Inductively coupled plasma mass spectrometry and atomic emission spectrometry coupled to high-performance liquid chromatography for speciation and detection of organotin compounds

Inductively coupled plasma mass spectrometry (ICP/MS) is utilized as a detector for several organotin species separated by high-performance liquid chromatography. Detection limits obtained by ICP/MS are 3 orders of magnitude lower than those obtained with inductively coupled plasma atomic emission spectrometry (ICP/AES) detection under the same chromatographic conditions. Chromatographic detection limits are higher than conventional solution nebulization for the same compound by a factor of 20. Ion-exchange chromatography yields linear response over 3 orders of magnitude, while ion pair chromatography gives a linear response of only 2 orders of magnitude as a result of poor resolution. The relative standard deviation for the injection of 20 ng of tin compounds is less than 10%.     

Extraction and detection of arsenicals in seaweed via accelerated solvent extraction with ion chromatographic separation and ICP-MS detection

An accelerated solvent extraction (ASE) device was evaluated as a semi-automated means of extracting arsenicals from ribbon kelp. The effect of the experimentally controllable ASE parameters (pressure, temperature, static time, and solvent composition) on the extraction efficiencies of arsenicals from seaweed was investigated. The extraction efficiencies for ribbon kelp (approximately 72.6%) using the ASE were fairly independent (< 7%) of pressure, static time and particle size after 3 ASE extraction cycles. The optimum extraction conditions for the ribbon kelp were obtained by using a 3 mL ASE cell, 30/70 (w/w) MeOH/H2O, 500 psi (1 psi = 7 KPa), ambient temperature, 1 min heat step, 1 min static step, 90% vol. flush, and a 120 s purge. Using these conditions, two other seaweed products produced extraction efficiencies of 25.6% and 50.5%. The inorganic species present in the extract represented 62.5% and 27.8% of the extracted arsenic. The speciation results indicated that both seaweed products contained 4 different arsenosugars, DMA (dimethylarsinic acid), and As(V). One seaweed product also contained As(III). Both of these seaweed products contained an arsenosugar whose molecular weight was determined to be 408 and its structure was tentatively identified using ion chromatography-electrospray ionization-mass spectrometry/mass spectrometry (IC-ESI-MS/MS).     

Sampling Eulerian orientations of triangular lattice graphs

We consider the problem of sampling from the uniform distribution on the set of Eulerian orientations of subgraphs of the triangular lattice. Although Mihail and Winkler (1989) showed that this can be achieved in polynomial time for any graph, the algorithm studied here is more natural in the context of planar Eulerian graphs. We analyse the mixing time of a Markov chain on the Eulerian orientations of a planar graph which moves between orientations by reversing the edges of directed faces. Using path coupling and the comparison method we obtain a polynomial upper bound on the mixing time of this chain for any solid subgraph of the triangular lattice. By considering the conductance of the chain we show that there exist non-solid subgraphs (subgraphs with holes) for which the chain will always take an exponential amount of time to converge. Finally, we show that the problem of counting Eulerian orientations remains #P-complete when restricted to planar graphs (Mihail and Winkler had already established this for general graphs).     

An investigation of the chemical stability of arsenosugars in basic environments using IC-ICP-MS and IC-ESI-MS/MS

This paper evaluates the chemical stability of four arsenosugars using tetramethylammonium hydroxide (TMAOH) as an extraction solvent. This solvent was chosen because of the near quantitative removal of these arsenicals from difficult to extract seafood (oysters and shellfish). Four arsenosugars (3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropylene glycol--As(328), 3-5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropanesulfonic acid--As(392), 3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropyl hydrogen sulfate--As(408), and 3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropyl-2,3-hydroxypropyl phosphate--As(482)) were evaluated. The stability of these four arsenosugars were studied independently in a solution of 2.5% TMAOH at 60 degrees C over a period of up to 8 h. Two arsenosugars, As(328) and As(392), were found to be relatively stable in this solution for up to 8 h. However, As(408) and As(482) formed detectable quantities of dimethylarsinic acid (DMAA) and As(328) within 0.5 and 2 h, respectively. It was found that 97% of As(408) degrades after 8 h of treatment producing 3.4 times as much DMAA as As(328). This is contrary to As(482), which produces 13 times as much As(328) as DMAA and only 37% of the As(482) was converted by the 8 h treatment at 60 degrees C. These degradation products led to the investigation of weaker TMAOH extraction solvents. Three different concentrations (2.5%, 0.83% and 0.25%) were used to determine the effect of TMAOH concentration on the degradation rate of As(408). By reducing the TMAOH concentration to 0.83%, the conversion of the arsenosugar to As(328) and DMAA is nearly eliminated (less than 5% loss). Arsenosugars, As(408) and As(482), were also studied in 253 mM NaOH to verify the degradation products. The NaOH experiments were conducted to investigate a possible hydroxide based reaction mechanism. Similar degradation plots were found for each arsenosugar when compared to the 2.5% TMAOH data. A mechanism has been proposed for the formation of As(328) from As(408) and As(482) in base via an SN2 reaction (hydroxide attack) at the side chain carbon adjacent to the inorganic ester. The formation of DMAA is observed in all arsenosugars after prolonged exposure. This probably occurs via an SN2 attack at the arsenic atom.     

