Thermal behavior of Cu(II)-, Cd(II)-, and Hg(II)-exchanged montmorillonite complexedwith cysteine

The thermal behavior of montmorillonite and organically modified montmorillonite, both treated with heavy metal cations [Cu(II), Cd(II) and Hg(II)], was characterized via thermal analyses (TG, DTG and DTA) combined with evolved species gas mass spectrometry (MS-EGA), and X-ray diffraction at in situ controlled temperature (HTXRD). The reactions involving Cu(II)- and Cd(II)-montmorillonite samples are mostly related to H₂O and OH loss, unlike Hg(II)-montmorillonite, where effects associated to Hg(II) loss are also present. Finally reactions related to dehydration, dehydroxylation and to organic matter decomposition can be observed in montmorillonite samples treated with cysteine.     

Cyclodehydrogenation reactions to cyclopentafused polycyclic aromatic hydrocarbons

B3LYP/6-31G(d,p) electronic structure calculations are employed to elucidate the reaction mechanisms for the conversion of the alternant C(18)H(12) polycyclic aromatic hydrocarbon benzo[c]phenanthrene into the nonalternant C(18)H(10) PAHs cyclopenta[cd]pyrene and benzo[ghi]fluoranthene. Isomerization reactions such as 5/6-ring switching and hydrogen atom scrambling are analyzed. Bay region chemistry, involving the rupture of one benzene ring followed by the formation of a new five-membered ring, is also studied, together with the mechanism for the formation of an aryne. The rearrangement of the latter yields annelated cyclopentadienylidenecarbene, which is then trapped intramolecularly.     

Structure and stereochemistry of a new cytotoxic polychlorinated sulfolipid from Adriatic shellfish

A detailed analysis of the causative toxins contained in the hepatopancreas of toxic mussels from the northern Adriatic sea has been carried out. Along with some DSP (diarrhetic shellfish poisoning) type toxins, such as okadaic acid, yessotoxin, and their derivatives, which are involved in a number of human intoxications throughout the world, we have now isolated a new cytotoxin, a polychlorinated sulfolipid 1, whose gross structure has been elucidated by spectral analysis, including various 2D NMR techniques. The relative stereochemistry of 1 was elucidated by successful application of the J-based configuration analysis developed for acyclic compounds using carbon-proton spin-coupling constants ((2,3)J(C,H)) and proton-proton spin-coupling constants ((3)J(H,H)); its absolute stereochemistry was established by the Mosher method. Compound 1 possesses in vitro cytotoxicity against WEHI 164 and RAW 264.7 cells.     

Herbicide and degradate flux in the Yazoo River Basin

During 1996-1997, water samples were collected from five sites in the Yazoo River Basin and analysed for 14 herbicides and nine degradates. These included acetochlor, alachlor, atrazine, cyanazine, fluometuron, metolachlor, metribuzin, molinate, norflurazon, prometryn, propanil, propazine, simazine, trifluralin, three degradates of fluometuron, two degradates of atrazine, one degradate of cyanazine, norflurazon, prometryn, and propanil. Fluxes generally were higher in 1997 than in 1996 due to a greater rainfall in 1997 than 1996. Fluxes were much larger from streams in the alluvial plain (an area of very productive farmland) than from the Skuna River in the bluff hills (an area of small farms, pasture, and forest). Adding the flux of the atrazine degradates to the atrazine flux increased the total atrazine flux by an average of 14.5%. The fluometuron degradates added about 10% to the total fluometuron flux, and adding the norflurazon degradate flux to the norflurazon flux increased the flux by 82% in 1996 and by 171% in 1997.     

Model-based clustering of probability density functions

Complex data such as those where each statistical unit under study is described not by a single observation (or vector variable), but by a unit-specific sample of several or even many observations, are becoming more and more popular. Reducing these sample data by summary statistics, like the average or the median, implies that most inherent information (about variability, skewness or multi-modality) gets lost. Full information is preserved only if each unit is described by a whole distribution. This new kind of data, a.k.a. “distribution-valued data”, require the development of adequate statistical methods. This paper presents a method to group a set of probability density functions (pdfs) into homogeneous clusters, provided that the pdfs have to be estimated nonparametrically from the unit-specific data. Since elements belonging to the same cluster are naturally thought of as samples from the same probability model, the idea is to tackle the clustering problem by defining and estimating a proper mixture model on the space of pdfs. The issue of model building is challenging here because of the infinite-dimensionality and the non-Euclidean geometry of the domain space. By adopting a wavelet-based representation for the elements in the space, the task is accomplished by using mixture models for hyper-spherical data. The proposed solution is illustrated through a simulation experiment and on two real data sets.