Dissolution of metal salts in bis(trifluoromethylsulfonyl)imide-based ionic liquids: Studying the affinity of metal cations toward a "weakly coordinating" anion

Despite the weakly coordinating ability of the bis(trifluoromethylsulfonyl)imide anion ([Tf2N]-) the corresponding ionic liquids (ILs) are able to dissolve relevant amounts of metal salts having the same anion, M[Tf2N]x. To better understand the metal dissolution process we evaluated the interaction ability of a set of metal cations (Y(III), Al(III), Co(II), Ni(II), Cu(II), Zn(II), Ag(I), Li(I), and Na(I)) toward the [Tf2N]- anion measuring the relative aptitude to give the corresponding anionic monocharged complex, [M(Tf2N)x+1]- using the ESI-MS technique. UV-vis and NMR measurements were carried out to verify the consistence between the liquid and the gas phase. Density functional theory calculations have been used to identify the metal-containing species and determine their relative stability. An interesting correlation between interaction ability and chemical properties (Lewis acidity) was found

Resolving protein mixtures using microfluidic diffusional sizing combined with synchrotron radiation circular dichroism

Circular dichroism spectroscopy has become a powerful tool to characterise proteins and other biomolecules. For heterogeneous samples such as those present for interacting proteins, typically only average spectroscopic features can be resolved. Here we overcome this limitation by using free-flow microfluidic size separation in-line with synchrotron radiation circular dichroism to resolve the secondary structure of each component of a model protein mixture containing monomers and fibrils. To enable this objective, we have integrated far-UV compatible measurement chambers into PDMS-based microfluidic devices. Two architectures are proposed so as to accommodate for a wide range of concentrations. The approach, which can be used in combination with other bulk measurement techniques, paves the way to the study of complex mixtures such as the ones associated with protein misfolding and aggregation diseases including Alzheimer’s and Parkinson’s diseases

Integrated multidisciplinary ecological analysis from the Uluzzian settlement at the Uluzzo C Rock Shelter, south-eastern Italy

open20siThe Middle to Upper Palaeolithic transition, between 50 000 and 40 000 years ago, is a period of important ecological and cultural changes. In this framework, the Rock Shelter of Uluzzo C (Apulia, southern Italy) represents an important site due to Late Mousterian and Uluzzian evidence preserved in its stratigraphic sequence. Here, we present the results of a multidisciplinary analysis performed on the materials collected between 2016 and 2018 from the Uluzzian stratigraphic units (SUs) 3, 15 and 17. The analysis involved lithic technology, use-wear, zooarchaeology, ancient DNA of sediments and palaeoproteomics, completed by quartz single-grain optically stimulated luminescence dating of the cave sediments. The lithic assemblage is characterized by a volumetric production and a debitage with no or little management of the convexities (by using the bipolar technique), with the objective to produce bladelets and flakelets. The zooarchaeological study found evidence of butchery activity and of the possible exploitation of marine resources, while drawing a picture of a patchy landscape, composed of open forests and dry open environments surrounding the shelter. Ancient mitochondrial DNA from two mammalian taxa were recovered from the sediments. Preliminary zooarchaeology by mass spectrometry results are consistent with ancient DNA and zooarchaeological taxonomic information, while further palaeoproteomics investigations are ongoing. Our new data from the re-discovery of the Uluzzo C Rock Shelter represent an important contribution to better understand the meaning of the Uluzzian in the context of the Middle/Upper Palaeolithic transition in south-eastern Italy.First published: 13 July 2021openSARA SILVESTRINI, MATTEO ROMANDINI, GIULIA MARCIANI, SIMONA ARRIGHI, LISA CARRERA, ANDREA FIORINI, JUAN MANUEL LÓPEZ-GARCÍA, FEDERICO LUGLI, FILOMENA RANALDO, VIVIANE SLON, LAURA TASSONI, OWEN ALEXANDER HIGGINS, EUGENIO BORTOLINI, ANTONIO CURCI, MATTHIAS MEYER, MICHAEL CHRISTIAN MEYER, GREGORIO OXILIA, ANDREA ZERBONI, STEFANO BENAZZI, SPINAPOLICE ENZA ELENASARA SILVESTRINI, MATTEO ROMANDINI, GIULIA MARCIANI, SIMONA ARRIGHI, LISA CARRERA, ANDREA FIORINI, JUAN MANUEL LÓPEZ-GARCÍA, FEDERICO LUGLI, FILOMENA RANALDO, VIVIANE SLON, LAURA TASSONI, OWEN ALEXANDER HIGGINS, EUGENIO BORTOLINI, ANTONIO CURCI, MATTHIAS MEYER, MICHAEL CHRISTIAN MEYER, GREGORIO OXILIA, ANDREA ZERBONI, STEFANO BENAZZI, SPINAPOLICE ENZA ELEN

