Role of Intragap States in Sensitized Sb-Doped Tin Oxide Photoanodes for Solar Fuels Production.

In view of developing photoelectrosynthetic cells which are able to store solar energy in chemical bonds, water splitting is usually the reaction of choice when targeting hydrogen production. However, alternative approaches can be considered, aimed at substituting the anodic reaction of water oxidation with more commercially capitalizable oxidations. Among them, the production of bromine from bromide ions was investigated long back in the 1980s by Texas Instruments. Herein we present optimized perylene-diimide (PDI)-sensitized antimony-doped tin oxide (ATO) photoanodes enabling the photoinduced HBr splitting with >4 mA/cm2 photocurrent densities under 0.1 W/cm2 AM1.5G illumination and 91 ± 3% faradaic efficiencies for bromine production. These remarkable results, among the best currently reported for the photoelectrochemical Br- oxidation by dye sensitized photoanodes, are strongly related to the occupancy extent of ATO's intragap (IG) states, generated upon Sb-doping, as demonstrated by comparing their performances with PDI-sensitized analogues on both undoped SnO2- and TiO2-passivated ATO scaffolds by means of (spectro)electrochemistry and electrochemical impedance spectroscopy. The architecture of the ATO-PDI photoanodic assembly was further modified via the introduction of a molecular iridium-based water oxidation catalyst, thus proving the versatility of the proposed hybrid interfaces as photoanodic platforms for photoinduced oxidations in PEC devices.

Combined Covalent and Supramolecular Polymerization To Reinforce Perylenebisimide Photosynthetic "Quantasomes".

Invited for the cover of this issue are the groups of Marcella Bonchio at the University of Padova and Jérôme Canivet at the CNRS-University of Lyon. The image depicts the hierarchical self-organization of bio-inspired quantasomes, crosslinked within a polystyrene network to enchain their lateral and orthogonal proximity for long-lasting oxygen evolution using green photons. Read the full text of the article at 10.1002/chem.202303784.

Celebrating Maurizio Prato's Passion, Talent and Imagination.

This Editorial introduces a Special Collection of papers dedicated to Maurizio Prato, featuring prominent examples of his team's efforts to integrate complex frontier research with pioneering achievements in the field of carbon nanostructures and molecular nanoscience.

Combined Covalent and Supramolecular Polymerization to Reinforce Perylenebisimide Photosynthetic "Quantasomes".

PSII-inspired quantasomes have emerged as promising artificial photosystems evolving oxygen from water due to their integrated multi-chromophore asset, hierarchical architecture, and efficient light-harvesting capabilities. In this study, we adopt a combined covalent and supramolecular strategy by implementing a poly-styrene backbone that reinforces proximity and pairing between adjacent perylenebisimide (PBI) quantasome units. The covalent fixation of the quantasome network results in a significant enhancement of the photoelectrocatalytic performance on engineered IO-ITO photoanodes, with up to 290 % photocurrent increase (J up to 100 µA cm-2, λ >450 nm, applied bias <1.23 V vs RHE, F.E.O2 >80 %) compared to the non-polymerized analog. Moreover, the direct PBI-quantasome polymerization on the photoanode surface was performed by light irradiation of the radical initiator 2,2'-Azobis(2-methylpropionamidine), improving the photoelectrode robustness under high solar irradiance (>8 suns) and limiting the photocurrent loss (<20 %) at 1.52 V vs RHE compared to the non-polymerized system.

A breath of sunshine: oxygenic photosynthesis by functional molecular architectures.

The conversion of light into chemical energy is the game-changer enabling technology for the energetic transition to renewable and clean solar fuels. The photochemistry of interest includes the overall reductive/oxidative splitting of water into hydrogen and oxygen and alternatives based on the reductive conversion of carbon dioxide or nitrogen, as primary sources of energy-rich products. Devices capable of performing such transformations are based on the integration of three sequential core functions: light absorption, photo-induced charge separation, and the photo-activated breaking/making of molecular bonds via specific catalytic routes. The key to success does not rely simply on the individual components' performance, but on their optimized integration in terms of type, number, geometry, spacing, and linkers dictating the photosynthetic architecture. Natural photosynthesis has evolved along this concept, by integrating each functional component in one specialized "body" (from the Greek word "soma") to enable the conversion of light quanta with high efficiency. Therefore, the natural "quantasome" represents the key paradigm to inspire man-made constructs for artificial photosynthesis. The case study presented in this perspective article deals with the design of artificial photosynthetic systems for water oxidation and oxygen production, engineered as molecular architectures then rendered on electrodic surfaces. Water oxidation to oxygen is indeed the pervasive oxidative reaction used by photosynthetic organisms, as the source of reducing equivalents (electrons and protons) to be delivered for the processing of high-energy products. Considering the vast and abundant supply of water (including seawater) as a renewable source on our planet, this is also a very appealing option for photosynthetic energy devices. We will showcase the progress in the last 15 years (2009-2023) in the strategies for integrating functional building blocks as molecular photosensitizers, multi-redox water oxidation catalysts and semiconductor materials, highlighting how additional components such as redox mediators, hydrophilic/hydrophobic pendants, and protective layers can impact on the overall photosynthetic performance. Emerging directions consider the modular tuning of the multi-component device, in order to target a diversity of photocatalytic oxidations, expanding the scope of the primary electron and proton sources while enhancing the added-value of the oxidation product beyond oxygen: the selective photooxidation of organics combines the green chemistry vision with renewable energy schemes and is expected to explode in coming years.

