Interpretation of CALUX results in view of the EU maximal TEQ level in milk

Analyses of dioxins in food have become increasingly important since the European Commission has enforced maximal toxic equivalent concentration (TEQ) levels in various food and feed products. Screening methodologies are usually used to exempt those samples that are below the maximum permitted limit and that can, therefore, be released to the market. In addition, one needs to select those samples that require confirmation of their dioxin TEQ level. When bioassays are used as screening tools, the interpretation of the obtained results should consider the higher variability and uncertainty associated with them. This paper explores the use of CALUX data as quantitative screening results. The validation of the method for the polychlorinated dibenzo-p-dioxins (PCDD)/F TEQ determination in milk samples is described with emphasis on the decision limit (CC) and the precision of the method. The decision limit amounts to 4.53 pg TEQ/g fat. Repeatability and within-lab reproducibility coefficients of variation are below 30%. The newly introduced parameter CC^* of 1.47 pg TEQ/g fat delimits with CC a range of suspicious results. These data are not significantly different from the maximum limit of 3 pg TEQ/g fat and should be confirmed by a confirmatory analytical method such as HRGC–HRMS.     

Rhodium(I) catalysis of cycloprop[a]acenaphthylene isomerizations

Cycloprop [a] acenaphthylene was found to rearrange to phenalene in the presence of rhodium dicarbonyl chloride dimer. Deuterium labeling of this molecule at C(7) (both exo and endo), at C(8), at C(7) (exo) and C(8) and at C(7) (exo), C(8), and C(8') indicated that the C(7) (exo) deuterium was migrating stereospecifically. Furthermore, all of the isotopic label present in the cycloprop[a]acenaphthylene was found statistically distributed over positions 1, 3, 4, 6, 7, and 9 of the phenalene product. Control experiments established the need of the catalyst, the inability to achieve rearrangement of the exo-7-methyl derivative, and the susceptibility of a monodeuterated phenalene for extensive isotopic scrambling in its own right when exposed to rhodium(I). These results have been interpreted on the basis of oxidative addition by rhodium(I) into the central bond of cycloprop[a]acenaphthylene from above the “flap”, followed by shifting of the C(7) (exo) hydrogen (or deuterium) to give a η³-allylrhodim-(III) complex. The experimental data further support a mechanism involving subsequent rearrangement of this intermediate around the periphery of the phenalene ring. This process which is otherwise degenerate is thought to be facilitated by the special electronic features of the phenalenyl system.     

Matter and light wave interferometry in gravitational fields

We consider the problem of finding the quantum mechanical phase associated with the propagation of a particle in a given external gravitational field, and conclude that it ism ds. In weak fieldsh this allows us to calculate the gravitationally induced phase on a freely traveling particle as 1/2 h P dx whereP is the ordinary momentum. This formula has the expected Newtonian limit and is then used to calculate effects in matter wave interferometry such as those due to gravity waves and the dragging of the ether frame by rotating bodies. Light wave interferometry is then considered and is shown to be also described by 1/2 h K dx , whereK is the wave vector of the light, and the integral is along the path of the ray. Matter and light wave interferometry are compared in various cases.A preliminary version of this work was presented at the Grenoble Workshop on Neutron Interferometry, June 1978.     

Variational approximations for renormalization group transformations

Approximate recursion relations which give upper and lower bounds on the free energy are described. Optimal calculations of the free energy can then be obtained by treating parameters within the renormalization equations variationally. As an example, a particularly simple lower bound approximation which preserves the symmetry of the Hamiltonian (the one-hypercube approximation) is described. The approximation is applied to both the Ising model and the Wilson-Fisher model. At the fixed point a parameter is set variationally and critical indices are calculated. For the Ising model the agreement with the exact results atd = 2 is surprisingly good, 0.1%, and is good atd=3 and evend=4. For the Wilson-Fisher model the recursion relation is reduced to a one-dimensional integral equation which can be solved numerically givingv=0.652 atd=3, or by expansion in agreement with the results of Wilson and Fisher to leading order in . The method is also used to calculate thermodynamic functions for thed = 2 Ising model; excellent agreement with the Onsager solution is found.Supported in part by the National Science Foundation under Grants Nos. MPS73-04886A01 and GH-41512 and by the Brown University Materials Research Laboratory supported by the National Science Foundation. M.C.Y. was supported by a grant from the Scientific and Technical Research Council of Turkey.     

Double Diastereoselection Operative During π-Facially Selective Addition of Chiral 1-Cyclopentenyllithium Reagents to (7R)-7-Methyl-7-Vinylbicyclo[3.2.0]Hept-2-En-6-One

Reaction of the title cyclobutanone with chiral cyclopentenyllithium reagents occurs exclusively from the convex face with low diastereoselectivity. Nonetheless, polycyclic networks with as many as nine stereogenic centers can be elaborated in very few steps.     

Polymers of Carbonic Acid. 16. High Molecular Weight Poly(Neopentanediol Carbonate) by Ring-Opening Polymerization with nBuSnCl3 or SnOct2 as Initiators

Abstract

Neopentanediol carbonate, NPC, was polymerized in bulk at 120°C. Either nBuSnCl₃ or Sn(II)2-ethylhexanoate (SnOct₂) were used as initiators. The reaction time and the monomer/initiator (M/I) ratio were varied. Polymerizations initiated with nBuSnCl₃ were more rapid and yielded higher molecular weights (M _n up to 150,000 and M _w up to 270,000). Furthermore, the molecular weights were almost independent of the M/I ratio, provided the reaction time was optimized. In contrast, the molecular weights of the SnOct₂-initiated polymers paralled the M/I ratios more or less. This finding and the ¹H-NMR spectra suggest that stoichiometric reactions between monomer and SnOct₂ take place, yielding polymers with covalently bound octoate and OH endgroups. Finally, the polymerizability of NPC recrystallized from CCl₄ or from tetrahydrofuran was compared. No significant difference was found when nBuSnCl₃ was used as initiator, whereas in the case of SnOct₂ a difference was observed. NPC recrystallized from CCl₄ polymerized more rapidly and gave higher molecular weights than NPC recrystallized from THF.     

Weak Liouville-Arnol′d Theorems and Their Implications

This paper studies the existence of invariant smooth Lagrangian graphs for Tonelli Hamiltonian systems with symmetries. In particular, we consider Tonelli Hamiltonians with n independent but not necessarily involutive constants of motion and obtain two theorems reminiscent of the Liouville-Arnol′d theorem. Moreover, we also obtain results on the structure of the configuration spaces of such systems that are reminiscent of results on the configuration space of completely integrable Tonelli Hamiltonians.     

Adamantyl ferrocene derivatives: Antioxidant abilities and effects on model lipid membranes

A series of homoannularly and heteroannularly substituted adamantyl ferrocene derivatives has been synthesized and their effects on membrane fluidity were investigated using liposomes as the membrane models. The liposome formulations of adamantyl ferrocene derivatives were characterized by using dynamic light scattering, differential scanning calorimetry and fluorescence anisotropy measurements. It was demonstrated that adamantyl ferrocene derivatives incorporated into the liposome significantly affect the structure of the lipid bilayer. The results of the study have revealed that adamantyl ferrocene derivatives, compounds 9 – 12, partition into the hydrophobic/hydrophilic interface of the membrane, causing a significant decrease in membrane fluidity. The antioxidant potential of synthesized compounds was assessed with DPPH method and it was shown that the examined compounds possess certain antioxidant activity.