Reversible Redox‐Driven Crystallization in a Paracyclophane Monolayer at a Solid–Liquid Interface

The development and integration of cyclophanes into future functional materials require a detailed understanding of the physicochemical principles that underlie their properties, phase behavior, and in particular the relationship between structure and function. Here, electrochemically switchable crystallization of a ferrocene‐bearing 3D Janus tecton (M‐Fc) at the interface between highly oriented pyrolytic graphite (HOPG) and an electrolyte solution is demonstrated. The M‐Fc adlayer is successfully visualized under both ambient and electrochemical conditions using scanning tunneling microscopy. Voltammetric measurements show a surface‐confined redox process for the M‐Fc modified surface that drives the phase transition between a visible 2D ordered linear phase (M‐Fc0, with ferrocene in the neutral state) and an invisible gas‐like adsorption layer with high mobility when ferrocene is oxidized, M‐Fc+, and a “square scheme” mechanism explains the data. Analogous experiments in a ferrocene‐free tecton adlayer show no phase transition and confirm that the dynamics in M‐Fc are redox‐driven. On‐surface 3D nanoarchitectures are also demonstrated by forming inclusion complexes between M‐Fc and β‐cyclodextrin and device behavior through electrochemical scanning tunneling spectroscopy (STS). These results showcase the functional potential of this class of cyclophanes, which can find use in actuators, optical crystals, and other smart materials

Characterization of an Alkali- and Halide-Resistant Laccase Expressed in E. coli: CotA from <i>Bacillus clausii</i>

The limitations of fungal laccases at higher pH and salt concentrations have intensified the search for new extremophilic bacterial laccases. We report the cloning, expression, and characterization of the bacterial cotA from Bacillus clausii, a supposed alkalophilic ortholog of cotA from B. subtilis. Both laccases were expressed in E. coli strain BL21(DE3) and characterized fully in parallel for strict benchmarking. We report activity on ABTS, SGZ, DMP, caffeic acid, promazine, phenyl hydrazine, tannic acid, and bilirubin at variable pH. Whereas ABTS, promazine, and phenyl hydrazine activities vs. pH were similar, the activity of B. clausii cotA was shifted upwards by ~0.5-2 pH units for the simple phenolic substrates DMP, SGZ, and caffeic acid. This shift is not due to substrate affinity (K(M)) but to pH dependence of catalytic turnover: The k(cat) of B. clausii cotA was 1 s⁻¹ at pH 6 and 5 s⁻¹ at pH 8 in contrast to 6 s⁻¹ at pH 6 and 2 s⁻¹ at pH 8 for of B. subtilis cotA. Overall, k(cat)/K(M) was 10-fold higher for B. subtilis cotA at pH(opt). While both proteins were heat activated, activation increased with pH and was larger in cotA from B. clausii. NaCl inhibited activity at acidic pH, but not up to 500-700 mM NaCl in alkaline pH, a further advantage of the alkali regime in laccase applications. The B. clausii cotA had ~20 minutes half-life at 80°C, less than the ~50 minutes at 80°C for cotA from B. subtilis. While cotA from B. subtilis had optimal stability at pH~8, the cotA from B. clausii displayed higher combined salt- and alkali-resistance. This resistance is possibly caused by two substitutions (S427Q and V110E) that could repel anions to reduce anion-copper interactions at the expense of catalytic proficiency, a trade-off of potential relevance to laccase optimization

An electrochromic ionic liquid: design, characterisation and performance in a solid state platform

This work describes the synthesis and characteristics of a novel electrochromic ionic liquid (IL) based on a phosphonium core tethered to a viologen moiety. When integrated into a solid-state electrochromic platform, the viologen modified IL behaved as both the electrolyte and the electrochromic material. Platform fabrication was achieved through in situ photo-polymerisation and encapsulation of this novel IL within a hybrid sol-gel. Important parameters of the platform performance, including its coloration efficiency, switching kinetics and optical properties were characterised using UV/Vis spectroscopy and cyclic voltammetry in tandem. The electrochromic platform exhibits a coloration efficiency of 10.72 cm2C-1, and a varied optical output as a function of the incident current. Despite the rather viscous nature of the material, the platform exhibited approximately two orders of magnitude faster switching kinetics (221 seconds to reach 95 % absorbance) when compared to previously reported electrochromic ILs (18,000 seconds)

Ionic liquids at electrified interfaces

Until recently, “room-temperature” (<100–150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)–(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of “first-generation” room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the “later generation” RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in “cocktails” of one’s choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost “universal” solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) “sister-systems”.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules

Organic-inorganic supramolecular solid catalyst boosts organic reactions in water

[EN] Coordination polymers and metal-organic frameworks are appealing as synthetic hosts for mediating chemical reactions. Here we report the preparation of a mesoscopic metal-organic structure based on single-layer assembly of aluminium chains and organic alkylaryl spacers. The material markedly accelerates condensation reactions in water in the absence of acid or base catalyst, as well as organocatalytic Michael-type reactions that also show superior enantioselectivity when comparing with the host-free transformation. The mesoscopic phase of the solid allows for easy diffusion of products and the catalytic solid is recycled and reused. Saturation transfer difference and two-dimensional H-1 nuclear Overhauser effect NOESY NMR spectroscopy show that non-covalent interactions are operative in these host-guest systems that account for substrate activation. 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«One pot synthesis of hydroxylated and amino-hydroxylated triglycerides»

International audienc

«Cyclodextrins in mechanochemical synthesis and catalysis»

International audienc

«Host-Guests Relations and Selforganization in Homogeneous Catalysis»

International audienc

Hydroformylation of vegetable oils: More than 50 years of technical innovation, successful research, and development

International audienceno abstrac

«One pot synthesis of hydroxylated or amino-hydroxylated triglycerides»

International audienc