Identification of slow relaxing spin components by pulse EPR techniques in graphene-related materials

Electron Paramagnetic Resonance (EPR) is a powerful technique that is suitable to study graphene-related materials. The challenging ability requested to the spectroscopy is its capability to resolve the variety of structures, relatively similar, that are obtained in materials produced through different methods, but that also coexist inside a single sample. In general, because of the intrinsic inhomogeneity of the samples, the EPR spectra are therefore a superposition of spectra coming from different structures. We show that by pulse EPR techniques (echo-detected EPR, ESEEM and Mims ENDOR) we can identify and characterize species with slow spin relaxing properties. These species are generally called molecular states, and are likely small pieces of graphenic structures of limited dimensions, thus conveniently described by a molecular approach. We have studied commercial reduced graphene oxide and chemically exfoliated graphite, which are characterized by different EPR spectra. Hyperfine spectroscopies enabled us to characterize the molecular components of the different materials, especially in terms of the interaction of the unpaired electrons with protons (number of protons and hyperfine coupling constants). We also obtained useful precious information about extent of delocalization of the molecular states

Depth Distribution of Spin-Labeled Liponitroxides within Lipid Bilayers: A Combined EPR and Molecular Dynamics Approach

The distribution in an egg\u2013phosphatidylcholine bilayer of a series of spin-labeled nitroxides, potentially useful as targeted antioxidants, has been investigated using molecular dynamics (MD) simulations. The in silico method has been tested at first for a series of n-doxyl-phosphocholine-doped bilayers, with the doxyl moiety located at different positions (n) of the lipid chain, in analogy to electron paramagnetic resonance (EPR) spin labeling and other MD studies. As a result, a novel calibration curve has been obtained, suitable to determine the absolute membrane penetration depth of any paramagnetic solute from EPR measurements. A second series of MD simulations was then carried out on the newly synthesized series of liponitroxides (NOXs) recently tested as antioxidants against the lipid peroxidation of polyunsaturated fatty acids in membranes: their penetration depths, as determined by EPR in phosphatidylcholine liposomes, were correlated with their antioxidant efficacy. In these NOXs, a glycerol moiety is esterified with a carboxy derivative of a pyrroline nitroxide and one or two oleic acid residues. A very good agreement between the EPR experimental results and those from the current MD simulations indicates that the short distance of the nitroxide moiety from the fatty acid double bonds has been now definitively assessed; moreover, it indicates that our MD methodology could be successfully employed in the absence of nonparamagnetic species

The electronic structure and dynamics of the excited triplet state of octaethylaluminum(III)-porphyrin investigated with advanced EPR methods

The photoexcited triplet state of octaethylaluminum(III)-porphyrin (AlOEP) was investigated by time-resolved Electron Paramagnetic Resonance, Electron Nuclear Double Resonance and Electron Spin Echo Envelope Modulation in an organic glass at 10 and 80 K. This main group element porphyrin is unusual because the metal has a small ionic radius and is six-coordinate with axial covalent and coordination bonds. It is not known whether triplet state dynamics influence its magnetic resonance properties as has been observed for some transition metal porphyrins. Together with density functional theory modelling, the magnetic resonance data of AlOEP allow the temperature dependence of the zero-field splitting (ZFS) parameters, D and E, and the proton AZZ hyperfine coupling (hfc) tensor components of the methine protons, in the zero-field splitting frame to be determined. The results provide evidence that the ZFS, hfc and spin–lattice relaxation are indeed influenced by the presence of a dynamic process that is discussed in terms of Jahn-Teller dynamic effects. Thus, these effects should be taken into account when interpreting EPR data from larger complexes containing AlOEP

Higgs mass implications on the stability of the electroweak vacuum

We update instability and metastability bounds of the Standard Model electroweak vacuum in view of the recent ATLAS and CMS Higgs results. For a Higgs mass in the range 124--126 GeV, and for the current central values of the top mass and strong coupling constant, the Higgs potential develops an instability around $10^{11}$ GeV, with a lifetime much longer than the age of the Universe. However, taking into account theoretical and experimental errors, stability up to the Planck scale cannot be excluded. Stability at finite temperature implies an upper bound on the reheat temperature after inflation, which depends critically on the precise values of the Higgs and top masses. A Higgs mass in the range 124--126 GeV is compatible with very high values of the reheating temperature, without conflict with mechanisms of baryogenesis such as leptogenesis. We derive an upper bound on the mass of heavy right-handed neutrinos by requiring that their Yukawa couplings do not destabilize the Higgs potential.Comment: 14 pages, 8 figure

Radicals and Ions Formed in Plasma-Treated Organic Solvents: A Mechanistic Investigation to Rationalize the Enhancement of Electrospinnability of Polycaprolactone

