In this study, cold atmospheric pressure plasma (CAPP) was used to synthesise "electron-rich" multi-metallic nanocluster catalysts (NCs) from precursors containing Pt, Pd, Os, Ru, Re, W and Cr, with potential applications in hydrogenation reactions. To this end, direct-current atmospheric pressure glow discharge (dc-APGD) was operated in two configurations: a flowing liquid anode (FLA) and a flowing liquid cathode (FLC). The CAPP system was fabricated using stereolithography. The NCs were characterised by dynamic light scattering and electrophoretic light scattering. Catalytic activity was evaluated using the reduction of 4-nitrophenol (4-NP) to 4-aminophenol. Morphology and surface composition were examined by high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. The NCs were predominantly smaller than 1 nm forming clustered atoms. The NCs synthesised by FLA- and FLC-dc-APGD with ruthenium as the dominant metal and tungsten as the secondary metal ((RuNCs)-N-W) exhibited zeta potentials of 32.58 +/- 0.16 mV and 32.42 +/- 0.46 mV, respectively, indicating good colloidal stability. (RuNCs)-N-W synthesised by FLA- and FLC-dc-APGD also showed the highest 4-NP reduction activity, with mass-normalised rate constants (k(1m)(b)) of 17.81 min(-1) mg(-1) and 18.09 min(-1) mg(-1) (75% and 81% conversion), respectively. (OsNCs)-N-Pd/Cr synthesised by FLA-dc-APGD demonstrated comparable catalytic performance (k(1m)(b) = 15.87 min(-1) mg(-1)), achieving 86% 4-NP conversion. Notably, this conversion was attained within 1.2 min, whereas all reported values correspond to a reaction time of 8 min.

This study examines polymer-based semiconducting materials as functional candidates for subretinal prosthetic interfaces designed to restore visual function in individuals affected by photoreceptor degeneration. Polymer blend thin films designed to couple high photosensitivity with efficient charge transport and favourable biological interactions were characterized in terms of their physicochemical and optoelectronic properties, stability under physiological conditions, and cytocompatibility with retinal pigment epithelium (RPE) cells. Because retinal cells operate under variable illumination, light-dependent polymer-cell interactions were also analyzed using controlled day-night irradiation cycles. Finally, phase separation in ternary blends was investigated to determine whether spontaneous formation of light-sensitive domains could mimic the spatial organization of photoreceptors and support growth and physiological arrangement of RPE cells. These findings demonstrate the feasibility of designing multifunctional polymeric materials that integrate customized optoelectronic behavior with biologically relevant surface properties, thus establishing a foundational material framework for the development of next-generation organic subretinal prostheses.

A hybrid membrane-catalytic process was developed for the continuous-flow synthesis of 4-aminophenol (4-AP) via reduction of 4-nitrophenol (4-NP). The system integrates dispersed heterogeneous catalysis with microfiltration-based separation, enabling simultaneous reaction and product purification within a single operation. Polymeric microsphere catalysts based on vinylbenzyl chloride–divinylbenzene (VBC-co-DVB) matrices were synthesized, functionalized with amines, and loaded with active species of Re, Os, and W. Structural characterization confirmed the formation of highly dispersed metal species within the polymer network.The catalysts exhibited high activity in the NaBH4-assisted reduction of 4-NP, following apparent pseudo-first-order kinetics, with rate constants up to 0.758 min-1. The Os-based microspheres exhibited the highest activity, while the W-based systems showed a higher turnover frequency. When implemented in the hybrid membrane reactor, the catalysts enabled continuous operation with high 4-NP conversion. A complete conversion and a stable operation without breakthrough were achieved for the Os-based system, yielding the catalyst-free 4-AP directly in permeate.Compared to conventional flow systems, the proposed approach combines the advantages of dispersed catalysts with effective phase separation, elimination of mass-transfer limitations, and downstream purification. This work demonstrates a process-intensified strategy for the efficient and scalable synthesis of aromatic amines.

