Analysis of cyanobacterial toxins by hydrophilic interaction liquid chromatography-mass spectrometry

The combination of hydrophilic interaction liquid chromatography with electrospray mass spectrometry (HILIC-MS) has been investigated as a tool for the analysis of assorted toxins produced by cyanobacteria. Toxins examined included saxitoxin and its various analogues (1-18), anatoxin-a (ATX-a, 19), cylindrospermopsin (CYN, 20), deoxycylindrospermopsin (doCYN, 21), and microcystins-LR (22) and -RR (23). The saxitoxins could be unequivocally detected in one isocratic analysis using a TSK gel Amide-80 column eluted with 65% B, where eluent A is water and B is a 95% acetonitrile/water solution, both containing 2.0 mM ammonium formate and 3.6 mM formic acid. The analysis of ATX-a, CYN and doCYN required 75% B isocratic. Simultaneous determination of 1-21 was also possible by using gradient elution. HILIC proved to be suitable for the analysis of microcystins, but peak shape was not symmetric and it was concluded that these compounds are best analysed using existing reversed-phase methods. The HILIC-MS method was applied to the analysis of field and cultured samples of Anabaena circinalis and Cylindrospermopsis raciborskii. In general, the method proved quite robust with similar results obtained in two different laboratories using different instrumentation.     

Platinum Carbonyl Clusters Chemistry: Four Decades of Challenging Nanoscience

The state of art of the chemical, spectroscopic and structural characterization of platinum carbonyl clusters is reviewed. We begin by enlightening the fundamental contribution given to this chemistry of two great scientists: Paolo Chini and Larry Dahl, two without equal maestros of science and life. We then focus the main body of this review on the challenge represented by studying molecular ions already belonging to the nano regime by size almost 50 years ago, and the challenges their chemistry continues to present also nowadays. In detail, the possible reasons which enable the [Pt_3n (CO)_6n ]^2? oligomers to grow up to n = 10, and why the oligomers with n > 5 may self-assemble in infinite molecular conductor wires are suggested. The interplay between the CO/Pt_surface ratios and electronic effects in driving the platinum cluster from pseudo one- to tri-dimensional globular structures, often representing chunks of the fcc metal lattice or interpenetrated pentagonal prisms and icosahedra, is examined by means of two significant examples. The nanocapacitor behavior of most high-nuclearity carbonyl clusters is briefly recalled and is confirmed by most recent results. The size-induced transition of their metal kernels from insulator to semiconductor and the expected consequences of their eventual transition to a metallic state are also discussed. Finally, we conclude by commenting the present lack of Pt cluster interstitially lodging a main group element and not yet quantitatively-assessed aggregation phenomena in solution, perhaps peculiar of ionic salts of carbonyl clusters, which could make undetectable the NMR signal of any spin-active nuclei beyond a cluster nuclearity of ca. 20–25.     

A convenient preparation of 3-isopropyl-1-methylcyclopentylmethanol and 1-isopropyl-3-methylcyclopentylmethanol via Favorskii rearrangement

The Favorskii rearrangement of suitable α-chloro derivatives of commercially available (+)- and (−)-carvone, and (−)-menthone served efficiently to prepare the title compounds featuring delicious fruity, floral olfactory notes.     

A new look at XRD patterns of archaeological ceramic bodies

In this paper, the general rules of phase transformations in calcareous clay bodies during firing were used to estimate the equivalent firing temperature (EFT) of seventeenth century polychrome Persian haft rang tiles based on their X-ray diffraction (XRD) patterns. The novelty of this work is, however, that it handles the XRD patterns of archaeological clay bodies with principal component analysis (PCA) in order to have a new look at their firing and thermal behaviour. Statistically handling the XRD patterns, different clusters were discriminated in the clay bodies whose mineralogical composition showed various proportions of amorphous and quartz contents. The results showed interesting trends in the different clusters in terms of the EFT, quartz content and the density of the bodies. The present work uses PCA to have a new look at XRD patterns of archaeological clay bodies and, moreover, to interpret the PCA results in order to estimate the EFT of a large number of archaeological clay bodies.     

Effects of temperature on the triplet behavior of the styrylphenanthrene isomers

The properties of the triplet state of five styrylphenanthrene (StPh) trans isomers were studied in 2-methyltetrahydrofuran (MTHF) as a function of temperature. At room temperature the T-T absorption was observed only for 4- and 9-StPh, while under these conditions 1-, 2-, and 3-StPh have too low a quantum yield of triplet formation (Φ_T <0.02); their T-T absorption spectra were obtained at low temperature. Φ_T of 1- and 2-StPh increases more than tenfold on going from 293 to 77 K, and the triplet lifetime (τ_T) increases by four orders of magnitude and approaches values of 5–40 ms at 77 K. The change in τ_T is explained in terms of an equilibrium between trans and perpendicular (perp) conformations of the lowest triplet state in fluid solution and temperature and viscosity effects on the trans → perp rotation. Evidence is presented for the existence of two conformeric trans triplet states of 3-StPh at 77 K. Semi-empirical calculations were performed to obtain the energy of the triplet state, the wavelengths of several T-T absorption maxima (λ_T), and the oscillator strength. The calculated λ_T values coincide with those measured in n-hexane.     

Direct detection of yessotoxin and its analogues by liquid chromatography coupled with electrospray ion trap mass spectrometry

A liquid chromatography mass spectrometry (LC-MS) method is proposed for the sensitive, specific and direct detection of yessotoxin and its analogues, marine biotoxins which are associated with diarrhetic shellfish poisoning (DSP) and which have been found in the North Adriatic sea since 1995. The LC-MS method provided a detection limit of 70 pg for yessotoxin in full scan mode and was applied to determine the toxic profiles of a number of extracts or partially purified fractions of toxic mussels collected along the Emilia Romagna coasts (Italy) in the period 1995-1999. Detection of a desulfo-yessotoxin derivative from Mytilus galloprovincialis collected in 1998 is also reported.     

Isolation and structure elucidation of ovatoxin-a, the major toxin produced by Ostreopsis ovata

Since 2005, the benthic dinoflagellate Ostreopsis cf. ovata has bloomed across the Mediterranean basin, provoking serious toxic outbreaks. LC/MS studies have identified a number of palytoxin-like compounds, termed ovatoxins, along with trace amounts of putative palytoxin as the causative agents of the O. cf. ovata -related human sufferings. So far, any risk assessment for ovatoxins as well as establishment of their allowance levels in seafood has been prevented by the lack of pure toxins. The present paper reports on the isolation, NMR-based structural determination, and preliminary mouse lethality evaluation of ovatoxin-a, the major toxic compound contained in O. cf. ovata extracts. Availability of pure ovatoxin-a will open the double prospect of fully evaluating its toxicity and preparing reference standards to be employed in LC/MS quantitative analyses. Elucidation of ovatoxin-a's complex structure will ultimately herald the understanding of the molecular bases of ovatoxins bioactivity.