Advances in Palladium-Catalyzed Carboxylation Reactions

In this short review, we highlight the advancements in the field of palladium-catalyzed carbon dioxide utilization for the synthesis of high value added organic molecules. The review is structured on the basis of the kind of substrate undergoing the Pd-catalyzed carboxylation process. Accordingly, after the introductory section, the main sections of the review will illustrate Pd-catalyzed carboxylation of olefinic substrates, acetylenic substrates, and other substrates (aryl halides and triflates).     

Ultratrace determination of 1,2,4-trichlorobenzene in waste water by purge and trap/gas chromatography coupled to different detectors: Flame ionization (FID), electron capture (ECD), and multiple ion detection-mass spectrometry (MID-MS)

High resolution gas chromatography (HRGC) coupled to a “purge and trap” extraction-injection technique is described as a method of determining 1,2,4-trichlorobenzene in water at levels as low as parts-per-trillion (ppt). In order to investigate the interference from other volatile organic compounds (VOCs) several detection systems were compared: flame ionization, electron capture, and mass spectrometry-multiple ion detection. Concentrations ranging from 15 to 600 ng/L were analyzed in 20 ml standard aqueous solutions. The mean accuracy of the method varied from 89 to 103%, and its mean precision varied from ± 0.85 to ± 7.5 % for all detectors. The detection limits were 20 ng/L for FID, 2 ng/L for ECD and 0.5 ng/L for MID-MS detectors. The procedure was successfully applied to the analysis of industrial waste waters. The necessity of an appropriate internal standard to improve the quantitative determination and to determine possible losses or degradation of 1,2,4-trichlorobenzene during handling or storage is discussed.     

Healthy Properties of a New Formulation of Pomegranate-Peel Extract in Mice Suffering from Experimental Autoimmune Encephalomyelitis

A new formulation of a pomegranate-peel extract (PEm) obtained by PUAE (Pulsed Ultrasound-Assisted Extraction) and titrated in both ellagic acid (EA) and punicalagin is proposed, characterized and then analyzed for potential health properties in mice suffering from the experimental autoimmune encephalomyelitis (EAE). PEm effects were compared to those elicited by a formulation containing EA (EAm). Control and EAE mice were chronically administered EAm and Pem dissolved in the drinking water, starting from the day 10 post-immunization (d.p.i.), with a “therapeutic” protocol to deliver daily 50 mg/kg of EA. Treated EAE mice did not limit their daily access to the beverage, nor did they show changes in body weight, but they displayed a significant amelioration of “in vivo” clinical symptoms. “Ex vivo” histochemical analysis showed that spinal-cord demyelination and inflammation in PEm and EAm-treated EAE mice at 23 ± 1 d.p.i. were comparable to those in the untreated EAE animals, while microglia activation (measured as Ionized Calcium Binding Adaptor 1, Iba1 staining) and astrocytosis (quantified as glial fibrillar acid protein, GFAP immunopositivity) significantly recovered, particularly in the gray matter. EAm and PEm displayed comparable efficiencies in controlling the spinal pathological cellular hallmarks in EAE mice, and this would support their delivery as dietary supplementation in patients suffering from multiple sclerosis (MS).     

About Earthquake Forecasting by Markov Renewal Processes

We propose and validate a new method for the evaluation of seismic hazard. In particular, our aim is to model large earthquakes consistently with the underlying geophysics. Therefore we propose a non-Poisson model, which takes into account occurrence history, improved with some physical constraints. Among the prevalent non-Poisson models, we chose the Markov renewal process, which is expected to be sufficient to capture the main characteristics, maintaining simplicity in analysis. However, due to the introduction of some physical constraint, our process differs significantly from others already presented in literature. A mixture of exponential + Weibull distributions is proposed for the waiting times and their parameters are estimated following the likelihood method. We validated our model, using data of earthquakes of high severity occurred in Turkey during the 20th century. Our results exhibit a good accordance with the real events.     

Baeyer-Villiger oxidation in compressed CO2

The aerobic Baeyer-Villiger oxidation of a wide range of ketones, both cyclic and acyclic to the corresponding esters or lactones can be efficiently carried out in compressed carbon dioxide in the presence of an aldehyde as co-reductant.     

Highly enantioselective nickel-catalyzed hydrovinylation with chiral phosphoramidite ligands

Readily available chiral phosphoramidites are a promising class of ligands for nickel-catalyzed asymmetric hydrovinylation of vinyl arenes. Cooperative effects are operative when ligands with more than one element of chirality are used. Choosing the proper stereochemistry in each part of the modular ligand system leads to high chemoselectivities and excellent enantioselectivities up to 94%. Moreover, the catalysts derived from these ligands proved extremely efficient and remarkably robust performing up to 8300 catalytic turnovers at an initial turnover frequency beyond 1000 h-1. The large potential for structural variation and their straightforward synthesis make the phosphoramidites currently the best lead structure for catalyst development in this field.     

Cholesterol oxidation in meat-based baby foods

Cholesterol oxidation in commercial meat-based homogenized and freeze-dried baby foods was examined. The 7 major products of this reaction were determined by gas chromatography coupled with mass spectrometry (GC-MS). As far as single cholesterol oxidation products (COP) are concerned, 7-ketocholesterol was the major product of direct cholesterol oxidation in the 2 groups of analyzed samples, and this study confirmed that it is a useful marker of the whole cholesterol oxidation process. Nevertheless, the amounts of cholesterol-5beta,6beta-epoxide were often similar to and sometimes higher than the amounts of 7-ketocholesterol, thus showing a strong development of both direct and indirect cholesterol oxidation pathways. Total COP content was significantly higher in freeze-dried than in homogenized products. Moreover, in freeze-dried samples, the COP content per serving was quite variable and, in 2 samples, it was close to or even higher than 500 microg. The greater development of cholesterol oxidation in the freeze-dried samples was confirmed by their highest total COP/cholesterol percent ratios. A constant correlation between the fatty acid composition and the development of cholesterol oxidation was not found, although a positive correlation between unsaturated fatty acid content and total COP content occasionally exists in samples of the same brand.     

Ozone monitoring in a Mediterranean forest using diffusive and continuous sampling

Ambient ozone was measured in a forest in Castelporziano (Italy) characterised by the prevailing presence of Holm-oak trees (Quercus ilex L.) from June to November 2003. Two methods for measuring ozone were used: long-term monitoring using diffusive samplers at three heights within the canopy, and continuous monitoring at two heights using the UV method. Results for one week mean ozone levels above and below the canopy from the diffusive samplers were compared to those obtained using the automatic analyser at the same levels. A good correlation between the two sampling techniques was found. Continuous monitoring showed a daily cycle with a midday maximum and a nocturnal minimum. While the forest floor consistently had the lowest ozone concentration, there were no differences during most daytime hours. The midday maximum is clearly due to downward mixing with O₃-rich air from above. The night-time ozone decay within the canopy is the result of dry deposition of O₃ and most likely due to reaction with biogenically produced NO. AOT40 within and above the canopy mostly exceeded the critical levels.