A spectroelectrochemical study of copper chloro-complexes for high performance all-copper redox flow batteries

Redox Flow Batteries (RFB) are an ideal choice for large stationary applications. Among the different chemistries that can be exploited, all-copper aqueous RFB (CuRFB) use low-cost, earth-abundant raw materials with a well defined European supply chain. The CuRFB takes advantage of the three oxidation states of copper. As Cu(I) is not stable in aqueous media, the system is based on the chlorocomplexation of the copper cations. We demonstrated that it is possible to evaluate the complexation characteristic of the concentrated solutions used in CuRFB by investigating the speciation of copper (II) in electrolytes with increasing Cu(II) concentration. Spectroelectrochemical tests in diluted solution give information on the electrochemical behavior of electrolytes with a fare different chloro‑complexes distribution. Quantum chemical calculations elucidate the molecular structure and electronic transitions of water solvated copper chloro‑complexes, thus complementing the experimental picture

Effect of the iodine atom position on the phosphorescence of BODIPY derivatives: a combined computational and experimental study

A new BODIPY derivative (o-I-BDP) containing an iodine atom in the ortho position of the meso-linked phenyl group was prepared. Photophysical and electrochemical properties of the molecule were compared to previously reported iodo BODIPY derivatives, as well as to the non-iodinated analog. While in the case of derivatives featuring iodine substituents in the BODIPY core, efficient population of the triplet state is accompanied by a substantial positive shift of the reduction potential compared to pristine BODIPY, o-I-BDP displays phosphorescence and simultaneously maintains the electrochemical properties of unsubstituted BODIPYs. A theoretical investigation was settled to analyze results and rationalize the influence of iodine position on electronic and photophysical properties, with the purpose of preparing a fully organic phosphorescent BODIPY derivative. TD-DFT and spin-orbit coupling calculations shed light on the subtle effects played by the introduction of iodine atom in different positions of BODIPY

Disclosing Early Excited State Relaxation Events in Prototypical Linear Carbon Chains

One-dimensional (1D) linear nanostructures comprising sp-hybridized carbon atoms, as derivatives of the prototypical allotrope known as carbyne, are predicted to possess outstanding mechanical, thermal, and electronic properties. Despite recent advances in the synthesis, their chemical and physical properties are still poorly understood. Here, we investigate the photophysics of a prototypical polyyne (i.e., 1D chain with alternating single and triple carbon bonds), as the simplest model of finite carbon wire and as a prototype of sp-carbon-based chains. We perform transient absorption experiments with high temporal resolution (<30 fs) on monodispersed hydrogen-capped hexayne H$-$(C$\equiv$C)$_6-$H synthesized by laser ablation in liquid. With the support of detailed computational studies based on ground state density functional theory (DFT) and excited state time-dependent (TD)-DFT calculations, we provide a comprehensive description of the excited state relaxation processes at early times following photoexcitation. We show that the internal conversion from a bright high-energy singlet excited state to a low-lying singlet dark state is ultrafast and takes place with a 200-fs time constant, followed by thermalization on the picosecond timescale and decay of the low-energy singlet state with hundreds of picoseconds time constant. We also show that the timescale of these processes does not depend on the end groups capping the sp-carbon chain. The understanding of the primary photo-induced events in polyynes is of key importance both for fundamental knowledge and for potential optoelectronic and light-harvesting applications of low dimensional nanostructured carbon-based materials.Comment: 24 pages, 6 figure

Light-Responsive Oligothiophenes Incorporating Photochromic Torsional Switches (PTS)

We present a quaterthiophene and sexithiophene that can reversibly change their effective π-conjugation length via photoexcitation. The reported compounds make use of light-responsive molecular actuators consisting of an azobenzene attached to a bithiophene unit by both direct and linker-assisted bonding. Upon exposure to 350 nm light the azobenzene undergoes trans -to- cis isomerization mechanically inducing the oligothiophene to assume a planar conformations (extended π-conjugation). Exposure to 254 nm wavelenght promotes azobenzene cis -to- trans isomerization, forcing the thiophenic backbones to twist out of planarity (confined π-conjugation). Twisted conformations are also reached by cis -to- trans thermal relaxation with rate that increases proportionally with the conjugation length of the oligothiophene moiety. The molecular conformations of quaterthiophene and sexithiophene were characterized using steady-state UV-vis, X-ray crystallography and quantum-chemical modelling. Finally, we tested the proposed light-responsive oligothiophenes into field-effect transistors to probe the photo-induced tuning of their electronic properties

