Search

Xe ions and Mo ions with 49-keV energy were implanted into an austenite stainless steel at doses between 1×1015 and 35×1015 ions cm-2. Grazing incidence X-ray diffraction was used to analyze the surface structure of implanted sample. Xe implantation went through differentiation of two types of austenite crystallites and formation of constrained ferrite. For low implantation doses, Mo first inserted into austenite cells inducing austenite lattice expansion. Then, as the Mo dose increased, this expansion was combined with the differentiation of two types of austenite crystallites. Above 6×1015 ions cm-2 a new bcc structure appeared: a ferrite with Mo was formed. High dose implantation leads to partial amorphisation. [Copyright &y& Elsevier]

Implantations of 59Co ions into nickel films at energies between 150 and 1000 keV have been performed. Cobalt depth profiles are measured by secondary ion mass spectrometry. The influence of oxygen flooding on the development of surface roughness has been studied in detail. Under the chosen measuring conditions, the mean sputtering rate is constant. Values of the most probable projected range have been extracted from the measured depth profiles and compared with SRIM calculations yielding a close agreement for the highest energies. However, it is found that SRIM underestimates the stopping power at low energy (E<400 keV) by 10–20%. [Copyright &y& Elsevier]

In this work, a water-soluble (hydrophilic) polymer was used to form a hydrophobic coating on silicon substrates (Si) in a two-step process comprising (i) the transformation of the polymer into an insoluble material and (ii) the structuring of this coating at nanometric and micrometric scales to achieve the desired hydrophobic behavior. Polyvinylpyrrolidone (PVP), a water-soluble commodity polymer, was crosslinked using benzophenone and UV irradiation to produce a water-insoluble PVP coating. The nanometric scale roughness of the coating was achieved by the addition of silica nanoparticles (NPs) in the coating. The micrometric scale roughness was achieved by forming vertical pillars of PVP/NP coating. To prepare these pillars, a perforated polystyrene (PS) template was filled with a PVP/NP suspension. Micrometer scale vertical pillars of PVP/silica NPs were produced by this method, which allowed us to tune the wettability of the surface, by combining the micrometric scale roughness of the pillars to the nanometric scale roughness provided by the nanoparticles at the surface. By adjusting the various experimental parameters, a hydrophobic PVP coating was prepared with a water contact angle of 110°, resulting in an improvement of more than 80% compared to the bare flat film with an equal amount of nanoparticles. This study paves the way for the development of a more simplified experimental approach, relying on a blend of polymers containing PVP and NPs, to form the micro/nano-structured PVP pillars directly after the deposition step and the selective etching of the sacrificial major phase.

Chiral naphthalene diimide ligands (NDIPhos) were exploited in rhodium-catalyzed enantioselective hydrogenation. The key feature of these ligands is their ability to self-assemble via π-π interactions to mimic bidentate ligands, offering a complementary method to traditional supramolecular strategies. This concept was further substantiated by computations with the composite electronic-structure method r 2 SCAN-3c.

