Imidazole-Fused Enediynes by Selective C5–C4 Alkynylations of 4,5-Dibromoimidazoles

An efficient synthesis of symmetrical 1,2-disubstituted 4,5-dialkynylimidazoles by Sonogashira alkynylation of the corresponding 4,5-dibromo derivatives was developed. Moreover, through a careful tuning of the palladium ligand, unsymmetrical 1,2-disusbtituted 4,5-dialkynylimidazoles were also prepared through a regioselective C5 alkynylation of 4,5-dibromoimidazoles, followed by a second alkynylation involving the 4-bromo derivatives so obtained. This interesting class of imidazole-fused enediynes is also able to give thermal Bergman cycloaromatization (BC), as proved by DSC experiments

Persistence of wild Streptococcus thermophilus strains on wooden vat and during the manufacture of a traditional Caciocavallo type cheese

The present work was undertaken to evaluate the influence of the wooden dairy plant equipment on the microbiological characteristics of curd to be transformed into Caciocavallo Palermitano cheese. Traditional raw milk productions were performed concomitantly with standard cheese making trials carried out in stainless steel vat inoculated with a commercial starter. Milk from two different farms (A and B) was separately processed. The wooden vat was found to be a reservoir of lactic acid bacteria (LAB), while unwanted (spoilage and/or pathogenic) microorganisms were not hosted or were present at very low levels. All microbial groups were numerically different in bulk milks, showing higher levels for the farm B. LAB, especially thermophilic cocci, dominated the whole cheese making process of all productions. Undesired microorganisms decreased in number or disappeared during transformation, particularly after curd stretching. LAB were isolated from the wooden vat surface and from all dairy samples, subjected to phenotypic and genetic characterization and identification. Streptococcus thermophilus was the species found at the highest concentration in all samples analyzed and it also dominated the microbial community of the wooden vat. Fourteen other LAB species belonging to six genera (Enterococcus, Lactobacillus, Lactococcus, Leuconostoc, Streptococcus and Weissella) were also detected. All S. thermophilus isolates were genetically differentiated and a consortium of four strains persisted during the whole traditional production process. As confirmed by pH and the total acidity after the acidification step, indigenous S. thermophilus strains acted as a mixed starter culture

Geophysical monitoring of Stromboli volcano: insight into recent volcanic activity

Stromboli is an open conduit strato-volcano of the Aeolian archipelago (Italy), characterized by typical Strom-bolian explosive activity, lasting for several centuries, and by the emission of huge amounts of gas. The normalactivity of Stromboli is characterized by some hundreds of moderate explosions per day. Major explosions, whichlaunch scoria up to hundreds of meters from the craters, lava flows and paroxysmal explosions, which producelarge ballistic blocks, sometimes take place. During the effusive eruption in 2002 - 2003, which caused a tsunamiwith waves of about 10 meters high along the coasts of the Island, the monitoring system was enhanced. In 2006INGV has added two Sacks-Evertson borehole volumetric dilatometers to the surveillance system, in order to mon-itor changes in the local strain field by measuring areal strain. Today we have a large amount of geophysical dataand observations that allow us to better understand how this volcano works. After a period of low explosive activitystarted in mid-2014, Stromboli has shown a more intense explosive activity in the last few months. During the re-cent phase of increased activity, the geophysical monitoring system detected four major explosions occurred on 26July, 23 October, 1 November and 1 December 2017, respectively. The current phase of reawakening of Strombolivolcano has led the Italian civil protection authorities to decree the "attention" alert level (yellow) on the Island.PublishedVienna, Austria1IT. Reti di monitoraggio e sorveglianz

Mechanistic Studies on the Palladium-Catalyzed Direct C-5 Arylation of Imidazoles: The Fundamental Role of the Azole as a Ligand for Palladium

An in-depth mechanistic study on the palladium-catalyzed direct arylation of imidazoles at the C-5 position is presented. The interactions of triphenylphosphine (PPh3)-ligated aryl-Pd species with 1,2-dimethyl-1H-imidazole (dmim) have been studied in detail. In contrast with previous suggestions, phosphine-ligated organo-Pd species are not active and the reaction proceeds through imidazole-ligated organo-Pd intermediates. The kinetics of the oxidative addition of aryl halides with dmim-ligated Pd(0) species have been characterized in a Pd(dba)2/dmim model system. A thorough study of the equilibria involving novel [ArPd(dmim)2X] complexes (X=I, OAc) and the unexpected cationic [ArPd(dmim)3]+is also reported. The ability of these species to effect the C-H arylation of dmim at room temperature in the presence of acetate is also demonstrated

