Supramolecular Luminescent Lanthanide Dimers for Fluoride Sequestering and Sensing

Lanthanide complexes (Ln=Eu, Tb, and Yb) that are based on a C₂‐symmetric cyclen scaffold were prepared and characterized. The addition of fluoride anions to aqueous solutions of the complexes resulted in the formation of dinuclear supramolecular compounds in which the anion is confined into the cavity that is formed by the two complexes. The supramolecular assembly process was monitored by UV/Vis absorption, luminescence, and NMR spectroscopy and high‐resolution mass spectrometry. The X‐ray crystal structure of the europium dimer revealed that the architecture of the scaffold is stabilized by synergistic effects of the Eu? F? Eu bridging motive, π stacking interactions, and a four‐component hydrogen‐bonding network, which control the assembly of the two [EuL] entities around the fluoride ion. The strong association in water allowed for the luminescence sensing of fluoride down to a detection limit of 24 nM .     

Lithiation of a Silyl Ether: Formation of an ortho‐Fries Hydroxyketone

A hydroxy‐directed alkylation of an N,N‐diethylarylamide using CIPE‐assisted α‐silyl carbanions (CIPE=complex‐induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3‐kinase (PI3K) inhibitor LY294002, are reported.     

Stripping the latex: the challenge of miniemulsion polymerization without initiator,costabilizer and surfactant

When finally processed to provide the function for which the latex was selected―binding, protecting, finishing―components such as surfactant, costabilizer or initiator become generally useless, not to say detrimental. In this study, we show that miniemulsion photopolymerization provides a suitable method to create latex without the apparent addition of these three compounds. Indeed, UV-driven monomer self-initiation can create initiating radicals without the aid of initiator, the fast in situ photogenerated polymer can hinder Ostwald ripening with the assistance of external costabilizer, and finally, UV-transparent clay can replace conventional surfactant to ensure colloidal stabilization. Each strategy has been developed individually before being combined together to end up with a unique miniemulsion procedure free of initiator, costabilizer and surfactant. Such approach paves the way to a simplified and environmentally improved pathway towards aqueous polymer dispersions.     

Nephrotoxicity assessments of benzo(a)pyrene during zebrafish embryogenesis

Benzo(a)pyrene is a chemical produced during the process of making fried, roasted, and smoked foods. It remains unclear whether benzo(a)pyrene affects the early development of human organs. In this study, we used the transgenic zebrafish line Tg(wt1b:GFP) as a model to assess benzo(a)pyrene-induced kidney malformation. By soaking zebrafish embryos in benzo(a)pyrene at various doses (2, 20, and 200 ppb), only a minor effect on the survival rate was detected (0 ppb: 97.8 ± 1.9 %; 2–200 ppb: 89.1 ± 5.8–91.5 ± 8.3 %). However, benzo(a)pyrene significantly affected the development of the kidney (malformation rates ranges from 50.0 ± 3.5 to 77.4 ± 5.3 %). Various abnormalities, such as unusual curving of pronephric tubes, swollen glomerulus, and incomplete development of pronephric ducts, were observed. This study provides a rapid and effective protocol for the evaluation of the notable effects of benzo(a)pyrene on embryonic kidney development.     

Thermal and Nonthermal Effects in Plasmon-Mediated Electrochemistry at Nanostructured Ag Electrodes

Hot carriers (HCs) and thermal effects, stemming from plasmon decays, are crucial for most plasmonic applications. However, quantifying these two effects remains extremely challenging due to the experimental difficulty in accurately measuring the temperature at reaction sites. Herein, we provide a novel strategy to disentangle HCs from photothermal effects based on the different traits of heat dissipation (long range) and HCs transport (short range), and quantitatively uncover the dominant and potential-dependent role of photothermal effect by investigating the rapid- and slow-response currents in plasmon-mediated electrochemistry at nanostructured Ag electrode. Furthermore, the plasmoelectric surface potential is found to contribute to the rapid-response currents, which is absent in the previous studies.     