A many-analysts approach to the relation between religiosity and well-being

The relation between religiosity and well-being is one of the most researched topics in the psychology of religion, yet the directionality and robustness of the effect remains debated. Here, we adopted a many-analysts approach to assess the robustness of this relation based on a new cross-cultural dataset (N=10,535 participants from 24 countries). We recruited 120 analysis teams to investigate (1) whether religious people self-report higher well-being, and (2) whether the relation between religiosity and self-reported well-being depends on perceived cultural norms of religion (i.e., whether it is considered normal and desirable to be religious in a given country). In a two-stage procedure, the teams first created an analysis plan and then executed their planned analysis on the data. For the first research question, all but 3 teams reported positive effect sizes with credible/confidence intervals excluding zero (median reported β=0.120). For the second research question, this was the case for 65% of the teams (median reported β=0.039). While most teams applied (multilevel) linear regression models, there was considerable variability in the choice of items used to construct the independent variables, the dependent variable, and the included covariates

A Many-analysts Approach to the Relation Between Religiosity and Well-being

The relation between religiosity and well-being is one of the most researched topics in the psychology of religion, yet the directionality and robustness of the effect remains debated. Here, we adopted a many-analysts approach to assess the robustness of this relation based on a new cross-cultural dataset (N = 10, 535 participants from 24 countries). We recruited 120 analysis teams to investigate (1) whether religious people self-report higher well-being, and (2) whether the relation between religiosity and self-reported well-being depends on perceived cultural norms of religion (i.e., whether it is considered normal and desirable to be religious in a given country). In a two-stage procedure, the teams first created an analysis plan and then executed their planned analysis on the data. For the first research question, all but 3 teams reported positive effect sizes with credible/confidence intervals excluding zero (median reported β = 0.120). For the second research question, this was the case for 65% of the teams (median reported β = 0.039). While most teams applied (multilevel) linear regression models, there was considerable variability in the choice of items used to construct the independent variables, the dependent variable, and the included covariates

Dissolution of Metal Salts in Bis-(trifluoromethylsulfonyl)imide Based Ionic Liquids: Studying the Affinity of Metal Cations towards a “Weakly Coordinating” Anion

Despite the weakly coordinating ability of the bis(trifluoromethylsulfonyl)imide anion ([Tf2N]-) the corresponding ionic liquids (ILs) are able to dissolve relevant amounts of metal salts having the same anion, M[Tf2N]x. To better understand the metal dissolution process we evaluated the interaction ability of a set of metal cations (Y(III), Al(III), Co(II), Ni(II), Cu(II), Zn(II), Ag(I), Li(I), and Na(I)) toward the [Tf2N]- anion measuring the relative aptitude to give the corresponding anionic monocharged complex, [M(Tf2N)x+1]- using the ESI-MS technique. UV-vis and NMR measurements were carried out to verify the consistence between the liquid and the gas phase. Density functional theory calculations have been used to identify the metal-containing species and determine their relative stability. An interesting correlation between interaction ability and chemical properties (Lewis acidity) was found

Formation, oxidation and fate of the Breslow intermediate in the N-heterocyclic carbenes catalyzed aerobic oxidation of aldehydes

The reaction paths and intermediate structures related to the formation of the Breslow intermediate and its oxidation along the oxidative/oxygenative lanes have been studied from a mechanistic point of view, with the support of gasphase and computational studies. The results confirm the occurrence of a single-electron transfer from the Breslow intermediate to the molecular oxygen with formation of a radical couple that recombines either as a peroxide anion 7′ to afford the aldehydeto- carboxylic acid product or as a hydroperoxy derivative 7″ that evolved into an electrophilic acyl azolium, opening to the aldehyde-to-ester conversion. Steric factors enter into determining the different reactivity. All of the intermediates of both catalytic paths have been observed and characterized under mass spectrometric conditions. In particular, for the imidazoline catalyst, the (+)ESI-MS/(MS) detection of the genuine Breslow intermediate was made possible in virtue of its limited reactivity. Mechanistic aspects of the N-heterocyclic carbenes catalyzed aerobic oxidation of aldehydes shares important similarities with that one of the recently revisited benzoin condensatio

Formation, Oxidation, and Fate of the Breslow Intermediate in the <i>N</i>‑Heterocyclic Carbene-Catalyzed Aerobic Oxidation of Aldehydes

The reaction paths and intermediate structures related to the formation of the Breslow intermediate and its oxidation along the oxidative/oxygenative lanes have been studied from a mechanistic point of view, with the support of gas-phase and computational studies. The results confirm the occurrence of a single-electron transfer from the Breslow intermediate to the molecular oxygen with formation of a radical couple that recombines either as a peroxide anion <b>7′</b> to afford the aldehyde-to-carboxylic acid product or as a hydroperoxy derivative <b>7″</b> that evolved into an electrophilic acyl azolium, opening to the aldehyde-to-ester conversion. Steric factors enter into determining the different reactivity. All of the intermediates of both catalytic paths have been observed and characterized under mass spectrometric conditions. In particular, for the imidazoline catalyst, the (+)­ESI-MS/(MS) detection of the genuine Breslow intermediate was made possible in virtue of its limited reactivity. Mechanistic aspects of the <i>N</i>-heterocyclic carbenes catalyzed aerobic oxidation of aldehydes shares important similarities with that one of the recently revisited benzoin condensation