A sustainable two-phase procedure for V-catalyzed toluene oxidative bromination with H2O2–KBr

A sustainable V(V) and Mo(VI) catalysed two-phase procedure for bromination of toluene under quite mild conditions is proposed; H2O2 is the primary oxidant and KBr is the bromine source; metal precursors are commercially available salts. The reaction is efficient without any additional solvent. By using PhCH3 as a solvent/substrate good yields, together with interesting selectivity toward the formation of PhCH2Br, are obtained with both metal ions. Recycling of the catalytic phase is also possible. Useful information on the V-peroxido chemistry was obtained

Nitinol Carbofilm coated stents for peripheral applications: Study in the porcine model

Purpose: Testing the safety and foreign body reaction (FBR) of a nitinol self-expandable carbon-coated stent system in the porcine animal model at different follow-up (FU) periods. Methods: Fifteen minipigs received 30 carbon-coated self-expandable nitinol stents in iliac arteries. Explants were carried out at 7 (3 animals), 30 (4 animals), 90 (4 animals) and 180 (4 animals) day FU, for evaluation of acute, sub-acute and chronic biological response to the implanted devices. Histological, immunohistochemical, histomorphometric and scanning electron microscopy (SEM) analyses were performed to assess inflammatory reaction, endothelialization process, neointimal growth and cellular composition. Results: Thirty stents were successfully implanted. No mural thrombi were observed at gross examination or by angiography. Histologically no significant inflammatory reaction was detected: the stents appeared covered by a thin monolayer of endothelial cells even at 7 day FU. The neointima presented homogeneous growth and moderate thickness after 30, 90 and 180 days explants (0.38± 0.36 mm, 0.33± 0.30 mm, 0.27± 0.25 mm respectively). Internal and external elastic laminae were intact in 95% of stented arteries. Histological data validations of vessel endothelialization was obtained with SEM for the seven day follow-up group. Conclusions: This study showed good remarkable technical performances, minimal FBR and biocompatibility comparable with other available pre-clinical experimentation

Towards the “Eldorado” of pKa Determination: A Reliable and Rapid DFT Model

The selection of a “perfect tool” for the theoretical determination of acid-base dissociation constants (Ka) is still puzzling. Recently, we developed a user-friendly model exploiting CAM-B3LYP for determining pKa with impressive reliability. Herein, a new challenge is faced, examining a panel of functionals belonging to different rungs of the “Jacob’s ladder” organization, which classifies functionals according to their level of theory. Specifically, meta-generalized gradient approximations (GGAs), hybrid-GGAs, and the more complex range-separated hybrid (RSH)-GGAs were investigated in predicting the pKa of differently substituted carboxylic acids. Therefore, CAM-B3LYP, WB97XD, B3PW91, PBE1PBE, PBEPBE and TPSSTPSS were used, with 6-311G+(d,p) as the basis set and the solvation model based on density (SMD). CAM-B3LYP showed the lowest mean absolute error value (MAE = 0.23) with relatively high processing time. PBE1PBE and B3PW91 provided satisfactory predictions (MAE = 0.34 and 0.38, respectively) with moderate computational time cost, while PBEPBE, TPSSTPSS and WB97XD led to unreliable results (MAE > 1). These findings validate the reliability of our model in predicting carboxylic acids pKa, with MAE well below 0.5 units, using a simplistic theoretical level and a low-cost computational approach

