Hybrid Nanoparticles from Random Polyelectrolytes and Carbon Dots.

The present study concerns the preparation of hybrid nanostructures composed of carbon dots (CDs) synthesized in our lab and a double-hydrophilic poly(2-dimethylaminoethyl methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate) (P(DMAEMA-co-OEGMA)) random copolymer through electrostatic interactions between the negatively charged CDs and the positively charged DMAEMA segments of the copolymer. The synthesis of P(DMAEMA-co-OEGMA) copolymer was conducted through RAFT polymerization. Furthermore, the copolymer was converted into a strong cationic random polyelectrolyte through quaternization of the amine groups of DMAEMA segments with methyl iodide (CH3I), and it was subsequently utilized for the complexation with the carbon dots. The molecular, physicochemical, and photophysical characterization of the aqueous solution of the copolymers and their hybrid nanoparticles was conducted using dynamic and electrophoretic light scattering (DLS, ELS) and spectroscopic techniques, such as UV-Vis, fluorescence (FS), and FT-IR spectroscopy. In addition, studies of their aqueous solution using DLS and ELS showed their responsiveness to external stimuli (pH, temperature, ionic strength). Finally, the interaction of selected hybrid nanoparticles with iron (III) ions was confirmed through FS spectroscopy, demonstrating their potential application for heavy metal ions sensing.

Sustainable Photocatalytic Acylation of Transition Metal Dichalcogenides with Atom Economy.

Transition metal dichalcogenides (TMDs) are promising 2D nanomaterials for diverse applications, but their intrinsic chemical inertness hinders their modification. Herein, a novel approach is presented for the photocatalytic acylation of 2H-MoS2 and 2H-MoSe2, utilizing tetrabutyl ammonium decatungstate ((nBu4N)4W10O32) polyoxometalate complex as a catalyst and a conventional halogen lamp as a source of irradiation. By harnessing the semiconducting properties of TMDs, new avenues emerge for the functionalization of these materials. This novel photocatalytic protocol constitutes the first report on the chemical modification of 2D nanomaterials based on a catalytic protocol and applies to both aliphatic and aromatic substrates. The scope of the decatungstate-photocatalyzed acylation reaction of TMDs is explored by employing an alkyl and an aromatic aldehyde and the success of the methodology is confirmed by diverse spectroscopic, thermal, microscopy imaging, and redox techniques. This catalytic approach on modifying 2D nanomaterials introduces the principles of atom economy in a functionalization protocol for TMDs. It marks a transformative shift toward more sustainable and efficient methodologies in the realm of TMD modification and nanomaterial chemistry.

VAR Fabric Modification: Inducing Antibacterial Properties, Altering Wettability/Water Repellence, and Understanding Reactivity at the Molecular Level.

The present work focuses on the surface coating of VAR technical fibers, consisting of 64% viscose (cellulose), 24% Kevlar, 10% other types of polyamides, and 2% antistatic polymers. Kevlar is an aramid material exhibiting excellent mechanical properties, while cellulose is a natural linear polymer composed of repeating ß-d-glucose units, having several applications in the materials industry. Herein, we synthesized novel, tailor-designed organic molecules possessing functional groups able to anchor on VAR fabrics and cellulose materials, thus altering their properties on demand. To this end, we utilized methyl-α-d-glucopyranose as a model compound, both to optimize the reaction conditions, before applying them to the material and to understand the chemical behavior of the material at the molecular level. The efficient coating of the VAR fabric with the tailor-made compounds was then implemented. Thorough characterization studies using Raman and IR spectroscopies as well as SEM imaging and thermogravimetric analysis were also carried out. The wettability and water repellency and antibacterial properties of the modified VAR fabrics were also investigated in detail. To the best of our knowledge, such an approach has not been previously explored, among other factors regarding the understanding of the anchoring mechanism at the molecular level. The proposed modification protocol holds the potential to improve the properties of various cellulose-based materials beyond VAR fabrics.

Noncontact Layer Stabilization of Azafullerene Radicals: Route toward High-Spin-Density Surfaces.