β-Arylethylamines are prevalent structural motifs in molecules exhibiting biological activity. Here we report a sequential one-pot protocol for the 1,2-aminoarylation of alkenes with hydroxylammonium triflate salts and (hetero)arenes. Unlike existing methods, this reaction provides a direct entry to unprotected β-arylethylamines with remarkable functional group tolerance, allowing key drug-oriented functional groups to be installed in a two-step process. The use of hexafluoroisopropanol as a solvent in combination with an iron(II) catalyst proved essential to reaching high-value nitrogen-containing molecules., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The oxa-Pictet-Spengler reaction is arguably the most straightforward and modular way to construct the privileged isochroman motif, but its scope is largely limited to benzaldehyde derivatives and to electron-rich β-phenylethanols that lack substitution along the aliphatic chain. Here we describe a variant of this reaction starting from an epoxide, rather than an aldehyde, that greatly expands the scope and rate of the reaction (<1 h, 20 °C). Besides facilitating the initial Meinwald rearrangement, the use of hexafluoroisopropanol (HFIP) as a solvent expands the electrophile scope to include partners equivalent to ketones, aliphatic aldehydes, and phenylacetyl aldehydes, and the nucleophile scope to include modestly electronically deactivated and highly substituted β-phenylethanols. The products could be easily further derivatised in the same pot by subsequent ring-opening, reductions, and intra- and intermolecular Friedel-Crafts reactions, also in HFIP. Finally, owing to the high pharmacological relevance of the isochroman motif, the synthesis of drug analogues was demonstrated., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Photocatalysis has become a prominent tool in the arsenal of organic chemists to develop and (re)imagine transformations. However, only a handful of versatile organic photocatalysts (PCs) are available, hampering the discovery of new reactivities. Here, we report the design and complete physicochemical characterization of 9-aryl dihydroacridines (9ADA) and 12-aryl dihydrobenzoacridines (12ADBA) as strong reducing organic PCs. Punctual structural variations modulate their molecular orbital distributions and unlock locally or charge-transfer (CT) excited states. The PCs presenting a locally excited state showed better performances in photoredox defunctionalization processes (yields up to 92%), whereas the PCs featuring a CT excited state produced promising results in atom transfer radical polymerization under visible light (up to 1.21 Đ , and 98% I*). Unlike all the PC classes reported so far, 9ADA and 12ADBA feature a free NH group that enables a catalytic multisite proton-coupled electron transfer (MS-PCET) mechanism. This manifold allows the reduction of redox-inert substrates including aryl, alkyl halides, azides, phosphate and ammonium salts ( E red up to -2.83 vs SCE) under single-photon excitation. We anticipate that these new PCs will open new mechanistic manifolds in the field of photocatalysis by allowing access to previously inaccessible radical intermediates under one-photon excitation.

We report an unexpected rearrangement of 3-hydroxyoxindoles into benzoxazinones using electrochemistry. Our reaction employs mild and environmentally friendly conditions, and the benzoxazinone products are obtained in moderate to excellent yields. Mechanistic experiments suggest that a peroxide intermediate is likely involved.

Herein, we present a general electrochemical method to access unsymmetrical 3,3-disubstituted oxindoles by direct C-H functionalization where the oxindole fragment behaves as an electrophile. This Umpolung approach does not rely on stoichiometric oxidants and proceeds under mild, environmentally benign conditions. Importantly, it enables the functionalization of these scaffolds through C-O, and by extension to C-C or even C-N bond formation.

Film-forming systems are highly relevant to the topical administration of active ingredients (AI) to the body. Enhanced contact with the skin can increase the efficacy of delivery and penetration during prolonged exposure. However, after the evaporation of volatile solvents to form a thin film, the distribution of the ingredient should remain homogenous in order to ensure the effectiveness of the formula. This is especially critical for the use of hydrophobic molecules that have poor solubility in hydrophilic films. In order to address this concern, hydroxyphenethyl esters (PHE) of Punica granatum seed oil were prepared as a nanosuspension stabilised by poloxamers (NanoPHE). NanoPHE was then added to a formulation containing polyvinyl alcohol (PVA) as a film forming agent, Glycerol as a plasticiser and an antimicrobial agent, Sepicide TM HB. Despite their reliability, reference methods such as high-performance liquid chromatography are increasingly challenged due to the need for consumables and solvents, which is contrary to current concerns about green industry in the cosmetics field. Moreover, such methods fail to provide spatially resolved chemical information. In order to investigate the distribution of ingredients in the dried film, Confocal Raman imaging (CRI) coupled to Non-negatively Constrained Least Squares (NCLS) analysis was used. The reconstructed heat maps from a range of films containing systematically varying PHE concentrations highlighted the changes in spectral contribution from each of the ingredients. First, using NCLS scores it was demonstrated that the distributions of PVA, Glycerol, Sepicide TM HB and PHE were homogenous, with respective relative standard deviations (RSD) of 3.33%, 2.48%, 2.72% and 6.27%. Second, the respective relationships between ingredient concentrations in the films and their Raman responses, and the spectral abundance were established. Finally, a model for absolute quantification for PHE was be constructed using the percentage of spectral abundance. The prepared % w / w concentrations regressed against predicted % w / w concentrations, displaying high correlation (R 2 = 0.995), while the Root Mean Squared Error (0.0869% w / w PHE) confirmed the precision of the analysis. The mean percent relative error of 3.75% indicates the accuracy to which the concentration in dried films could be determined, further supporting the suitability of CRI for analysis of composite solid film matrix. Ultimately, it was demonstrated that nanoformulation of hydrophobic PHE provides homogenous distribution in PVA based film-forming systems independent of the concentration of NanoPHE used in the formula.