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Surface display of functional groups with specific reactivity around living cells is an emerging, low cost and highly eco-compatible technology that serves multiple applications, ranging from basic biochemical studies to biomedicine, therapeutics and environmental sciences. Conversely to classical methods exploiting hazardous organic synthesis of precursors or monovalent functionalization via genetics, here we perform functional decoration of individual living microalgae using suitable biocoatings based on polydopamine, a melanin-like synthetic polymer. Here we demonstrate the one-pot synthesis of a functional polydopamine bearing phenylboronic units which can decorate the living cell surfaces via a direct ester formation between boronic units and surface glycoproteins. Furthermore, biosorption of fluorescent sugars on functionalized cell membranes is triggered, demonstrating that these organic coatings act as biocompatible soft shells, still functional and reactive after cell engineering., (© 2024. The Author(s).)

CVD graphene layers are intrinsically polycrystalline; depending on grain size, their structure at the atomic level is scarcely free of defects, which affects the properties of graphene. On the one hand, atomic-scale defects act as scattering centers and lead to a loss of carrier mobility. On the other hand, structural disorder at grain boundaries provides additional resistance in series that affects material conductivity. Graphene chemical functionalization has been demonstrated to be an effective way to improve its conductivity mainly by increasing carrier concentration. The present study reports the healing effects of sulfur doping on the electrical transport properties of single-layer CVD graphene. A post-growth thermal sulfurization process operating at 250 °C is applied on single layers of graphene on Corning-glass and Si/SiO 2 substrates. XPS and Raman analyses reveal the covalent attachment of sulfur atoms in graphene carbon lattice without creating new C-sp 3 defects. Measurements of transport properties show a significant improvement in hole mobility as revealed by Hall measurements and related material conductivity. Typically, Hall mobility values as high as 2500 cm 2 V -1 s -1 and sheet resistance as low as 400 Ohm per square are measured on single-layer sulfurized graphene., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

The gallium monochalcogenides family, comprising gallium sulfide (GaS), gallium selenide (GaSe), and gallium telluride (GaTe), is capturing attention for its applications in energy storage and production, catalysis, photonics, and optoelectronics. This interest originates from their properties, which include an optical bandgap larger than those of most common transition metal dichalcogenides, efficient light absorption, and significant carrier mobility. For any application, stability to air exposure is a fundamental requirement. Here, we perform a comparative study of the stability of layered GaS, GaSe, and GaTe nanometer-thick films down to a few layers with the goal of identifying the most suitable Ga chalcogenide for future integration in photonic and optoelectronic devices. Our study unveils a trend of decreasing air stability from sulfide to selenide and finally to telluride. Furthermore, we demonstrate a hydrogen passivation process to prevent the oxidation of GaSe with a higher feasibility and durability than other state-of-the-art passivation methods proposed in the literature., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Diatom microalgae are a natural source of fossil biosilica shells, namely the diatomaceous earth (DE), abundantly available at low cost. High surface area, mesoporosity and biocompatibility, as well as the availability of a variety of approaches for surface chemical modification, make DE highly profitable as a nanostructured material for drug delivery applications. Despite this, the studies reported so far in the literature are generally limited to the development of biohybrid systems for drug delivery by oral or parenteral administration. Here we demonstrate the suitability of diatomaceous earth properly functionalized on the surface with n -octyl chains as an efficient system for local drug delivery to skin tissues. Naproxen was selected as a non-steroidal anti-inflammatory model drug for experiments performed both in vitro by immersion of the drug-loaded DE in an artificial sweat solution and, for the first time, by trans-epidermal drug permeation through a 3D-organotypic tissue that better mimics the in vivo permeation mechanism of drugs in human skin tissues. Octyl chains were demonstrated to both favour the DE adhesion onto porcine skin tissues and to control the gradual release and the trans-epidermal permeation of Naproxen within 24 h of the beginning of experiments. The evidence of the viability of human epithelial cells after permeation of the drug released from diatomaceous earth, also confirmed the biocompatibility with human skin of both Naproxen and mesoporous biosilica from diatom microalgae, disclosing promising applications of these drug-delivery systems for therapies of skin diseases.