Unveiling the impact of the light-source and steric factors on [2+2] heterocycloaddition reactions.

Information gained from in-depth mechanistic investigations can be used to control the selectivity of reactions, leading to the expansion of the generality of synthetic processes and the discovery of new reactivity. Here, we investigate the mechanism of light-driven [2+2] heterocycloadditions (Paternò-Büchi reactions) between indoles and ketones to develop insight into these processes. Using ground-state UV-Vis absorption and transient absorption spectroscopy (TAS), together with DFT calculations, we found that the reactions can proceed via an exciplex or electron-donor-acceptor (EDA) complex, which are key intermediates in determining the stereoselectivity of the reactions. We used this discovery to control the diastereoselectivity of the reactions, gaining access to previously inaccessible diastereoisomeric variants. When moving from 370 to 456 nm irradiation, the EDA complex is increasingly favoured, and the diastereomeric ratio (d.r.) of the product moves from >99:<1 to 47:53. In contrast, switching from methyl to ipropyl substitution favours the exciplex intermediate, reversing the d.r. from 89:11 to 16:84. Our study shows how light and steric parameters can be rationally used to control the diastereoselectivity of photoreactions, creating mechanistic pathways to previously inaccessible stereochemical variants.

Fluoropolymer Membranes for Membrane Distillation and Membrane Crystallization.

Fluoropolymer membranes are applied in membrane operations such as membrane distillation and membrane crystallization where hydrophobic porous membranes act as a physical barrier separating two phases. Due to their hydrophobic nature, only gaseous molecules are allowed to pass through the membrane and are collected on the permeate side, while the aqueous solution cannot penetrate. However, these two processes suffer problems such as membrane wetting, fouling or scaling. Membrane wetting is a common and undesired phenomenon, which is caused by the loss of hydrophobicity of the porous membrane employed. This greatly affects the mass transfer efficiency and separation efficiency. Simultaneously, membrane fouling occurs, along with membrane wetting and scaling, which greatly reduces the lifespan of the membranes. Therefore, strategies to improve the hydrophobicity of membranes have been widely investigated by researchers. In this direction, hydrophobic fluoropolymer membrane materials are employed more and more for membrane distillation and membrane crystallization thanks to their high chemical and thermal resistance. This paper summarizes different preparation methods of these fluoropolymer membrane, such as non-solvent-induced phase separation (NIPS), thermally-induced phase separation (TIPS), vapor-induced phase separation (VIPS), etc. Hydrophobic modification methods, including surface coating, surface grafting and blending, etc., are also introduced. Moreover, the research advances on the application of less toxic solvents for preparing these membranes are herein reviewed. This review aims to provide guidance to researchers for their future membrane development in membrane distillation and membrane crystallization, using fluoropolymer materials.

Enhancing Oxygenic Photosynthesis by Cross-Linked Perylenebisimide "Quantasomes".

As the natural-born photoelectrolyzer for oxygen delivery, photosystem II (PSII) is hardly replicated with man-made constructs. However, building on the "quantasome" hypothesis ( Science 1964, 144, 1009-1011), PSII mimicry can be pared down to essentials by shaping a photocatalytic ensemble (from the Greek term "soma" = body) where visible-light quanta trigger water oxidation. PSII-inspired quantasomes (QS) readily self-assemble into hierarchical photosynthetic nanostacks, made of bis-cationic perylenebisimides (PBI2+) as chromophores and deca-anionic tetraruthenate polyoxometalates (Ru4POM) as water oxidation catalysts ( Nat. Chem. 2019, 11, 146-153). A combined supramolecular and click-chemistry strategy is used herein to interlock the PBI-QS with tetraethylene glycol (TEG) cross-linkers, yielding QS-TEGlock with increased water solvation, controlled growth, and up to a 340% enhancement of the oxygenic photocurrent compared to the first generation QS, as probed on 3D-inverse opal indium tin oxide electrodes at 8.5 sun irradiance (λ > 450 nm, 1.28 V vs RHE applied bias, TOFmax = 0.096 ± 0.005 s-1, FEO2 > 95%). Action spectra, catalyst mass-activity, light-management, photoelectrochemical impedance spectroscopy (PEIS) together with Raman mapping of TEG-templated hydration shells point to a key role of the cross-linked PBI/Ru4POM nanoarrays, where the interplay of hydrophilic/hydrophobic domains is reminiscent of PSII-rich natural thylakoids.

