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Oxo-graphene nanoribbons (oxo-GNRs) can be prepared by the oxidative unzipping of single-walled carbon nanotubes. We present an orthogonal functionalization method for the functionalization of the rims and the π-surface, respectively, what is only possible due to the high rim portion in oxo-GNRs. In particular, X-ray photoelectron spectroscopy could be used to follow the reaction and detect the marker atoms contained in the addends. We propose that the reported orthogonal functionalization strategy can also be applied on other oxo-functionalized carbon materials, such as graphene quantum dots, or reduced graphene oxide flakes., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Isostructural metal-organic frameworks (MOFs), namely MFU-4 and MFU-4-Br, in which the pore apertures are defined by anionic side ligands (Cl - and Br - , respectively), were synthesized and loaded with noble gases. By selecting the type of side ligand, one can fine-tune the pore aperture size, allowing for precise regulation of the entry and release of gas guests. In this study, we conducted experiments to examine gas loading and release using krypton and xenon as model gases, and we complemented our findings with computational modeling. Remarkably, the loaded gas guests remained trapped inside the pores even after being exposed to air under ambient conditions for extended periods, in some cases for up to several weeks. Therefore, we focused on determining the energy barrier preventing gas release using both theoretical and experimental methods. The results were compared in relation to the types of hosts and guests, providing valuable insights into the gas trapping process in MOFs, as well as programmed gas release in air under ambient conditions. Furthermore, the crystal structure of MFU-4-Br was elucidated using the three-dimensional electron diffraction (3DED) technique, and the bulk purity of the sample was subsequently verified through Rietveld refinement., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

The rapid advancement of covalent organic frameworks (COFs) in recent years has firmly established them as a new class of molecularly precise and highly tuneable porous materials. However, compared to other porous materials, such as zeolites and metal-organic frameworks, the successful integration of hierarchical porosity into COFs remains largely unexplored. The challenge lies in identifying appropriate synthetic methods to introduce secondary pores without compromising the intrinsic structural porosity of COFs. In this study, a template-induced synthetic methodology is realized to facilitate the construction of hierarchically porous COFs (hCOFs). This novel approach utilizes commercially available zinc oxide nanoparticles as a hard template, enabling to increase the total pore volume of a series of β-ketoenamine-linked COFs as well as an imine-based COF while preserving their surface areas. In addition to transmission electron microscopy and gas adsorption analyses, small-angle X-ray scattering and pulsed field gradient nuclear magnetic resonance techniques are employed to investigate the hierarchical porosity and diffusivity of guest molecules within hCOFs. This study demonstrates that the hierarchically porous nature of hCOFs significantly reduces diffusion limitations, thus leading to simultaneous enhancements in adsorption capacity, diffusivity, and catalytic performance., (© 2025 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

This study unveils a novel property of polyaniline by establishing its catalytic activity in heterogeneous hydrogenation with molecular hydrogen. Polyaniline was activated by heat-treating at different temperatures in a hydrogen atmosphere. The sample treated at 300 °C exhibited the highest catalytic activity for ethylene hydrogenation in the gas phase at atmospheric pressure and for p-nitrotoluene or α-methylstyrene hydrogenation in the liquid phase. XRD, HRTEM, Raman, XPS, UV-VIS, FTIR, and elemental analysis data as well as electrochemical study indicate that catalytic activity is associated with the conjugated structure of undoped emeraldine base, whereas the polymer cross-linking or an increase in chlorine residues correlates with catalyst deactivation. These results pave the way to use conducting polymers as catalysts for hydrogenation with molecular hydrogen, opening new avenues for their application in catalysis., (© 2025 Wiley‐VCH GmbH.)

We demonstrate the application of mechanochemistry in the synthesis of indolone-based photoswitches (hemiindigos, hemithioindigos, and oxindoles) via Knoevenagel condensation reactions. Utilizing ball-milling and an organic base (piperidine) acting as catalyst and solvent for liquid assisted grinding (LAG) conditions, we achieve rapid, solvent-free transformations, obtaining a set of known and previously unreported photoswitches, including highly functional amino acid-based photoswitches, multichromophoric derivatives and photoswitchable cavitands based on resorcin[4]arenes. The reaction under mechanochemical conditions gives moderate-to-high yields and is highly stereoselective leading to Z-isomers of hemiindigos and hemithioindigos and E-isomers of oxindoles. For selected examples, reversible visible-light photoswiching properties have been demonstrated., (© 2025 Wiley-VCH GmbH.)

To study the effect of a dye on the photoluminescence (PL) properties of metal complexes, a series of gold(I) complexes were synthesized, containing a 7-amino-4-methylcoumarin luminophore. The complexes are comprised of a coumarin moiety featuring different ancillary ligands, specifically N-heterocyclic carbenes, triphenylphosphine, and diphenyl-2-pyridylphosphine. The synthesized gold(I) complexes are luminescent both in solution and the solid state at room temperature and 77 K. Complexes of different nuclearity, i.e., mono-, di- and trinuclear compounds were synthesized. A clear trend between the nuclearity and the quantum yields can be seen. The coumarin dye not only improves the PL properties, but also enhances the luminescence of trinuclear clusters, which are otherwise known to be weak emitters in solution. The optical absorption properties were investigated in detail by quantum chemical calculations., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Depending on their aspect ratio, rod-shaped particles exhibit a much richer 2D and 3D phase behavior than their spherical counterparts, with additional nematic and smectic phases accompanied by defined orientational ordering. While the phase diagram of colloidal hard rods is extensively explored, little is known about the influence of softness in such systems, partly due to the absence of appropriate model systems. Additionally, investigating higher volume fractions for long rods is usually complicated because non-equilibrium dynamical arrest is likely to precede the formation of more defined states. This has motivated us to develop micrometric rod-like microgels with limited sedimentation that can respond to temperature and reversibly reorganize into defined phases via annealing and seeding procedures. A detailed procedure is presented for synthesizing rod-shaped hollow poly(N-isopropylacrylamide) microgels using micrometric silica rods as sacrificial templates. Their morphological characterization is conducted through a combination of microscopy and light scattering techniques, evidencing the unconstrained swelling of rod-shaped hollow microgels compared to core-shell microgel rods. Different aspects of their assembly in dispersion and at interfaces are further tested to illustrate the opportunities and challenges offered by such systems that combine softness, anisotropy, and thermoresponsivity., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Polymer cubosomes (PCs) are a recent class of self-assembled nanostructures with great application potential due to their high porosity and surface area. Currently, most reported PCs consist of polystyrene block copolymers (BCPs), for which self-assembly parameters are rather well understood. Changing the block chemistry would be desirable to introduce more functionality; however, knowledge of adapting the self-assembly process to new chemistries remains limited. This work, reports on synthesizing poly(ethylene oxide)-block-poly(4-acetoxystyrene) and its copolymers with styrene, and provide conditions for their self-assembly into PCs with high yield and high inner order. It is shown that the polarity of the starting solvent toward the corona block allows tuning of the final morphology by controlling the corona volume and packing parameter., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

