Differential reactivity of the inner and outer positions of Au25(SCH2CH2Ph)18 dimeric staples under place exchange conditions

The kinetic anal. of the place exchange reaction on the neutral Au25(SCH2CH2Ph)\u200b18 cluster by using 4-\u200bfluorobenzylthiol and a series of substituted arylthiols allowed us to establish, for the first time, that the selectivity for the inner and outer positions of the dimeric staples of the cluster can be modulated by using incoming thiols with different structures

Stereoselective Solvolysis in the Synthesis of Dorzolamide Intermediates

The key intermediate in the synthesis of dorzolamide,(4S,6S)-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-ol-7,7-dioxide,can beobtained in the diastereoisomerically pure form in two straightforwardsteps starting from diastereoisomeric mixtures of cis/trans-(6S)-6-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-yl acetate,regardless of their ratio. The reaction of crucial importance in thisscheme is a remarkably stereoselective solvolysis of the acetate esterin an acetone/phosphate buffer mixture as the solvent system. Investigationof this so far unrecognized stereoselective reaction reveals thatit proceeds via an S(N)1-like pathway as indicated by thecorrelation of the solvolysis rate constants with the Y (OTs) values of different solvent mixtures and by trappingof the reaction intermediate with sodium azide. The structure of (4S,6S)-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-ol-7,7-dioxide was confirmedby single-crystal X-ray analysis

Air quality during uncontrolled fires: a multi-years case of study

Exposure to high level of pollutant as a consequence of uncontrolled fire is a issue that must be managed in the right way in order to protect environment and ensure a safe habitat for humans, flora and fauna, because is well know that emissions occurred during those events could serious contaminate air soil and water, and some pollutant could be hazardous for the human health (Lemieux, 2002). During uncontrolled fires a lot of contaminants may be emitted, but in high concern for the human health are persistent organic pollutants (POPs) and PAHs (Coudon et al., 2019, Zhang et al., 2008). Moreover uncontrolled burning could release polychlorinated biphenyls dioxin-like (PCB dl), that are generated as by-product during industrial combustions. Those pollutants are all of high concern for human health because they have well-known carcinogenic and mutagenic properties, e.g. is well known that PAHs is the main carcinogenic constituent of ambient aerosol (Zhang et al., 2008, Fent et al., 2018; Ravindra et al., 2008). Moreover, PCDD/PCDF, frequently referred as dioxin, are recognized as toxic chemical pollutant, with endocrine proprieties and toxic dioxin congener is classified as group1 carcinogen by the international agency for research in cancer (IARC). The aim of this study is evaluate how uncontrolled fires can affect air quality by characterizing persistent organic pollutant emitted from some events occurred from 2015 to 2018 in Veneto region (northern Italy). This area is one of the most polluted and urbanized areas in Europe (Larsen et al., 2012)and uncontrolled fire can further enhance this severe situation, leading air pollution to critical level. During those accidental events the Environmental Protection Agency of Veneto (ARPAV), in order to monitoring the effect of fires, and ensure public health, collected some air samples using Hi-vol samplers equipped with quartz fiber filter (QFF) for collecting “particulate” phase compounds and a polyurethane foam plug (PUF) for retaining “gas-phase” compounds. Subsequently, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF), polychlorinated biphenyls dioxin-like (PCB dl) and Polycyclic aromatic hydrocarbons (PAHs), were analysed using a High Resolution Gas Chromatography (HRGC), coupled with High Resolution Mass Spectrometry (HRMS). As expected results show large increase of PCDD/PCDF, PCB dl and PAHs during and immediately after incidental fires, with differences in pollutant composition. It’s noticeable how, in a few time (hours to days) pollutant concentration presented a clear and strong drop, leading air quality to better conditions. This drop is probably due to meteorological factors, that will be investigated

Risk of recurrence after a first episode of symptomatic venous thromboembolism provoked by a transient risk factor: a systematic review.