Mechanism of CK2 Inhibition by a Ruthenium-Based Polyoxometalate.

CK2 is a Ser/Thr protein kinase involved in many cellular processes such as gene expression, cell cycle progression, cell growth and differentiation, embryogenesis, and apoptosis. Aberrantly high CK2 activity is widely documented in cancer, but the enzyme is also involved in several other pathologies, such as diabetes, inflammation, neurodegeneration, and viral infections, including COVID-19. Over the last years, a large number of small-molecules able to inhibit the CK2 activity have been reported, mostly acting with an ATP-competitive mechanism. Polyoxometalates (POMs), are metal-oxide polyanionic clusters of various structures and dimensions, with unique chemical and physical properties. POMs were identified as nanomolar CK2 inhibitors, but their mechanism of inhibition and CK2 binding site remained elusive. Here, we present the biochemical and biophysical characterizing of the interaction of CK2α with a ruthenium-based polyoxometalate, [Ru4(µ-OH)2(µ-O)4(H2O)4 (γ-SiW10O36)2]10- (Ru4POM), a potent inhibitor of CK2. Using analytical Size-Exclusion Chromatography (SEC), Isothermal Titration Calorimetry (ITC), and SAXS we were able to unravel the mechanism of inhibition of Ru4POM. Ru4POM binds to the positively-charged substrate binding region of the enzyme through electrostatic interactions, triggering the dimerization of the enzyme which consequently is inactivated. Ru4POM is the first non-peptide molecule showing a substrate-competitive mechanism of inhibition for CK2. On the basis of SAXS data, a structural model of the inactivated (CK2α)2(Ru4POM)2 complex is presented.

The Photochemical Activity of a Halogen-Bonded Complex Enables the Microfluidic Light-Driven Alkylation of Phenols.

A mild light-driven protocol for the direct alkylation of phenols is reported. The process is driven by the photochemical activity of a halogen-bonded complex formed upon complexation of the in situ generated electron-rich phenolate anion with the α-iodosulfone. The reaction proceeds rapidly (10 min) under microfluidic conditions, delivering a wide variety of ortho-alkylated products (27 examples, up to 97% yield, >20:1 regioselectivity, on a gram scale), including densely functionalized bioactive phenol derivatives.

Basicity as a Thermodynamic Descriptor of Carbanions Reactivity with Carbon Dioxide: Application to the Carboxylation of α,ß-Unsaturated Ketones.

The utilization of carbon dioxide as a raw material represents nowadays an appealing strategy in the renewable energy, organic synthesis, and green chemistry fields. Besides reduction strategies, carbon dioxide can be exploited as a single-carbon-atom building block through its fixation into organic scaffolds with the formation of new C-C bonds (carboxylation processes). In this case, activation of the organic substrate is commonly required, upon formation of a carbanion C-, being sufficiently reactive toward the addition of CO2. However, the prediction of the reactivity of C- with CO2 is often problematic with the process being possibly associated with unfavorable thermodynamics. In this contribution, we present a thermodynamic analysis combined with density functional theory calculations on 50 organic molecules enabling the achievement of a linear correlation of the standard free energy (ΔG0) of the carboxylation reaction with the basicity of the carbanion C-, expressed as the pKa of the CH/C- couple. The analysis identifies a threshold pKa of ca 36 (in CH3CN) for the CH/C- couple, above which the ΔG0 of the carboxylation reaction is negative and indicative of a favorable process. We then apply the model to a real case involving electrochemical carboxylation of flavone and chalcone as model compounds of α,ß-unsaturated ketones. Carboxylation occurs in the ß-position from the doubly reduced dianion intermediates of flavone and chalcone (calculated ΔG0 of carboxylation in ß = -12.8 and -20.0 Kcalmol-1 for flavone and chalcone, respectively, associated with pKa values for the conjugate acids of 50.6 and 51.8, respectively). Conversely, the one-electron reduced radical anions are not reactive toward carboxylation (ΔG0 > +20 Kcalmol-1 for both substrates, in either α or ß position, consistent with pKa of the conjugate acids < 18.5). For all the possible intermediates, the plot of calculated ΔG0 of carboxylation vs. pKa is consistent with the linear correlation model developed. The application of the ΔG0 vs. pKa correlation is finally discussed for alternative reaction mechanisms and for carboxylation of other C=C and C=O double bonds. These results offer a new mechanistic tool for the interpretation of the reactivity of CO2 with organic intermediates.

