Supramolecular Biohybrid Construct for Photoconversion Based on a Bacterial Reaction Center Covalently Bound to Cytochrome c by an Organic Light Harvesting Bridge.

A supramolecular construct for solar energy conversion is developed by covalently bridging the reaction center (RC) from the photosynthetic bacterium Rhodobacter sphaeroides and cytochrome c (Cyt c) proteins with a tailored organic light harvesting antenna (hCy2). The RC-hCy2-Cyt c biohybrid mimics the working mechanism of biological assemblies located in the bacterial cell membrane to convert sunlight into metabolic energy. hCy2 collects visible light and transfers energy to the RC, increasing the rate of photocycle between a RC and Cyt c that are linked in such a way that enhances proximity without preventing protein mobility. The biohybrid obtained with average 1 RC/10 hCy2/1.5 Cyt c molar ratio features an almost doubled photoactivity versus the pristine RC upon illumination at 660 nm, and ∼10 times higher photocurrent versus an equimolar mixture of the unbound proteins. Our results represent an interesting insight into photoenzyme chemical manipulation, opening the way to new eco-sustainable systems for biophotovoltaics.

Bio-Inspired Redox-Adhesive Polydopamine Matrix for Intact Bacteria Biohybrid Photoanodes.

Interfacing intact and metabolically active photosynthetic bacteria with abiotic electrodes requires both establishing extracellular electron transfer and immobilizing the biocatalyst on electrode surfaces. Artificial approaches for photoinduced electron harvesting through redox polymers reported in literature require the separate synthesis of artificial polymeric matrices and their subsequent combination with bacterial cells, making the development of biophotoanodes complex and less sustainable. Herein, we report a one-pot biocompatible and sustainable approach, inspired by the byssus of mussels, that provides bacterial cells adhesion on multiple surfaces under wet conditions to obtain biohybrid photoanodes with facilitated photoinduced electron harvesting. Purple bacteria were utilized as a model organism, as they are of great interest for the development of photobioelectrochemical systems for H2 and NH3 synthesis, biosensing, and bioremediation purposes. The polydopamine matrix preparation strategy allowed the entrapment of active purple bacteria cells by initial oxygenic polymerization followed by electrochemical polymerization. Our results unveil that the deposition of bacterial cells with simultaneous polymerization of polydopamine on the electrode surface enables a 5-fold enhancement in extracellular electron transfer at the biotic/abiotic interface while maintaining the viability of the cells. The presented approach paves the way for a more sustainable development of biohybrid photoelectrodes.

The periodic table of photosynthetic purple non-sulfur bacteria: intact cell-metal ions interactions.

Photosynthetic purple non-sulfur bacteria (PNB) have been widely utilized as model organisms to study bacterial photosynthesis. More recently, the remarkable resistance of these microorganisms to several metals ions called particular interest. As a result, several research efforts were directed toward clarifying the interactions of metal ions with PNB. The mechanisms of metal ions active uptake and bioabsorption have been studied in detail, unveiling that PNB enable harvesting and removing various toxic ions, thus fostering applications in environmental remediation. Herein, we present the most important achievements in the understanding of intact cell-metal ions interactions and the approaches utilized to study such processes. Following, the application of PNB-metal ions interactions toward metal removal from contaminated environments is presented. Finally, the possible coupling of PNB with abiotic electrodes to obtain biohybrid electrochemical systems is proposed as a sustainable pathway to tune and enhance metal removal and monitoring.

Multifunctional Carrier Based on Halloysite/Laponite Hybrid Hydrogel for Kartogenin Delivery.

A novel carrier system based on halloysite nanotubes (HNT), for the potential intraarticular delivery of kartogenin (KGN) by means laponite (Lap) hydrogel (HNT/KGN/Lap), is developed. The drug was first loaded into HNT, and the hybrid composite obtained was used as filler for laponite hydrogel. Both the filler and the hydrogel were thoroughly investigated by several techniques and the hydrogel morphology was imaged by transmission electron microscopy. Furthermore, the gelating ability of laponite in the presence of the filler and the rheological properties of the hybrid hydrogel were also investigated. The kinetic release of kartogenin from HNT and HNT/Lap hybrid hydrogel was studied both in physiological conditions and in ex vivo synovial fluid. In the last case, the kinetic results highlighted that HNT carrier can effectively release KGN in a sustained manner for at least 38 days. Finally, a preliminary biological assays showed that the HNT/KGN/Lap hybrid hydrogel did not exhibit any cytotoxic effect.

Rapid carbonylative coupling reactions using palladium(I) dimers: applications to 11CO-radiolabelling for the synthesis of PET tracers.

Palladium dimers with sterically hindered phosphines have been shown to be excellent pre-catalysts for the aminocarbonylation of aryl halides to yield amides and one of them has been successfully employed as a pre-catalyst for the synthesis of (11)C-radiolabelled amides for PET imaging.

Reactions of diazo compounds with alkenes catalysed by [RuCl(cod)(Cp)]: effect of the substituents in the formation of cyclopropanation or metathesis products.

The reaction of diazo compounds with alkenes catalysed by complex [RuCl(cod)(Cp)] (cod = 1,5-cyclooctadiene, Cp = cyclopentadienyl) has been studied. The catalytic cycle involves in the first step the decomposition of the diazo derivative to afford the reactive [RuCl(Cp){=C(R(1))R(2)}] intermediate and a mechanism is proposed for this step based on a kinetic study of the simple coupling reaction of ethyl diazoacetate. The evolution of the Ru-carbene intermediate in the presence of alkenes depends on the nature of the substituents at both the diazo N(2)=C(R(1))R(2) (R(1), R(2) = Ph, H; Ph, CO(2)Me; Ph, Ph; C(R(1))R(2) = fluorene) and the olefin substrates R(3)(H)C=C(H)R(4) (R(3), R(4) = CO(2)Et, CO(2)Et; Ph, Ph; Ph, Me; Ph, H; Me, Br; Me, CN; Ph, CN; H, CN; CN, CN). A remarkable reactivity of the complex was recorded, especially towards unstable aryldiazo compounds and electron-poor olefins. The results obtained indicate that either cyclopropanation or metathesis products can be formed: the first products are favoured by the presence of a cyano substituent at the double bond and the second ones by a phenyl.