A system for defining reference materials applicable to all food matrices

Recently the subcommittee on Food Definition of the AOAC INTERNATIONAL Task Force on Methods for Nutrition Labeling proposed a Food Matrix Organizational System [4] to systematically judge the applicability of collaboratively studied methods over a range of food matrices. This system describes a food matrix by its location in one of nine sectors in a triangle, with each point of the triangle defined as representing 100% and the opposite side representing 0% of the normalized contents of each of three major components of FAT, PROTEIN and CARBOHYDRATE. Foods falling within the same sector would be chemically similar and thus should behave in a similar analytical manner. This same scheme can be used to select one or two food matrices representing each sector, for development of a series of reference materials representing all foods. The list of 5250 foods contained in the USDA Nutrient Data Base for Standard Reference has been sorted and matched to this schematic to determine the scope of the selection process. In addition the list of foods in the USDA Data Base for Food Consumption Surveys has been examined. Results and progress of this selection process are reported.     

A convenient one-pot synthesis of 1,8-naphthyridones

In this paper, we disclose an efficient one-pot procedure for the preparation of substituted 1,8-naphthyridin-4-one analogues. Previous efforts to effect this type of transformation were complicated by the formation of benzene tricarboxylate. Via the use of excess base, the impurity formation was completely inhibited. This allowed for the clean preparation of the desired intermediate and subsequent formation of naphthyridone analogues in a single flask, which could then be crystallized directly from the reaction mixture in good yield and high purity.     

Solvent and substitution effects upon the phosphorescent triplet state of carbonyl pyridines

The effects of perturbing nitrogen upon localized triplet excitations are observed for several carbonyl pyridines. Conventional and pulse optically detected magnetic resonance (ODMR) techniques are used to characterize the spin-relaxation processes in these aromatic carbonyl molecules.     

Self aggregation of binary mixtures of sodium dodecyl sulfate and polyoxyethylene alkyl ethers in aqueous solution

The mixed micelles of sodium dodecyl sulphate (SDS) with Brij35 and Brij 97 were studied separately by fluorescence measurement using pyrene as fluorescent probe. In the range of 0–1.0 mole fraction (X) of added SDS to Brij solutions, the cmc value of the mixed micelles varies from 0.085 to 8 mmol with Brij 35 and 0.04 to 8 mmol with Brij 97. The aggregation number also changes. A measure of the stability of mixed micelles is also presented. The interaction parameter ₁₂ and the chain–chain contribution parameter (B₁) are extracted from the analysis of the results. This parameter B₁ is related to the standard free energy change associated with the introduction of one ionic species into a nonionic micelle coupled with the release of one nonionic species from the micelle. The clouding behaviour of Brij 97 in the presence of SDS was investigated and the associated thermodynamic parameters of clouding were generated and discussed.     

Comparison of micro- and mesoporous inorganic materials in the uptake and release of the drug model fluorescein and its analogues

The uptake of the three species of the drug model fluorescein (fluorescein sodium salt (FNa), fluorescein free acid (F), and fluorescein diacetate (FDA)) by zeolite NaX and the mesoporous zeotype MCM-41 was investigated as well as their release rates into solutions at pH 7 and pH 4.5. UV/Vis analysis was carried out at a wavelength of 490 nm. Uptakes of the sodium salt of 9 % for zeolite X and 14 % for MCM suggest little penetration of the pores. The use of ethanol as the loading solvent for F resulted in little uptake for both zeolitic materials due to the successful competition of the ethanol for binding sites. Use of acetone (weaker proton acceptor) as loading solvent significantly improved the uptake of F to 17 % and 12 % for zeolite X and MCM, respectively, whilst the uptake of FDA in acetone increased still further to 22 % and 17 % for zeolite X and MCM, respectively. Generally there was a large initial release of the fluorescein analogues from the surface of the zeolites with very little further increase over time. The prescence of an esterase enzyme in the release medium of FDA tripled the release from MCM to 15 % but left the release from zeolite X unaffected at 6 %. The results obtained show that uptake of fluorescein and its analogues is dependent on the loading solvent used, the amount released is influenced by not only the solvent but the pH and the presence of enzymes in the release medium.     