We deposit azafullerene C59N• radicals in a vacuum on the Au(111) surface for layer thicknesses between 0.35 and 2.1 monolayers (ML). The layers are characterized using X-ray photoemission (XPS) and X-ray absorption fine structure (NEXAFS) spectroscopy, low-temperature scanning tunneling microscopy (STM), and by density functional calculations (DFT). The singly unoccupied C59N orbital (SUMO) has been identified in the N 1s NEXAFS/XPS spectra of C59N layers as a spectroscopic fingerprint of the molecular radical state. At low molecular coverages (up to 1 ML), films of monomeric C59N are stabilized with the nonbonded carbon orbital neighboring the nitrogen oriented toward the Au substrate, whereas in-plane intermolecular coupling into diamagnetic (C59N)2 dimers takes over toward the completion of the second layer. By following the C59N• SUMO peak intensity with increasing molecular coverage, we identify an intermediate high-spin-density phase between 1 and 2 ML, where uncoupled C59N• monomers in the second layer with pronounced radical character are formed. We argue that the C59N• radical stabilization of this supramonolayer phase of monomers is achieved by suppressed coupling to the substrate. This results from molecular isolation on top of the passivating azafullerene contact layer, which can be explored for molecular radical state stabilization and positioning on solid substrates.

Preclinical evaluation of modified carbon nanohorns and their complexation with insulin.

The current study emphasizes the minimal toxicity observed in vitro and in vivo for carbon nanohorns (CNHs) modified with third generation polyamidoamine (PAMAM) dendrimers. Initially, we investigated the interactions between CNH-PAMAM and lipid bilayers, which were utilized as representative models of cellular membranes for the evaluation of their toxicity in vitro. We found that the majority of those interactions occur between the modified CNHs and the polar groups of phospholipids, meaning that CNH-PAMAM does not incorporate into the lipid chains, and thus, disruption of the lipid bilayer structure is avoided. This outcome is a very important observation for further evaluation of CNH-PAPAM in cell lines and in animal models. Next, we demonstrated the potential of CNH-PAMAM for complexation with insulin, as a proof of concept for its employment as a delivery platform. Importantly, our study provides comprehensive evidence of low toxicity for CNH-PAMAM both in vitro and in vivo. The assessment of cellular toxicity revealed that the modified CNHs exhibited minimal toxicity, with concentrations of 151 µg mL-1 and 349 µg mL-1, showing negligible harm to EO771 cells and mouse embryonic fibroblasts (MEFs), respectively. Moreover, the histological analysis of the mouse livers demonstrated no evidence of tissue necrosis and inflammation, or any visible signs of severe toxicity. These findings collectively indicate the safe profile of CNH-PAMAM and further contribute to the growing body of knowledge on the safe and efficient utilization of CNH-based nanomaterials in drug and protein delivery applications.

Covalently Modified Kevlar Fabric Incorporating Graphene Oxide with Enhanced Antibacterial Properties and Preserved Strength.

This work describes a multi-step modification process for the covalent transformation of Kevlar fabric en route to the incorporation of graphene oxide (GO) nanosheets. Spectroscopic, thermal and microscopy imaging techniques have been employed to follow step-by-step the modification of Kevlar and the formation of the corresponding Kevlar-GO hybrid fabric. The level of Kevlar's functionalization can be controlled with the nitration time, the first reaction in the multi-sequence organic transformations, for obtaining the hybrid fabric with a content of GO up to 30 %. Most importantly, the covalent post-modification of Kevlar does not occur in the expense of the other excellent mechanical properties of the fabric. Under optimal conditions, the Kevlar-GO hybrid fabric shows a 20 % enhancement of the ultimate strength. Notably, when the Kevlar-GO hybrid fabric was exposed to cyanobacterial Synechococcus the bacteria growth was fully inhibited. Overall, the covalently modified fabric demonstrated significant antibacterial behavior, excellent strength and stability under common processes. Due to its simplicity, the methodology presented in this work not only promises to result in a standard procedure to functionalize the mer units of Kevlar with a variety of chemicals and nanomaterials but it can be also extended for the modification and hybridization of other fabrics.

Covalently Modified MoS2 Bearing a Hamilton-Type Receptor for Recognizing a Redox-Active Ferrocene-Barbiturate Guest via Multiple H-Bonds.

The covalent modification of the metallic phase of MoS2 with a Hamilton-type ligand is presented, transforming MoS2 to a recognition platform which is able to embrace barbiturate moieties via hydrogen bonding. The successful hydrogen bonding formation is easily monitored by simple electrochemical assessments, if a ferrocene-labeled barbiturate analogue is utilized as a proof of concept. Full spectroscopic, thermal, and electron microscopy imaging characterization is provided for the newly formed recognition system, along with valuable insights concerning the electrochemical sensing. The given methodology expands beyond the sensing applications, confidently entering the territory of supramolecular interactions on the surface of 2D transition metal dichalcogenides. The well-designed host-guest chemistry presented herein, constitutes a guide and an inspiration for hosting customized-structured functional building blocks on MoS2 and its relatives via hydrogen bonding, opening up new opportunities regarding potential applications.

