Platinum‐Promoted Ga/Al2O3 as Highly Active,Selective, and Stable Catalyst for the Dehydrogenation of Propane

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga³⁺ species are the active species and where Pt functions as a promoter.     

Multicomponent Peptide Stapling as a Diversity‐Driven Tool for the Development of Inhibitors of Protein–Protein Interactions

Stapled peptides are chemical entities in‐between biologics and small molecules, which have proven to be the solution to high affinity protein–protein interaction antagonism, while keeping control over pharmacological performance such as stability and membrane penetration. We demonstrate that the multicomponent reaction‐based stapling is an effective strategy for the development of α‐helical peptides with highly potent dual antagonistic action of MDM2 and MDMX binding p53. Such a potent inhibitory activity of p53‐MDM2/X interactions was assessed by fluorescence polarization, microscale thermophoresis, and 2D NMR, while several cocrystal structures with MDM2 were obtained. This MCR stapling protocol proved efficient and versatile in terms of diversity generation at the staple, as evidenced by the incorporation of both exo‐ and endo‐cyclic hydrophobic moieties at the side chain cross‐linkers. The interaction of the Ugi‐staple fragments with the target protein was demonstrated by crystallography.     

Site‐Selective Oxidation of Monolayered Liquid‐Exfoliated WS2 by Shielding the Basal Plane through Adsorption of a Facial Amphiphile

In recent years, various functionalization strategies for transition‐metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS₂ with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS₂ is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization.     

Half-metallicity at the non-polar surfaces of rock-salt and zinc-blende MgN

We discuss the electronic properties of non-polar surfaces of MgN rock-salt and zinc-blende crystals. We studied the (001) surface of the rock-salt and the (110) surface of the zinc-blende MgN with the use of an ab initio full-electron linearized augmented plane wave method within density functional theory. The structural parameters of the two surfaces were optimized by relaxing the position of the atoms in the unit cells in the force directions. The results of the calculations indicate that both rock-salt MgN (001) and ZB MgN (110) demonstrate half-metallic properties. The zinc-blende MgN (110) surface is electronically more stable as a half-metal than the rock-salt MgN (001) surface. The magnetic properties of the two systems are tailored mainly by the spin-polarization of electrons of N atoms.     

The synthesis and properties of bis-1,1'-(porphyrinyl)ferrocenes

Ferrocene-bridged bisporphyrins have been synthesized by the condensation of corresponding dipyrromethane-derived diols with a bisdipyrromethane. Purification of the final compounds has been achieved without chromatography. The specific geometry of these bisporphyrins makes them valuable starting points for building complex molecular and supramolecular structures. In particular it provides a core to which multiple sites of attractive intermolecular interactions can be attached thereby creating compounds predisposed to form complex networks by association. We have studied the structure of bis-1,1'-(porphyrinyl)ferrocenes by 1H NMR, UV-Vis and electrochemistry. Results have shown that complex dynamic processes occur in these molecules (which may involve conformers, formation of H-aggregates and tautomers) and that they have non-typical electrochemical behaviour.     

The umpolung of substituent effect in nucleophilic aromatic substitution. A new approach to the synthesis of N,N-disubstituted melamines (triazine triskelions) under mild reaction conditions

By the umpolung of substituent effect 1,3,5-triazines substituted with three dialkylamino groups were prepared under mild reaction conditions by treatment of cyanuric chloride with tertiary amines. Quaternary N-triazinylammonium salts were identified as reactive intermediates activating the triazine ring and strongly promoting the persubstitution of all chlorine atoms. The final degradation of intermediate N-triazinylammonium chlorides proceeded at room temperature or in boiling dichloromethane spontaneously within irreversible evolution of appropriate chloroalkane.     

The design, synthesis, and application of a chiral coupling reagent derived from strychnine for the enantioselective activation of a carboxylic group

The concept of a chiral coupling reagent for the enantioselective synthesis of peptides with a predictable configuration and enantiomeric purity from racemic substrates is presented. The reagent was prepared by treatment of strychninium tetrafluoroborate with 2-chloro-4,6-dimethoxy-1,3,5-triazine in the presence of sodium bicarbonate yielding N-(4,6-dimethoxy-1,3,5-triazin-2-yl)strychninium tetrafluoroborate in high yield, which is stable at room temperature, and in a broad range of solvents gave enriched Z-Ala-Phe-OMe (dr from 95/5 to 60/40) in high yield with d-configuration on the alanine residue starting from rac-Z-Ala-OH.     

