Characterization of fatty acid esters of okadaic acid and related toxins in blue mussels (Mytilus edulis) from Norway

Marine algal toxins of the okadaic acid group can occur as fatty acid esters in blue mussels, and are commonly determined indirectly by transformation to their parent toxins by alkaline hydrolysis. Some data are available regarding the identity of the fatty acid esters, mainly of palmitic acid (16:0) derivatives of okadaic acid (OA), dinophysistoxin-1 (DTX1) and dinophysistoxin-2 (DTX2). Other fatty acid derivatives have been described, but with limited mass spectral data. In this paper, the mass spectral characterization of the [M-H](-) and [M+Na](+) ions of 16 fatty acid derivatives of each of OA, DTX1 and DTX2 is presented. The characteristic fragmentation of [M+Na](+) ions of OA analogues provided a useful tool for identifying these, and has not been described previously. In addition, a set of negative ion multiple reaction monitoring (MRM) methods was developed for direct determination of 16 fatty acid esters of OA, 16 fatty acid esters of DTX1 and 16 fatty acid esters of DTX2 in shellfish extracts. The MRM methods were employed to study the profiles of fatty acid esters of OA analogues in blue mussels and to compare these with fatty acid ester profiles reported for other groups of marine algal toxins.     

Structural reassignment of the alleged 6-hydroxy-1,2,4-triazine-3,5-(2H,4H)dione

The reaction of 6-amino-1,2,4-triazine-3,5-(2H,4H)clione with sodium hydroxide or nitrous acid has been shown to give 5-hydroxy-1,2,4-triazole-3-carboxylic acid instead of 6-hydroxy-1,2,4-triazine-3,5-(2H,4H)dione as reported in the literature. The triazolecarboxylic acid was also obtained from the aminotriazine and hydrochloric acid.     

A Catalytic Method for the Enantioselective Synthesis of α-Quaternary Ketones, α-Ketoesters and Aldehydes

A practical method for the efficient and enantioselective preparation of versatile ketones and aldehydes that contain an α-quaternary stereocenter is described. Reactions utilize simple carboxylic acid or ester starting materials, a monodentate chiral phosphine, and afford a variety of aryl, alkenyl, alkynyl, and alkyl-substituted ketone and aldehyde products in 25–94 % yield and 90 : 10 to >99 : 1 enantiomeric ratio. Reactions proceed by acyl substitution with in situ formed chiral allylic nucleophiles, and display selectivity and conversion dependence on a protic additive. The utility of the approach is demonstrated through several product transformations.     

Antibodies with broad specificity to azaspiracids by use of synthetic haptens

The development of general, sensitive, portable, and quantitative assays for the azaspiracid (AZA) class of marine toxins is urgently needed. Use of a synthetic hapten containing rings F-I of AZA to generate antibodies that cross-react with the AZAs via their common C28-C40 domain and use of these antibodies in ELISA and immunoaffinity columns are reported. This approach has many advantages over using intact azaspiracids (AZAs) derived from environmental samples or total synthesis as haptens for antibody development. A derivative of the levorotatory C28-C40 azaspiracid domain (1) was synthesized efficiently using a one-pot Staudinger reduction/intramolecular aza-Wittig reaction-imine capture sequence to form the H-I ring spiroaminal and a double intramolecluar hetero-Michael addition to assemble the F-G ring ketal. Conjugation of the hapten 1 to cBSA and immunization in sheep generated antibodies that recognized and bound to ovalbumin-conjugated 1 in the absence of AZA1. This binding was inhibited by 1 in a concentration-dependent manner. A mixture of AZA1, AZA2, AZA3, and AZA6 caused a degree of inhibition of antibody binding consistent with its total AZA content, rather than just its content of AZA1. This result suggests that the antibodies also have a similar affinity for AZA2, AZA3, and AZA6 as they do for AZA1 and that such antibodies are suitable for analysis of AZAs in shellfish samples.     

Blocks with nonabelian defect groups which have cyclic subgroups of index p

In representation theory of finite groups, one of the most important and interesting problems is that, for a p-block A of a finite group G where p is a prime, the numbers k(A) and ℓ(A) of irreducible ordinary and Brauer characters, respectively, of G in A are p-locally determined. We calculate k(A) and ℓ(A) for the cases where A is a full defect p-block of G, namely, a defect group P of A is a Sylow p-subgroup of G and P is a nonabelian metacyclic p-group M _n+1(p) of order p ⁿ⁺¹ and exponent p ⁿ for n \geqslant 2{n \geqslant 2}, and where A is not necessarily a full defect p-block but its defect group P = M _n+1(p) is normal in G. The proof is independent of the classification of finite simple groups.     

A model for optimal execution of atomic orders

Atomic Orders are the basic elements of any algorithm for automated trading in electronic stock exchanges. The main concern in their execution is achieving the most efficient price. We propose two optimal strategies for the execution of atomic orders based on minimization of impact and volatility costs. The first considered strategy is based on a relatively simple nonlinear optimization model while the second allows re-optimization at some time point within a given execution time. In both cases a combination of market and limit orders is used. The key innovation in our approach is the introduction of a Fill Probability function which allows a combination of market and limit orders in the two optimization models we are discussing in this paper. Under certain conditions the objective functions of both considered problems are convex and therefore standard optimization tools can be applied. The efficiency of the resulting strategies is tested against two benchmarks representing common market practice on a representative sample of real trading data.     

Existence and qualitative theory for stratified solitary water waves

This paper considers two-dimensional gravity solitary waves moving through a body of density stratified water lying below vacuum. The fluid domain is assumed to lie above an impenetrable flat ocean bed, while the interface between the water and vacuum is a free boundary where the pressure is constant. We prove that, for any smooth choice of upstream velocity field and density function, there exists a continuous curve of such solutions that includes large-amplitude surface waves. Furthermore, following this solution curve, one encounters waves that come arbitrarily close to possessing points of horizontal stagnation.We also provide a number of results characterizing the qualitative features of solitary stratified waves. In part, these include bounds on the wave speed from above and below, some of which are new even for constant density flow; an a priori bound on the velocity field and lower bound on the pressure; a proof of the nonexistence of monotone bores in this physical regime; and a theorem ensuring that all supercritical solitary waves of elevation have an axis of even symmetry.     

Novel optical techniques for measurements of light extinction,scattering and absorption by single aerosol particles

Aerosol particles play important roles in a broad range of scientific disciplines, from atmospheric chemistry and physics, to the delivery of fuels for combustion and drugs to the lungs, and extending to industrial processes such as spray drying. Measurements of the light extinction, scattering and absorption by ensembles of aerosol particles can be used to non‐intrusively characterise aerosol particle samples. However, such measurements often lead to ambiguity in interpreting the properties and processes occurring on individual particles. In this review, recent developments in the use of laser based techniques to isolate and manipulate single particles and to characterise them will be highlighted. In particular, the use of cavity ring down spectroscopy, Bessel beams and optical tweezers for investigating light extinction, scattering and absorption, respectively, will be considered. The prospects for using optical techniques to interrogate the fundamental processes occurring in aerosol at the single particle level are discussed.     

Temperature measurements by coherent Rayleigh scattering

We demonstrate, for the first time to our knowledge, the utility of coherent Rayleigh scattering (CRS) for temperature measurements in low-density gases and weakly ionized plasmas by measuring the translational temperature of neutral argon in a glow discharge. By analysis of the near-Gaussian spectral profile of the CRS signal, we determine temperatures with an uncertainty of 相似文献