Carbon Dots Strongly Immobilized onto Carbon Nanohorns as Non-Metal Heterostructure with High Electrocatalytic Activity towards Protons Reduction in Hydrogen Evolution Reaction.

Highly performing, non-metal inexpensive electrocatalysts for the production of hydrogen via electrochemical water splitting are called for the replacement of current platinum-based ones. In order to speed up the electrocatalytic hydrogen evolution, abundant active sites but also efficient charge transfer is needed. In this context, 0D carbon dots (CDs) with large specific surface area, low cost, high conductivity, and rich functional groups emerge as promising non-metal electrocatalysts. Additionally, the use of conductive substrates provides an effective strategy to boost their electrocatalytic performance. Herein, the unique 3D superstructure of carbon nanohorns (CNHs), as well as without any metal content in their structure, is used to provide a conductive support of high porosity, large specific surface area, and good electrical conductivity, for the in situ growth and immobilization of CDs, via a simple hydrothermal method. The direct contact of CDs with the 3D conductive network of CNHs promotes charge transfer, accelerating hydrogen evolution. The all-carbon non-metal CDs/CNHs nanoensembleshows an onset potential close to the one of Pt/C, low charge transfer resistance, and excellent stability.

Tungsten Disulfide-Interfacing Nickel-Porphyrin For Photo-Enhanced Electrocatalytic Water Oxidation.

Covalent functionalization of tungsten disulfide (WS2 ) with photo- and electro-active nickel-porphyrin (NiP) is reported. Exfoliated WS2 interfacing NiP moieties with 1,2-dithiolane linkages is assayed in the oxygen evolution reaction under both dark and illuminated conditions. The hybrid material presented, WS2 -NiP, is fully characterized with complementary spectroscopic, microscopic, and thermal techniques. Standard yet advanced electrochemical techniques, such as linear sweep voltammetry, electrochemical impedance spectroscopy, and calculation of the electrochemically active surface area, are used to delineate the catalytic profile of WS2 -NiP. In-depth study of thin films with transient photocurrent and photovoltage response assays uncovers photo-enhanced electrocatalytic behavior. The observed photo-enhanced electrocatalytic activity of WS2 -NiP is attributed to the presence of Ni centers coordinated and stabilized by the N4 motifs of tetrapyrrole rings at the tethered porphyrin derivative chains, which work as photoreceptors. This pioneering work opens wide routes for water oxidation, further contributing to the development of non-noble metal electrocatalysts.

Graphene performs the role of an electron donor in covalently interfaced porphyrin-boron azadipyrromethene dyads and manages photoinduced charge-transfer processes.

Herein, we introduced the versatility of free-base and zinc-metallated porphyrin (H2P and ZnP, respectively) to combine with boron azadipyrromethene (azaBDP) NIR absorbing species, for extending their photophysical interest and covalently anchored onto graphene. In particular, the covalent functionalization of graphene with those H2P-azaBDP and ZnP-azaBDP dyads ensured an invariable structure, in which both chromophores and graphene are in intimate contact, free of aggregations and impurities. Both H2P-azaBDP and ZnP-azaBDP dyads were found to perform energy transfer processes between the chromophores, however, only ZnP-azaBDP confirmed additional charge separation between the chromophores yielding the ZnP˙+-azaBDP˙- charge-separated state. On the other hand, graphene in (H2P-azaBDP)-graphene and (ZnP-azaBDP)-graphene hybrids was found to act as an electron donor, yielding (H2P-azaBDP˙-)-graphene˙+ and (ZnP-azaBDP˙-)-graphene˙+ charge-separated states at an ultrafast timescale. The creation of such donor-acceptor systems, featuring graphene as an electron donor and Vis-to-NIR electron-acceptor dyads, expands their utility when considered in optoelectronic applications.

Pyridine vs. Imidazole Axial Ligation on Cobaloxime Grafted Graphene: Hydrogen Evolution Reaction Insights.

While cobaloximes have been protagonists in the molecular (photo)catalytic hydrogen evolution reaction field, researchers originally shed light on the catalytically active metallic center. However, the specific chemical environment of cobalt, including equatorial and axial ligation, has also a strong impact on the catalytic reaction. In this article, we aim to demonstrate how pyridine vs. imidazole axial ligation of a cobaloxime complex covalently grafted on graphene affects the hydrogen evolution reaction performance in realistic acidic conditions. While pyridine axial ligation mirrors a drastically superior electrocatalytic performance, imidazole exhibits a remarkable long-term stability.

Photo/Electrocatalytic Hydrogen Peroxide Production by Manganese and Iron Porphyrin/Molybdenum Disulfide Nanoensembles.

