Radical-mediated dehydrogenation of bile acids by means of hydrogen atom transfer to triplet carbonyls.

The aim of the present paper is to explore the potential of radical-mediated dehydrogenation of bile salts (BSs), which is reminiscent of the enzymatic action of hydroxysteroid dehydrogenase enzymes (HSDH). The concept has been demonstrated using triplet carbonyls that can be efficiently generated upon selective UVA-excitation. Hydrogen atom transfer (HAT) from BSs to triplet benzophenone (BP) derivatives gave rise to radicals, ultimately leading to reduction of the BP chromophore with concomitant formation of the oxo-analogs of the corresponding BSs. The direct reactivity of triplet BP with BSs in the initial step was evaluated by determining the kinetic rate constants using laser flash photolysis (LFP). The BP triplet decay was monitored (λmax = 520 nm) upon addition of increasing BS concentrations, and the obtained rate constant values indicated a reactivity of the methine hydrogen atoms in the order of C-3 < C-12 < C-7. The steady-state kinetics of the overall process, monitored through the disappearance of the typical BP absorption band at 260 nm, was much faster under N2 than under O2, also supporting the role of the oxygen-quenchable triplet in the dehydrogenation process. Furthermore, irradiation of deaerated aqueous solutions of sodium cholate in the presence of KPMe provided the oxo-analogs, 3[O],7[O]-CA, 3[O]-CA and 7[O]-CA, arising from the HAT process.

Bridging the opposite chemistries of tantalum and tungsten polyoxometalates.

The disparate solubility, redox activity, and pH stability of the group V and group VI polyoxometalates (POMs) confer very different functionality on these species, and tailoring cluster properties by varying the ratio of group V to group VI metals poses both an opportunity and a synthetic challenge. A classic series of studies reported over 40 years ago provided some insight into W/Nb POMs, from which researchers have built on to date. However, the analogous W/Ta series has never been addressed in a systematic manner. Three members of this W/Ta series are presented here, synthesized from simple oxo- and peroxocoltanate precursors. [Ta3W3O19](5-) displays the Lindqvist-type structure, while [TaW9O32](5-) and [Ta2W8O32](6-) are isostructural with decatungstate ([W10O32](4-)). Additionally, the use of peroxoniobate instead of hexaniobate as the starting material drives the formation of the decatungstate-type structure [NbW9O32](5-) instead of the Lindqvist ion that was established to be the foundational cluster geometry in prior work. The electronic structure of the Nb/Ta substituted decatungstates is directly related to the degree of substitution inasmuch as the HOMO-LUMO energy gap (Egap) slightly increases as more Nb/Ta atoms are incorporated into the structure. The poor mixing of the d-orbitals of Nb/Ta and W is responsible for the observed trends in the UV spectra and cyclic voltammetry. Moreover, the stability of the molecular frameworks in the gas phase is also related to the extent of substitution as revealed by electrospray mass-spectrometry (ESI-MS).

Effect of organic species on the solar detoxification of water polluted with pesticides.

The effect of organic species on a solar-driven photo-Fenton treatment of a mixture of pesticides (methyl-oxydemethon, methidathion, carbaryl and dimethoate) has been studied in this paper. Triethoxyisododecyl alcohol, acetophenone and ethylenediaminetetraacetic acid (EDTA) have been used as examples of surfactants, solvents and complexing agents, respectively. An inhibitory effect on mineralization as well as on the elimination of the pesticides was observed in the case of the aliphatic surfactants, most probably due to the competition between the pesticides and the added organic matter for reaction with the relatively unselective hydroxyl radical. A methodology combining chemical analyses and bioassays was tested in order to explore the applicability of coupling a photo-Fenton process with a biological treatment in the presence of the surfactant. Despite the complexity of the mixture under study, a reliable monitoring of the process was accomplished; the biocompatibility of the mixture was enhanced and the optimal irradiation intensity was achieved just after complete removal of the pesticides.

Effect of inorganic ions on the solar detoxification of water polluted with pesticides.

The effect of eleven inorganic ions (Cl(-), NO(3)(-), SO(4)(2-); PO(4)(3-), Na(+); NH(4)(+), Ca(2+), Mg(2+), Zn(2+), Cu(2+) and Al(3+)) on the photo-Fenton elimination of pesticides has been investigated. Phosphate and chloride have been demonstrated to have an inhibitory role; on the other hand, the reaction was accelerated in the presence of Cu(2+), most probably due to a copper-driven Fenton-like process. The solar photo-Fenton treatment of a mixture of four commercial pesticides was studied at pilot plant scale in the presence of chlorides. Samples with coincident dissolved organic carbon (DOC) showed similar chemical composition, which resulted in a comparable biocompatibility, however longer irradiation periods were needed to reach the desired mineralization when Cl(-) was present. It was demonstrated that the chemical process was able to improve significantly the biocompatibility of the effluent, as shown by the inhibition of respiration of activated sludge, BOD/COD ratio and Zahn-Wellens test.

Predicting survival in critical patients by use of body temperature regularity measurement based on approximate entropy.

Body temperature is a classical diagnostic tool for a number of diseases. However, it is usually employed as a plain binary classification function (febrile or not febrile), and therefore its diagnostic power has not been fully developed. In this paper, we describe how body temperature regularity can be used for diagnosis. Our proposed methodology is based on obtaining accurate long-term temperature recordings at high sampling frequencies and analyzing the temperature signal using a regularity metric (approximate entropy). In this study, we assessed our methodology using temperature registers acquired from patients with multiple organ failure admitted to an intensive care unit. Our results indicate there is a correlation between the patient's condition and the regularity of the body temperature. This finding enabled us to design a classifier for two outcomes (survival or death) and test it on a dataset including 36 subjects. The classifier achieved an accuracy of 72%.

MR imaging of the abnormal sternoclavicular joint--a pictorial essay.

The sternoclavicular (SC) joint can be affected by a wide variety of pathologic conditions. Imaging is usually needed for diagnosis and staging. Although the use of magnetic resonance (MR) imaging has become indispensable in the evaluation of most joints, MR has received little attention in SC joint evaluation. Recently, however, it has been shown that detailed MR images of the normal SC joint can be obtained. This pictorial essay explores the differential diagnosis of the abnormal SC joint and helps to determine the role of MR imaging in the SC joint imaging algorithm.

MR imaging of the normal sternoclavicular joint: spectrum of findings.

Although MR imaging has become an important imaging method in the evaluation of most joints, it is rarely used to evaluate the sternoclavicular joint. The purpose of this study was to determine the spectrum of findings identified on MR images of the normal sternoclavicular joint as seen on images of cadavers, healthy volunteers, and patients with normal joints. Knowledge of these findings can prevent misdiagnosis of a normal variant as an abnormality.