Effectiveness of measures of performance during speculative bubbles

Statistical analysis of financial data mostly focused on testing the validity of Brownian motion (Bm). Analyses performed on several time series have shown deviation from the Bm hypothesis, that is at the base of the evaluation of many financial derivatives. We analyze the behavior of performance measures based on maximum drawdown movements (MDD(T)), testing their stability when the underlying process deviates from the Bm hypothesis. In particular we consider the fractional Brownian motion (fBm), and fluctuations estimated empirically on raw market data. The case study of the rising part of speculative bubbles is reported.     

Three-electron auger process from beam-foil excited multiply charged ions

Electron emission from collisions of C3+ ions (22.7 A MeV) with carbon foils (21, 49 and 90 microg/cm(2)) was studied by the time-of-flight method. Two prominent emission patterns can be readily identified as "binary encounter" electrons and "cusp" electrons. With the thinnest target only, a third structure is visible at slightly lower time-of-flight (thus slightly higher energy) than the cusp electrons. The energy of these electrons would correspond to 647(+116)/(-104) eV if they were emitted from the projectile frame of reference. A possible explanation is a rare three-electron-Auger K(2)L(2)L(1) process.     

Peptide-Functionalized Silk Fibers as a Platform to Stabilize Gelatin for Use in Ingestible Devices

The combination of pharmacologic and endoscopic therapies is the gold standard for treating intestinal failures. The possibility of chemical solubility in water is mandatory for intelligent capsules. Functionalised silk fibroin with peptides and covalently linking different molecular entities to its structure make this protein a platform for preparing gels dissolving in the small and large intestine for drug delivery. In the present study, we linked a peptide containing the cell-adhesive motif Arginine–Glycine–Aspartic acid (RGD) to degummed silk fibres (DSF). Regenerated silk fibroin (RS) films obtained by dissolving functionalised DSF in formic acid were used to prepare composite gelatin. We show that such composite gelatin remains stable and elastic in the simulated gastric fluid (SGF) but can dissolve in the small and large intestines’ neutral-pH simulated intestine fluid (SIF). These findings open up the possibility of designing microfabricated and physically programmable scaffolds that locally promote tissue regeneration, thanks to bio-enabled materials based on functionalised regenerated silk.     

Modelling the Interaction between Carboxylic Acids and Zinc Oxide: Insight into Degradation of ZnO Pigments

Computational modelling applied to cultural heritage can assist the characterization of painting materials and help to understand their intrinsic and external degradation processes. The degradation of the widely employed zinc oxide (ZnO)—a white pigment mostly used in oil paints—leads to the formation of metal soaps, complexes of Zn ions and long-chain fatty acids coming from the degradation of the oil binder. Being a serious problem affecting the appearance and the structural integrity of many oil paintings, it is relevant to characterize the structure of these complexes and to understand the reaction pathways associated with this degradation process. Density functional theory (DFT) calculations were performed to investigate the adsorption of the acetate and acetic acid on relatively large ZnO clusters and the formation of Zn–acetate complexes. Carboxylic acids with longer alkyl chains were then investigated as more realistic models of the fatty acids present in the oil medium. In addition, DFT calculations using a periodic ZnO slab were performed in order to compare the obtained results at different levels of theory. Optimization calculations as well as the formation energies of the ZnO@carboxylate coupled systems and the thermodynamics leading to possible degradation products were computed. Our results highlight the potential for DFT calculations to provide a better understanding of oil paint degradation, with the aim of contributing to the development of strengthening and conservation strategies of paintings.     

Toughening Polyamidoamine Hydrogels through Covalent Grafting of Short Silk Fibers

Linear amphoteric polyamidoamines (PAAs) are usually water-soluble, biodegradable and biocompatible. Crosslinked PAAs form in water hydrogels, retaining most of the favorable properties of their linear counterparts. The hydrogels prepared by the radical post-polymerization of the oligo-α,ω-bisacrylamido-terminated PAA called AGMA1, obtained by the polyaddition of 4-aminobutylguanidine (agmatine) with 2,2-bis(acrylamido)acetic acid, exhibit excellent cell-adhesion properties both in vitro and in vivo. However, due to their low mechanical strength, AGMA1 hydrogels cannot be sewn to biological tissues and need to be reinforced with fibrous materials. In this work, short silk fibers gave excellent results in this sense, proving capable of establishing covalent bonds with the PAA matrix, thanks to their lysine content, which provided amino groups capable of reacting with the terminal acrylamide groups of the AGMA1 precursor in the final crosslinking phase. Morphological analyses demonstrated that the AGMA1 matrix was intimately interconnected and adherent to the silk fibers, with neither visible holes nor empty volumes. The silk/H-AGMA1 composites were still reversibly swellable in water. In the swollen state, they could be sewn and showed no detachment between fibers and matrix and exhibited significantly improved mechanical properties compared with the plain hydrogels, particularly as regards their Young’s modulus and elongation at break.     