The oxygen reduction reaction (ORR) 2e- pathway provides an alternative and green route for industrial hydrogen peroxide (H2 O2 ) production. Herein, the ORR photo/electrocatalytic activity in the alkaline electrolyte of manganese and iron porphyrin (MnP and FeP, respectively) electrostatically associated with modified 1T/2H MoS2 nanosheets is reported. The best performing catalyst, MnP/MoS2 , exhibits excellent electrocatalytic performance towards selective H2 O2 formation, with a low overpotential of 20 mV for the 2e- ORR pathway (Eons  = 680 mV vs RHE) and an H2 O2 yield up to 99%. Upon visible light irradiation, MnP/MoS2 catalyst shows significant activity enhancement along with good stability. Electrochemical impedance spectroscopy assays suggest a reduced charge transfer resistance value at the interface with the electrolyte, indicating an efficient intra-ensemble transfer process of the photo-excited electrons through the formation of a type II heterojunction or Schottky contact, and therefore justifies the boosted electrochemical activities in the presence of light. Overall, this work is expected to inspire the design of novel advanced photo/electrocatalysts, paving the way for sustainable industrial H2 O2 production.

Electrocatalytic activity for proton reduction by a covalent non-metal graphene-fullerene hybrid.

A non-metal covalent hybrid of fullerene and graphene was synthesized in one step via fluorographene chemistry. Its electrocatalytic performance for the hydrogen evolution reaction and durability was ascribed to intrahybrid charge-transfer phenomena, exploiting the electron-accepting properties of C60 and the high conductivity and large surface area of graphene.

Methylammonium Lead Bromide Perovskite Nano-Crystals Grown in a Poly[styrene-co-(2-(dimethylamino)ethyl Methacrylate)] Matrix Immobilized on Exfoliated Graphene Nano-Sheets.

Development of graphene/perovskite heterostructures mediated by polymeric materials may constitute a robust strategy to resolve the environmental instability of metal halide perovskites and provide barrierless charge transport. Herein, a straightforward approach for the growth of perovskite nano-crystals and their electronic communication with graphene is presented. Methylammonium lead bromide (CH3NH3PbBr3) nano-crystals were grown in a poly[styrene-co-(2-(dimethylamino)ethyl methacrylate)], P[St-co-DMAEMA], bi-functional random co-polymer matrix and non-covalently immobilized on graphene. P[St-co-DMAEMA] was selected as a bi-modal polymer capable to stabilize the perovskite nano-crystals via electrostatic interactions between the tri-alkylamine amine sites of the co-polymer and the A-site vacancies of the perovskite and simultaneously enable Van der Waals attractive interactions between the aromatic arene sites of the co-polymer and the surface of graphene. The newly synthesized CH3NH3PbBr3/co-polymer and graphene/CH3NH3PbBr3/co-polymer ensembles were formed by physical mixing of the components in organic media at room temperature. Complementary characterization by dynamic light scattering, microscopy, and energy-dispersive X-ray spectroscopy revealed the formation of uniform spherical perovskite nano-crystals immobilized on the graphene nano-sheets. Complementary photophysical characterization by UV-Vis absorption, steady-state, and time-resolved fluorescence spectroscopy unveiled the photophysical properties of the CH3NH3PbBr3/co-polymer colloid perovskite solution and verified the electronic communication within the graphene/CH3NH3PbBr3/co-polymer ensembles at the ground and excited states.

One-step covalent hydrophobic/hydrophilic functionalization of chemically exfoliated molybdenum disulfide nanosheets with RAFT derived polymers.

The covalent functionalization of chemically exfoliated molybdenum disulfide (ce-MoS2) with hydrophobic poly(methyl methacrylate) and hydrophilic poly(acrylic acid) polymers, in a single-step without additives, is presented. The nature of chemical modification and the impact on the structure of ce-MoS2 were spectroscopically investigated. Complexation of Eu3+ was accomplished on grafted polycarboxylate chains on MoS2.

Molybdenum Diselenide and Tungsten Diselenide Interfacing Cobalt-Porphyrin for Electrocatalytic Hydrogen Evolution in Alkaline and Acidic Media.