An exceptional efficiency of pyrazine-annelated porphyrin as a general photocatalyst for the oxidation of organic sulfides is demonstrated. It is shown that phosphonate-substituted pyrazinoporphyrin 2H-1 brings together sufficient photostability and high efficiency in the aerobic photooxidation of a series of various sulfides. The influence of the reaction conditions onto the efficiency of homogeneous sulfide photooxidation in the presence of the photosensitizer (PS) was investigated and strong dependence on the solvent system was observed. The use of methanol is required for the photocatalytic sulfoxidation and the ratio of the alcohol/other solvent can significantly affect the conversion and selectivity of the reaction. The application of the prepared PS in 0.001 mol % loading allowed achieving complete conversion (97-100 %, turnover number up to 1,00,000, turnover frequency up to 6250 h -1 ) of substrates bearing substituents of different nature, namely aromatic and aliphatic sulfides with donor or acceptor substituents and substituents prone to oxidation, as well as cyclic sulfides. The selectivity of the of the corresponding sulfoxides formation of 96-100 % was revealed. Finally, a gram-scale synthesis of several sulfoxides was successfully performed with the PS under investigation, providing desired products in 66-96 % yield with over 98 % purity., (© 2024 Wiley-VCH GmbH.)

Concentration gradients of soluble signaling molecules-morphogens-determine the cellular organization in tissue development. Morphogen-releasing microgels have shown potential to recapitulate this principle in engineered tissue constructs, however, with limited control over the molecular cues in space and time. Inspired by the functionality of sulfated glycosaminoglycans (sGAGs) in morphogen signaling in vivo, a library of sGAG-based microgels is developed and designated as µGel Units to Instruct Development (µGUIDEs). Adjustment of the microgel's sGAG sulfation patterns and concentration enabled the programming of electrostatic affinities that control the release of morphogens. Based on computational analyses of molecular transport processes, µGUIDEs provided unprecedented precision in the spatiotemporal modulation of vascular endothelial growth factor (VEGF) gradients in a microgel-in-gel vasculogenesis model and kidney organoid cultures. The versatile approach offers new options for creating morphogen signaling centers to advance the understanding of tissue and organ development., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

The investigation of proton conduction processes within artificial nanopores using phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ) not only sheds light on the mechanisms of proton conduction for these strong acids in confined environments, while also provides critical insights into the proper understanding of biological transmembrane proton transport. However, the synthesis of stable and acid-resistant host frameworks is yet a major challenges. By following that, the present study is conducted with the aim of improving the chemical stability of an imine-based COF (CPOF-10) by converting it into an amide-linked COF (CPOF-11) via a post-oxidative approach. In which, the integration of an appropriate amount of imidazole groups into the framework facilitates the efficient impregnation of liquid proton-conducting acids. The obtained results indicate the ten times greater proton conductivity of H 3 PO 4 @CPOF-11 than that of H 3 PO 4 @CPOF-10, thereby, successfully achieving 8.63 × 10 -2 S cm -1 at 160 °C, under nitrogen (N 2 ) atmosphere. Moreover, the highly stable CPOF-11 tolerated H 2 SO 4 doping, delivering a high proton conductivity of up to 1.70 × 10 -1 S cm -1 at 140 °C, with a significantly low activation energy of 0.05 eV. To the best of the knowledge, this activation energy (0.05 eV) of H 2 SO 4 @CPOF-11 is found to be one of the lowest value among all the reported proton-conducting materials. Thus, this study will provide new understanding for the fabrication of advanced porous organic materials in fuel cells application., (© 2024 Wiley‐VCH GmbH.)

The introduction of 4,5-dihydroazuleno[2,1,8-ija]azulene as a central core between two 1,4-dithiafulvene (DTF) units provides a novel class of extended tetrathiafulvalene (TTF) electron donors. Herein we present the synthesis of such compounds with the azulenoazulene further expanded by annulation to benzene, naphthalene, or thiophene rings. Moreover, unsymmetrical donor-acceptor chromophores with one DTF and one carbonyl at the central core are presented. The effect of the odd-membered rings of the polycyclic aromatic hydrocarbon cores on the geometrical features and the extent of bond conjugation in these systems were investigated by UV-Vis absorption spectroscopy, (spectro)electrochemical studies, X-ray and electron diffraction, and computational studies. Altogether these studies reveal that, upon oxidation, the non-planar core of the bis(benzo)-fused dihydro-azulenoazulene-extended TTF generates a large 22π-aromatic system (together with two 6π-aromatic 1,3-dithiolium appendages) characterized by significant bond length equalizations. The dication formed by oxidation is EPR silent, indicating a singlet ground state. Computations reveal that the closed-shell singlet species and its open-shell singlet counterpart are nearly degenerate and of lower energy than a triplet species. According to cyclic voltammetry, the compounds can be oxidized further and present multi-redox systems., (© 2024 Wiley‐VCH GmbH.)