Water-Assisted Concerted Proton-Electron Transfer at Co(II)-Aquo Sites in Polyoxotungstates With Photogenerated RuIII (bpy)33+ Oxidant.

The cobalt substituted polyoxotungstate [Co6 (H2 O)2 (α-B-PW9 O34 )2 (PW6 O26 )]17- (Co6) displays fast electron transfer (ET) kinetics to photogenerated RuIII (bpy)33+ , 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II)-OH2 and Co6(II)-OH, respectively, whose speciation in aqueous solution is associated to a pKa of 7.6), and generates a Co(III)-OH moiety (Co6(III)-OH), as proven by transient absorption spectroscopy; (ii) at pH>pKa , the Co6(II)-OH→RuIII (bpy)33+ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH

Enhancing the biological activity of polyoxometalate-peptide nano-fibrils by spacer design.

Polyoxometalates (POMs) and peptides can be conjugated to yield novel bio-hybrids with potential application as nanodrugs. However, the observed POM-induced folding of the peptide prevents its availability towards biological targets. An Anderson-Evans POM was functionalized with a bombesin analog peptide and engineered by adding a tailored hydrophilic and anionic spacer between the two moieties, to make the targeting sequence more accessible and enable an unprecedented cancer cell recognition capability.

Aldosterone synthase inhibitors for cardiovascular diseases: A comprehensive review of preclinical, clinical and in silico data.

Aldosterone, the main mineralocorticoid hormone, plays a fundamental role in maintaining blood pressure (BP)and volume under hypovolemic conditions. However, in numerous diseases, where it is produced in excess, it plays a detrimental role and contributes to cardiovascular events and ultimately to death in a multitude of patients. The seminal observation that the fungicide-derivative fadrozole blunted steroidogenesis has led to develop several agents to inhibit aldosterone synthase (AS, CYP11B2), the mitochondrial NADH-dependent enzyme that is necessary for aldosterone biosynthesis. Aldosterone synthase inhibitors (ASI) have, thereafter, been conceived and investigated in phase I and phase II studies. We herein reviewed the ASIs available so far considering their chemical structure, the related aldosterone synthase binding and pharmacodynamic properties. We also examined the promising results obtained with ASIs that have already been tested in phase II human studies.

Electrochemical Conversion of CO2 to CO by a Competent FeI Intermediate Bearing a Schiff Base Ligand.

Iron complexes with a N2 O2 -type N,N'-bis(salicylaldehyde)-1,2-phenylenediamine salophen ligand catalyze the electrochemical reduction of CO2 to CO in acetonitrile with phenol as the proton donor, giving rise to 90-99 % selectivity, faradaic efficiency up to 58 %, and turnover frequency up to 103  s-1 at an overpotential of 0.65 V. This novel class of molecular catalyst for CO2 reduction operate through a mononuclear FeI intermediate, with phenol being involved in the process with first-order kinetics. The molecular nature of the catalyst and the low cost, easy synthesis and functionalization of the salophen ligand paves the way for catalyst engineering and optimization. Competitive electrodeposition of the coordination complex at the electrode surface results in the formation of iron-based nanoparticles, which are active towards heterogeneous electrocatalytic processes mainly leading to proton reduction to hydrogen (faradaic efficiency up to 80 %) but also to the direct reduction of CO2 to methane with a faradaic efficiency of 1-2 %.

Novel iridium complexes with N-heterocyclic dicarbene ligands in light-driven water oxidation catalysis: photon management, ligand effect and catalyst evolution.