Photosynthetic organisms such as diatoms microalgae provide innovative routes to eco-friendly technologies for environmental pollution bioremediation. Living diatoms are capable to incorporate in vivo a wide variety of chemical species dispersed in seawater, thus being promising candidates for eco-friendly removal of toxic contaminants. However, their exploitation requires immobilization methods that allow to confine microalgae during water treatment. Here we demonstrate that a biofilm of Phaeodactylum tricornutum diatom cells grown on the surface of a glassy substrate bearing boronic acid protruding moieties is stably anchored to the substrate resisting mechanical stress and it is suitable for removal of up to 80 % metal ions (As, Cr, Cu, Zn, Sn, Pb, Sb) in a model polluted water sample. Control experiments also suggest that stabilization of the biofilm adhesion occurs by interaction of boronic acid surface groups of the substrate with the hydroxyl groups of diatoms extracellular polysaccharides., (© 2023 The Authors. ChemBioChem published by Wiley-VCH GmbH.)

Bombyx mori silk fibroin (SF) has been reported as a convenient natural material for regenerative medicine, optoelectronics, and many other technological applications. SF owes its unique features to the hierarchical organization of the fibers. Many efforts have been made to set up protocols for dissolution since many applications of SF are based on regenerated solutions and fibers, but chaotropic conditions required to disassemble the packing of the polymer afford solutions with poor crystalline behavior. Our previous research has disclosed a dissolution and regeneration process of highly crystalline fibers involving lanthanide ions as chaotropic agents, demonstrating that each lanthanide has its own unique interaction with SF. Herein, we report elucidation of the structure of Ln-SF fibers by the combined use of Raman spectroscopy, wide-angle X-ray scattering (WAXS), and solid-state NMR techniques. Raman spectra confirmed the coordination of metal ions to SF, WAXS results highlighted the crystalline content of fibers, and solid-state NMR enabled the assessment of different ratios of secondary structures in the protein., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Polydopamine (PDA) is a synthetic eumelanin polymer mimicking the biopolymer secreted by mussels to attach to surfaces with a high binding strength. It exhibits unique adhesive properties and has recently attracted considerable interest as a multifunctional thin film coating. In this study, we demonstrate that a PDA coating on silica- and polymer-based materials improves the entrapment and retention of uremic toxins produced in specific diseases. The low-cost natural nanotextured fossil diatomaceous earth (DE), an abundant source of mesoporous silica, and polyvinylpyrrolidone-co-Styrene (PVP-co-S), a commercial absorbent comprising polymeric particles, were easily coated with a PDA layer by oxidative polymerization of dopamine at mild basic aqueous conditions. An in-depth chemical-physical investigation of both the resulting PDA-coated materials was performed by SEM, AFM, UV-visible, Raman spectroscopy and spectroscopic ellipsometry. Finally, the obtained hybrid systems were successfully tested for the removal of two uremic toxins (indoxyl sulfate and p-cresyl sulfate) directly from patients' sera.

Interest in layered van der Waals semiconductor gallium monosulfide (GaS) is growing rapidly because of its wide band gap value between those of two-dimensional transition metal dichalcogenides and of insulating layered materials such as hexagonal boron nitride. For the design of envisaged optoelectronic, photocatalytic and photonic applications of GaS, the knowledge of its dielectric function is fundamental. Here we present a combined theoretical and experimental investigation of the dielectric function of crystalline 2H-GaS from monolayer to bulk. Spectroscopic imaging ellipsometry with micron resolution measurements are corroborated by first principle calculations of the electronic structure and dielectric function. We further demonstrate and validate the applicability of the established dielectric function to the analysis of the optical response of c-axis oriented GaS layers grown by chemical vapor deposition (CVD). These optical results can guide the design of novel, to our knowledge, optoelectronic and photonic devices based on low-dimensional GaS.

Many microorganisms produce specific structures, known as spores or cysts, to increase their resistance to adverse environmental conditions. Scientists have started to produce biomimetic materials inspired by these natural membranes, especially for industrial and biomedical applications. Here, we present biological data on the biocompatibility of a polydopamine-based artificial coating for diatom cells. In this work, living Thalassiosira weissflogii diatom cells are coated on their surface with a polydopamine layer mimicking mussel adhesive protein. Polydopamine does not affect diatoms growth kinetics, it enhances their resistance to degradation by treatment with detergents and acids, and it decreases the uptake of model staining emitters. These outcomes pave the way for the use of living diatom cells bearing polymer coatings for sensors based on living cells, resistant to artificial microenvironments, or acting as living devices for cells interface study., (© 2022. The Author(s).)