Highly Planarized Naphthalene Diimide-Bifuran Copolymers with Unexpected Charge Transport Performance

The synthesis, characterization, and charge transport performance of novel copolymers PNDIFu2 made from alternating naphthalene diimide (NDI) and bifuran (Fu2) units are reported. Usage of potentially biomass-derived Fu2 as alternating repeat unit enables flattened polymer backbones due to reduced steric interactions between the imide oxygens and Fu2 units, as seen by density functional theory (DFT) calculations and UV-vis spectroscopy. Aggregation of PNDIFu2 in solution is enhanced if compared to the analogous NDI-bithiophene (T2) copolymers PNDIT2, occurring in all solvents and temperatures probed. PNDIFu2 features a smaller π-π stacking distance of 0.35 nm compared to 0.39 nm seen for PNDIT2. Alignment of aggregates in films is achieved by using off-center spin coating, whereby PNDIFu2 exhibits a stronger dichroic ratio and transport anisotropy in field-effect transistors (FET) compared to PNDIT2, with an overall good electron mobility of 0.21 cm2/(V s). Despite an enhanced backbone planarity, the smaller π-π stacking and the enhanced charge transport anisotropy, the electron mobility of PNDIFu2 is about three times lower compared to PNDIT2. Density functional theory calculations suggest that charge transport in PNDIFu2 is limited by enhanced polaron localization compared to PNDIT2

Disclosing Early Excited State Relaxation Events in Prototypical Linear Carbon Chains

One-dimensional (1D) linear nanostructures comprising sp-hybridized carbon atoms, as derivatives of the prototypicalallotropeknown as carbyne, are predicted to possess outstanding mechanical,thermal, and electronic properties. Despite recent advances in theirsynthesis, their chemical and physical properties are still poorlyunderstood. Here, we investigate the photophysics of a prototypicalpolyyne (i.e., 1D chain with alternating single and triple carbonbonds) as the simplest model of finite carbon wire and as a prototypeof sp-carbon-based chains. We perform transient absorptionexperiments with high temporal resolution (&lt;30 fs) on monodispersedhydrogen-capped hexayne H (C C)(6)Hsynthesized by laser ablation in liquid. With the support of computationalstudies based on ground state density functional theory (DFT) andexcited state time-dependent (TD)-DFT calculations, we provide a comprehensivedescription of the excited state relaxation processes at early timesfollowing photoexcitation. We show that the internal conversion froma bright high-energy singlet excited state to a low-lying singletdark state is ultrafast and takes place with a 200 fs time constant,followed by thermalization on the picosecond time scale and decayof the low-energy singlet state with hundreds of picoseconds timeconstant. We also show that the time scale of these processes doesnot depend on the end groups capping the sp-carbonchain. The understanding of the primary photoinduced events in polyynesis of key importance both for fundamental knowledge and for potentialoptoelectronic and light-harvesting applications of low-dimensionalnanostructured carbon-based materials

Stable and Solution-Processable Cumulenic sp-Carbon Wires: A New Paradigm for Organic Electronics

[EN] Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp(2)-hybridized carbon molecules, either in the form of pi-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to molecular devices. The recent observation of the field-effect in microcrystalline cumulenes suggests their potential applications in solution-processed thin-film transistors but concerns surrounding the stability and electronic performance have precluded developments in this direction. In the present study, ideal field-effect characteristics are demonstrated for solution-processed thin films of tetraphenyl[3]cumulene, the shortest semiconducting CAW. Films are deposited through a scalable, large-area, meniscus-coating technique, providing transistors with hole mobilities in excess of 0.1 cm(2 )V(-1 )s(-1), as well as promising operational stability under dark conditions. These results offer a solid foundation for the exploitation of a vast class of molecular semiconductors for organic electronics based on sp-hybridized carbon systems and create a previously unexplored paradigm.E.G.F. acknowledges the support through the EU Horizon 2020 research and innovation program, H2020-FETOPEN-01-2018-2020 (FET-Open Challenging Current Thinking), "LION-HEARTED", grant agreement no. 828984. C.S.C. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program ERC-Consolidator Grant (ERC CoG 2016 EspLORE grant agreement no. 724610, website: ). R.R.T. acknowledges funding from the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Canada Foundation for Innovation (CFI). This work was partially supported by the European Union's H2020-EU.4.b. - Twinning of research institutions "GREENELIT", grant agreement number 951747. GIWAXS experiments were performed at BL11 NCD-SWEET beamline at ALBA Synchrotron (Spain) with the collaboration of ALBA staff. This work was in part carried out at Polifab, the micro- and nanotechnology centre of the Politecnico di Milano. Open access funding provided by Istituto Italiano di Tecnologia within the CRUI-CARE Agreement