Ferric Ion Driven Assembly of Catalase-like Supramolecular Photosensitizing Nanozymes for Combating Hypoxic Tumors

A facile approach to assemble catalase-like photosensitizing nanozymes with a self-oxygen-supplying ability was developed. The process involved Fe³⁺-driven self-assembly of fluorenylmethyloxycarbonyl (Fmoc)-protected amino acids. By adding a zinc(II) phthalocyanine-based photosensitizer (ZnPc) and the hypoxia-inducible factor 1 (HIF-1) inhibitor acriflavine (ACF) during the Fe³⁺-promoted self-assembly of Fmoc-protected cysteine (Fmoc-Cys), the nanovesicles Fmoc-Cys/Fe@Pc and Fmoc-Cys/Fe@Pc/ACF were prepared, which could be disassembled intracellularly. The released Fe³⁺ could catalyze the transformation of H₂O₂ enriched in cancer cells to oxygen efficiently, thereby ameliorating the hypoxic condition and promoting the photosensitizing activity of the released ZnPc. With an additional therapeutic component, Fmoc-Cys/Fe@Pc/ACF exhibited higher in vitro and in vivo photodynamic activities than Fmoc-Cys/Fe@Pc, demonstrating the synergistic effect of ZnPc and ACF.     

Direct fabrication and IV characterization of sub-surface conductive channels in diamond with MeV ion implantation

In the present work we report about the investigation of the conduction mechanism of sp² carbon micro-channels in single crystal diamond. The structures are fabricated with a technique which employs a MeV focused ion-beam to damage diamond in conjunction with variable thickness masks. This process changes significantly the structural properties of the target material, because the ion nuclear energy loss induces carbon conversion from sp³ to sp² state mainly at the end of range of the ions (few micrometers). Furthermore, placing a mask with increasing thickness on the sample it is possible to modulate the channels depth at their endpoints, allowing their electrical connection with the surface. A single-crystal HPHT diamond sample was implanted with 1.8 MeV He⁺ ions at room temperature, the implantation fluence was set in the range 2.1×10¹⁶-6.3×10¹⁷ ions cm^-2, determining the formation of micro-channels with a graded level of damage extending down to a depth of about 3 μm. After deposition of metallic contacts at the channels’ endpoints, the electrical characterization was performed measuring the I-V curves at variable temperatures in the 80-690 K range. The Variable Range Hopping model was used to fit the experimental data in the ohmic regime, allowing the estimation of characteristic parameters such as the density of localized states at the Fermi level. A value of 5.5×10¹⁷ states cm^-3 eV^-1 was obtained, in satisfactory agreement with values previously reported in literature. The power-law dependence between current and voltage is consistent with the space charge limited mechanism at moderate electric fields.     

Endemic infrared divergences in QED3 at finite temperature

We demonstrate that massless QED in three dimensions contains endemic infrared divergences. It is argued that these divergences do not affect observables; furthermore, it is possible to choose a gauge that renders the theory finite.     

On the cryogenic magnetic transition and martensitic transformation of the austenite phase of 7MoPLUS duplex stainless steel

The magnetic behaviour and martensitic transformation at cryogenic temperatures (down to 4 K) of the austenite phase of the duplex stainless steel (DSS), 7MoPLUS, were studied. As regards the prediction of Neel temperature, the empirical expressions for austenitic stainless steels are not applicable to the austenite phase of 7MoPLUS, although the composition of the austenite phase falls within the composition ranges within which the expressions were developed. Regarding the prediction of martensitic point Ms, the applicability of ‘old’ and recently developed expressions has been examined. The recently developed expressions, which take into account more alloying elements and their interactions, are not suitable for the austenite phase of 7MoPLUS. But for the ‘old’, simpler expressions, they seem to be valid in the sense that they all predict high stability of the austenite phase. Results obtained from 7MoPLUS were qualitatively the same as those obtained from another DSS, designated as 2205. Reasons for the applicability and inapplicability of these empirical expressions are suggested.