Silicon is a promising negative electrode material for solid-state batteries (SSBs) due to its high specific capacity and ability to prevent lithium dendrite formation. However, SSBs with silicon electrodes currently suffer from poor cycling stability, despite chemical engineering efforts. This study investigates the cycling failure mechanism of composite Si/Li 6 PS 5 Cl electrodes by decoupling the effects of interface chemical degradation and mechanical cracking. Chlorine-rich Li 5.5 PS 4.5 Cl 1.5 suppresses interface chemical degradation when paired with silicon, while small-grained Li 6 PS 5 Cl shows 4.3-fold increase of interface resistance due to large Si/Li 6 PS 5 Cl contact area for interface degradation. Despite this, small-grained Li 6 PS 5 Cl improves the microstructure homogeneity of the electrode composites, effectively alleviating the stress accumulation caused by the expansion/shrinkage of silicon particles. This minimizes bulk cracks in Li 6 PS 5 Cl during the lithiation processes and interface delamination during the delithiation processes. Mechanical cracking shows a dominant role in increasing interface resistance than interface chemical degradation. Therefore, electrodes with small-grained Li 6 PS 5 Cl show better cycling stability than those with Li 5.5 PS 4.5 Cl 1.5 . This work not only provides an approach to decouple the complex effects for cycling failure analysis but also provides a guideline for better use of silicon in negative electrodes of SSBs., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Transition metal phosphide (TMP) nanoparticles (NPs) are versatile materials for energy conversion/storage applications due to their robustness and many possibilities to tailor NPs' electronic, physical, and chemical properties. One of the hurdles toward their broader implementation is their challenging synthesis exacerbated by the limited choice of phosphorus precursors. On the one hand, the synthesis of TMP NPs can employ various alkyl- or arylphosphines requiring prolonged heating at high temperatures, while on the other hand, highly reactive P(SiMe 3 ) 3 , white phosphorus, or PH 3 pose additional obstacles associated with their hazardous nature, high cost, and limited availability. This work introduces the use of acylphosphines as a new class of phosphorus sources for synthesizing phosphide NPs. They are shown to react with respective metal chlorides at moderate temperatures as low as 250 °C yielding poorly crystalline NPs, which can later be crystallized at 305 °C. After ligand stripping with HPF 6 , NPs are found to be an effective electrocatalyst for the hydrogen evolution reaction in the acidic medium exhibiting overpotentials as low as 50 mV at a current density of 10 mA cm -2 , which is among the lowest overpotentials for these materials and is quite competitive to commercial platinum-based catalysts., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Conventional laser panel displays are developed through the mass integration of electrically pumped lasers or through the incorporation of a beam steering system with an array of optically pumped lasers. Here a novel configuration of a laser panel display consisting of a non-steered pumping beam and an array of electrically Q-switchable lasers is reported. The laser oscillator consists of a robust, self-standing, and deformable minute droplet that emits laser through Whispering-Gallery Mode resonance when optically pumped. The laser oscillation is electrically switchable during optical pumping by applying a vertical electric field to the droplet. Electromagnetic and fluid dynamics simulations reveal the deformation of the droplet into a prolate spheroid under the electric field and associated attenuation of quality factor (Q-factor), leading to the halt of the laser oscillation. A 2 × 3 array of droplets is fabricated by inkjet printing as a prototype of a laser panel display, and it successfully achieves the pixel-selective switching of the oscillation., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Increasing the upper cut-off voltage (UCV) enhances the specific energy of Li-ion batteries (LIBs), but is accompanied by higher capacity fade as a result of electrode cross-talk, i.e., transition metals (TM) dissolution from cathode and deposition on anode, finally triggering high surface area lithium (HSAL) formation due to locally enhanced resistance. Here, LiPF 6 , LiBF 4 , lithium difluoro(oxalate)borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in carbonate-based solvents are investigated in LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) || graphite pouch cells with 4.5 V UCV. Despite the lower oxidative stabilities of LiBF 4 and LiDFOB, thus enhanced HF formation, TM dissolution, and consequently electrode cross-talk, higher capacity retention is observed compared to the case of LiPF 6 electrolyte. Counterintuitively, it is not the TM deposit amount but rather the Li plating morphology that governs capacity fade, as these salts cause more uniform and compact lithium plating, i.e., lower surface area. In contrast, the dendritic HSAL with LiPF 6 has a higher surface area, and more parasitic reactions, thus active Li ("Li inventory") losses and capacity fade. Although NCM initiates the failure cascade, the capacity losses and cycle life of high-voltage LIBs are predominantly determined by the anode, in particular the Li plating morphology and the corresponding surface area., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

The direct hydrogenation of 2-nitroacylbenzene to 2,1-benzisoxazole presents a significant challenge in the pharmaceutical and fine chemicals industries. In this study, a defect engineering strategy is employed to create bifunctional single-atom catalysts (SACs) by anchoring Pt single atoms onto metal vacancies within MgO(Al) nanosheets. The resultant Pt 1 /MgO(Al) SAC displays an exceptional catalytic activity and selectivity in the hydrogenation-cyclization of 2-nitroacylbenzene, achieving a 97.5 % yield at complete conversion and a record-breaking turnover frequency of 458.8 h -1 under the mild conditions. The synergistic catalysis between the fully exposed single-atom Pt sites within a unique Pt-O-Mg/Al moiety and the abundant basic sites of the MgO(Al) support is responsible for this outstanding catalytic performance. The current work, therefore, paves the way for developing bifunctional or multifunctional SACs that can enhance efficient organocatalytic conversions., (© 2024 Wiley-VCH GmbH.)

The double-perovskite material Cs 2 TiBr 6 shows excellent photovoltaic potential, making it a promising alternative to lead-based materials. However, its high susceptibility to degradation in air has raised concerns about its practical application. This study introduces an interesting synthesis approach that significantly enhances the stability of Cs 2 TiBr 6 powder. We implemented a gradual cation exchange process by substituting Ti 4+ with Sn 4+ in the efficient microwave-assisted synthesis method, developing a double perovskite Cs 2 Sn x Ti 1-x Br 6 type. A systematic study of increasing concentration of Sn 4+ in Cs 2 TiBr 6 perovskite has been performed to analyze the effect of Sn-doping degree on the chemical and thermal stability of the material and the optical features in both nitrogen and ambient atmospheres, significantly increasing the stability of the material in the air for over a week. Furthermore, introducing Sn 4+ results in a more uniform polygonal crystal morphology of the powders and a slight band gap broadening. We show that microwave-assisted synthesis is highly efficient and cost-effective in producing more sustainable lead-free perovskite materials with enhanced stability and desirable electrical characteristics. This work suggests a promising method for synthesizing perovskite materials, opening new routes for scientific research and applications., (© 2024 The Author(s). ChemSusChem published by Wiley-VCH GmbH.)

The combination of continuous wave electron paramagnetic resonance (cw-EPR) with electrochemistry is highly attractive as it allows a clean in-situ generation and the subsequent spectroscopic characterisation of radical ions, which are important intermediates in many photocatalytic cycles as well as light-induced processes occurring in biological systems or optoelectronic devices. Although commercial setups for spectroelectrochemical EPR are available, they are often expensive and tailored to a particular spectroscopic setup. Here we present a design for a low-cost electrochemical EPR cell that can be used in combination with any commercial cw-EPR instrumentation. The cell design is compared to existing setups and the performance of the cell is evaluated by comparison of EPR spectra obtained by chemical and electrochemical oxidation of a graphene fragment., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Precision graphene nanoribbons (GNRs) offer distinctive physicochemical properties that are highly dependent on their geometric topologies, thereby holding great potential for applications in carbon-based optoelectronics and spintronics. While the edge structure and width control has been a popular strategy for engineering the optoelectronic properties of GNRs, non-hexagonal-ring-containing GNRs remain underexplored due to synthetic challenges, despite offering an equally high potential for tailored properties. Herein, we report the synthesis of a wavy GNR (wGNR) by embedding periodic eight-membered rings into its carbon skeleton, which is achieved by the A 2 B 2 -type Diels-Alder polymerization between dibenzocyclooctadiyne (6) and dicyclopenta[e,l]pyrene-5,11-dione derivative (8), followed by a selective Scholl reaction of the obtained ladder-type polymer (LTP) precursor. The obtained wGNR, with a length of up to 30 nm, has been thoroughly characterized by solid-state NMR, FT-IR, Raman, and UV/Vis spectroscopy with the support of DFT calculations. The non-planar geometry of wGNR efficiently prevents the inter-ribbon π-π aggregation, leading to photoluminescence in solution. Consequently, the wGNR can function as an emissive layer for organic light-emitting electrochemical cells (OLECs), offering a proof-of-concept exploration in implementing luminescent GNRs into optoelectronic devices. The fast-responding OLECs employing wGNR will pave the way for advancements in OLEC technology and other optoelectronic devices., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Local detection of hydrogen concentration in metals is of central importance for many areas of hydrogen technology, such as hydrogen storage, detection, catalysis, and hydrogen embrittlement. A novel approach to measure the hydrogen concentration in a model system consisting of cubic palladium nanoparticles (Pd NPs), with a lateral resolution down to 4 nm is demonstrated. By measuring the shift of the Pd bulk plasmon peak with scanning transmission electron microscopy (STEM) combined with energy electron loss spectroscopy (EELS) during in situ hydrogen gas loading and unloading, local detection of the hydrogen concentration is achieved in TEM. With this method, concentration changes inside the NPs at various stages of hydrogenation/dehydrogenation are observed with nanometer resolution. The versatility of in situ TEM allows to link together microstructure, hydrogen concentration, and local strain, opening up a new chapter in hydrogen research., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