To overcome the current limitations of organic photovoltaic cells in efficiency and durability, systematic improvements across all mechanistic aspects are essential. This paper examines the impact of incorporating rodshaped one-dimensional (1D) ZnSe nanocrystals (NCs) with various ligands on the morphology and photovoltaic (PV) performance of a model bulk heterojunction solar cells based on poly[N-9 '-heptadecanyl-2,7-carbazolealt-5,5-(4 ',7 '-di-2-thienyl-2 ',1 ',3 '-benzo-thiadia zole)] (PCDTBT) and [6,6]-phenyl C61-butyric acid methyl ester (PC70BM). Ligands with aromatic or aliphatic characteristics, binding through amino or thiol groups, were selected to investigate both morphological and electronic effects. We successfully demonstrate control over the self-organization of 1D ZnSe NCs within the active layer of an organic solar cell. 1D ZnSe NCs were added to the donor-acceptor solution PCDTBT/PC70BM, and we show that tuning the ZnSe NCs surface stabilizer determines the final 3D film composition of PV devices. The 1D ZnSe NCs were synthesized with a simple hot injection method. The original insulating charge carrier ligands used for the synthesis of 1D ZnSe nanocrystals were replaced partially by non-insulating organic compounds containing the aromatic ring and a alkyl chain. With ophenylenediamine, a surface-segregated interfacial buffer array of ZnSe NCs formed through self-organization during the spin-coating process of the active layer solution. The morphology of the devices and the distribution of individual compounds in the active layer were studied with Atomic Force Microscopy (AFM) and Time-ofFlight Secondary Ion Mass Spectrometry (TOF-SIMS). These results indicated that ZnSe NCs mixed into the coating solution spontaneously accumulated on the surface of the active layer due to the low surface energy. The introduction of the 1D ZnSe NCs containing a surface modified with o-phenylenediamine in a model bulk heterojunction solar cells of ITO/PEDOT:PSS/PCDTBT:PC70BM/Al resulted in a 20 % improvement of the power conversion efficiency of the photovoltaic cells from 1.87 % to 2.25 % on average. Only in this case, a selforganized buffer array of 1D ZnSe NCs formed in a single step between the polymer and the aluminum metal electrode, likely improving solar efficiency by suppressing charge carrier recombination at the organic/metal interface.

Carbyne-containing materials offer significant potential for biosensor applications due to their unique chemical and mechanical properties. In this study, carbyne-enriched carbon coatings deposited on SiO2/Si chips using ion-assisted pulse-plasma deposition were evaluated for the first time as substrates for optical biosensing. At first, the carbyne-enriched coatings were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, Atomic Force Microscopy, and the sessile drop method to assess their composition, structure, and wettability. After that, chips with carbyne-enriched coatings were modified with biomolecules through physical absorption or covalent bonding, and the respective biomolecular interactions were monitored in real-time by White Light Reflectance Spectroscopy (WLRS). In both cases, SiO2/Si chips modified with an aminosilane were used as reference substrates. Physical adsorption was tested through immobilization of an antibody against C-reactive protein (CRP) to enable its immunochemical detection, whereas covalent bonding was tested through coupling of biotin and monitoring its reaction with streptavidin. It was found that the carbyne-enriched carbon-coated chips retained both their antibody adsorption capability and their covalent bonding ability for over 18 months, while the modified with aminosilane SiO2/Si chips lost 90% of their antibody adsorption capacity and covalent bonding ability after two months of storage. These findings highlight the strong potential of carbyne-enriched carbon-coated chips as robust biosensing substrates, with applications extending beyond WLRS.

Renewable polymer coatings grafted onto glass via SI-ARGET ATRP from castor seed oil-based monomers (CSM) exhibited unexpected dual temperature- and pH-dependent responses in wettability and morphology in the range of 5-45 degrees C. Homogeneous coatings (after 3 h, < 25 nm) were characterized with XPS, ToF-SIMS, AFM, ellipsometry, water contact angle CA, and the three-liquid method. The 'as-prepared' coatings (15 h of graft) revealed a temperature-dependent minimum in CA and a coincident maximum in surface roughness at 15-20 degrees C, with a U-shaped and an inverted U-shaped dependence, respectively. Temperature-induced transitions between rubbery, rubbery-flow, and viscous-flow states are postulated, with grafted chain rearrangements also reflected in the increase of the polar component of surface energy. After immersion in pH buffers, the U-shaped thermal response in the wettability of the coatings (15 h graft) is enhanced, with increased hydrophilicity, for pH 5 and 7 but destroyed for pH 3 and 9. The opposite temperature variation of surface roughness, determined for pH 7, is accompanied by pH-dependent morphological changes, observed at 20 degrees C. The pH-responsive behavior is related to the hydroxyl groups present in CSM. The polyCSM grafting coating is an excellent biobased candidate for the fabrication of biomaterials that additionally possess temperature- and pH-responsive properties.

