Introduction of the year 2020

Herein we introduce the volume and its three parts: critical reviews, highlights on recent topics and finally SPR lectures in photochemistry. We then summarize the most significant advancements in photochemistry in 2020 by presenting awards, special issues, handbooks and some representative examples of the new discoveries in the field. </p

Aryl–Cl vs heteroatom–Si bond cleavage on the route to the photochemical generation of σ,π-heterodiradicals

The photochemistry of aryl chlorides having a X-SiMe3 group (X = O, NR, S, SiMe2) tethered to the aromatic ring has been investigated in detail, with the aim to generate valuable ϭ,π-heterodiradicals. Two competitive pathways arising from the excited triplet state of the aromatics have been observed, namely heterolysis of the aryl–chlorine bond and homolysis of the X–silicon bond. The former path is found in chlorinated phenols and anilines, whereas the latter is exclusive in the case of silylated thiophenols and aryl silanes. A combined experimental/computational approach was pursued to explain such a photochemical behavior. Graphical abstract[Figure not available: see fulltext.

Correction: Role of solute-solvent hydrogen bonds on the ground state and the excited state proton transfer in 3-hydroxyflavone. A systematic spectrophotometric study

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Metal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes

Authors are grateful to have received generous funding from the European Union H2020 research and innovation program under the Marie S. Curie Grant Agreement (PhotoReAct, No 956324, S.B., M.L., A.L., G.M., E.Z.C., T.N.; CHAIR, No 860762, A.P., M.J., T.N.)In contemporary drug discovery, enhancing the sp3-hybridized character of molecular structures is paramount, necessitating innovative synthetic methods. Herein, we introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation. This approach serves as a versatile, metal-free C(sp3)−C(sp3) cross-coupling platform. We demonstrate its synthetic value as a safer, broadly applicable C1 homologation of carboxylic acids, offering an alternative to the traditional Arndt-Eistert reaction. Additionally, our method provides direct access to cyclic and acyclic β-arylethylamines using diverse aldehyde-derived sulfonyl hydrazones. Notably, the methodology proves to be compatible with the late-stage functionalization of peptides on solid-phase, streamlining the modification of intricate peptides without the need for exhaustive de-novo synthesis.Peer reviewe

Generation of Alkyl Radicals:From the Tyranny of Tin to the Photon Democracy

Alkyl radicals are key intermediates in organic synthesis. Their classic generation from alkyl halides has a severe drawback due to the employment of toxic tin hydrides to the point that "flight from the tyranny of tin"in radical processes was considered for a long time an unavoidable issue. This review summarizes the main alternative approaches for the generation of unstabilized alkyl radicals, using photons as traceless promoters. The recent development in photochemical and photocatalyzed processes enabled the discovery of a plethora of new alkyl radical precursors, opening the world of radical chemistry to a broader community, thus allowing a new era of photon democracy

Lung anatomy, energy load, and ventilator-induced lung injury

High tidal volume can cause ventilator-induced lung injury (VILI), but positive end-expiratory pressure (PEEP) is thought to be protective. We aimed to find the volumetric VILI threshold and see whether PEEP is protective per se or indirectly

The Management of Dry Eye Disease: Proceedings of Italian Dry Eye Consensus Group Using the Delphi Method

Dry eye disease (DED) is a highly prevalent, chronic and progressive condition that affects 5–33% of the world’s adult population [1]. The 1995 definition of DED only considered patient-reported symptoms (ocular discomfort) and damage to the inter-palpebral ocular surface [2]. However, as it became apparent that this failed to reflect the complexity of the disease and its impact on visual function, inducing a risk of under-diagnosis, the 2007 International Dry Eye WorkShop (DEWS) redefined it as follows: “A multifactorial disease of the tears and ocular surface that results in symptoms of discomfort, visual disturbance, and tear film instability with potential damage to the ocular surface. It is accompanied by increased osmolarity of the tear film and inflammation of the ocular surface” [3]. This introduced the concept that the ocular surface is a single system, added visual disturbances to the symptoms of ocular discomfort and drew attention to the key concepts of inflammation and tear hyperosmolarity. Subsequently, as it is not unusual in everyday clinical practice to encounter patients with moderate–severe symptoms who have no pathological signs on the ocular surface or, conversely, patients with severe signs who are asymptomatic because of decreased corneal sensitivity, DEWS II revised its definition to read “Dry eye is a multifactorial disease of the ocular surface characterized by a loss of homeostasis of the tear film, and accompanied by ocular symptoms, in which tear film instability and hyperosmolarity, ocular surface inflammation and damage, and neurosensory abnormalities play etiological roles” [4] in order to indicate the occurrence of corneal nerves impairment, too. The symptoms characterizing the disease can severely affect the patients’ quality of life and everyday activities such as reading, driving or working on a computer [5–8] and are also associated with high levels of anxiety and depression [9]. Consequently, it is not only important to prescribe the appropriate treatment, but also to monitor its effects over time in order to ensure long-term relief and prevent disease chronicity [10,11]. Clinicians are clearly aware of the need to adopt a standardized approach to diagnose and treat DED that includes counselling, patient education and the establishment of a medical alliance to promote effective treatment [12,13]. The aim of this paper is to describe the process used by a group of Italian ophthalmologists (“Italian Dry Eye Consensus Group”) focused on DED for identifying four major statements related to the disease aimed at improving overall DED patient care [14]. Given the complexity of the disease and the different clinical contexts in which it may occur, the method used was based on real-life experience, as well as scientific data, and allowed the consideration of areas of still uncertain or unproven knowledge that may nevertheless help to guide everyday clinical practice and future research

Recent advances in the development of high-resolution 3D cadmium zinc telluride drift strip detectors

In the last two decades, great efforts have been made in the development of 3D cadmium-zinc-Telluride (CZT) detectors operating at room temperature for gamma-ray spectroscopic imaging. This work presents the spectroscopic performance of new high-resolution CZT drift strip detectors, recently developed at IMEM-CNR of Parma (Italy) in collaboration with due2lab (Italy). The detectors (19.4 mm × 19.4 mm × 6 mm) are organized into collecting anode strips (pitch of 1.6 mm) and drift strips (pitch of 0.4 mm) which are negatively biased to optimize electron charge collection. The cathode is divided into strips orthogonal to the anode strips with a pitch of 2 mm. Dedicated pulse processing analysis was performed on a wide range of collected and induced charge pulse shapes using custom 32-channel digital readout electronics. Excellent room-Temperature energy resolution (1.3% FWHM at 662 keV) was achieved using the detectors without any spectral corrections. Further improvements (0.8% FWHM at 662 keV) were also obtained through a novel correction technique based on the analysis of collected-induced charge pulses from anode and drift strips. These activities are in the framework of two Italian research projects on the development of spectroscopic gamma-ray imagers (10-1000 keV) for astrophysical and medical applications