Dimethylthioarsinic anhydride: a standard for arsenic speciation

Dimethylthioarsinic acid (DMTA^V) has recently been identified in biological, dietary and environmental matrices. The relevance of this compound to the toxicity of arsenic in humans is unknown and further exposure assessment and metabolic studies are difficult to conduct because of the unavailability of a well characterized standard. The synthesis of DMTA^V was accomplished by the reaction of dimethylarsinic acid (DMA^V) with hydrogen sulfide. The initial reaction product produced is DMTA^V but multiple products over the course of the reaction are also observed. Therefore, a chromatographic separation was developed to monitor the reaction progress via LC-ICP-MS. In this synthesis, conversion of DMA^V to DMTA^V was not taken to completion to avoid the production of side products. The product was isolated from the starting material by standard organic techniques. Single crystal diffraction demonstrated that solid DMTA^V is present in the form of the oxygen-bridged dimethylthioarsinic anhydride. Dissolution of the anhydride in water produces the acid form of DMTA^V and the aqueous phase DMTA^V provided a characteristic molecular ion of m/z 155 by LC-ESI-MS. The synthesis and isolation of dimethylthioarsinic anhydride provides a stable crystalline standard suitable for identification, toxicological study and exposure assessment of dimethylthioarsinic acid.     

Charge transfer states in the photophysics and photochemistry of polyimides and related phthalimides

Polyimides such as 6F-6F and 6F-ODA and model N-arylphthalimides are stabilized against photooxidative degradation by their electron donor (D) – acceptor (A) character. We have investigated the precise origin(s) of this effect using D and A substituents on the N-aryl groups of these compounds. The lowest excited singlet state (S₁) of N-arylphthalimides is an intramolecular charge transfer (ICT) state. A nominally twisted compound, N-(2-t-butylphenyl)phthalimide, shows greatly diminished CT absorption and blue-shifted fluorescence with reduced quantum yield when compared to the 4-t-butyl isomer with an identical N-aryl donor group. It therefore seems unnecessary to claim that the ICT state of phthalimides is a so-called TICT state. Quantum yield and fluorescence lifetime measurements lead to the conclusion that enhanced internal conversion from the ICT state (S₁) to the ground state makes a significant contribution to photostabilization of these compounds by suppressing formation of the reactive triplet state. Further stabilization of polymer films may be afforded by triplet state self-quenching which is enhanced for 6F-ODA in increasingly poor solvents. N-alkylarylphthalimides in which the aryl and phthalimide groups are not formally conjugated but, rather, joined by flexible methylene ‘spacers’, exhibit a different kind of fluorescent intramolecular CT singlet state whose formation can also stabilize these compounds by suppressing triplet state formation.     

THE PHOTOPHYSICS AND PHOTOCHEMISTRY OF THE NEAR-UV ABSORBING AMINO ACIDS–I. TRYPTOPHAN AND ITS SIMPLE DERIVATIVES

Abstract— The photophysics and photochemistry of tryptophan and its simple derivatives is comprehensively reviewed with special emphasis on excitation by near-UV radiation. Topics explicitly discussed include the origins of large Stokes shifts in the fluorescence spectra, photoionization, the puzzle of multiple tryptophan fluorescence decay time, photochemical reactions in the presence and absence of oxygen, and the possible mechanisms of these reactions. A separate section reviews the photosensitizing properties of N-formylkynurenine, an important photooxidation product of tryptophan.     

Mammalian Alkaloids: O-methylation of (S)- and (R)-dideoxynorlaudanosoline-1-carboxylic acid by catechol O-methyltransferase and identification of a yellow pigment obtained at physiological pH

O-Methylation of optically active 3′,4′-dideoxynorlaudanosoline-l-carboxylic acids 1 with O-methyltransferase in vitro afforded almost exclusively the 7-O-methylated acids 3 . A similar result was obtained with the yellow quinonemethide 4A obtained from 1 at neutral or slightly alkaline pH by oxidative decarboxylation and affording the 3,4-dihydroisoquinoline 15 on methylation with catechol O-methyltransferase (COMT). The structure of quinonemethide 4A was determined on the basis of spectral data, by its conversion into isoquinolines of established structure, and by synthesis. Quinonemethide 4A was found to be a weak inhibitor of monoamine oxidase A (MAO A) but not a substrate. Nonenzymatic oxidative decarboxylation of dopamine-derived tetrahydroisoquinoline-l-carboxylic acids to quinonemethides may be a major factor in biochemical experimentation and should be considered in the interpretation of data.