Antimony sulfide, Sb 2 S 3 , is interesting as the phase-change material for applications requiring high transmission from the visible to telecom wavelengths, with its band gap tunable from 2.2 to 1.6 eV, depending on the amorphous and crystalline phase. Here we present results from an interlaboratory study on the interplay between the structural change and resulting optical contrast during the amorphous-to-crystalline transformation triggered both thermally and optically. By statistical analysis of Raman and ellipsometric spectroscopic data, we have identified two regimes of crystallization, namely 250°C ≤ T  < 300°C, resulting in Type-I spherulitic crystallization yielding an optical contrast Δ n ∼ 0.4, and 300 ≤ T  < 350°C, yielding Type-II crystallization bended spherulitic structure with different dielectric function and optical contrast Δ n ∼ 0.2 below 1.5 eV. Based on our findings, applications of on-chip reconfigurable nanophotonic phase modulators and of a reconfigurable high-refractive-index core/phase-change shell nanoantenna are designed and proposed., Competing Interests: The authors declare no competing interests., (© 2022 The Author(s).)

We have synthetized two classes of dibenzofulvene-arylamino derivatives with an H-shape design, for a total of six different molecules. The molecular structures consist of two D-A-D units connected by a thiophene or bitiophene bridge, using diarylamino substituents as donor groups anchored to the 2,7- (Group A) and 3,6- (Group B) positions of the dibenzofulvene backbone. The donor units and the thiophene or bithiophene bridges were used as chemico-structural tools to modulate electro-optical and morphological-electrical properties. A combination of experiments, such as absorption measurements (UV-Vis spectroscopy), cyclic voltammetry, ellipsometry, Raman, atomic force microscopy, TD-DFT calculation and hole-mobility measurements, were carried out on the synthesized small organic molecules to investigate the differences between the two classes and therefore understand the relevance of the molecular design of the various properties. We found that the anchoring position on dibenzofulvene plays a crucial key for fine-tuning the optical, structural, and morphological properties of molecules. In particular, molecules with substituents in 2,7 positions (Group A) showed a lower structural disorder, a larger molecular planarity, and a lower roughness.

From the group-III monochalcogenide (MX, M  =  Ga, In; X  =  S, Se, Te) layered semiconductors, gallium monosulfide, GaS, has emerged as a promising material for electronics, optoelectronics, and catalysis applications. In this work, GaS samples of various thicknesses in the range from 38 to 1665 nm have been obtained by mechanical exfoliation to study the interplay between structural, morphological, optical, and photoresponsivity properties as a function of thickness. This interplay has been established by analyzing the structure through Raman spectroscopy and X-ray diffraction, the morphology through scanning electron microscopy and atomic force microscopy, the density and optical properties through spectroscopic ellipsometry, and the photoresponsivity through current-voltage measurements under UV light. This work shows that photoresponsivity increases with increases in GaS thickness, resulting in a UV photoresponsivity of 1.5·10 -4 AW -1 stable over several on/off cycles.

Group III layered monochalcogenide gallium sulfide, GaS, is one of the latest additions to the two-dimensional (2D) materials family, and of particular interest for visible-UV optoelectronic applications due to its wide bandgap energy in the range 2.35-3.05 eV going from bulk to monolayer. Interestingly, when going to the few-layer regime, changes in the electronic structure occur, resulting in a change in the properties of the material. Therefore, a systematic study on the thickness dependence of the different properties of GaS is needed. Here, we analyze mechanically exfoliated GaS layers transferred to glass substrates. Specifically, we report the dependence of the Raman spectra, photoluminescence, optical transmittance, resistivity, and work function on the thickness of GaS. Those findings can be used as guidance in designing devices based on GaS., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Gutiérrez, Giangregorio, Dicorato, Palumbo and Losurdo.)