Ligand-switchable directing effects of tethered alkenes in nickel-catalyzed additions to alkynes

Nickel-catalyzed reductive couplings of aldehydes with alkynes that contain tethered olefins are described, in which the degree and sense of regioselectivity are controlled by the length of the tether and the presence or absence of an additive. When the alkyne and alkene are separated by four bonds, very high (>95:5) regioselectivities are observed. Use of a monodentate phosphine as an additive leads to formation of the opposite regioisomer in equal and opposite selectivity (5: >95). These results provide strong evidence for an interaction between the remote alkene and the metal center during the regioselectivity-determining step and suggest that reactions with and without an additive proceed via fundamentally distinct mechanisms.     

Molecular ordering and 2D conductivity in ultrathin poly(3-hexylthiophene)/gold nanoparticle composite films

This paper reports the first comparison of the structure and electrical conductivity properties of spin cast (SC) and Langmuir-Schaeffer (LS) films of regioregular poly(3-hexylthiophene) (P3HT). In addition, the effect of incorporating highly monodisperse Au nanoparticles (NPs), with a core diameter of approximately 5 nm, into SC and LS P3HT films is described. A detailed picture of molecular organization in the films has been obtained using ultraviolet-visible absorption spectroscopy, atomic force microscopy, field-emission scanning electron microscopy, X-ray diffraction, and X-ray reflectivity. Film morphology was correlated with pseudo-two-dimensional conductivity measured using scanning electrochemical microscopy, with P3HT in the semiconducting regime. It was found that SC films, which were slightly thicker than those formed with the LS technique, exhibited greater organization. This resulted in an order of magnitude higher lateral conductivity for the SC films. Inclusion of Au NPs (50 wt %) into both SC and LS films resulted in the formation of uniform and relatively flat (rms roughness approximately 1 nm) composite films. Surprisingly, the addition of NPs did not disrupt the characteristic crystal structure found for the native P3HT films. The effect of Au NPs on film lateral conductivity was found to be determined by the distribution of Au NPs within the polymer, which varied significantly between SC and LS films. Whereas Au NPs aggregated into hexagonally packed clusters in SC films, NPs in LS films were predominantly uniformly distributed between the lamella bilayer. It was found that, while the inclusion of Au NPs caused the lateral conductivity to decrease in SC films, in LS films, the lateral conductivity increased by a factor of 2.     

Chemical reactions of double bonds in activated carbon: microwave and bromination methods

The reaction of localised C[double bond, length as m-dash]C bonds on the surface of activated carbons has been shown to be an effective method of chemical modification especially using microwave-assisted reactions.     

Macrocycles in the construction of acyclic stereochemistry

The conformations of macrocyclic intermediates provide a useful medium through which distant chiral centers may control chemical reactions. In this paper, we show that macrocycles made by cyclization of simple acyclic starting materials with an auxiliary spacer may be used to prepare stereochemically complex acyclic products.     

Visible and near-IR luminescence via energy transfer in rare earth doped mesoporous titania thin films with nanocrystalline walls

Selected photoluminescence in the wavelength range of 600-1540 nm is generated by energy transfer from a light-gathering mesostructured host lattice to an appropriate rare earth ion. The mesoporous titania thin films, which have a well-ordered pore structure and two-phase walls made of amorphous titania and TiO₂ nanocrystallites, were doped with up to 8 mol% lanthanide ions, and the ordered structure of the material was preserved. Exciting the titania in its band gap results in energy transfer and it is possible to observe photoluminescence from the crystal field states of the rare earth ions. This process is successful for certain rare earth ions (Sm³⁺, Eu³⁺, Yb³⁺, Nd³⁺, Er³⁺) and not for others (Tb³⁺, Tm³⁺). A mechanism has been proposed to explain this phenomenon, which involves energy transfer through surface states on titania nanocrystals to matching electronic states on the rare earth ions.