correction on the stability of manganese tris β diketonate complexes as redox mediators in dsscs

Correction for 'On the stability of manganese tris(β-diketonate) complexes as redox mediators in DSSCs' by Stefano Carli et al., Phys. Chem. Chem. Phys., 2016, 18, 5949–5956

Palaeogenomics of Upper Palaeolithic to Neolithic European hunter-gatherers

: Modern humans have populated Europe for more than 45,000 years1,2. Our knowledge of the genetic relatedness and structure of ancient hunter-gatherers is however limited, owing to the scarceness and poor molecular preservation of human remains from that period3. Here we analyse 356 ancient hunter-gatherer genomes, including new genomic data for 116 individuals from 14 countries in western and central Eurasia, spanning between 35,000 and 5,000 years ago. We identify a genetic ancestry profile in individuals associated with Upper Palaeolithic Gravettian assemblages from western Europe that is distinct from contemporaneous groups related to this archaeological culture in central and southern Europe4, but resembles that of preceding individuals associated with the Aurignacian culture. This ancestry profile survived during the Last Glacial Maximum (25,000 to 19,000 years ago) in human populations from southwestern Europe associated with the Solutrean culture, and with the following Magdalenian culture that re-expanded northeastward after the Last Glacial Maximum. Conversely, we reveal a genetic turnover in southern Europe suggesting a local replacement of human groups around the time of the Last Glacial Maximum, accompanied by a north-to-south dispersal of populations associated with the Epigravettian culture. From at least 14,000 years ago, an ancestry related to this culture spread from the south across the rest of Europe, largely replacing the Magdalenian-associated gene pool. After a period of limited admixture that spanned the beginning of the Mesolithic, we find genetic interactions between western and eastern European hunter-gatherers, who were also characterized by marked differences in phenotypically relevant variants

Palaeogenomics of Upper Palaeolithic to Neolithic European hunter-gatherers

Publisher Copyright: © 2023, The Author(s).Modern humans have populated Europe for more than 45,000 years1,2. Our knowledge of the genetic relatedness and structure of ancient hunter-gatherers is however limited, owing to the scarceness and poor molecular preservation of human remains from that period3. Here we analyse 356 ancient hunter-gatherer genomes, including new genomic data for 116 individuals from 14 countries in western and central Eurasia, spanning between 35,000 and 5,000 years ago. We identify a genetic ancestry profile in individuals associated with Upper Palaeolithic Gravettian assemblages from western Europe that is distinct from contemporaneous groups related to this archaeological culture in central and southern Europe4, but resembles that of preceding individuals associated with the Aurignacian culture. This ancestry profile survived during the Last Glacial Maximum (25,000 to 19,000 years ago) in human populations from southwestern Europe associated with the Solutrean culture, and with the following Magdalenian culture that re-expanded northeastward after the Last Glacial Maximum. Conversely, we reveal a genetic turnover in southern Europe suggesting a local replacement of human groups around the time of the Last Glacial Maximum, accompanied by a north-to-south dispersal of populations associated with the Epigravettian culture. From at least 14,000 years ago, an ancestry related to this culture spread from the south across the rest of Europe, largely replacing the Magdalenian-associated gene pool. After a period of limited admixture that spanned the beginning of the Mesolithic, we find genetic interactions between western and eastern European hunter-gatherers, who were also characterized by marked differences in phenotypically relevant variants.Peer reviewe

Rethinking Electronic Effects in Photochemical Hydrogen Evolution Using CuInS2@ZnS Quantum Dots Sensitizers

Molecular catalysts based on coordination complexes for the generation of hydrogen via photochemical water splitting exhibit a large versatility and tunability of the catalytic properties through chemical functionalization. In the present work, we report on light-driven hydrogen production in an aqueous solution using a series of cobalt polypyridine complexes as hydrogen evolving catalysts (HECs) in combination with CuInS2@ZnS quantum dots (QDs) as sensitizers, and ascorbate as the electron donor. A peculiar trend in activity has been observed depending on the substituents present on the polypyridine ligand. This trend markedly differs from that previously recorded using [Ru(bpy)3]2+ (where bpy = 2,20-bipyridine) as the sensitizer and can be ascribed to different kinetically limiting pathways in the photochemical reaction (viz. protonation kinetics with the ruthenium chromophore, catalyst activation via electron transfer from the QDs in the present system). Hence, this work shows how the electronic effects on light-triggered molecular catalysis are not exclusive features of the catalyst unit but depend on the whole photochemical system

Electrochemical characterization of polypyridine iron(II) and cobalt(II) complexes for organic redox flow batteries