With ordered and periodic network structures, adjustable pore sizes and high chemical stability, covalent organic frameworks (COFs) have drawn much attention for the fabrication of superior separation membranes. However, it is challenging to prepare COF membranes with a molecular sieving property for gas separation due to their relatively large pore size. In this work, we develop the MOF-in-COF concept for vacuum-assisted synthesis of metal-organic framework (MOF) ZIF-8 inside the pores of TB-COF formed from trihydroxy-benzene-tricarbaldehyde (T) and diamino-biphenyl-disulfonic acid (B), thus constructing a novel ZIF-8@TB-COF membrane. Attributing to the formation of a well-defined one-dimensional (1D) nanoscale transport channel, the ZIF-8@TB-COF membrane displays a high hydrogen permselectivity. At 100 °C and 200 kPa, the mixture separation factors of H 2 /CO 2 , H 2 /CH 4 and H 2 /C 3 H 8 are 21.9, 63.1 and 134.4, respectively, which are much higher than those of the pristine TB-COF membrane due to the precise size sieving channels brought about by the incorporated MOF. The synthesis of ZIF-67@TB-COF membrane demonstrates the versatility of the synthesis strategy., (© 2024 Wiley-VCH GmbH.)

Copper-exchanged zeolite omega (Cu-omega) is a potent material for the selective conversion of methane-to-methanol (MtM) via the oxygen looping approach. However, its performance exhibits substantial variation depending on the operational conditions. Under an isothermal temperature regime, Cu-omega demonstrates subdued activity below 230 °C, but experiences a remarkable increase in activity at 290 °C. Applying a high-temperature activation protocol at 450 °C causes a rapid deactivation of the material. This behavioral divergence is investigated by combining reactivity studies, neutron diffraction and in situ high-resolution anomalous X-ray powder diffraction (HR-AXRPD), as well as electron paramagnetic resonance spectroscopy, to reveal that the migration of Cu throughout the framework is the primary cause of these behaviors, which in turn is predominantly governed by the degree of hydration of the system. This work suggests that control over the Cu migration throughout the zeolite framework may be harnessed to significantly increase the activity of Cu-omega by generating more active sites for the MtM conversion. These results underscore the power of in situ HR-AXRPD for unraveling the behavior of materials under reaction conditions and suggest that a re-evaluation of Cu-zeolites priorly deemed inactive for the MtM conversion across a broader range of conditions and looping protocols may be warranted., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Metal-organic framework (MOF)-based membranes excel in molecular separation, attracting significant research interest. The crystallographic microstructure and selective adsorption capacity of MOFs closely correlate with their gas separation performance. Here, aniline was added to the ZIF-8 synthesis in varying concentrations. Aniline, encapsulated within ZIF-8 cavities, interacts strongly with the 2-methylimidazole linker, resulting in both a shift in crystallographic phase from I_43 m to Cm in Rietveld refinement of X-ray diffraction (XRD) patterns and the selective adsorption behavior between propylene and propane. Consequently, an aniline decorative ZIF-8 (Ani x -ZIF-8) membrane was prepared using a fast current-driven synthesis method, which exhibits good propylene/propane separation selectivity of up to 85. Calculation of the interaction energy between aniline and the various crystallographic phases of ZIF-8 using density functional theory (DFT) further verifies that aniline not only promotes the formation of crystallographic Cm phase, but also enhances the adsorption selectivity of propylene over propane. Aniline modification effectively tunes the crystallographic microstructure of ZIF-8, thereby, improving molecular sieving capabilities., (© 2024 Wiley-VCH GmbH.)

Riboswitches control gene regulation upon external stimuli such as environmental factors or ligand binding. The fluoride sensing riboswitch from Thermotoga petrophila is a complex regulatory RNA proposed to be involved in resistance to F - cytotoxicity. The details of structure and dynamics underpinning the regulatory mechanism are currently debated. Here we demonstrate that a combination of pulsed electron paramagnetic resonance (ESR/EPR) spectroscopies, detecting distances in the angstrom to nanometre range, can probe distinct regions of conformational flexibility in this riboswitch. PELDOR (pulsed electron-electron double resonance) revealed a similar preorganisation of the sensing domain in three forms, i.e. the free aptamer, the Mg 2+ -bound apo, and the F - -bound holo form. 19 F ENDOR (electron-nuclear double resonance) was used to investigate the active site structure of the F - -bound holo form. Distance distributions without a priori structural information were compared with in silico modelling of spin label conformations based on the crystal structure. While PELDOR, probing the periphery of the RNA fold, revealed conformational flexibility of the RNA backbone, ENDOR indicated low structural heterogeneity at the ligand binding site. Overall, the combination of PELDOR and ENDOR with sub-angstrom precision gave insight into structural organisation and flexibility of a riboswitch, not easily attainable by other biophysical techniques., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Iron phosphide/carbon (FeP/C) serving as electrocatalysts exhibit excellent activity in oxygen reduction reaction (ORR) process. H 2 O 2 catalyzed by peroxidase (POD) is similar to the formation of new electron transfer channels and the optimization of adsorption of oxygen-containing intermediates or desorption of products in ORR process. However, it is still a challenge to discover FeP/C with enhanced POD-like catalytic activity in the electrocatalytic database for biocatalysis. The discovery of FeP/carbon dots (FeP/CDs) nanozymes driven by electrocatalytic activity for enhanced POD-like ability is demonstrated. FeP/CDs derived from CDs-Fe 3+ chelates show enhanced POD-like catalytic and antibacterial activity. FeP/CDs exhibit enhanced POD-like activities with a specific activity of 31.1 U mg -1 that is double higher than that of FeP. The antibacterial ability of FeP/CDs nanozymes with enhanced POD-like activity is 98.1%. The antibacterial rate of FeP/CDs nanozymes (250 µg mL -1 ) increased by 5%, 15%, and 36% compared with FeP, Fe 2 O 3 /CDs, and Cu 3 P/CDs nanozymes, respectively. FeP/CDs nanozymes will attract more efforts to discover or screen transition metal phosphide/C nanozymes with enhanced POD-like catalytic activity for biocatalysis in the electrocatalytic database., (© 2024 Wiley‐VCH GmbH.)

