors of both studies. This current work includes a detailed study of the identity of the BINAP-ligated palladium complexes present in reactions of amines with aryl halides and rate measurements of these catalytic reactions initiated with pure precatalysts and precatalysts generated in situ from [Pd2(dba)3] and BINAP. This work reveals errors in both previous studies, and we describe our current state of understanding of the mechanism of this synthetically important transformation. 31P NMR spectroscopy shows that several palladium(0) species are present in the catalytic system when the catalyst is generated in situ from [Pd2(dba)3] and BINAP, and that at least two of these complexes generate catalytic intermediates. Further, these spectroscopic studies and accompanying kinetic data demonstrate that an apparent positive order in the concentration of amine during reactions of secondary amines is best attributed to catalyst decomposition. Kinetic studies with isolated precatalysts show that the rates of the catalytic reactions are independent of the identity and the concentration of amine, and studies with catalysts generated in situ show that the rates of these reactions are independent of the concentration of amine. Further, reactions catalyzed by [Pd(BINAP)2] with added BINAP are found to be first-order in bromoarene and inverse first-order in ligand, in contrast to previous work indicating zero-order kinetics in both. These data, as well as a correlation between the decay of bromobenzene in the catalytic reaction and the predicted decay of bromobenzene from rate constants of studies on stoichiometric oxidative addition, are consistent with a catalytic process in which oxidative addition of the bromoarene occurs to [Pd(BINAP)] prior to coordination of amine and in which [Pd(BINAP)2], which generates [Pd(BINAP)] by dissociation of BINAP, lies off the cycle. By this mechanism, the amine and base react with [Pd(BINAP)(Ar)(Br)] to form an arylpalladium amido complex, and reductive elimination from this amido complex forms the arylamine.     

Domains of holomorphy for Fourier transforms of solutions to discrete convolution equations

We study solutions to convolution equations for functions with discrete support in R~n, a special case being functions with support in the integer points. The Fourier transform of a solution can be extended to a holomorphic function in some domains in C~n, and we determine possible domains in terms of the properties of the convolution operator.     

Hydrogen-bond driven assembly of a molecular capsule facilitated by supramolecular chelation

Resorcinarene-based cavitands functionalized with acetamido groups capable of self-complementary hydrogen-bond interactions, were synthesized in order to construct supramolecular capsules. The 1,3-bifunctionalized cavitand produced a polymeric assembly, whereas the tetra-functionalized analogue yielded a discrete capsule held together via N-H···O hydrogen bonds. The ethynyl species attached to the rim of these host molecules deepen each cavitand and expands the volume of the resulting capsule.     

Experience with a Stochastic Replacement Model

This paper reports on a study initiated to check the validity of an existing six-monthly block replacement policy for a set of filling valves in a canning line. After dealing with inadequacies in the data and changing to a production-based time measure, the paper shows how a renewal function measure of the expected number of valve replacements was obtained and led to the conclusion that the current block replacement policy could not be justified.The possibility of an age-based replacement policy being of value remained. In order to model such a policy, it was necessary to reverse the usual analysis of renewal-type processes in that an estimate was required of the distribution function of time between renewals, given the renewal function.A finite optimal replacement age was found which depended upon the objective being to minimize a measure of downtime due to replacements, or operating costs attributable to replacements. Calculations were further complicated by part of the plant having a finite remaining life before being upgraded.     

Mechanistic aspects of reductions of allylic ethers and acetates with organocuprates

The rate of substitution to reduction has been investigated for reactions of three phenyl-substituted allylic ethers and the corresponding acetates with EtMgBr plus 10 or 25% copper(I) bromide in THF. It is found that the relative amount of reduction increases with increased electron delocalization in the postulated copper(III)-bound allyl ligand, and is also dependent on the nature of the leaving group; methoxy giving much more reduction product than acetoxy. Furthermore, for one acetate investigated there was more reduction at −65° than at −25°C. The results are interpreted in terms of relative binding strength of allyl ligands to a copper(III) intermediate.