Easy and effective modification approaches for transition metal dichalcogenides are highly desired in order to make them active toward electrocatalysis. In this manner, we report functionalized molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2) via metal-ligand coordination with pyridine rings for the subsequent covalent grafting of a cobalt-porphyrin. The new hybrid materials were tested towards an electrocatalytic hydrogen evolution reaction in both acidic and alkaline media and showed enhanced activity compared to intact MoSe2 and WSe2. Hybrids exhibited lower overpotential, easier reaction kinetics, higher conductivity, and excellent stability after 10,000 ongoing cycles in acidic and alkaline electrolytes compared to MoSe2 and WSe2. Markedly, MoSe2-based hybrid material showed the best performance and marked a significantly low onset potential of -0.17 V vs RHE for acidic hydrogen evolution reaction. All in all, the ease and fast modification route provides a versatile functionalization procedure, extendable to other transition metal dichalcogenides, and can open new pathways for the realization of functional nanomaterials suitable in electrocatalysis.

Chemically modified carbon nanostructures and 2D nanomaterials for fabrics performing under operational tension and extreme environmental conditions.

The extensive research on carbon nanostructures and 2D nanomaterials will come to fruition once these materials steadily join everyday-life applications. Their chemical functionalization unlocks their potential as carriers of customized properties and counterparts to fabric fibers. The scope of the current review covers the chemical modification of carbon nanostructures and 2D nanomaterials for hybrid fabrics with enhanced qualities against critical operational and weather conditions, such as antibacterial, flame retardant, UV resistant, water repellent and high air and water vapor permeability activities.

Robust coherent spin centers from stable azafullerene radicals entrapped in cycloparaphenylene rings.

Molecular entities with robust spin-1/2 are natural two-level quantum systems for realizing qubits and are key ingredients of emerging quantum technologies such as quantum computing. Here we show that robust and abundant spin-1/2 species can be created in situ in the solid state from spin-active azafullerene C59N cages supramolecularly hosted in crystals of [10]cycloparaphenylene ([10]CPP) nanohoops. This is achieved via a two-stage thermally-assisted homolysis of the parent diamagnetic [10]CPP⊃(C59N)2⊂[10]CPP supramolecular complex. Upon cooling, the otherwise unstable C59N˙ radical is remarkably persistent with a measured radical lifetime of several years. Additionally, pulsed electron paramagnetic resonance measurements show long coherence times, fulfilling a basic condition for any qubit manipulation, and observed Rabi oscillations demonstrate single qubit operation. These findings together with rapid recent advances on the synthesis of carbon nanohoops offer the potential to fabricate tailored cycloparaphenylene networks hosting C59N˙ centers, providing a promising platform for building complex qubit circuits.

First Synthesis of the Inherently Chiral Trans-4' Bisadduct of C59 N Azafullerene by Using Cyclo-[2]-dodecylmalonate as a Tether.

The multiaddition chemistry of azafullerene C59 N has been scarcely explored, and the isolation of pure bisadducts is in its infancy. Encouraged by the recent regioselective synthesis of the inherently chiral equatorialface bisadduct of C59 N, we focused on the isolation of the first trans-4 bisadduct in a simple two-step approach. The first regioselective synthesis of the trans-4 bisadduct of C59 N by using cyclo-[2]-dodecylmalonate as a tether is now reported. The newly synthesized bisadduct has C1 symmetry, as evidenced by 13 C NMR, while X-ray crystallography validated the trans-4' addition pattern. Furthermore, the inherently chiral trans-4' C59 N bisadduct was enantiomerically resolved, and the mirror-image relation of the two enantiomers was probed by circular dichroism spectroscopy. Finally, UV-Vis and redox assays suggested that the addition pattern has a reflection in the light-harvesting and redox properties of the bisadduct.

An ion-selective crown ether covalently grafted onto chemically exfoliated MoS2 as a biological fluid sensor.

We describe the basal plane functionalization of chemically exfoliated molybdenum disulfide (ce-MoS2) nanosheets with a benzo-15-crown-5 ether (B15C5), promoted by the chemistry of diazonium salts en route to the fabrication and electrochemical assessment of an ion-responsive electrode. The success of the chemical modification of ce-MoS2 nanosheets was investigated by infrared and Raman spectroscopy, and the amount of the incorporated crown ether was estimated by thermogravimetric analysis. Raman spatial mapping at on-resonance excitation allowed us to disclose the structural characteristics of the functionalized B15C5-MoS2 nanosheets and the impact of basal plane functionalization to the stabilization of the 1T phase of ce-MoS2. Morphological investigation of the B15C5-MoS2 hybrid was implemented by atomic force microscopy and high-resolution transmission electron microscopy. Furthermore, fast-Fourier-transform analysis and in situ energy dispersive X-ray spectroscopy revealed the crystal lattice of the modified nanosheets and the presence of crown-ether addends, respectively. Finally, B15C5-MoS2 electrodes were constructed and evaluated as ion-selective electrodes for sodium ions in aqueous solution and an artificial sweat matrix.