Rhenium nanoparticles are an attractive alternative to noble metal-based approaches, which show a limited applicability. The catalytic potential and environmental impact of rhenium nanoparticles (ReNPs) were assessed in conjunction with those of platinum nanoparticles (PtNPs). Both of these nanomaterials were synthesized via low-cost pulse-modulated radiofrequency atmospheric pressure glow discharge (pm-rf-APGD). In this context, pm-rf-APGD was used for the first time to synthesize Re-based nanomaterials. The obtained nanoparticles were used as nanocatalysts for hydrogenation of nitroaromatic compounds. Subsequent characterization revealed high efficacy of rhenium nanoparticles in catalysing the reduction of nitroaromatic compounds, which reached up to 100% conversion yields at a rate constant k1 of 5.5 × 10− 2 min− 1. Although the k1 values obtained for rhenium nanoparticles were lower than those recorded for platinum nanoparticles, this research highlights the economic aspects and explores the possible optimization of catalytic systems. Some putatively disadvantageous environmental impact of rhenium nanoparticles and platinum nanoparticles was demonstrated by the exposure of Raphanus sativus var. oleiferus L. seeds to either rhenium nanoparticles or platinum nanoparticles that resulted in development of the shorter sprouts. Despite this negative environmental impact, the outcomes of this study highlight the potential of rhenium nanoparticles for chemical transformation and emphasize the importance of further insights into the economic and environmental aspects of their application and mitigation strategies.

This study focuses on developing catalytic dialysis membranes incorporating rhenium (Re) apparent nanoparticles (nPs) to enable simultaneous reduction of 4-nitrophenol (4-NP) and extraction of 4-aminophenol (4AP). To reach this aim, membranes based on interpolymer networks (IPNs) of polyethylene and styrene-codivinylbenzene were synthesized, chlorosulfonated, aminated, and functionalized with Re apparent nPs. These membranes were tested in a dialysis cell where a simultaneous reduction of 4-NP and separation of 4-AP was achieved. The pseudo-first order rate constants for the reaction reached 4.07 x 10- 2 min- 1, with 34-50 % of 4AP successfully extracted from the reaction environment. Notably, the process achieved high molecular-level purity of the reaction product without residual 4-NP in the receiving solution. These findings suggest that IPN membranes loaded with Re apparent nPs offer a viable solution for the environmental remediation of nitroaromatic compounds, and the sustainable production of aromatic amines.

Poly(methacrylic acid) (PMAA) is a well-known pH-responsive polymer with under-explored temperature-responsive properties. This study investigated the temperature-responsive properties of PMAA-grafted brush coatings, synthesized via the SI-ATRP polymerization of sodium methacrylate (NaMAA) and methacrylic acid (MAA) on glass surfaces. Distinct water contact angles were observed for PMAA brush coatings fabricated from NaMAA (38 deg) and MAA (60 deg) solutions. The reduced wettability of PMAA brushes from MAA indicates a reduced exposure of the hydrophilic moieties acquired during synthesis, which is postulated to occur with a lower grafting density. PMAA brush coatings showed a lower critical solution temperature (LCST), characterized by changes in wettability and thickness; however, this transition was not observed after immersion in various pH buffer solutions. Although inhibited growth of cells cultured on PMAA brushes was previously reported, we observed that the increased hydrophobicity of PMAA coatings from MAA resulted in excellent biocompatibility, demonstrated by growth and viability of dermal fibroblast cultures, making them prospective for biomedical applications. However, the LCST transition of these coatings did not induce temperature-controlled changes in protein (BSA) adsorption and cell (fibroblast) morphology.

