Ge nanocrystals in magnetron sputtered SiO2

Structural and optical properties of Ge nanocrystals in SiO₂ films created by magnetron sputtering and heat treatment have been investigated. The formation of nanocrystals is found to be influenced by the temperature of heat treatment and the Ge concentration in the films. After heat treatment at 1000 °C nanocrystals are present throughout the film, with the exception of a region close to the surface that does not contain nanocrystals. This effect is assigned to oxidation of Ge in this part of the film. The size distribution of the nanocrystals is analyzed by transmission electron microscopy for a range of deposition and heat-treatment parameters. By analyzing the transmission electron microscopy images, it is possible to estimate the fraction of nanoclusters that are crystalline for a given set of growth parameters. This analysis shows that all the nanoclusters are created in the crystalline state. Raman spectroscopy is employed to probe the Ge–Ge bonds. In combination with transmission electron microscopy, this information can be used to distinguish between growth modes such as nucleation or Ostwald ripening. The photoluminescence spectra exhibit a strong broad line at 625 nm, the presence of which is demonstrated to correlate to the presence of Ge nanocrystals. PACS 61.46.+w; 78.55.-m; 78.67.-n     

Lugdunomycin,an Angucycline‐Derived Molecule with Unprecedented Chemical Architecture

The angucyclines form the largest family of polycyclic aromatic polyketides, and have been studied extensively. Herein, we report the discovery of lugdunomycin, an angucycline‐derived polyketide, produced by Streptomyces species QL37. Lugdunomycin has unique structural characteristics, including a heptacyclic ring system, a spiroatom, two all‐carbon stereocenters, and a benzaza‐[4,3,3]propellane motif. Considering the structural novelty, we propose that lugdunomycin represents a novel subclass of aromatic polyketides. Metabolomics, combined with MS‐based molecular networking analysis of Streptomyces sp. QL37, elucidated 24 other rearranged and non‐rearranged angucyclines, 11 of which were previously undescribed. A biosynthetic route for the lugdunomycin and limamycins is also proposed. This work demonstrates that revisiting well‐known compound families and their producer strains still is a promising approach for drug discovery.     

Solid-State Nuclear Magnetic Resonance Techniques for the Structural Characterization of Geminal Alane-Phosphane Frustrated Lewis Pairs and Secondary Adducts

The first comprehensive solid-state nuclear magnetic resonance (NMR) characterization of geminal alane-phosphane frustrated Lewis pairs (Al/P FLPs) is reported. Their relevant NMR parameters (isotropic chemical shifts, direct and indirect ²⁷Al-³¹P spin-spin coupling constants, and ²⁷Al nuclear electric quadrupole coupling tensor components) have been determined by numerical analysis of the experimental NMR line shapes and compared with values computed from the known crystal structures by using density functional theory (DFT) methods. Our work demonstrates that the ³¹P NMR chemical shifts for the studied Al/P FLPs are very sensitive to slight structural inequivalences. The ²⁷Al NMR central transition signals are spread out over a broad frequency range (>200 kHz), owing to the presence of strong nuclear electric quadrupolar interactions that can be well-reproduced by the static ²⁷Al wideband uniform rate smooth truncation (WURST) Carr-Purcell-Meiboom-Gill (WCPMG) NMR experiment. ²⁷Al chemical shifts and quadrupole tensor components offer a facile and clear distinction between three- and four-coordinate aluminum environments. For measuring internuclear Al⋅⋅⋅P distances a new resonance-echo saturation-pulse double-resonance (RESPDOR) experiment was developed by using efficient saturation via frequency-swept WURST pulses. The successful implementation of this widely applicable technique indicates that internuclear Al⋅⋅⋅P distances in these compounds can be measured within a precision of ±0.1 Å.     

