Determination of rotenone residues in raw honey by solid-phase extraction and high-performance liquid chromatography

A method for determining residues of the insecticide rotenone in raw-honey by high-performance liquid chromatography (HPLC) is described. To extract the residues, organic solvents such as ethyl acetate, n-hexane/dichloromethane and solid-phase extraction with octadecylsilane cartridges or Florisil packed columns were tested. Determination was carried out by reversed-phase HPLC using acetonitrile-buffer phosphate (pH 7) (60:40, v/v) as mobile phase and detection at 210 nm. Although the data showed that the two extraction methods were able to isolate the pesticide residues, the extraction on octadecylsilane cartridges was preferred due to its simplicity and higher recovery. Recoveries depended strongly on the fortification level for the two extraction procedures. Practical determination limits of 0.015 mg/kg were obtained. In the analysis of honeys, from beehives treated with rotenone at therapeutical doses for 1 month, residual amounts below 0.2 mg/kg were found.     

Global minima of (C60)nCa, (C60)nF and (C60)nI clusters

Likely candidates for the lowest potential energy minima of (C₆₀)_nCa²⁺, (C₆₀)_nF⁻ and (C₆₀)_nI⁻ clusters are located using basin-hopping global optimisation. In each case, the potential energy surface is constructed using the Girifalco form for the C₆₀ intermolecular interaction, an averaged Lennard–Jones C₆₀–ion interaction, and a polarisation potential, which depends on the first few non-vanishing C₆₀ multipole polarisabilities. We find that the ions generally occupy the interstitial sites of a (C₆₀)_n cluster, the coordination shell being tetrahedral for Ca²⁺ and F⁻. The I⁻ ion has an octahedral coordination shell in the global minimum for (C₆₀)₆I⁻, however for 12  n  8 the preferred coordination geometry is trigonal prismatic.     

Productive trapping of NAD-type radicals. Non-biomimetic reduction of pyridinium salts

One-electron reduction of pyridinium salts (NAD+ analogues) generates dihydropyridyl radicals which may then be engaged in radical addition processes to regioselectively form gamma-substituted dihydropyridines.     

Catalytic activity of dodecacarbonyltetracobalt in aqueous media: a "greening" of the Pauson-Khand reaction

The unprecedented reactivity of Co(4)(CO)(12) with enynes under aqueous conditions, representing the development of a mild and simple aqueous-phase cobalt-catalyzed PK reaction protocol, is described herein.     

Applications of electrokinetic phenomena in materials science

The discovery of electrokinetic phenomena by Reuss in 1808 and further investigations that gave rise to the concept of the electrical double layer have played an important role in the understanding of colloidal stability. Electrokinetic phenomena are a family of effects in which a liquid moves tangentially to a charged surface. Well-known phenomena of this kind are electrophoresis, electro-osmosis, streaming potential, and sedimentation potential. A review of parameters involved in the electrochemistry of suspensions is made. The practical applications of these phenomena have become widespread in a broad range of research fields such as biomaterials, biofilms, electrokinetic waste remediation, membranes, nuclear and fossil-fired power plants, adhesive and sealant science, and concrete science. The purpose of this paper is to provide an overview of electrokinetic phenomena and their application to surface modification and characterization in a large number of research fields such as corrosion and protection processes, environmental remediation (soil and sediments, transport processes, inorganic pollutants, solid particle surfaces, filter membranes, and biosorption phenomena), cement-based systems, and biological systems.     

Synthesis of macrocycles via cobalt-mediated [2 + 2 + 2] cycloadditions

We investigated the formation of macrocycles from alpha,omega-diynes in cobalt-mediated co-cyclotrimerization reactions. Long-chain alpha,omega-diynes underwent metal-mediated [2 + 2 + 2] cycloadditions with nitriles, cyanamides, or isocyanates in the presence of CpCo(CO)2 (Cp = cyclopentadienide) to yield pyridine-containing macrocycles, i.e., meta- and para-pyridinophanes, such as 5m/5p, 35m/35p, and 41m/41p. The regioselectivity of these reactions was affected by the length and type of linker unit between the alkyne groups, as well as by certain stereoelectronic factors. An analogous alpha,omega-cyano-alkyne, 28, combined with an alkyne to yield two isomeric meta-pyridinophanes, such as 5m and 29m, and an ortho cycloadduct (benzannulation product), such as 29o. We developed a reaction protocol for these cobalt-based [2 + 2 + 2] cycloadditions that involves markedly improved conditions such that this process offers a convenient, flexible synthetic approach to macrocyclic pyridine-containing compounds. For example, diyne 6 reacted with p-tolunitrile in 1,4-dioxane to give 7p and 7m (7:1 ratio) in 87% yield at a moderate temperature of ca. 100 degrees C in 24 h without photoirradiation or syringe-pump addition. Isocyanates were also effective reactants, as exemplified by the formation of 44p almost exclusively (44p:44m > 50:1) in 64% yield from diyne 8 and 2-phenylethylisocyanate. By using this improved protocol we were able to co-cyclotrimerize long-chain alpha,omega-diynes with alkynes in certain cases to demonstrate a successful macrocyclic variant of the Vollhardt reaction. For instance, diyne 6 reacted with dipropylacetylene to give paracyclophane 57p and benzannulene 57o (2:1 ratio) in 29% yield.     

Self-similar sets with optimal coverings and packings

We prove that if a self-similar set E in Rn with Hausdorff dimension s satisfies the strong separation condition, then the maximal values of the Hs-density on the class of arbitrary subsets of Rn and on the class of Euclidean balls are attained, and the inverses of these values give the exact values of the Hausdorff and spherical Hausdorff measure of E. We also show that a ball of minimal density exists, and the inverse density of this ball gives the exact packing measure of E. Lastly, we show that these elements of optimal densities allow us to construct an optimal almost covering of E by arbitrary subsets of Rn, an optimal almost covering of E by balls and an optimal packing of E.     

Physical properties of small water clusters in low and moderate electric fields

Likely candidates for the lowest minima of water clusters (H(2)O)(N) for N ≤ 20 interacting with a uniform electric field strength in the range E ≤ 0.6 V/? have been identified using basin-hopping global optimization. Two water-water model potentials were considered, namely TIP4P and the polarizable Dang-Chang potential. The two models produce some consistent results but also exhibit significant differences. The cluster internal energy and dipole moment indicate two varieties of topological transition in the structure of the global minimum as the field strength is increased. The first takes place at low field strengths (0.1 V/? 10) usually forming helical structures.     

Chemical analysis of vinyl-crosslinked poly(dimethylsiloxane) model networks and use of the resulting structural information in the interpretation of their elastomeric properties

Model networks were prepared by selective crosslinking through vinyl groups occurring as either chain ends or as side-groups on a poly(dimethylsiloxane) backbone. Iodometric titrations were used to determine the number of unreacted groups, thereby providing detailed information on the completeness of the reactions and the structure of the resulting networks. The end-linking reaction of the vinyl-terminated chains was generally found to be at least 95% complete. In the case of very high junction functionality, however, the extent of reaction was significantly lower, presumably because of steric interferences in the vicinity of the junctions, as was concluded in a previous investigation. Lower extents of reaction were also found in the case of vinyl groups located along the chains, probably because such groups are constrained by two chain sequences instead of one. The equilibrium elastomeric properties of both types of networks were interpreted using the structural information thus obtained and were found to be in good agreement with previous experimental results. They are also in satisfactory agreement with theory, without introduction of the highly questionable assumption of large contributions from interchain entanglements.