This paper reports and discusses the beneficial effects on the quality of electrospun polycaprolactone nanofibers brought about by pretreatment of the solvent with non-thermal plasma. Chloroform/dimethylformamide 9:1 (CHCl3:DMF 9:1) and pure chloroform were pretreated by a few minute exposure to the plasma generated by an atmospheric pressure plasma jet (APPJ). Interestingly, when pure chloroform was used, the advantages of plasma pretreatment of the solvent were way less pronounced than found with the CHCl3:DMF 9:1 mixture. The chemical modifications induced by the plasma in the solvents were investigated by means of complementary analytical techniques. GC-MS revealed the formation of solvent-derived volatile products, notably tetrachloroethylene (C2Cl4), 1,1,2,2-tetrachloroethane (C2H2Cl4), pentachloroethane (C2HCl5), hexachloroethane (C2Cl6) and, in the case of the mixed solvent, also N-methylformamide (C2H5NO). The chlorinated volatile products are attributed to reactions of ·Cl and Cl-containing methyl radicals and carbenes formed in the plasma-treated solvents. ·Cl and ·CCl3 radicals were detected and identified by EPR spectroscopy analyses. Ion chromatography revealed the presence of Cl−, NO3-, and HCOO− (the latter only in the presence of DMF) in the plasma-treated solvents, thus accounting for the observed increased conductivity and acidification of the solvent after plasma treatment. Mechanisms for the formation of these solvent derived products induced by plasma are proposed and discussed. The major role of radicals and ions in the plasma chemistry of chloroform and of the chloroform/dimethylformamide mixture is highlighted. The results provide insight into the interaction of plasma with organic solvents, a field so far little explored but holding promise for interesting applications

Burnout among surgeons before and during the SARS-CoV-2 pandemic: an international survey

Background: SARS-CoV-2 pandemic has had many significant impacts within the surgical realm, and surgeons have been obligated to reconsider almost every aspect of daily clinical practice. Methods: This is a cross-sectional study reported in compliance with the CHERRIES guidelines and conducted through an online platform from June 14th to July 15th, 2020. The primary outcome was the burden of burnout during the pandemic indicated by the validated Shirom-Melamed Burnout Measure. Results: Nine hundred fifty-four surgeons completed the survey. The median length of practice was 10 years; 78.2% included were male with a median age of 37 years old, 39.5% were consultants, 68.9% were general surgeons, and 55.7% were affiliated with an academic institution. Overall, there was a significant increase in the mean burnout score during the pandemic; longer years of practice and older age were significantly associated with less burnout. There were significant reductions in the median number of outpatient visits, operated cases, on-call hours, emergency visits, and research work, so, 48.2% of respondents felt that the training resources were insufficient. The majority (81.3%) of respondents reported that their hospitals were included in the management of COVID-19, 66.5% felt their roles had been minimized; 41% were asked to assist in non-surgical medical practices, and 37.6% of respondents were included in COVID-19 management. Conclusions: There was a significant burnout among trainees. Almost all aspects of clinical and research activities were affected with a significant reduction in the volume of research, outpatient clinic visits, surgical procedures, on-call hours, and emergency cases hindering the training. Trial registration: The study was registered on clicaltrials.gov "NCT04433286" on 16/06/2020

Metodi EPR impulsati per la caratterizzazione delle radiazioni ionizzanti

Il rilascio di energia da parte di radiazioni ionizzanti all\u2019 interno di materiali \ue8 associato alla formazione di centri paramagnetici con efficienze variabili. Questo processo nella scala dimensionale micrometrica non avviene in maniera omogenea, ma in maniera disomogenea, portando alla conseguente distribuzione di centri paramagnetici non uniformi. La distribuzione di tali centri dipende sia dal tipo di sorgente usata per l\u2019irraggiamento sia dalla sua energia; ad esempio in materiali organici raggi \u3b3 emessi da un campione di 60Co portano ad una distribuzione di radicali quasi uniforme, mentre protoni con energia di 20 MeV producono distribuzioni di radicali allineati lungo delle direzioni (tracks) specifiche [1]. Le differenze fra i due tipi di irraggiamento non sono facilmente rivelate mediante normali tecniche di Electron Paramagnetic Resonance (EPR) in onda continua, anche se vari tipi di tentativi sono stati tentati [2]. Il modo pi\uf9 naturale di studiare queste diverse tipi di distribuzioni \ue8 quello di ricorrere alle tecniche impulsate. La tecnica sicuramente pi\uf9 informative \ue8 il Double Electron-Electron Resonance (DEER), che permette la determinazione diretta della distribuzione di distanze fra due centri paramagnetici. Informazioni sulle concentrazioni locali si possono ottenere mediante la misura della Diffusione Istantanea (ID), fenomeno che si manifesta durante il periodo di azione degli impulsi. La concentrazione locale che \ue8 misurata \ue8 funzione delle caratteristiche della radiazione ionizzante. Una overview dello stato dell\u2019 arte delle tecniche sar\ue0 affiancata ad una presentazione di casi-studio in cui l\u2019 EPR impulsato viene utilizzato anche con finalit\ue0 di valutazione retrospettiva del danno da radiazione

Trasferimenti elettronici intramolecolari fotoindotti

Dottorato di ricerca in scienze chimiche. Relatore G. GennariConsiglio Nazionale delle Ricerche - Biblioteca Centrale - P.le Aldo Moro, 7, Rome; Biblioteca Nazionale Centrale - P.za Cavalleggeri, 1, Florence / CNR - Consiglio Nazionale delle RichercheSIGLEITItal