A stoichiometric solvent-free protocol for acetylation reactions

Considering the remarkable relevance of acetylated derivatives of phenols, alcohols, and aryl and alkyl thiols in different areas of biology, as well as in synthetic organic chemistry, a sustainable solvent-free approach to perform acetylation reactions is proposed here. Acetylation reactions are classically performed using excess of acetic anhydride (Ac2O) in solvent-free conditions or by eventually working with stoichiometric amounts of Ac2O in organic solvents; both methods require the addition of basic or acid catalysts to promote the esterification. Therefore, they usually lead to the generation of high amounts of wastes, which sensibly raise the E-factor of the process. With the aim to develop a more sustainable system, a solvent-free, stoichiometric acetylation protocol is, thus, proposed. The naturally occurring phenol, thymol, can be converted to the corresponding-biologically active-ester with good yields, in the presence of 1% of VOSO4. Interestingly, the process can be efficiently adopted to synthesize other thymyl esters, as well as to perform acetylation of alcohols and aryl and alkyl thiols. Remarkably, a further improvement has been achieved replacing Ac2O with its greener alternative, isopropenyl acetate (IPA)

Amplituhedron meets Jeffrey-Kirwan Residue

The tree amplituhedra A^(m)_n,k are mathematical objects generalising the notion of polytopes into the Grassmannian. Proposed for m=4 as a geometric construction encoding tree-level scattering amplitudes in planar N=4 super Yang-Mills theory, they are mathematically interesting for any m. In this paper we strengthen the relation between scattering amplitudes and geometry by linking the amplituhedron to the Jeffrey-Kirwan residue, a powerful concept in symplectic and algebraic geometry. We focus on a particular class of amplituhedra in any dimension, namely cyclic polytopes, and their even-dimensional conjugates. We show how the Jeffrey-Kirwan residue prescription allows to extract the correct amplituhedron volume functions in all these cases. Notably, this also naturally exposes the rich combinatorial and geometric structures of amplituhedra, such as their regular triangulations.Peer reviewedFinal Accepted Versio

Panchromatic light harvesting and stabilizing charge-separated states in corrole–phthalocyanine conjugates through coordinating a subphthalocyanine

Owing to the electron-donating and -accepting nature of corroles (Corr) and phthalocyanines (Pc), respectively, we designed and developed two novel covalently linked Corr-Pc conjugates. The synthetic route allows the preparation of the target conjugates in satisfying yields. Comprehensive steady-state absorption, fluorescence, and electrochemical assays enabled insights into energy and electron-transfer processes upon photoexcitation. Coordinating a pyridine-appended subphthalocyanine (SubPc) to the Pc of the conjugate sets up the ways and means to realize the first example of an array composed by three different porphyrinoids, which drives a cascade of energy and charge-transfer processes. Importantly, the SubPc assists in stabilizing the charge-separated state, that is, one-electron oxidized Corr and the one electron-reduced Pc, upon photoexcitation by means of a reductive charge transfer to the SubPc. To the best of our knowledge, this is the first case of an intramolecular oxidation of a Corr within electron-donor–acceptor conjugates by means of just photoexcitation. Moreover, the combination of Corr, Pc, and SubPc guarantees panchromatic absorption across the visible range of the solar spectrum, with the SubPc covering the „green gap“ that usually affects porphyrinoids

Search for a pseudoscalar boson decaying into a ZZ boson and the 125 GeV Higgs boson in ℓ+ℓ−bbˉb\bar{b} final states

Results are reported on a search for decays of a pseudoscalar A boson into a $Z$ boson and a light scalar h boson, where the Z boson decays into a pair of oppositely-charged electrons or muons, and the h boson decays into $b\bar{b}$. The search is based on data from proton–proton collisions at a center-of-mass energy $\sqrt{s}$=8 TeV collected with the CMS detector, corresponding to an integrated luminosity of 19.7 $fb^{−1}$ . The h boson is assumed to be the standard model-like Higgs boson with a mass of 125 GeV. With no evidence for signal, upper limits are obtained on the product of the production cross section and the branching fraction of the A boson in the Zh channel. Results are also interpreted in the context of two Higgs doublet models

Wild birds of the Italian Middle Ages: diet, environment and society

Wild birds are intrinsically associated with our perception of the Middle Ages. They often feature in heraldic designs, paintings, and books of hours; few human activities typify the medieval period better than falconry. Prominent in medieval iconography, wild birds feature less frequently in written sources (as they were rarely the subject of trade transactions or legal documents) but they can be abundant in archaeological sites. In this paper we highlight the nature of wild bird exploitation in Italian medieval societies, ranging from their role as food items to their status and symbolic importance. A survey of 13 Italian medieval sites corresponding to 19 ‘period sites’, dated from the fifth to the fifteenth centuries, reveals the occurrence of more than 100 species (certainly an under-estimate of the actual number). Anseriformes and Columbiformes played a prominent role in the mid- and late medieval Italian diet, though Passeriformes and wild Galliformes were also important. In the late Middle Ages, there is an increase in species diversity and in the role of hunting as an important marker of social status

Constraints on the χ_(c1) versus χ_(c2) polarizations in proton-proton collisions at √s = 8 TeV

The polarizations of promptly produced χ_(c1) and χ_(c2) mesons are studied using data collected by the CMS experiment at the LHC, in proton-proton collisions at √s=8  TeV. The χ_c states are reconstructed via their radiative decays χ_c → J/ψγ, with the photons being measured through conversions to e⁺e⁻, which allows the two states to be well resolved. The polarizations are measured in the helicity frame, through the analysis of the χ_(c2) to χ_(c1) yield ratio as a function of the polar or azimuthal angle of the positive muon emitted in the J/ψ → μ⁺μ⁻ decay, in three bins of J/ψ transverse momentum. While no differences are seen between the two states in terms of azimuthal decay angle distributions, they are observed to have significantly different polar anisotropies. The measurement favors a scenario where at least one of the two states is strongly polarized along the helicity quantization axis, in agreement with nonrelativistic quantum chromodynamics predictions. This is the first measurement of significantly polarized quarkonia produced at high transverse momentum