Beewatching: A project for monitoring bees through photos

Bees play a key role in natural and agro-ecosystems and their diversity is worldwide threatened by anthropogenic causes. Despite this, there is little awareness of the existence of the numerous species of wild bees, and the common name “bee” is very often exclusively associated with Apis mellifera. Our aim was to create a citizen science project in Italy with the following objectives: (a) raising awareness of the importance and diversity of bees, (b) obtaining data on the biology, ecology and distribution of Italian species, and (c) launching the monitoring of alien bees. The first step of the project was to create a website platform with a section containing informative datasheets of the wild bee families and of the most common bee genera present in Italy, a form to send reports of observed bees and an interactive map with all citizen’s reports. During the 2 years of the project 1086 reports were sent by 269 users, with 38 Apoidea genera reported on 190 plant genera; furthermore, 22 reports regarding the alien species Megachile sculpturalis arrived. The majority of bees (34 genera) were observed on spontaneous plants, including 115 genera native to Italy. Considering the increasing number of reports and data obtained in these first two years of the project, our objectives seem to be achieved. Future steps will be to outline the profile of beewatchers, to plan activities in a more targeted way, and also to start some sub-projects for conservation purposes

Ionic Liquids as Reaction Media in Catalytic Oxidations with Manganese and Iron Pyridyl Triazacyclononane Complexes

A family of bioinspired iron and manganese complexes of general formula [MII(CF3SO3)2(Me,XPyTACN)], where Me,XPyTACN = 1-[2’-(6-X-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, and M = Fe, and Mn has been studied as efficient catalytic systems for hydrogen peroxide oxidation reactions. Previous work revealed that the manganese derivative [MnII(CF3SO3)2(Me,HPyTACN)], 1, in acetonitrile exhibits a high catalytic activity in the epoxidation of a wide range of olefins (TON: 810-4500), using acetic acid and hydrogen peroxide as primary oxidant. The analogous iron based complex [FeII(CF3SO3)2(Me,HPyTACN)], 2a and [FeII(CF3SO3)2(Me,MePyTACN)], 2b promote the high added value oxidation reaction of alkanes in mild conditions. In this work sustainability and selectivity of the oxidative system is improved with the use of the ionic liquids (ILs) as reaction medium. The possibility to recycle the catalytic phase without loss of the activity with respect to the original reaction in acetonitrile (MeCN) is reported

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

Finding the Center of Mass of a Soft Spring

This article shows how to use calculus to find the center of mass position of a soft cylindrical helical spring that is suspended vertically. The spring is non-uniformly stretched by the action of gravity. A general expression for the vertical position of the center of mass is obtained.Comment: LaTeX, 7 pages, 2 figures. Minor changes to agree with published versio

Biodiversity evaluation: From endorsed indexes to inclusion of a pollinator indicator

There is increasing interest in evaluating biodiversity to preserve ecosystem services. Researchers can sustain policymakers by providing tools, such as indexes and indicators, that need constant implementation to become accepted standards. Implementation may vary from re-evaluation of existing indicators to introduction of new ones based on emerging threats to biodiversity. With the aim of contributing to the compelling need to estimate and counterbalance pollinator loss, we screened existing bioindicators. We first selected indexes/indicators applied to agricultural contexts and concurrently endorsed by a regulatory agency. We then extended our analysis to indexes/indicators based on arthropod taxa and formally recognized at least by national bodies. Our procedure identified a combination of surveys of various animal taxa and remote landscape analyses (e.g., using a GIS and other cartographic tools). When the animals are arthropods, most indexes/indicators can only address confined environments (e.g., grasslands, riversides). Indicator strength was improved by the simultaneous inclusion of biotic and abiotic components. Pollinator sensitivity to changes at micro-habitat level is widely appreciated and may help distinguish agricultural practices. A biodiversity index based on pollinators, including a wide monitoring scheme supplemented by citizen science, is currently fostered at the European level. The results obtained using such an index may finally enable focusing of strategic funding. Our analysis will help to reach this goal

Tetraferrocenylporphyrins as active components of self-assembled monolayers on gold surface.

Novel tetraferrocenylporphyrins-containing self-assembled monolayers were prepared employing two different approaches. Self-assembled monolayers were characterized using UV-Vis spectroscopy and cyclic voltammetry (CV) whereas their photoelectrochemical properties were investigated by photocurrent generation (PG) experiments