The muscle-tendon junction (MTJ) plays a pivotal role in efficiently converting the muscular contraction into a controlled skeletal movement through the tendon. Given its complex biomechanical intricacy, the biofabrication of such tissue interface represents a significant challenge in the field of musculoskeletal tissue engineering. Herein, a novel method to produce MTJ-like hydrogel yarns using a microfluidics-assisted 3D rotary wet-spinning strategy is developed. Optimization of flow rates, rotational speed, and delivery time of bioinks enables the production of highly compartmentalized scaffolds that recapitulate the muscle, tendon, and the transient MTJ-like region. Additionally, such biofabrication parameters are validated in terms of cellular response by promoting an optimal uniaxial alignment for both muscle and tendon precursor cells. By sequentially wet-spinning C2C12 myoblasts and NIH 3T3 fibroblasts, a gradient-patterned cellular arrangement mirroring the intrinsic biological heterogeneity of the MTJ is successfully obtained. The immunofluorescence assessment further reveals the localized expression of tissue-specific markers, including myosin heavy chain and collagen type I/III, which demonstrate muscle and tenogenic tissue maturation, respectively. Remarkably, the muscle-tendon transition zone exhibits finger-like projection of the multinucleated myotubes in the tenogenic compartment, epitomizing the MTJ signature architecture., (© 2024 The Author(s). Advanced Healthcare Materials published by Wiley‐VCH GmbH.)

Cutting-edge research in advanced materials is increasingly turning toward the development of novel multifunctional nanomaterials for use in high-tech applications. This research uses the solid-state method as a solvent-free technique to create multifunctional quantum dot (QD) hydroxyapatite (HA) crystals from bovine bone waste. By incorporating cobalt (Co) and magnesium (Mg) into the HA structure, the crystallinity of the hexagonal HA nanoparticles (99.7%), showing QD crystals is enhanced. Oxygen vacancies on the surfaces of the HA nanoparticles contributed to their bandgap falling within the visible light range. In addition, the dopants substituted calcium in the HA crystal structure and generated a divalent oxidation state, shifting the bandgap of natural HA toward red wavelengths (3.26 to 1.94 eV). Moreover, the incorporation of Co led to magnetization within the HA structure through spin polarization. Additionally, the doped QD crystals of HA nanoparticles showed significant antimicrobial activity against Escherichia coli, Staphylococcus aureus, and bacteriophages MS2, particularly under visible light exposure. In short, the Co/Mg co-doped HA nanoparticles exhibited ferromagnetic properties, sensitivity to visible light, biocompatibility, and considerable antimicrobial effects, establishing their potential as sustainable multifunctional materials for biomedical applications, especially in anti-infection treatments., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Due to their ultra-high sensitivity, solution-gated graphene-based field-effect transistors (SG-GFET) have been proposed for applications in bio-sensing. However, challenges regarding the functionalization of GFETs have prevented their applications in clinical diagnostics so far. Here GFET sensors based on van der Waals (vdW) heterostructures of single-layer graphene layered with a molecular ≈1 nm thick carbon nanomembrane (CNM) are presented. The CNM acts as an ultrathin molecular interposer between the graphene channel and the analyte and allows bio-functionalization without impairing the graphene properties including its charge carrier mobility. To achieve specificity and reliability in the detection of biomarkers in real patient samples, the functionalization incorporates biostable aptamers in the non-natural l-configuration and hydrophilic polyethylene glycol for avoiding non-specific adsorption. A rapid (≈5 min) detection of the clinically relevant inflammatory mediator CXCL8/IL-8 within the concentration range of 0.5 - 500 pM (5 - 5000 pg ml -1 ) is demonstrated in nasal swab samples collected from patients with respiratory tract infections. This detection range may aid in diagnostics of early-stage infectious diseases making the reported approach promising for the development of future medical tools., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Polymer solid-state electrolytes offer great promise for battery materials with high energy density, mechanical stability, and improved safety. However, their low ion conductivities have so far limited their potential applications. Here, it is shown for poly(ethylene oxide) block copolymers that the super-stoichiometric addition of lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as lithium salt leads to the formation of a crystalline PEO block copolymer phase with exceptionally high ion conductivities and low activation energies. The addition of LiTFSI further induces block copolymer phase transitions into bi-continuous Fddd and gyroid network morphologies, providing continuous 3D conduction pathways. Both effects lead to solid-state block copolymer electrolyte membranes with ion conductivities of up to 1·10 -1  S cm -1 at 90 °C, decreasing only moderately to 4·10 -2  S cm -1 at room temperature, and to >1·10 -3  S cm -1 at -20 °C, corresponding to activation energies as low as 0.19 eV. The co-crystallization of PEO and LiTFSI with ether and carbonate solvents is observed to play a key role to realize a super-ionic conduction mechanism. The discovery of PEO super-ionic conductivity at high lithium concentrations opens a new pathway for fabrication of solid polymer electrolyte membranes with sufficiently high ion conductivities over a broad temperature range with widespread applications in electrical devices., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Due to their nanoscale thickness (≈1 nm) and exceptional selectivity for permeation of gases, nanomembranes made of 2D materials possess high potential for energy-efficient nanofiltration applications. In this respect, organic carbon nanomembranes (CNMs), synthesized via electron irradiation-induced crosslinking of aromatic self-assembled monolayers (SAMs), are particularly attractive, as their structure can be flexibly tuned by choice of molecular precursors. However, tailored permeation of CNMs, defined by their molecular design, has not been yet demonstrated. In this work, it is shown that the permeation of helium (He), deuterium (D 2 ) and heavy water (D 2 O) for CNMs synthesized from biphenyl-based SAMs on silver (C 6 H 5 -C 6 H 4 -(CH 2 ) n -COO/Ag, n = 2-6) can be tuned by orders of magnitude by changing the structure of the molecular precursors by just a single methylene unit. The selectivity in permeation of D 2 O/D 2 with an unprecedented value of 200 000 can be achieved in this way. The temperature-dependent study reveals a clear correlation between the molecular design and the permeation mechanisms facilitating therewith tailored synthesis of molecular 2D materials for separation technologies., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Using as example the [Fe(bpca)(μ-bpca)Gd(NO 3 ) 4 ]×4CH 3 NO 2 ×CH 3 OH system, where Hbpca=bis(2-pyridilcarbonyl)amine), we perform the analysis of bonding components inside the d and f coordination units and between molecular entities from crystal. Aside the nominal long-range interactions between molecular components of the crystal, we considered that the bonding inside the coordination units is also not a covalent regime. We performed Density Functional Theory (DFT) calculations, with plane-waves (PW), in band-structure mode, and with atom-centred bases, by molecular procedures. Observing that the PW-DFT frame is free of basis set superposition errors, which is an important methodological hint underlined here, we estimated various non-covalent terms. E.g. the interaction between inversion-related FeGd units amounts -394.47 kcal/mol, only about -37 kcal/mol being due to Coulomb effects, the remainder being assignable to dispersion forces. One FeGd binuclear interacts with the closest methanol molecule by -9.30 kcal/mol and by -36.57 kcal/mol with the set of four nitromethane molecules. The energy decomposition analysis of molecular calculations showed, aside the expected ionic character (about 82 % of the total cohesion energy of lanthanide ion in molecule), the important role of empty 5d orbitals. The d virtuals are contributing with 68.4 kcal/mol, out of 97.15 kcal/mol quantity estimated as ligand-to-metal donor-acceptor effects., (© 2024 Wiley-VCH GmbH.)