Evaluation of the Terrestrial ²²²Rn Flux from ²¹⁰Pb Deposition Measurements

The study of the 222Rn terrestrial flux (Bq/(m2·s) or Bq/(m2·h)) is a complex issue involving both radiation-protection and environmental aspects. While the radiation-protection aspects are quite obvious—it has been well known for several decades that soil is the major source of indoor radon—environmental issues such as the correlation with conventional pollutants (PM2.5, PM10, NOX, etc.) and the use of radon for the esmation of the natural component of GHG (CO2) emissions are relatively less discussed in spite of their growing relevance. In this work we present a method for the estimation of the average value of 222Rn flux from HPGe γ-spectrometry 210Pb measurements performed on wet and dry deposition samples gathered monthly in the period 2006–2020. The results obtained with this technique give an average radon flux in the period Φ = 57 ± 27 Bq/(m2·h), the value of which is comparable with those coming from other methods and direct radon flux measurements as well. The method can thus be used to obtain a worldwide map of the radon flux

Synthesis of Multiply Arylated Heteroarenes, including Bioactive Derivatives, via Palladium-Catalyzed Direct C?H Arylation of Heteroarenes with (Pseudo)Aryl Halides or Aryliodonium Salts

This review with 387 references covers the literature un- til the end of November 2013 on the synthesis of multiply arylated heteroarenes via highly selective palladium-catalyzed direct C–H arylation reactions of heteroarene derivatives with aryl halides or pseudohalides or aryliodonium salts. Particular attention has been made to describe the synthesis of biologically active compounds and substances that are privileged structural motifs in organic mate- rials. The practicality, versatility, and limitations of the various de- veloped arylation protocols are discussed

Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole

The palladium-catalyzed direct arylation of azoles with (hetero)aryl halides is nowadays one of the most versatile and efficient procedures for the selective synthesis of heterobiaryls. Although this procedure is, due to its characteristics, also of great interest in the industrial field, the wide use of a reaction medium such as DMF or DMA, two polar aprotic solvents coded as dangerous according to environmental, health, safety (EHS) parameters, strongly limits its actual use. In contrast, the use of aromatic solvents as the reaction medium for direct arylations, although some of them show good EHS values, is poorly reported, probably due to their low solvent power against reagents and their potential involvement in undesired side reactions. In this paper we report an unprecedented selective C-5 arylation procedure involving anisole as an EHS green reaction solvent. In addition, the beneficial role of benzoic acid as an additive was also highlighted, a role that had never been previously described

Measurements of 22Na in the Atmosphere: Ground Level Activity Concentration Values from Wet and Dry Deposition Samples

Sodium-22 (22Na, half-life 2.603 years) is a cosmogenic radionuclide mainly produced in the stratosphere by nuclear spallation reactions of cosmic rays on 40Ar. Due to the very low concentration levels normally reached in the environment, 22Na poses no significant radioprotection threats: actually, the effective doses delivered to humans can hardly exceed a few nSv per year, a very negligible value. However, the measurements of this radionuclides can be very interesting for atmospheric circulation and climatic studies. Unfortunately, the difficulty of 22Na detection, due to its very low concentration levels, has prevented the gathering of large and widespread time series of this radionuclide. In this paper, a method for the retrospective measurements of 22Na in the atmosphere, starting from the gamma spectra (hyperpure germanium detectors (HPGe) detectors) of wet and dry deposition samples stored in our databases is proposed and validated. The method was applied to spectra samples gathered in the context of the Italian National Radioactivity Monitoring Network (RESORAD) and allowed the detection of the very low atmospheric activity concentration values of 22Na present at ground level. The results obtained with the new method are discussed and compared for validation with the available experimental values. Finally, some possible applications to environmental studies are also highlighted and suggested

Recent Applications of Phosphane-based Palladium Catalysts in Suzuki-Miyaura Reactions Involved in Total Syntheses of Natural Products

This review with 800 references illustrates applications of Suzuki-Miyaura (S.-M.) reactions in the total syntheses of 147 natural products that were made in the period 2010–2013. The review has been organized on the basis of the seven classes of phosphane-based Pd catalysts that have been used in the reported total syntheses. Emphasis has been given to describe and discuss the experimental conditions of the Pd-catalyzed (S.-M.) cross-coupling reactions also outlining the methods used to prepare the reactants. A focus has also been set on the biological and pharmacological properties of the reported natural products as well as on the most significant steps of the reported total syntheses