Green Solvents for Eco-Friendly Synthesis of Dimethindene: A Forward-Looking Approach

Dimethindene is a selective histamine H₁ antagonist and is commercially available as a racemate. Upon analyzing the synthetic pathways currently available for the industrial preparation of dimethindene, we set up a sustainable approach for the synthesis of this drug, switching from petroleum-based volatile organic compounds (VOCs) to eco-friendly solvents, such as 2-methyltetrahydrofuran (2-MeTHF) and cyclopentyl methyl ether (CPME) belonging to classes 3 and 2, respectively. Beyond decreasing the environmental impact of the synthesis (E-factor: 24.1–54.9 with VOCs; 12.2–22.1 with 2-MeTHF or CPME), this switch also improved the overall yield of the process (from 10% with VOCs to 21–22% with 2-MeTHF or CPME) and remarkably simplified the manual operations, working under milder conditions. Typical metrics applied at the first and second pass, according to the CHEM21 metrics toolkit, were also calculated for the whole synthetic procedure of dimethindene, and the results were compared with those of the classical procedure.     

Thermal Oxidation Products of Nylon 6 Determined by MALDI‐TOF Mass Spectrometry

Matrix‐assisted laser desorption ionisation (MALDI) mass spectrometry was used, in an attempt to find firm evidence for the structure of the species produced in the thermal oxidative degradation of Nylon 6 (Ny6), at 250°C in air. The MALDI spectra of the products showed the presence of polymer chains containing aldehydes, amides, methyl and N‐formamide terminal groups. The aldehydes undergo further oxidation to produce carboxylic end groups. The formation of azomethines, from the further reaction of aldehydes with amino‐terminated Ny6 chains, is also supported by the appearance of specific peaks in the MALDI spectra.     

Introducing Water and Deep Eutectic Solvents in Organosodium Chemistry: Chemoselective Nucleophilic Functionalizations in Air

Advancing the development of perfecting the use of polar organometallics in bio-inspired solvents, we report on the effective generation in batch of organosodium compounds, by the oxidative addition of a C−Cl bond to sodium, a halogen/sodium exchange, or by direct sodiation, when using sodium bricks or neopentylsodium in hexane as sodium sources. C(sp³)-, C(sp²)-, and C(sp)-hybridized alkyl and (hetero)aryl sodiated species have been chemoselectively trapped (in competition with protonolysis), with a variety of electrophiles when working “on water”, or in biodegradable choline chloride/urea or L-proline/glycerol eutectic mixtures, under hydrous conditions and at room temperature. Additional benefits include a very short reaction time (20 s), a wide substrate scope, and good to excellent yields (up to 98 %) of the desired adducts. The practicality of the proposed protocol was demonstrated by setting up a sodium-mediated multigram-scale synthesis of the anticholinergic drug orphenadrine.     

Activation and Deactivation of Benzylic C−H Bonds Guided by Stereoelectronic Effects in Hydrogen Atom Transfer from Amides and Amines to Alkoxyl Radicals

Kinetic and product studies on the reactions of tert-alkoxyl radicals with secondary and tertiary alkanamides bearing benzylic α-C−H bonds, isoindoline, tetrahydroisoquinoline and the corresponding N-acetyl derivatives were carried out. Product studies on the reactions with the tert-butoxyl radical (tBuO⋅) point toward exclusive HAT from the benzylic α-C−H bonds. Comparison of the k_H values measured for reaction with the cumyloxyl radical (CumO⋅) with those obtained previously for the corresponding reactions of N-alkyl- and N,N-dialkylalkanamides, are indicative of a lack of benzylic activation and the operation of steric and stereoelectronic effects. Compared to N-methyl and N-ethyl groups, the presence of N-benzyl groups increases the barrier required to reach the optimal conformation for HAT, where the α-C−H bond to be cleaved is perpendicular to the plane of the amide, precluding concurrent overlap with the phenyl π-system. When the benzylic α-C−H bonds are in a conformation that allows for optimal overlap with both the phenyl π-system and the amide π-system or amine nitrogen lone pair, as in the isoindoline and tetrahydroisoquinoline derivatives, increases in k_H that exceed 2-orders of magnitude were observed, highlighting the strong contribution provided by stereoelectronic activation to these HAT processes.     

Intergranular Shielding for Ultrafine-Grained Mo-Doped Ni-Rich Li[Ni0.96Co0.04]O2 Cathode for Li-Ion Batteries with High Energy Density and Long Life

Deploying Ni-enriched (Ni≥95 %) layered cathodes for high energy-density lithium-ion batteries (LIBs) requires resolving a series of technical challenges. Among them, the structural weaknesses of the cathode, vigorous reactivity of the labile Ni⁴⁺ ion species, gas evolution and associated cell swelling, and thermal instability issues are critical obstacles that must be solved. Herein, we propose an intuitive strategy that can effectively ameliorate the degradation of an extremely high-Ni-layered cathode, the construction of ultrafine-scale microstructure and subsequent intergranular shielding of grains. The formation of ultrafine grains in the Ni-enriched Li[Ni_0.96Co_0.04]O₂ (NC96) cathode, achieved by impeding particle coarsening during cathode calcination, noticeably improved the mechanical durability and electrochemical performance of the cathode. However, the buildup of the strain-resistant microstructure in Mo-doped NC96 concurrently increased the cathode-electrolyte contact area at the secondary particle surface, which adversely accelerated parasitic reactions with the electrolyte. The intergranular protection of the refined microstructure resolved the remaining chemical instability of the Mo-doped NC96 cathode by forming an F-induced coating layer, effectively alleviating structural degradation and gas generation, thereby extending the battery's lifespan. The proposed strategies synergistically improved the structural and chemical durability of the NC96 cathode, satisfying the energy density, life cycle performance, and safety requirements for next-generation LIBs.