Si-based anodes can increase specific energy and energy density of Li ion batteries. However, the volume-induced material stress and capacity loss necessitates only a partial Si utilization within composite anodes, typically with state-of-the-art graphite, so called Si/Gr composites. In this work, various Si nanowires (SiNWs), a promising Si architecture for these composites, are investigated and modified via pre-lithiation. Though, charged pre-lithiated anodes show potentials below 0 V vs. Li|Li + in the initial cycles, they do not show indications for metallic Li, which is likely a hint for a triggered surface Li depletion in course of a continuous "transfer-lithiation" from lithiated Gr to Si, which is indicated by decreasing LiC 6 and increasing Li x Si y signals via nuclear magnetic resonance (NMR), X-ray diffraction (XRD) as well as shifts in capacities of respective voltage plateaus during discharge after storage. A relevant contribution of self-discharge is unlikely as shown by a stable open-circuit-voltage during storage in charged state and similar subsequent discharge capacities, being consequently a hint for an intra-electrode capacity shift. The process of transfer lithiation is finally validated via solid-state 7 Li NMR for varied Si morphology, i. e., amorphous and crystalline, as well as during pre-lithiation with passivated lithium metal powder (PLMP)., (© 2024 The Author(s). ChemSusChem published by Wiley-VCH GmbH.)

Non-aqueous organic redox flow batteries (RFB) utilizing verdazyl radicals are increasingly explored as energy storage technology. Verdazyl cations in RFBs with acidic aqueous electrolytes, however, have not been investigated yet. To advance the application in aqueous RFBs it is crucial to examine the interaction with the utilized membranes. Herein, the interactions between the 1,3,5-triphenylverdazyl cation and commercial Nafion 211 and self-casted polybenzimidazole (PBI) membranes are systematically investigated to improve the performance in RFBs. The impact of polymer backbones is studied by using mPBI and OPBI as well as different pre-treatments with KOH and H 3 PO 4 . Nafion 211 shows substantial absorption of the 1,3,5-triphenylverdazylium cation resulting in loss of conductivity. In contrast, mPBI and OPBI are chemically stable against the verdazylium cation without noticeable absorption. Pre-treatment with KOH leads to a significant increase in ionic conductivity as well as low absorption and permeation of the verdazylium cation. Symmetrical RFB cell tests on lab-scale highlight the beneficial impact of PBI membranes in terms of capacity retention and I-V curves over Nafion 211. With only 2 % d -1 capacity fading 1,3,5-triphenylverdazyl cations in acidic electrolytes with low-cost PBI based membranes exhibit a higher cycling stability compared to state-of-the-art batteries using verdazyl derivatives in non-aqueous electrolytes., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Here, results on the tailored growth of monolayers (MLs) of transition metal dichalcogenides (TMDs) are presented using chemical vapor deposition (CVD) techniques. To enable reproducible growth, the flow of chalcogen precursors is controlled by Knudsen cells providing an advantage in comparison to the commonly used open crucible techniques. It is demonstrated that TMD MLs can be grown by CVD on large scale with structural, and therefore electronic, photonic and optoelectronic properties similar to TMD MLs are obtained by exfoliating bulk crystals. It is shown that besides the growth of the "standard" TMD MLs also the growth of MLs that are not available by the exfoliation is possible including examples like lateral TMD 1 -TMD 2 ML heterostructures and Janus TMDs. Moreover, the CVD technique enables the growth of TMD MLs on various 3D substrates on large scale and with high quality. The intrinsic properties of the grown MLs are analyzed by complementary microscopy and spectroscopy techniques down to the nanoscale with a particular focus on the influence of structural defects. Their functional properties are studied in devices including field-effect transistors, photodetectors, wave guides and excitonic diodes. Finally, an outlook of the developed methodology in both applied and fundamental research is given., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Magnetic anisotropy and magnetic exchange interactions are crucial parameters that characterize the hybrid metal-organic interface, a key component of an organic spintronic device. It is shown that the incorporation of 4f RE atoms to hybrid metal-organic interfaces of CuPc/REAu 2 type (RE = Gd, Ho) constitutes a feasible approach toward on-demand magnetic properties and functionalities. The GdAu 2 and HoAu 2 substrates differ in their magnetic anisotropy behavior. Remarkably, the HoAu 2 surface promotes the inherent out-of-plane anisotropy of CuPc, owing to the match between the anisotropy axis of substrate and molecule. Furthermore, the presence of RE atoms leads to a spontaneous antiferromagnetic exchange coupling at the interface, induced by the 3d-4f superexchange interaction between the unpaired 3d electron of CuPc and the 4f electrons of the RE atoms. It is shown that 4f RE atoms with unquenched quantum orbital momentum ( L $L$ ), as it is the case of Ho, induce an anisotropic interfacial exchange coupling., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Retention index prediction based on the molecule structure is not often used in practice due to low accuracy, the need to use paid software to calculate molecular descriptors (MD), and the narrow applicability domain of many models. In recent years, relatively accurate and versatile deep learning (DL)-based models have emerged. These models are now used in practice as an additional criterion in gas chromatography-mass spectrometry identification. The DB-225ms stationary phase (usually described as 50%-cyanopropylphenyl-50%-dimethylpolysiloxane in available sources) is widely used, but ready-to-use retention index estimation models are not available for it. This study presents such models. The models are linear and use simple constitutional MD and retention indices predicted by DL for the DB-WAX and DB-624 stationary phases as MD (we show that it is their use that allows us to achieve satisfactory accuracy). The accuracy obtained for a completely unseen hold-out test set: root mean square error 73.2; mean absolute error 45.7; median absolute error 22.0. The models were trained using a retention data set of 266 volatile compounds. All calculations can be performed using the convenient open-source software CHERESHNYA. The final equations are implemented as a spreadsheet and a code snippet and are available online: https://doi.org/10.6084/m9.figshare.26800789., (© 2024 Wiley‐VCH GmbH.)