In an effort to provide a universal platform for remotely controlling the behavior of various cell lines, we present a strategy for fabricating 'smart' polymer sandwiches using a nanogel attached to temperature-responsive grafted brush coatings. These coatings can be easily modified to meet the requirements of specific cell types while preserving responsiveness. First, temperature-responsive grafted copolymer brush coatings of poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) with a small amount of hydroxyethyl methacrylate (HEMA) were synthesized on glass surfaces. Subsequent modifications involved using multifunctional alcohols, amines, or their combinations with proteins to react with divinyl sulfone, forming a cross-linked polymer matrix with a surface nanogel structure attached to grafted copolymer brushes containing hydroxyl groups. The resulting sandwich coatings were comprehensively characterized, revealing maintained temperature-responsiveness for various structures of the grafted nanogel. Compared with P(OEGMA-co-HEMA) brushes, these temperature-responsive sandwich coatings exhibited improved biocompatibility while retaining the ability to regulate cell morphology and detachment of dermal fibroblasts through external temperature control. Rheological analysis of live cells was performed on the developed platforms to reveal their impact on cellular behavior. The application of these new materials opens exciting possibilities for tissue engineering.

AbstractHere, the fabrication method of ultrathin Zener diodes is presented utilizing a novel hybrid system of zinc sulfide (ZnS) nanoparticles embedded within a poly(methacrylic acid) (PMAA) matrix, surface‐grafted via ARGET‐ATRP polymerization. The controlled polymerization method facilitates precise control over layer thickness, while the in situ synthesis of ZnS nanoparticles ensures uniform coverage throughout the polymer matrix. The obtained hybrid systems with nanometric thickness (<40 nm) are characterized by diode conductivity with a clear breakdown characteristic of the Zener system. The obtained ultra‐thin layers on p‐doped silicon, in addition to their electrical characteristics, are studied using an atomic force microscope (AFM) and secondary ion mass spectrometry (SIMS) to examine the structure and composition of a hybrid polymer‐nanoparticle system.

In industrial processes, catalysts—materials that speed up chemical reactions without being consumed—are essential. The goal of this research was to create two new rhenium-based nanocomposite catalysts that can effectively and sustainably reduce nitroaromatic compounds to aromatic amines in continuous-flow systems. Nitroaromatic hydrocarbons (NACs), widely used in manufacturing pharmaceuticals, insecticides, and herbicides, often contaminate soil and water, posing significant environmental and health risks. However, their reduction to aromatic amines enables potential industrial reuse. In this study, we synthesized two nanocomposite catalysts based on a copolymer functionalized with N-methyl-D-glucamine, embedded with rhenium (Re)-based apparent nanoparticles, and used them to reduce the NACs in continuous-flow mode to their aromatic amines using newly designed and stereolithographic (SLA) 3D-printed reactors. Advanced characterization techniques were employed to evaluate their structure, morphology, and catalytical performance. Catalyst 1, prepared from a self-modified Purolite D4869 resin and characterized by higher Re loading, exhibited superior conversion rates in batch mode (k1 up to 1.406 s−1). In contrast, Catalyst 2, based on a commercial NMDG-functionalized Dowex resin with a mesoporous structure, demonstrated remarkable stability and catalytic capacity under continuous flow (up to 1.383 mmolNAC mLcat−1). Overall, Catalyst 1 was found to be better suited for rapid batch reactions, whereas Catalyst 2 was found to be more appropriate for long-term flow applications, offering a sustainable route for the efficient conversion of nitroaromatic compounds into valuable aromatic amines. The reactors enabled the efficient conversion of NACs into aromatic amines while enhancing process sustainability and efficiency.

Integrating antibacterial functionality directly into platforms for cell sheet engineering (CSE) would offer proactive defense against bacterial contamination and improve the safety and efficacy of CSE in cell-based therapies. This study demonstrates the potential of poly(4-vinylpyridine) polymer brushes with embedded copper nanoparticles (P4VP&Cu) as innovative CSE platforms, using the adult retinal pigment epithelial cell line (ARPE-19). The unique properties of such coatings, which combine the thermo-responsiveness of the polymer brush with the strong antibiocidal activity of copper, were traced using an interdisciplinary approach to provide information on the physicochemical properties of coatings, and confirm their cytocompatibility, and antibacterial effect through the contact- and release-killing mechanisms as a function of temperature. In particular, differentiated ARPE-19 cells cultured on P4VP coatings demonstrated spontaneous thermo-triggered detachment of intact cell sheets, which preserved their biological activity. This effect was maintained on P4VP&Cu coatings, which exhibited superior antibacterial activity without compromising cell viability in addition to resistance to protein adsorption. These findings highlight the potential of P4VP&Cu coatings as next-generation CSE platforms, combining effective antimicrobial defense with precise thermo-responsive functionality.