We aimed to determine the risk of recurrence for symptomatic venous thromboembolism (VTE) provoked by different transient risk factors. DATA SOURCES: MEDLINE, EMBASE, and Cochrane Collaboration Registry of Randomized Trials databases were searched. STUDY SELECTION: Prospective cohort studies and randomized trials of patients with a first episode of symptomatic VTE provoked by a transient risk factor and treated for at least 3 months were identified. DATA EXTRACTION: Number of patients and recurrent VTE during the 0- to 12-month and 0- to 24-month intervals after stopping therapy, study design, and provoking risk factor characteristics were extracted. DATA SYNTHESIS: Annualized recurrence rates were calculated and pooled across studies. At 24 months, the rate of recurrence was 3.3% per patient-year (11 studies, 2268 patients) for all patients with a transient risk factor, 0.7% per patient-year (3 studies, 248 patients) in the subgroup with a surgical factor, and 4.2% per patient-year (3 studies, 509 patients) in the subgroup with a nonsurgical factor. In the same studies, the rate of recurrence after unprovoked VTE was 7.4% per patient-year. The rate ratio for a nonsurgical compared with a surgical factor was 3.0 and for unprovoked thrombosis compared with a nonsurgical factor was 1.8 at 24 months. CONCLUSIONS: The risk of recurrence is low if VTE is provoked by surgery, intermediate if provoked by a nonsurgical risk factor, and high if unprovoked. These risks affect whether patients with VTE should undergo short-term vs indefinite treatment

Optical production and detection of dark matter candidates

The PVLAS collaboration is at present running, at the Laboratori Nazionali di Legnaro of I.N.F.N., Padova, Italy, a very sensitive optical ellipsometer capable of measuring the small rotations or ellipticities which can be acquired by a linearly polarized laser beam propagating in vacuum through a transverse magnetic feld (vacuum magnetic birefringence). The apparatus will also be able to set new limits on mass and coupling constant of light scalar/pseudoscalar particles coupling to two photons by both producing and detecting the hypothetical particles. The axion, introduced to explain parity conservation in strong interactions, is an example of this class of particles, all of which are considered possible dark matter candidates. The PVLAS apparatus consists of a very high finesse (> 140000), 6.4 m long, Fabry-Perot cavity immersed in an intense dipolar magnetic field (~6.5 T). A linearly polarized laser beam is frequency locked to the cavity and analysed, using a heterodyne technique, for rotation and/or ellipticity acquired within the magnetic field.Comment: presented at "Frontier Detectors for Frontier Physics - 8th Pisa Meeting on Advanced Detectors - May 21-27, 2000" to appear in: Nucl.Instr. and Meth.

Cryogenic Characteristics of the ATLAS Barrel Toroid Superconducting Magnet

ATLAS, one of the experiments of the LHC accelerator under commissioning at CERN, is equipped with a large superconducting magnet the Barrel Toroid (BT) that has been tested at nominal current (20500 A). The BT is composed of eight race-track superconducting coils (each one weights about 45 tons) forming the biggest air core toroidal magnet ever built. By means of a large throughput centrifugal pump, a forced flow (about 10 liter/second at 4.5 K) provides the indirect cooling of the coils in parallel. The paper describes the results of the measurements carried out on the complete cryogenic system assembled in the ATLAS cavern situated 100 m below the ground level. The measurements include, among other ones, the static heat loads, i.e., with no or constant current in the magnet, and the dynamic ones, since additional heat losses are produced, during the current ramp-up or slow dump, by eddy currents induced on the coil casing

First Cool-down and Test at 4.5 K of the ATLAS Superconducting Barrel Toroid Assembled in the LHC Experimental Cavern

The large ATLAS superconducting magnets system consists of the Barrel, two End-Caps Toroids and the Central Solenoid. The eight separate coils making the Barrel Toroid (BT) have been individually tested with success in a dedicated surface test facility in 2004 and 2005 and afterwards assembled in the underground cavern of the ATLAS experiment. In order to fulfil all the cryogenic scenarios foreseen for these magnets with a cold mass of 370 tons, two separate helium refrigerators and a complex helium distribution system have been used. This paper describes the results of the first cool-down, steady-state operation at 4.5 K and quench recovery of the BT in its final configuration

Digitally enabled health service for the integrated management of hypertension: A participatory user-centred design process

This article describes a user-centred approach taken by a group of five procurers to set specifications for the procurement of value-based research and development services for IT-sup-ported integrated hypertension management. The approach considered the unmet needs of patients and health systems of the involved regions. The procurers established a framework for requirements and a solution design consisting of nine building blocks, divided into three domains: service delivery, devices and integration, and health care organisation. The approach included the development of questionnaires, capturing patients’ and professionals’ views on possible system functionalities, and a template collecting information about the organisation of healthcare, professionals involved and existing IT systems at the procurers’ premises. A total of 28 patients diagnosed with hypertension and 26 professionals were interviewed. The interviewees identified 98 functional requirements, grouped in the nine building blocks. A total of nine use cases and their corresponding process models were defined by the procurers’ working group. As result, a digitally enabled integrated approach to hypertension has been designed to allow citizens to learn how to prevent the development of hypertension and lead a healthy lifestyle, and to receive comprehensive, individualised treatment in close collaboration with healthcare professionals