Input of solid-state 13C NMR to study permeation of wet archaeological bones by dicarboxylic fatty diacid-based chemicals

Conservation treatment of degraded archaeological osseous materials is still an open challenge, since no specific conservation protocol is currently available for restorers or museum curators. This work aims to test the efficiency of two original consolidant solutions in consolidating archaeological material. Archaeological osseous materials remain rare and sparsely available, it is a real drawback for optimization of conservation treatments, therefore in the present work a set of representative samples was chosen. The consolidants tested were a solution of disodium sebacate and a novel polyalcohol (SG1.2) obtained by esterification of 5 succinic diacids with 6 molecules of glycerol at 150°C. Characterization studies of archaeological bones, combining SEM microscopy, IR spectroscopy and high-resolution solid-state ¹³C NMR investigations, have been carried out to assess the effective permeation of bone by the consolidant solutions and to determine their chemical interactions with the residual components of archaeological bones. Although both water solutions significantly impregnate bone, we show that, the solution with disodium sebacate leads to chemical attack on the mineral component due to preferential precipitation of endogenous calcium by the sebacate ions. Such deleterious behaviour is not observed at all with the SG1,2 chemicals. The added value of the polyalcohol treatment as strengthening agent suitable for archaeological bony materials should be further demonstrated by mechanical and ageing tests.     

Dual nuclear magnetic resonance for probing intrinsic bone structure and a potential gut–bone axis in ovariectomized rats

Currently, the existence of a gut–bone axis receives massive attention, and while sound premises and indirect proofs exist for the gut–bone axis concept, few studies have provided actual data linking the gut and bone physically. This study aimed to exploit the versatile nature of nuclear magnetic resonance (NMR) to link NMR relaxometry data on bone mineralization with NMR spectroscopic profiling of gut metabolites. For this purpose, sample material was obtained from a 6-week intervention study with ovariectomized (OVX) rats (n = 49) fed with seven different diets varying in calcium content (0.2–6.0 mg/kg) and prebiotic fiber content (0–5.0% w/w). This design ensured a span in (i) calcium available for bone mineralization and (ii) metabolic activity in the gut. After termination of the intervention, longitudinal (T₁), transverse (T₂) relaxation, and mechanical bone strength were measured on the excised femur bones. A PLS model with high predictability (Q² = 0.86, R² = 0.997) was demonstrated between T₂ decay curves and femur mechanical strength. Correlations were established between bone T₂ populations and gut short-chain fatty acids. In conclusion, the present dual NMR approach showed strong correlation between T₂ relaxation and mechanical strength of the bone, and when metabolic activity in the gut was modulated by inulin, the potential existence of a gut–bone axis was demonstrated.     

Impact of Heteroatom Substitution on Dual-State Emissive Rigidified 2-(2’-hydroxyphenyl)benzazole Dyes: Towards Ultra-Bright ESIPT Fluorophores**

2-(2’-Hydroxyphenyl)benzazole (HBX) fluorophores are well-known excited-state intramolecular proton transfer (ESIPT) emitters largely studied for their synthetic versatility, photostability, strong solid-state fluorescence and ability to engineer dual emission, thus paving the way to applications as white emitters, ratiometric sensors, and cryptographic dyes. However, they are heavily quenched in solution, due to efficient non-radiative pathways taking place as a consequence of the proton transfer in the excited-state. In this contribution, the nature of the heteroring constitutive of these rigidified HBX dyes was modified and we demonstrate that this simple structural modification triggers major optical changes in terms of emission color, dual emission engineering, and importantly, fluorescent quantum yield. Investigation of the photophysical properties in solution and in the solid state of a series of ethynyl-TIPS extended HBX fluorophores, along with ab initio calculations demonstrate the very promising abilities of these dyes to act as bright dual-state emitters, in both solution (even in protic environments) and solid state.     

Evaluation of the Potential of Cobalamin Derivatives Bearing Ru(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy

The current photosensitizers (PSs) for photodynamic therapy (PDT) lack selectivity for cancer cells. To tackle this drawback, in view of selective cancer delivery, we envisioned conjugating two ruthenium polypyridyl complexes to vitamin B₁₂ (Cobalamin, Cbl) to take advantage of the solubility and active uptake of the latter. Ultimately, our results showed that the transcobalamin pathway is unlikely involved for the delivery of these ruthenium‐based PDT PSs, emphasizing the difficulty in successfully delivering metal complexes to cancer cells.