Controlled Lactonization of o-Coumaric Esters Mediated by Supramolecular Gels

Fragrances are volatile organic compounds widely used in our daily life. Unfortunately, the high volatility required to reach human receptors reduces their persistency in the air. To contrast this effect, several strategies may be used. Among them, we present here the combination of two techniques: the microencapsulation in supramolecular gels and the use of profragrances. We report a study on the controlled lactonization of four esters derived from o-coumaric acid. The ester lactonization spontaneously occurs after exposure to solar light, releasing coumarin and the corresponding alcohol. To determine the rate of fragrance release, we compared the reaction in solution and in a supramolecular gel and we demonstrated that the lactonization reaction always occurs slower in the gel. We also studied the more suitable gel for this aim, by comparing the properties of two supramolecular gels obtained with the gelator Boc-L-DOPA(Bn)(2)-OH in a 1:1 ethanol/water mixture in different gelator concentration (0.2% and 1% w/v). The gel prepared with 1% w/v gelator concentration is stronger and less transparent than the other and was used for the profragrances encapsulation. In any case, we obtained a significative reduction of lactonization reaction in gel, compared with the same reaction in solution

Boc-Protection on L-DOPA: an Easy Way to Promote Underwater Adhesion

The ability of mussels to adhere to underwater surfaces has attracted a lot of attention from the scientific community. As proteins containing L-DOPA (3,4-dihydroxyphenyl-l-alanine) are involved in their adhesion, a common strategy to synthesize adhesives is the incorporation of this amino acid into other compounds. Herein, we report a study on four compounds of the family of Bocx-(L-DOPA)n-OMe (x = 1–3; n = 1,2), that we prepared through simple synthetic steps. Three of them showed the capability of underwater adhesion: while they are not adhesive in the dry phase, the adhesiveness is triggered when the dried sample is immersed in water or any aqueous solutions. The introduction of protecting groups stabilizes L-DOPA, preventing the oxidation of the catechol moiety, and enhances the hydrophobicity, helping the removal of water from the surface to bind. These molecules show good adhesiveness, with different properties, so they may be all used as adhesives for different purposes. These outcomes pave the way for new applications for these materials as green and biocompatible adhesives

Fluorine Effect in the Gelation Ability of Low Molecular Weight Gelators

The three gelators presented in this work (Boc-D-Phe-L-Oxd-OH F0, Boc-D-F1Phe-L-Oxd-OH F1 and Boc-D-F2Phe-L-Oxd-OH F2) share the same scaffold and differ in the number of fluorine atoms linked to the aromatic ring of phenylalanine. They have been applied to the preparation of gels in 0.5% or 1.0% w/v concentration, using three methodologies: solvent switch, pH change and calcium ions addition. The general trend is an increased tendency to form structured materials from F0 to F1 and F2. This property ends up in the formation of stronger materials when fluorine atoms are present. Some samples, generally formed by F1 or F2 in 0.5% w/v concentration, show high transparency but low mechanical properties. Two gels, both containing fluorine atoms, show increased stiffness coupled with high transparency. The biocompatibility of the gelators was assessed exposing them to fibroblast cells and demonstrated that F1 and F2 are not toxic to cells even in high concentration, while F0 is not toxic to cells only in a low concentration. In conclusion, the presence of even only one fluorine atom improves all the gelators properties: the gelation ability of the compound, the rheological properties and the transparency of the final materials and the gelator biocompatibility

Rheological Tunability of Perovskite Precursor Solutions: From Spin Coating to Inkjet Printing Process

The high efficiencies (>22%) reached by perovskite-based optoelectronic devices in a very short period, demonstrates the great potential and tunability of this material. The current challenge lies in translating such efficiencies to commercially feasible forms produced through industrial fabrication methods. Herein, a novel first step towards the processability of starch-perovskite inks, developed in our previous work, is investigated, by using inkjet printing technology. The tunability of the viscosity of the starch-perovskite-based inks allows the selection of suitable concentrations to be used as printable inks. After exploration of several printing parameters, thick and opaque starch-perovskite nanocomposite films were obtained, showing interesting morphological and optical properties. The results obtained in this work underline the potential and versatility of our approach, opening the possibility to explore and optimize, in the future, further large-scale deposition methods towards fully printed and stable perovskite devices

Silicon resonant microcantilevers for absolute pressure measurement

This work is focused on the developing of silicon resonant microcantilevers for the measurement of the absolute pressure. The microcantilevers have been fabricated with a two-mask bulk micromachining process. The variation in resonance response of microcantilevers was investigated as a function of pressure 10−1-105 Pa, both in terms of resonance frequency and quality factor. A theoretical description of the resonating microstructure is given according to different molecular and viscous regimes. Also a brief discussion on the different quality factors contributions is presented. Theoretical and experimental data show a very satisfying agreement. The microstructure behavior demonstrates a certain sensitivity over a six decade range and the potential evolution of an absolute pressure sensor working in the same rang