Hydrogen is the key element to accomplish a carbon-free based economy. Here, the first evidence of plasmonic gallium (Ga) nanoantennas is provided as nanoreactors supported on sapphire (α-Al 2 O 3 ) acting as direct plasmon-enhanced photocatalyst for hydrogen sensing, storage, and spillover. The role of plasmon-catalyzed electron transfer between hydrogen and plasmonic Ga nanoparticle in the activation of those processes is highlighted, as opposed to conventional refractive index-change-based sensing. This study reveals that, while temperature selectively operates those various processes, longitudinal (LO-LSPR) and transverse (TO-LSPR) localized surface plasmon resonances of supported Ga nanoparticles open selectivity of localized reaction pathways at specific sites corresponding to the electromagnetic hot-spots. Specifically, the TO-LSPR couples light into the surface dissociative adsorption of hydrogen and formation of hydrides, whereas the LO-LSPR activates heterogeneous reactions at the interface with the support, that is, hydrogen spillover into α-Al 2 O 3 and reverse-oxygen spillover from α-Al 2 O 3. This Ga-based plasmon-catalytic platform expands the application of supported plasmon-catalysis to hydrogen technologies, including reversible fast hydrogen sensing in a timescale of a few seconds with a limit of detection as low as 5 ppm and in a broad temperature range from room-temperature up to 600 °C while remaining stable and reusable over an extended period of time., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Sulfur hexafluoride (SF 6 ) is one of the most harmful greenhouse gases producing environmental risks. Therefore, developing ways of degrading SF 6 without forming hazardous products is increasingly important. Herein, we demonstrate for the first time the plasmon-catalytic heterogeneous degradation of SF 6 into nonhazardous MgF 2 and MgSO 4 products by nontoxic and sustainable plasmonic magnesium/magnesium oxide (Mg/MgO) nanoparticles, which are also effective as a plasmon-enhanced SF 6 chemometric sensor. The main product depends on the excitation wavelength; when the localized surface plasmon resonance (LSPR) is in the ultraviolet, then MgF 2 forms, while visible light LSPR results in MgSO 4 . Furthermore, Mg/MgO platforms can be regenerated in few seconds by hydrogen plasma treatment and can be reused in a new cycle of air purification. Therefore, this research first demonstrates effectiveness of Mg/MgO plasmon-catalysis enabling environmental remediation with the concurrent functionalities of monitoring, degrading, and detecting sulfur and fluorine gases in the atmosphere.

Magnesium-based films and nanostructures are being studied in order to improve hydrogen reversibility, storage capacity, and kinetics, because of their potential in the hydrogen economy. Some challenges with magnesium (Mg) samples are their unavoidable oxidation by air exposure and lack of direct in situ real time measurements of hydrogen interaction with Mg and MgO surfaces and Mg plasmonic nanoparticles. Given these challenges, the present article investigates direct interaction of Mg with hydrogen, as well as implications of its inevitable oxidation by real-time spectroscopic ellipsometry for exploiting the optical properties of Mg, MgH 2 and MgO. The direct hydrogenation measurements have been performed in a reactor that combines a remote hydrogen plasma source with an in situ spectroscopic ellipsometer, which allows optical monitoring of the hydrogen interaction and results in optical property modification. The hydrogen plasma dual use is to provide the hydrogen-atoms and to reduce barriers to heterogeneous hydrogen reactions.

The present work focuses on the idea to prevent and/or inhibit the colonization of implant surfaces by microbial pathogens responsible for post-operative infections, adjusting antimicrobial properties of the implant surface prior to its insertion. An antibacterial coating based on chitosan and silver was developed by electrodeposition techniques on poly(acrylic acid)-coated titanium substrates. When a silver salt was added during the chitosan deposition step, a stable and scalable silver incorporation was achieved. The physico-chemical composition of the coating was studied by X-ray photoelectron spectroscopy (XPS), while atomic force microscopy in intermittent contact mode (ICAFM) was used to explore the coating morphology. The amount of silver released from the coating up to 21 days was evaluated by inductively coupled plasma mass spectrometry (ICP-MS). The capability of the proposed coating to interact in vitro with the biological environment in terms of compatibility and antibacterial properties was assessed using MG-63 osteoblast-like cell line and S. aureus and P. aeruginosa strains, respectively. These studies revealed that a coating showing a silver surface atomic percentage equal to 0.3% can be effectively used as antibacterial system, while providing good viability of osteoblast-like cells after 7 days. The antibacterial effectiveness of the prepared coating is mainly driven by a contact killing mechanism, although the low concentration of silver released (below 0.1 ppm up to 21 days) is enough to inhibit bacterial growth, advantaging MG-63 cells in the race for the surface.