Psychological treatments and psychotherapies in the neurorehabilitation of pain. Evidences and recommendations from the italian consensus conference on pain in neurorehabilitation

BACKGROUND: It is increasingly recognized that treating pain is crucial for effective care within neurological rehabilitation in the setting of the neurological rehabilitation. The Italian Consensus Conference on Pain in Neurorehabilitation was constituted with the purpose identifying best practices for us in this context. Along with drug therapies and physical interventions, psychological treatments have been proven to be some of the most valuable tools that can be used within a multidisciplinary approach for fostering a reduction in pain intensity. However, there is a need to elucidate what forms of psychotherapy could be effectively matched with the specific pathologies that are typically addressed by neurorehabilitation teams. OBJECTIVES: To extensively assess the available evidence which supports the use of psychological therapies for pain reduction in neurological diseases. METHODS: A systematic review of the studies evaluating the effect of psychotherapies on pain intensity in neurological disorders was performed through an electronic search using PUBMED, EMBASE, and the Cochrane Database of Systematic Reviews. Based on the level of evidence of the included studies, recommendations were outlined separately for the different conditions. RESULTS: The literature search yielded 2352 results and the final database included 400 articles. The overall strength of the recommendations was medium/low. The different forms of psychological interventions, including Cognitive-Behavioral Therapy, cognitive or behavioral techniques, Mindfulness, hypnosis, Acceptance and Commitment Therapy (ACT), Brief Interpersonal Therapy, virtual reality interventions, various forms of biofeedback and mirror therapy were found to be effective for pain reduction in pathologies such as musculoskeletal pain, fibromyalgia, Complex Regional Pain Syndrome, Central Post-Stroke pain, Phantom Limb Pain, pain secondary to Spinal Cord Injury, multiple sclerosis and other debilitating syndromes, diabetic neuropathy, Medically Unexplained Symptoms, migraine and headache. CONCLUSIONS: Psychological interventions and psychotherapies are safe and effective treatments that can be used within an integrated approach for patients undergoing neurological rehabilitation for pain. The different interventions can be specifically selected depending on the disease being treated. A table of evidence and recommendations from the Italian Consensus Conference on Pain in Neurorehabilitation is also provided in the final part of the pape

Multicenter Observational Retrospective Study on Febrile Events in Patients with Acute Myeloid Leukemia Treated with Cpx-351 in "Real-Life": The SEIFEM Experience

: In the present study, we aimed to evaluate the absolute risk of infection in the real-life setting of AML patients treated with CPX-351. The study included all patients with AML from 30 Italian hematology centers of the SEIFEM group who received CPX-351 from July 2018 to June 2021. There were 200 patients included. Overall, 336 CPX-351 courses were counted: all 200 patients received the first induction cycle, 18 patients (5%) received a second CPX-351 induction, while 86 patients (26%) proceeded with the first CPX-351 consolidation cycle, and 32 patients (10%) received a second CPX-351 consolidation. A total of 249 febrile events were recorded: 193 during the first or second induction, and 56 after the first or second consolidation. After the diagnostic work-up, 92 events (37%) were classified as febrile neutropenia of unknown origin (FUO), 118 (47%) were classifiable as microbiologically documented infections, and 39 (17%) were classifiable as clinically documented infections. The overall 30-day mortality rate was 14% (28/200). The attributable mortality-infection rate was 6% (15/249). A lack of response to the CPX-351 treatment was the only factor significantly associated with mortality in the multivariate analysis [p-value: 0.004, OR 0.05, 95% CI 0.01-0.39]. Our study confirms the good safety profile of CPX-351 in a real-life setting, with an incidence of infectious complications comparable to that of the pivotal studies; despite prolonged neutropenia, the incidence of fungal infections was low, as was infection-related mortality