This study delves into the innovative approach of enhancing the efficiency and stability of all-inorganic perovskite solar cells (I-PSCs) through the strategic incorporation of thiocyanate (SCN - ) ions via pseudohalide-based ionic liquid (IL) configurations. This straightforward methodology has exhibited captivating advancements in the kinetics of crystallization as well as the optoelectronic characteristics of the resulting perovskite films. These developments hold the promise of enhancing not only the quality and uniformity of the films but also aspects such as band alignment and the efficacy of charge transfer mechanisms. Calculation results corroborate that the incorporation of 1-butyl-3-methylimidazolium thiocyanate (BmimSCN) led to a significant redistribution of electron state density and enhanced electron-donating properties, indicating a substantial electron transfer between the perovskite material and the IL. Notably, the engineered devices demonstrate a remarkable efficiency surpassing 15%, a substantial enhancement attributed to the synergistic effects of the SCN - ion. Additionally, this approach offers inherent stability benefits, thereby addressing a significant challenge in I-PSC technology. This IL maintains >90% of the initial efficiency after 600 h, while the control device decreased to <20% of its initial value after only 100 h. 1-butyl-3-methylimidazolium iodide (BmimI) is also employed to further investigate the effects of SCN - ions on device performance., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Oxygen electrocatalysis, as the pivotal circle of many green energy technologies, sets off a worldwide research boom in full swing, while its large kinetic obstacles require remarkable catalysts to break through. Here, based on summarizing reaction mechanisms and in situ characterizations, the structure-activity relationships of oxygen electrocatalysts are emphatically overviewed, including the influence of geometric morphology and chemical structures on the electrocatalytic performances. Subsequently, experimental/theoretical research is combined with device applications to comprehensively summarize the cutting-edge oxygen electrocatalysts according to various material categories. Finally, future challenges are forecasted from the perspective of catalyst development and device applications, favoring researchers to promote the industrialization of oxygen electrocatalysis at an early date., (© 2024 Wiley‐VCH GmbH.)

The enhancement of the photovoltaic performance upon the aging process at particular environment is often observed in perovskite solar cells (PSCs), particularly for the devices with 2,2',7,7'-tetrakis(N,N-di(4-methoxyphenyl)amino)-9,9'-spirobifluorene (spiro-OMeTAD) as hole transporting material (HTM). In this work, for the first time the effect of aging the typical n-i-p PSCs employing nickel phthalocyanine (coded as Bis-PF-Ni) solely as dopant-free HTM is investigated and as an additive in spiro-OMeTAD solution. This study reveals that the prolong aging of these devices at dry air condition (RH = 2%, 25 °C) is beneficial for the improvement of their performances. Various bulk and surface characterization techniques are utilized to understand the factors behind the spontaneous efficiency enhancement of the devices after storage. As a result, the changes in properties of the Bis-PF-Ni layer are observed and at perovskite/Bis-PF-Ni interface, which ultimately improves the charge transport and reduces non-radiative recombination. In addition, the devices with Bis-PF-Ni HTM reveal enhanced long-term ambient and thermal stability compared to the PSCs based on doped spiro-OMeTAD., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Understanding the interfacial composition in heterostructures is crucial for tailoring heterogenous electrochemical and photoelectrochemical processes. This work aims to elucidate the structure of a series of Co-Fe Prussian blue analogue modified ZnO (PBA/ZnO) electrodes with interface-sensitive vibrational sum frequency generation (VSFG) spectroscopy. Our measurements revealed, for the first time, a cyanide linkage isomerism at the PBA/ZnO interface, when the composite is fabricated at elevated temperatures. In situ VSFG spectro-electrochemistry measurements correlate the Co II →Co III oxidation with the flip of the bridging CN ligand from Co-NC-Fe coordination mode to a Co-CN-Fe one. Photoluminescence measurements and X-ray photoelectron spectroscopy reveal that this unprecedented linkage isomerism originates from surface defects, which act as oxidation sites for the PBA. The presence of such surface defects is correlated with the fabrication temperature for PBA/ZnO. Thus, this contribution identifies the interplay between the surface states of the ZnO substrates and the chemical composition of PBA at the ZnO surface, suggesting an easily accessible approach to control the chemical composition of the interface., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

The catalytic performance of phosphate-stabilized WO x -ZrO 2 compositions in gas-phase glycerol dehydration has been investigated. Results show that varying WO 3 concentrations direct the process towards either acrolein or allyl alcohol formation. Catalysts with low WO x content exhibit strong Lewis acid sites (Zr 4+ and W 6+ ), where these metal ions likely function as redox sites, facilitating glycerol hydrogenolysis to produce allyl alcohol. Higher WO x concentrations (exceeding 20 wt %) lead to the shielding of some W 6+ and Zr 4+ sites by polytungstate surface complexes, which are strong Brønsted acid sites. This alteration promotes glycerol dehydration through the removal of two water molecules, thereby shifting the selectivity towards acrolein formation., (© 2024 Wiley-VCH GmbH.)

The recent discovery of frustrated Lewis pairs (FLPs) during the activation of small molecules has inspired extensive research across the full span of chemical science. Owing to the nature of weak interactions, it is experimentally challenging to directly observe and modulate FLP at the molecular scale. Here we design a boron cluster anion building block (B 10 H 8 2- ) and organic amine cations ([NR 4 ] + , R=-CH 3 , -C 2 ) as the FLP to prove the feasibility of controlling their interaction in the electric double layer (EDL) via an electrochemical strategy. In situ single-molecule electrical measurements and Raman monitoring of B 5 ) as the FLP to prove the feasibility of controlling their interaction in the electric double layer (EDL) via an electrochemical strategy. In situ single-molecule electrical measurements and Raman monitoring of B 10 H 8 2- -[NR 4 ] + near or below the potential of zero charge (PZC). Furthermore, this FLP chemistry leads to a shift in the local density of states of boron clusters towards the E 10 for enhancing electron transport, providing a new prototype of a reversible single-cluster switch that digitally switches upon controlling FLP chemistry in the electric double layer.8 2- near or below the potential of zero charge (PZC). Furthermore, this FLP chemistry leads to a shift in the local density of states of boron clusters towards the E F for enhancing electron transport, providing a new prototype of a reversible single-cluster switch that digitally switches upon controlling FLP chemistry in the electric double layer., (© 2024 Wiley-VCH GmbH.)