Crystallographic evidence of Gly‐d,l‐Met oxidation to its sulfoxide in the presence of gold(III): solid solution of the racemic mixture of two diastereoisomers

Crystallographic analysis of a solid solution of two diastereoisomers, i.e. ({(1S,R)‐1‐carboxy‐3‐[(R,S)‐methylsulfinyl]propyl}aminocarbonyl)methanaminium tetrachloridoaurate(III) and ({(1S,R)‐1‐carboxy‐3‐[(S,R)‐methylsulfinyl]propyl}aminocarbonyl)methanaminium tetrachloridoaurate(III), (C₇H₁₅N₂O₄S)[AuCl₄], has shown that in the presence of gold(III), the methionine part of the Gly‐d ,l ‐Met dipeptide is oxidized to sulfoxide, and no coordination to the Au^III cation through the S atom of the sulfoxide is observed. In view of our observation, literature reports that methionine acts as an N,S‐bidentate donor ligand forming stable gold(III) complexes require verification. Moreover, it has been demonstrated that crystallization of the oxidation product leads to a substantial 77:23 excess of both S‐methionine/R‐sulfoxide and R‐methionine/S‐sulfoxide over S‐methionine/S‐sulfoxide and R‐methionine/R‐sulfoxide. The presence of two different diastereoisomers at the same crystallographic site is a source of static disorder at this site.     

Small Noncytotoxic Carbon Nano‐Onions: First Covalent Functionalization with Biomolecules

Small carbon nano‐onions (CNOs, 6–8 shells) were prepared in high yield and functionalized with carboxylic groups by chemical oxidation. After functionalization these nanostructures were soluble in aqueous solutions. 3‐(4,5‐dimethylthiazol‐2‐yl)‐5‐(3‐carboxymethoxyphenyl)‐2‐(4‐sulfophenyl)‐2 tetrazolium (MTS) tests showed excellent cytocompatibility of all CNOs analyzed at 30 and 300 μg mL^?1, so these carbon nanostructures can be safely used for biological applications. The first covalent functionalization of oxidized CNOs (ox‐CNOs) with biomolecules, by using biotin–avidin interactions is reported here. Multilayers were prepared on a gold surface by layer‐by‐layer assembly and the process was monitored by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy (AFM). Covalent binding of molecules to the short amine‐terminated organosulfur monolayers was assessed by Fourier transform infrared spectroscopy using total attenuated reflactance mode (FT‐IR/HATR).     

Preparation, characterization and photocatalytic activity of metal-loaded NaNbO3

Fe-, Ni-, Co- and Ag- loaded NaNbO₃ catalysts were prepared and their activities have been investigated in the reaction of photocatalytic hydrogen generation. Me/NaNbO₃ were synthesized by impregnation of NaNbO₃ in an aqueous solution of metal nitrates and then by calcination at the temperature of 400 °C. The crystallographic phases and optical and vibronic properties were examined by X-ray diffraction (XRD) and diffuse reflectance (DR) UV-vis and resonance Raman spectroscopic methods, respectively. Morphology and chemical composition of the produced samples were studied using a high-resolution transmission electron microscope (HR-TEM) and an energy dispersive X-Ray spectrometer (EDX) as its mode. The detailed analysis has revealed that all the investigated catalysts exhibit high crystallinity and the presence of Fe₂O₃, NiO, Co₃O₄ and Ag₂O oxides on Me/NaNbO₃ was confirmed. Finally, the influence of different metal loadings (Fe, Ni, Co and Ag) on the photocatalytic activity of NaNbO₃ for photocatalytic hydrogen generation has been investigated. Here we report that among all the Me/NaNbO₃ photocatalysts Ag-loaded NaNbO₃ exhibited higher photocatalytic efficiency for photocatalytic hydrogen generation than NaNbO₃.