Iridium complexes [IrClCp*diNHC]PF6, with N-heterocyclic dicarbene (diNHC) and pentamethylcyclopentadienyl (Cp*) ligands, have been investigated in light driven water oxidation catalysis within the Ru(bpy)32+/S2O82- cycle (bpy = 2,2'-bipyridine). In particular, the effect of different diNHC ligands was evaluated by employing the complex 1a (diNHC = 1,1'-dimethyl-3,3'-ethylenediimidazol-2,2'-diylidene) and the novel and structurally characterised 2 (diNHC = 1,1'-dimethyl-3,3'-ethylene-5,5'-dibromodiimidazol-2,2'-diylidene) and 3 (diNHC = 1,1'-dimethyl-3,3'-ethylene-dibenzimidazol-2,2'-diylidene). The presented results include: (i) a photon management analysis of the 1a/Ru(bpy)32+/S2O82- system, revealing two regimes of O2 evolution rate, being dependent on the light intensity at low photon flux, where the system reaches an overall quantum yield up to 0.17 ± 0.01 (quantum efficiency 34 ± 2%), while being independent of light intensity at high photon flux thus indicating a change of limiting step; (ii) a trend of O2 evolution activity that follows the order 1a > 2 > 3 both under low and high photon flux conditions, with the reactivity that is favoured by the electron donating nature of the diNHC ligand, quantified on the basis of the carbene carbon chemical shift; (iii) an analogous trend also in the bimolecular rate constants of electron transfer kET from the iridium species to photogenerated Ru(bpy)33+, with kET values in the range 4.2-6.1 × 104 M-1 s-1, thus implying a significant reorganisation energy to the iridium sphere; (iv) the evolution of 1a, as the most active Ir species in the series, to mononuclear iridium species with lower molecular weight and originating from oxidative transformation of the organic ligand scaffold, as proven by converging UV-Vis, MALDI-MS and 1H-NMR evidences. These results can be used for the further design and engineering of novel catalysts.

Light-Triggered Catalytic Asymmetric Allylic Benzylation with Photogenerated C-Nucleophiles.

Herein is reported the asymmetric allylic benzylation of Morita-Baylis-Hillman (MBH) carbonates with 2-methylbenzophenone (MBP) derivatives as nonstabilized photogenerated C-nucleophiles. The dual activation of both reaction partners, chiral Lewis-base activation of the electrophile and light activation of the nucleophile, enables the stereoselective installation of benzyl groups at the allylic position to forge tertiary and quaternary carbon centers.

Photoanodes for water oxidation with visible light based on a pentacyclic quinoid organic dye enabling proton-coupled electron transfer.

A pentacyclic quinoid dye, KuQ(O)3OH, combining (i) extended visible absorption up to 600 nm, (ii) excited state reduction potential >2 V vs. NHE, and (iii) a photoinduced proton-coupled electron transfer mechanism, has been used for the fabrication of dye-sensitized SnO2 photoanodes integrating a ruthenium polyoxometalate water oxidation catalyst. The resulting photoelectrode SnO2|KuQ(O)3OH|Ru4POM displays a light harvesting efficiency up to 90% in the range 500-600 nm, an onset potential as low as 0.2 V vs. NHE at pH 5.8, photoinduced oxygen evolution with a faradaic efficiency of 70 ± 15% and an absorbed-photon-to-current efficiency up to 0.12 ± 0.01%.

Catalytic processing in ruthenium-based polyoxometalate coacervate protocells.

The development of programmable microscale materials with cell-like functions, dynamics and collective behaviour is an important milestone in systems chemistry, soft matter bioengineering and synthetic protobiology. Here, polymer/nucleotide coacervate micro-droplets are reconfigured into membrane-bounded polyoxometalate coacervate vesicles (PCVs) in the presence of a bio-inspired Ru-based polyoxometalate catalyst to produce synzyme protocells (Ru4PCVs) with catalase-like activity. We exploit the synthetic protocells for the implementation of multi-compartmentalized cell-like models capable of collective synzyme-mediated buoyancy, parallel catalytic processing in individual horseradish peroxidase-containing Ru4PCVs, and chemical signalling in distributed or encapsulated multi-catalytic protocell communities. Our results highlight a new type of catalytic micro-compartment with multi-functional activity and provide a step towards the development of protocell reaction networks.

A visible-light Paternò-Büchi dearomatisation process towards the construction of oxeto-indolinic polycycles.

A variety of highly functionalised N-containing polycycles (35 examples) are synthesised from simple indoles and aromatic ketones through a mild visible-light Paternò-Büchi process. Tetrahydrooxeto[2,3-b]indole scaffolds, with up to three contiguous all-substituted stereocenters, are generated in high yield (up to >98%) and excellent site- regio- and diastereocontrol (>20 : 1). The use of visible light (405 or 465 nm) ensures enhanced performances by switching off undesired photodimerisation side reactions. The reaction can be easily implemented using a microfluidic photoreactor with improved productivity (up to 0.176 mmol h-1) and generality. Mechanistic investigations revealed that two alternative reaction mechanisms can account for the excellent regio- and diastereocontrol observed.