2-Bromo-1-(3,3-dinitroazetidin-1-yl)ethan-1-one (RRx-001) is a hypoxic cell chemotherapeutics with already demonstrated synergism in combined chemo-radiation therapy. The interaction of the compound with secondary low-energy electrons formed in large amounts during the physico-chemical phase of the irradiation may lead to these synergistic effects. The present study focuses on the first step of RRx-001 interaction with low-energy electrons in which a transient anion is formed and fragmented. Combination of two experiments allows us to disentangle the decay of the RRx-001 anion on different timescales. Sole presence of the electron initiates rapid dissociation of NO 2 and HNO 2 neutrals while NO 2 - and Br - ) and σ*(C-Br) states explains the experimental spectra. The fast dynamics monitored will impact the condensed phase chemistry of the anion as well.2 ) and σ*(C-Br) states explains the experimental spectra. The fast dynamics monitored will impact the condensed phase chemistry of the anion as well., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Respiratory complex I (R-CI) is an essential enzyme in the mitochondrial electron transport chain but also a major source of reactive oxygen species (ROS), which are implicated in neurodegenerative diseases and ageing. While the mechanism of ROS production by R-CI is well-established, the feedback of ROS on R-CI activity is poorly understood. Here, we perform EPR spectroscopy on R-CI incorporated in artificial membrane vesicles to reveal that ROS (particularly hydroxyl radicals) reduce R-CI activity by making the membrane more polar and by increasing its hydrogen bonding capability. Moreover, the mechanism that we have uncovered reveals that the feedback of ROS on R-CI activity via the membrane is transient and not permanent; lipid peroxidation is negligible for the levels of ROS generated under these conditions. Our successful use of modular proteoliposome systems in conjunction with EPR spectroscopy and other biophysical techniques is a powerful approach for investigating ROS effects on other membrane proteins., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Axial modification of boron (III) subphthalocyanine bromides with 4-hydroxy-benzoic acid successfully led to the formation of the macrocycles with anchored 4-carboxyphenoxy group [RsPcPHBA] (R= t Bu, H) in the axial position and to a new dimer [sPcPHBAsPc] as minor product. Tri-tert-butyl and unsubstituted subphthalocyanines bearing benzoate ([ t BusPcBA], [sPcBA]), phenoxy-group ([ t BusPcOPh], [sPcOPh])) in the axial position, have been also investigated as well as control sPcs. All compounds were characterized by NMR, IR, UV-Vis and mass spectrometry. The electrochemical properties were studied using cyclic voltammetry (CV) and square wave voltammetry (SWV). Singlet oxygen generation was systematically measured for all synthesized [RsPcX] by kinetic method of chemical trap decomposition (DPBF) and by determination of phosphorescence of singlet oxygen (at 1270 nm). Axially modified subphthalocyanines exhibit high quantum yields of singlet oxygen ( 1 O 2 ) generation (0.47-0.62). The observed exceptional photostability in oxygen-saturated ethanol or toluene solutions and high 1 O 2 quantum yields allows to use [ t BusPcPHBA] as photocatalysts of selective oxidative transformations of organic sulfides to sulfoxides. Loading the catalyst to 9.7 ⋅ 10 -2  mol % made it possible to achieve complete conversion of the substrate (TON up to 1700)., (© 2024 Wiley-VCH GmbH.)

The self-assembly and nonsolvent-induced phase separation (SNIPS) process of block copolymers and solvents enables the fabrication of integral-asymmetric, isoporous membranes. An isoporous top layer is formed by evaporation-induced self-assembly (EISA) and imparts selectivity for ultrafiltration of functional macromolecules or water purification. This selective layer is supported by a macroporous bottom structure that is formed by nonsolvent-induced phase separation (NIPS) providing mechanical stability. Thereby the permeability/selectivity tradeoff is optimized. The SNIPS fabrication involves various physical phenomena-e.g., evaporation, self-assembly, macrophase separation, vitrification - and multiple structural, thermodynamic, kinetic, and process parameters. Optimizing membrane properties and rationally designing fabrication processes is a challenge which particle simulation can significantly contribute to. Using large-scale particle simulations, it is observed that 1) a small incompatibility between matrix-forming block of the copolymer and nonsolvent, 2) a glassy arrest that occurs at a smaller polymer concentration, or 3) a higher dynamical contrast between polymer and solvent results in a finer, spongy substructure, whereas the opposite parameter choice gives rise to larger macropores with an elongated shape. These observations are confirmed by comparison to experiments on polystyrene (PS)-block-poly(4-vinylpyridine) (P4VP) diblock copolymer membranes, varying the chemical nature of the coagulant or the temperature of coagulation bath., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Creating durable and efficient multifunctional electrocatalysts capable of high current densities at low applied potentials is crucial for widespread industrial use in hydrogen production. Herein, a Co-Ni-Fe-Cu-Mo (oxy)hydroxide electrocatalyst with abundant grain boundaries on nickel foam using a scalable coating method followed by chemical precipitation is synthesized. This technique efficiently organizes hierarchical Co-Ni-Fe-Cu-Mo (oxy)hydroxide nanoparticles within ultrafine crystalline regions (<4 nm), enriched with numerous grain boundaries, enhancing catalytic site density and facilitating charge and mass transfer. The resulting catalyst, structured into nanosheets enriched with grain boundaries, exhibits superior electrocatalytic activity. It achieves a reduced overpotential of 199 mV at 10 mA cm 2 current density with a Tafel slope of 48.8 mV dec 1 in a 1 m KOH solution, maintaining stability over 72 h. Advanced analytical techniques reveal that incorporating high-valency copper and molybdenum elements significantly enhances lattice oxygen activation, attributed to weakened metal-oxygen bonds facilitating the lattice oxygen mechanism (LOM). Synchrotron radiation studies confirm a synergistic interaction among constituent elements. Furthermore, the developed high-entropy electrode demonstrates exceptional long-term stability under high current density in alkaline environments, showcasing the effectiveness of high-entropy strategies in advancing electrocatalytic materials for energy-related applications., (© 2024 Wiley‐VCH GmbH.)

This work uses green sustainable reactions twice. Firstly, it is microwave synthesis: 2,4,6-tribiphenyl-4-yl-1,3,5-triazine and similar compounds were prepared in a closed microwave reactor in n-octane by the Friedel-Crafts reaction. Second, a hybrid electrocatalyst for the highly demanded electrochemical reaction of nitrate reduction to ammonia (NO 3 RR) was prepared based on this material. This reaction has great potential to replace the energy-intensive Haber-Bosch process, and in addition, has independent value for the elimination of nitrate contamination of water resources. As shown in the work, microwave synthesis is an eco-friendly method for the synthesis of complex organic compounds; fast, selective and with a high yield of the target product. The electrocatalyst deposited on the graphite electrode consisted of a layer of 2,4-bis([1,1'-biphenyl]-4-yl)-6-hydroxy-1,3,5-triazine and related compounds coated with cobalt oxide. The hybrid catalyst was firmly retained on the graphite electrode during NO 3 RR and the material showed impressive stability with almost no decrease in catalytic activity even after the fifth cycle. Both 2,4-bis([1,1'-biphenyl]-4-yl)-6-hydroxy-1,3,5-triazine and the catalyst based on this substance were characterized by SEM, XPS, XRD, UV-vis spectra, cyclic (and linear) voltammetry, and chronoamperometry. This work can serve as a starting point for the development of stable and durable electrocatalysts for NO 3 RR using triazine derivatives., (© 2024 Wiley-VCH GmbH.)

Nitroxides find application in various areas of chemistry, and a more in-depth understanding of factors controlling their reactivity with metal complexes is warranted to promote further developments. Here, we report on the effect of the metal centre Lewis acidity on both the distribution of the O- and N-centered spin density in 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and turning TEMPO from the O- to N-radical mode scavenger in metal-TEMPO systems. We use Et(Cl)Zn/TEMPO model reaction system with tuneable reactivity in the solid state and solution. Among various products, a unique Lewis acid-base adduct of Cl 2 Zn with the N-ethylated TEMPO was isolated and structurally characterised, and the so-called solid-state 'slow chemistry' reaction led to a higher yield of the N-alkylated product. The revealed structure-activity/selectivity correlations are exceptional yet are entirely rationalised by the mechanistic underpinning supported by theoretical calculations of studied model systems. This work lays a foundation and mechanistic blueprint for future metal/nitroxide systems exploration., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)