Reactivity of a phosphinito-bridged PtI-PtI complex with nucleophiles: substitution versus addition

As a result of the strong electrophilic character of the Pt bound to O, the phosphinito-bridged PtI complex [(PHCy2)Pt(micro-PCy2){kappa2P,O-micro-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) undergoes attack at the O-bound Pt atom by molecules such as di- and tricyclohexylphosphane, dicyclohexylphosphane oxide, and dicyclohexylphosphane sulfide. Thus, reaction of 1 with PHCy2 gives the symmetric PtI dimer [(PHCy2)Pt(micro-PCy2)]2(Pt-Pt) (2), while the hydrido-bridged complex syn-[(PHCy2){kappaP-P(O)Cy2}Pt(micro-PCy2)(micro-H)Pt(PHCy2){kappaP-P(O)Cy2}](Pt-Pt) (4) is obtained from reaction of 1 with P(O)HCy2; the thiophosphinito complex [(PHCy2)Pt(micro-PCy2){kappa2P,S-micro-P(S)Cy2}Pt(PHCy2)](Pt-Pt) (8) forms selectively in reaction of 1 with P(S)HCy2. For comparison, the reaction with PCy3 results only in ligand substitution, affording [(PCy3)Pt(micro-PCy2){kappa2P,O-micro-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (5). DFT studies confirmed the remarkable electrophilicity of the oxygen-bound Pt and shed light on the nature of the metal-metal bond in Pt dimers.     

New insights into the titanium-mediated enantioselective oxidation of fluorinated aryl benzyl sulfides and aryl phenacyl sulfides

A fruitful switch from tert-butyl to cumene hydroperoxide was able to overcome a difficulty arose in the enantioselective oxidation of fluorinated aryl benzyl sulfide with hydroperoxides in the presence of a titanium/(S, S)-hydrobenzoin catalyst. New experiments show the complementarity of the old and the new protocols and indicate unequivocally the right choice leading to the corresponding highly enantioenriched sulfoxides. Moreover, in a totally unexpected way, the new protocol was able to overcome another difficulty arose in another field of research, that is the enantioselective oxidation of a fluorinated aryl phenacyl sulfide. Also in this case, the complementarity of behavior is acting. Finally, this investigation gives new support to the attribution of configuration of sulfoxides with ECD techniques, but only if the protocol outlined in our past research was followed thoroughly.     

Global-local HROM for non-linear thermal problems with irreversible changes of material states

Highly concentrated moving nonlinearities are extremely difficult to solve numerically. The Selective Laser Melting Additive Manufacturing process is a problem of this kind. A material global-local scheme is proposed, which consists in describing the neighbourhood of the heat source by a moving local domain while the material phase fractions are represented in a global domain. The equations of the non-linear thermal problem are defined on the local domain only, assuming that the local domain is large enough to capture the most important variations of the temperature field. Additionally, a Hyper-Reduced-Order Model (HROM) is proposed for the local domain problem. The performance is studied by solving a SLM problem taken from the literature.     

Direct imaging rapidly-rotating non-Kerr black holes

Recently, two of us have argued that non-Kerr black holes in gravity theories different from General Relativity may have a topologically non-trivial event horizon. More precisely, the spatial topology of the horizon of non-rotating and slow-rotating objects would be a 2-sphere, like in Kerr space–time, while it would change above a critical value of the spin parameter. When the topology of the horizon changes, the black hole central singularity shows up. The accretion process from a thin disk can potentially overspin these black holes and induce the topology transition, violating the Weak Cosmic Censorship Conjecture. If the astrophysical black hole candidates are not the black holes predicted by General Relativity, we might have the quite unique opportunity to see their central region, where classical physics breaks down and quantum gravity effects should appear. Even if the quantum gravity region turned out to be extremely small, at the level of the Planck scale, the size of its apparent image would be finite and potentially observable with future facilities.     

Astrophysical Black Holes: A Compact Pedagogical Review

Black holes are among the most extreme objects that can be found in the Universe and an ideal laboratory for testing fundamental physics. Here, the basic properties of black holes as expected from general relativity, the main astronomical observations, and the leading astrophysical techniques to probe the strong gravity region of these objects are reviewed. The main intention is to provide a compact introductory overview on astrophysical black holes to new students entering this research field, as well as to senior researchers working in general relativity and alternative theories of gravity, who wish to quickly learn the state of the art of astronomical observations of black holes.     

Effect of the gelation process on the production of alginate microbeads by microfluidic chip technology

The present paper reports the production of Ba-alginate microspheres by microfluidic chip technology. The general production strategy is based on the formation of an alginate multiphase flow by a 'Y' junction squeezing mechanism. Special emphasis is given to the relationship existing between the gelation process and the final morphological characteristics of the produced microbeads. A series of different gelation strategies, namely: 'external gelation', 'internal gelation' and 'partial gelation' were compared in terms of size, size distribution and morphology of the produced microbeads.     

Nanocomposite Fibers for Cosmetotextile Applications

In this work, a series of nylon 6 nanocomposites with different nanoclay/jojoba oil contents have been prepared by direct melt compounding. Nanocomposite morphologies were characterized by means of WAXS analysis. Thermal and mechanical fibers properties were studied as well. The kinetic desorption of the cosmetic oil through the polymer matrix was evaluated by FT-IR microscopy. It was found that the state of the clay particles affected the thermal behaviour and the tensile mechanical properties of each polymer/clay hybrid. On the other hand, the release of the cosmetic oil, tested by FT-IR microscopy, is a good perspective for the application of polyamide 6 nanocomposite fibers as textiles in cosmetic field.     

New Antifungal Terpenoid Glycosides from Alibertia edulis (Rubiaceae)

Phytochemical investigation from the stems of Alibertia edulis led to the isolation and identification of a new iridoid 6β‐hydroxy‐7‐epigardoside methyl ester ( 1 ) and a new saponin 3β‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐O‐β‐D ‐glucopyranosyl‐(1→2)‐O‐β‐D ‐glucopyranosyl]‐28‐O‐β‐D ‐glucopyranoside pomolate ( 2 ), along with three known compounds, shanzhiside methyl ester ( 3 ), ixoside ( 4 ), and 3,4,5‐trimethoxyphenyl 1‐O‐β‐D ‐apiofuranosyl‐(1→6)‐O‐β‐D ‐glucopyranoside ( 5 ). The structures of 1 and 2 were established on the basis of their spectroscopic data. Iridoid 1 and saponin 2 exhibited moderate inhibitory activities against Candida albicans and C. krusei in a dilution assay.     

Effect of natural antioxidants on the stability of polypropylene films

A preliminary study on the efficiency of agri-food industry wastes as stabilizers for polypropylene (PP) films is reported. Several analytical techniques were employed to evaluate the stabilization effectiveness of the additives. DSC and CL analysis performed on unaged samples confirmed the antioxidant activity of natural additives, and provided the following order of efficiency: red grape seeds > white grape seeds > tomato extracts. The films were also artificially aged at 70 °C, and FTIR spectroscopy confirmed the stabilization trend obtained from the unaged films. Kinetic analysis of TG data alongside tensile tests indicated that the tomato extract is a good thermal and processing stabilizer, but it is sensitive to oxidation. In contrast, grape seeds provide long-term stabilization to PP under conditions of oxidative degradation. Our results show that tomato and wine processing by-products have good potential to be exploited as a low-cost source of value-added phytochemicals.