Direct detection of spin polarization in photoinduced charge transfer through a chiral bridge

It is well assessed that the charge transport through a chiral potential barrier can result in spin-polarized charges. The possibility of driving this process through visible photons holds tremendous potential for several aspects of quantum information science, e.g., the optical control and readout of qubits. In this context, the direct observation of this phenomenon via spin-sensitive spectroscopies is of utmost importance to establish future guidelines to control photo-driven spin selectivity in chiral structures. Here, we provide direct proof that time-resolved electron paramagnetic resonance (EPR) can be used to detect long-lived spin polarization generated by photoinduced charge transfer through a chiral bridge. We propose a system comprising CdSe quantum dots (QDs), as a donor, and C60, as an acceptor, covalently linked through a saturated oligopeptide helical bridge (χ) with a rigid structure of ∼10 Å. Time-resolved EPR spectroscopy shows that the charge transfer in our system results in a C60 radical anion, whose spin polarization maximum is observed at longer times with respect to that of the photogenerated C60 triplet state. Notably, the theoretical modelling of the EPR spectra reveals that the observed features may be compatible with chirality-induced spin selectivity, but the electronic features of the QD do not allow the unambiguous identification of the CISS effect. Nevertheless, we identify which parameters need optimization for unambiguous detection and quantification of the phenomenon. This work lays the basis for the optical generation and direct manipulation of spin polarization induced by chirality

Direct measurement of stellar angular diameters by the VERITAS Cherenkov Telescopes

The angular size of a star is a critical factor in determining its basic properties. Direct measurement of stellar angular diameters is difficult: at interstellar distances stars are generally too small to resolve by any individual imaging telescope. This fundamental limitation can be overcome by studying the diffraction pattern in the shadow cast when an asteroid occults a star, but only when the photometric uncertainty is smaller than the noise added by atmospheric scintillation. Atmospheric Cherenkov telescopes used for particle astrophysics observations have not generally been exploited for optical astronomy due to the modest optical quality of the mirror surface. However, their large mirror area makes them well suited for such high-time-resolution precision photometry measurements. Here we report two occultations of stars observed by the VERITAS Cherenkov telescopes with millisecond sampling, from which we are able to provide a direct measurement of the occulted stars' angular diameter at the $\leq0.1$ milliarcsecond scale. This is a resolution never achieved before with optical measurements and represents an order of magnitude improvement over the equivalent lunar occultation method. We compare the resulting stellar radius with empirically derived estimates from temperature and brightness measurements, confirming the latter can be biased for stars with ambiguous stellar classifications.Comment: Accepted for publication in Nature Astronom

Evidence for proton acceleration up to TeV energies based on VERITAS and Fermi-LAT observations of the Cas A SNR

We present a study of $\gamma$-ray emission from the core-collapse supernova remnant Cas~A in the energy range from 0.1GeV to 10TeV. We used 65 hours of VERITAS data to cover 200 GeV - 10 TeV, and 10.8 years of \textit{Fermi}-LAT data to cover 0.1-500 GeV. The spectral analysis of \textit{Fermi}-LAT data shows a significant spectral curvature around $1.3 \pm 0.4_{stat}$ GeV that is consistent with the expected spectrum from pion decay. Above this energy, the joint spectrum from \textit{Fermi}-LAT and VERITAS deviates significantly from a simple power-law, and is best described by a power-law with spectral index of $2.17\pm 0.02_{stat}$ with a cut-off energy of $2.3 \pm 0.5_{stat}$ TeV. These results, along with radio, X-ray and $\gamma$-ray data, are interpreted in the context of leptonic and hadronic models. Assuming a one-zone model, we exclude a purely leptonic scenario and conclude that proton acceleration up to at least 6 TeV is required to explain the observed $\gamma$-ray spectrum. From modeling of the entire multi-wavelength spectrum, a minimum magnetic field inside the remnant of $B_{\mathrm{min}}\approx150\,\mathrm{\mu G}$ is deduced.Comment: 33 pages, 9 Figures, 6 Table

How diverse is your team? Investigating gender and nationality diversity in GitHub teams

Open Access: This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.Background Building an effective team of developers is a complex task faced by both software companies and open source communities. The problem of forming a “dream” team involves many variables, including consideration of human factors and it is not a dilemma solvable in a mathematical way. Empirical studies might provide interesting insights to explain which factors need to be taken into account in building a team of developers and which levers act to optimise productivity among developers. Aim In this paper, we present the results of an empirical study aimed at investigating the link between team diversity (i.e., gender, nationality) and productivity (issue fixing time). Method We consider issues solved from the GHTorrent dataset inferring gender and nationality of each team’s members. We also evaluate the politeness of all comments involved in issue resolution. Results Results show that higher gender diversity is linked with a lower team average issue fixing time (higher productivity), that nationality diversity is linked with lower team politeness and that gender diversity is linked with higher sentiment.Peer reviewedFinal Published versio