The work is concerned with the deposition of ceramic layers of various morphologies, containing silicon and nitrogen, from a polysiloxane precursor in the chemical vapor deposition (CVD) process. The experiments involved the saturation of nitrogen as a gaseous carrier with polysiloxane molecules in the CVD reaction. Saturated nitrogen was supplied to the reaction zone and depending on the synthesis temperature (1000-1800 degrees C) and the concentration of resin in gas phase, various nanocrystalline and amorphous deposits were obtained on graphite foil, including polygranulated SiOC powders, fibrous layers composed of nanofibers (NFs) containing silicon and nitrogen, nanochains and composite fibrous components. The morphology, structure and chemical composition of the deposits formed in the CVD reaction changed with increasing temperature. Above 1300 degrees C, oxygen in the silicon oxycarbide deposits was gradually replaced by nitrogen, creating Si-N bonds. The dominant phase in the deposits obtained in the temperature range of 1700-1800 degrees C were two-phase silicon oxynitride NFs. The core of these NFs consisted of a polycrystalline structure surrounded by an amorphous shell. These structures grew preferentially in the [111] direction through heterogeneous nucleation in the vaporsolid process (VS). The changes in deposits morphology were influenced by the CVD temperature and the resin content in the gas carrier. The activation energy of the crystallization process of silicon oxynitride nanofibers was approximately 96 kJ/mol.

The orientation of the IgG antibody adsorbed on the biosensor surface determines the performance of the bioassay and depends on the pH of the adsorption solution, the amount Gamma of antibody adsorbed, and other factors. So far, the arrangement of IgG at various pH levels has been indirectly inferred from the antigen binding efficiency, evaluated from an assay after adsorption, often with limited control of Gamma. Instead, in this work, the dominant orientation of the antibody layer adsorbed at pH 6-10, in the Gamma range of vertical arrangements, is determined with Time -of -Flight Secondary Ion Mass Spectrometry combined with Principal Component Analysis. The proportions of molecules with tail-on and head -on alignment decrease with pH from 4:1 to 1:2 for physisorption to a 3-aminopropyltriethoxysilane (APTES) monolayer, and from 1:1 to 1:2 for chemisorption to glutaraldehyde-modified APTES. The impact of pH-controlled antibody orientation is then examined in two assays performed using high molarity PBS-based solutions (pH 7.4). The results of a static assay with an Fc-specific secondary antibody mimic those of TOF-SIMS for chemisorbed IgG molecules and show IgG reorientation for physisorption. They also anticorrelate with the antigen binding rate constant of the in -flow capture assay kinetics, monitored with a White Light Reflectance Spectroscopy sensor.

The possibility of application of poly(4-vinyl pyridine) layers cross-linked with transition metal complexes as active layers in biomedical sensors was tested. The successful modification of the P4VP coating with CuBr2 or ZnBr2 was verified using time of flight - secondary ion mass spectrometry and X-ray photoelectron spectroscopy. The topography and wettability of the coatings were examined by using atomic force microscopy and water contact angles measurements, respectively. Tests of biological activity of coatings indicated strong protein adsorption, good biocompatibility, and no antimicrobial activity. The potential of the coatings to be used as active layers of biosensors was verified, by systematic impedance-based measurements, which showed the sensitivity of the P4VP:CuBr2 coatings to the presence of proteins and cells in different concentrations. The high selectivity of the coatings toward the defined analyte was confirmed by the specific antigen–antibody immunoreaction, and the possibility of in situ monitoring of protein adsorption and cell adhesion also for individual cells was presented. Finally, the conductive response of a bilayer system that mimics Organic Field Effect Transistor was shown. These results point to a great potential for both coatings to serve as active layers of sensitive and highly selective biosensors.