The electrochemical properties of a series of complexes based on chelate ligands were explored with the aim of finding promising candidates for applications in high voltage organic flow cells. The combination of Co(II)/(I) and Fe(III)/(II) as the cathodic and the anodic couple leads to open circuit voltages close to 2 V and to limiting current of the order of 30 mA/cm2 in 0.3 M concentration in a mixture of Ethylene and Propylene carbonates. The best solubility was found for bis-cationic complexes as triflate (OTf) salts, reaching >0.6 M at room temperature. Potentiostatic and potentiodynamic experiments point to a substantial chemical and electrochemical stability at carbon based electrodes as well

The role of the capping agent and nanocrystal size in photoinduced hydrogen evolution using CdTe/CdS quantum dot sensitizers

Hydrogen production via light-driven water splitting is a key process in the context of solar energy conversion. In this respect, the choice of suitable light-harvesting units appears as a major challenge, particularly as far as stability issues are concerned. In this work, we report on the use of CdTe/CdS QDs as photosensitizers for light-assisted hydrogen evolution in combination with a nickel bis(diphosphine) catalyst (1) and ascorbate as the sacrificial electron donor. QDs of different sizes (1.7-3.4 nm) and with different capping agents (MPA, MAA, and MSA) have been prepared and their performance assessed in the above-mentioned photocatalytic reaction. Detailed photophysical studies have been also accomplished to highlight the charge transfer processes relevant to the photocatalytic reaction. Hydrogen evolution is observed with remarkable efficiencies when compared to common coordination compounds like Ru(bpy)32+ (where bpy = 2,2'-bipyridine) as light-harvesting units. Furthermore, the hydrogen evolution performance under irradiation is strongly determined by the nature of the capping agent and the QD size and can be related to the concentration of the surface defects within the semiconducting nanocrystal. Overall, the present results outline how QDs featuring large quantum yields and long lifetimes are desirable to achieve sustained hydrogen evolution upon irradiation and that a precise control of the structural and photophysical properties thus appears as a major requirement towards profitable photocatalytic applications

Coupling of Zinc Porphyrin Dyes and Copper Electrolytes: A Springboard for Novel Sustainable Dye-Sensitized Solar Cells

The combination of β-substituted Zn2+ porphyrin dyes and copper-based electrolytes represents a sustainable route for economic and environmentally friendly dye-sensitized solar cells. Remarkably, a new copper electrolyte, [Cu(2-mesityl-1,10-phenanthroline)2]+/2+, exceeds the performance reached by Co2+/3+ and I-/I3- reference electrolytes

Paleopathological analysis of a probable case of Jarcho-Levin Syndrome from the 18th century northern Italy

This case report examines the differential diagnosis of an unusually fused chest belonging to a perinatal human remain retrieved in the crypt of Roccapelago (Italy). This specimen, which dated back to the final 18th century, showed a severe synostosis of the costovertebral articulations and posterior arches. The specimen was examined macroscopically and radiologically for the purpose of identify differences in mineral density. It also underwent computed tomography scan in order to create a 3D digital model and virtually reposition in anatomical position. The radiological trophism, size, and osteological maturity of the specimen are compatible with a perinate. The chest structure shows a characteristic crab like morphology, with the costovertebral articulations and some posterior arches completely fused. Accordingly, a diagnosis of Jarcho-Levin Syndrome has been suggested. This case appears to be the first report, to the knowledge of the authors, of a probable Jarcho-Levin syndrome, which dated before Jarcho and Levin codified this pathology in the scientific literature

Enhancing Oxygenic Photosynthesis by Cross-Linked Perylenebisimide “Quantasomes

[Image: see text] As the natural-born photoelectrolyzer for oxygen delivery, photosystem II (PSII) is hardly replicated with man-made constructs. However, building on the “quantasome” hypothesis (Science1964, 144, 1009−101117811607), PSII mimicry can be pared down to essentials by shaping a photocatalytic ensemble (from the Greek term ”soma” = body) where visible-light quanta trigger water oxidation. PSII-inspired quantasomes (QS) readily self-assemble into hierarchical photosynthetic nanostacks, made of bis-cationic perylenebisimides (PBI(2+)) as chromophores and deca-anionic tetraruthenate polyoxometalates (Ru(4)POM) as water oxidation catalysts (Nat. Chem.2019, 11, 146−15330510216). A combined supramolecular and click-chemistry strategy is used herein to interlock the PBI-QS with tetraethylene glycol (TEG) cross-linkers, yielding QS-TEG(lock) with increased water solvation, controlled growth, and up to a 340% enhancement of the oxygenic photocurrent compared to the first generation QS, as probed on 3D-inverse opal indium tin oxide electrodes at 8.5 sun irradiance (λ > 450 nm, 1.28 V vs RHE applied bias, TOF(max) = 0.096 ± 0.005 s(–1), FE(O2) > 95%). Action spectra, catalyst mass-activity, light-management, photoelectrochemical impedance spectroscopy (PEIS) together with Raman mapping of TEG-templated hydration shells point to a key role of the cross-linked PBI/Ru(4)POM nanoarrays, where the interplay of hydrophilic/hydrophobic domains is reminiscent of PSII-rich natural thylakoids