We have investigated the formation of surface nanostructures caused by early-stage wear of polystyrene (PS) and poly(n-butyl methacrylate) (PnBMA) thin films as pure materials, or mixed in the form of a 1:1 blend. To this end, atomic force microscopy (AFM) was used to repeatedly scratch the sample surfaces, measure the accompanying friction forces, and image the resulting features. In the very first stage ordered ripples are formed in all cases. As the process goes on, hillocks are nucleated on the crests of the ripples, and progressively released in the form of nanoplastics while the ripples become wider and less regular. On the blend surface the more compliant PnBMA presents more corrugated ripple structures and larger friction oscillations than PS in the beginning, but the scenario becomes again more complex as the wear test is repeated and the original 'rim and hole' geometry of the blend is disrupted. Quite noticeably, the wear damage is reduced if the surfaces are scraped forth and back and not only in one direction. The influence of the scan pattern (distance between scan lines) and of the normal force (well below and above the force threshold of about 50 nN leading to surface ripples in the first stage) have been also addressed.

Efficient thin-thickness electromagnetic interference (EMI) shielding materials are a significant technological challenge. This study takes a unique approach to this issue by fabricating ultra-thin composite mats with superior EMI SE shielding efficiency, covering X- and S-bands. These mats exhibit tunable electrical and magnetic behavior, achieved through carbon nanofibers (CNF) and CoNi-based nanofillers. The process involves the formation of fibrous nanocomposites with a CoNi phase, which are created by electrospinning and heat-treating polyacrylonitrile fibers containing a metal-organic precursor in the form of metallic acetylacetonates (Me (Acac)) up to 4.5 % wt. The addition of acetylacetonates significantly enhances the conductivity of the nano- fibers, with a maximum value observed for 3 % CoNi(Acac)2 - sigma = 1570.6 S/m, more than double that of pure CNF (sigma = 733.6 S/m). A comprehensive study of the relationship between the concentration of the metal precursor and the quality/composition of CoNi dispersion, CNF structure, EMI SE, magnetization, and conductivity revealed the best EMI properties of the mat. Even a small concentration of Me-based particles significantly improved EMI SE from 25.3 dB to 56.7 dB in the 5 GHz band at a sample thickness of 50 mu m. The 3 % wt organometallic precursor (Me(acac)) sample achieved the highest EMI SE, conductivity, and magnetization. However, a higher concentration of Me(Acac) in the samples led to the inhibition of the EMI saturation effect due to the deterioration of individual CNF integrity in the sample, greater susceptibility of CoNi to oxidation, and loss of nanoparticles from the material.

The fabrication of multifunctional, thermoresponsive platforms for regenerative medicine based on polymers that can be easily functionalized is one of the most important challenges in modern biomaterials science. In this study, we utilized atom transfer radical polymerization (ATRP) to produce two series of novel smart copolymer brush coatings. These coatings were based on copolymerizing 2-hydroxyethyl methacrylate (HEMA) with either oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or N-isopropylacrylamide (NIPAM). The chemical compositions of the resulting brush coatings, namely, poly(oligo(ethylene glycol) methyl ether methacrylate-co-2-hydroxyethyl methacrylate) (P(OEGMA-co-HEMA)) and poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (P(NIPAM-co-HEMA)), were predicted using reactive ratios of the monomers. These predictions were then verified using time-of-flight-secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The thermoresponsiveness of the coatings was examined through water contact angle (CA) measurements at different temperatures, revealing a transition driven by lower critical solution temperature (LCST) or upper critical solution temperature (UCST) or a vanishing transition. The type of transition observed depended on the chemical composition of the coatings. Furthermore, it was demonstrated that the transition temperature of the coatings could be easily adjusted by modifying their composition. The topography of the coatings was characterized using atomic force microscopy (AFM). To assess the biocompatibility of the coatings, dermal fibroblast cultures were employed, and the results indicated that none of the coatings exhibited cytotoxicity. However, the shape and arrangement of the cells were significantly influenced by the chemical structure of the coating. Additionally, the viability of the cells was correlated with the wettability and roughness of the coatings, which determined the initial adhesion of the cells. Lastly, the temperature-induced changes in the properties of the fabricated copolymer coatings effectively controlled cell morphology, adhesion, and spontaneous detachment in a noninvasive, enzyme-free manner that was confirmed using optical microscopy.