A gallium-modified chitosan/poly(acrylic acid) bilayer was obtained by electrochemical techniques on titanium to reduce orthopaedic and/or dental implants failure. The bilayer in vitro antibacterial properties and biocompatibility were evaluated against Escherichia coli and Pseudomonas aeruginosa and on MG63 osteoblast-like cells, respectively. Gallium loading into the bilayer was carefully tuned by the electrochemical deposition time to ensure the best balance between antibacterial activity and cytocompatibility. The 30min deposition time was able to reduce in vitro the viable cell counts of E. coli and P. aeruginosa of 2 and 3 log cfu/sheet, respectively. Our results evidenced that the developed antibacterial coating did not considerably alter the mechanical flexural properties of titanium substrates and, in addition, influenced positively MG63 adhesion and proliferation. Therefore, the gallium-modified chitosan/poly(acrylic acid) bilayer can be exploited as a promising titanium coating to limit bacterial adhesion and proliferation, while maintaining osseointegrative potential., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Graphene/metal heterojunctions are ubiquitous in graphene-based devices and, therefore, have attracted increasing interest of researchers. Indeed, the literature on the field reports apparently contradictory results about the effect of a metal on graphene doping. Here, we elucidate the effect of metal nanostructuring and oxidation on the metal work function (WF) and, consequently, on the charge transfer and doping of graphene/metal hybrids. We show that nanostructuring and oxidation of metals provide a valid support to frame WF and doping variation in metal/graphene hybrids. Chemical vapour-deposited monolayer graphene has been transferred onto a variety of metal surfaces, including d-metals, such as Ag, Au, and Cu, and sp-metals, such as Al and Ga, configured as thin films or nanoparticle (NP) ensembles of various average sizes. The metal-induced charge transfer and the doping of graphene have been investigated using Kelvin probe force microscopy (KPFM), and corroborated by Raman spectroscopy and plasmonic ellipsometric spectroscopy. We show that when the appropriate WF of the metal is considered, without any assumption, taking into account WF variations by nanostructure and/or oxidation, a linear relationship between the metal WF and the doping of graphene is found. Specifically, for all metals, nanostructuring lowers the metal WF. In addition, using gold as an example, a critical metal nanoparticle size is found at which the direction of charge transfer, and consequently graphene doping, is inverted.

Fluorination of graphene enables tuning of its electronic properties, provided that control of the fluorination degree and of modification of graphene structure can be achieved. In this work we demonstrate that SF6 modulated plasma fluorination of monolayer graphene yields polyene-graphene hybrids. The extent of fluorination is determined by the plasma exposure time and controlled in real time by monitoring the change in the optical response by spectroscopic ellipsometry. Raman spectroscopy reveals the formation of polyenes in partially fluorinated graphene (F/C < 0.25), which are responsible for changes in conductivity and for opening a transport gap of ∼25 meV. We demonstrate that the cis- and trans-isomers of the polyenes in graphene are tunable using the photothermal switching. Specifically, the room temperature fluorination results in the cis-isomer that can be converted to the trans-isomer by annealing at T > 150 °C, whereas photoirradiation activates the trans-to-cis isomerization. The two isomers give to the polyene-graphene hybrids different optical and conductivity properties providing a way to engineer electrical response of graphene.

Metal nanoparticle (NP)-graphene multifunctional platforms are of great interest for exploring strong light-graphene interactions enhanced by plasmons and for improving performance of numerous applications, such as sensing and catalysis. These platforms can also be used to carry out fundamental studies on charge transfer, and the findings can lead to new strategies for doping graphene. There have been a large number of studies on noble metal Au-graphene and Ag-graphene platforms that have shown their potential for a number of applications. These studies have also highlighted some drawbacks that must be overcome to realize high performance. Here we demonstrate the promise of plasmonic gallium (Ga) nanoparticle (NP)-graphene hybrids as a means of modulating the graphene Fermi level, creating tunable localized surface plasmon resonances and, consequently, creating high-performance surface-enhanced Raman scattering (SERS) platforms. Four prominent peculiarities of Ga, differentiating it from the commonly used noble (gold and silver) metals are (1) the ability to create tunable (from the UV to the visible) plasmonic platforms, (2) its chemical stability leading to long-lifetime plasmonic platforms, (3) its ability to n-type dope graphene, and (4) its weak chemical interaction with graphene, which preserves the integrity of the graphene lattice. As a result of these factors, a Ga NP-enhanced graphene Raman intensity effect has been observed. To further elucidate the roles of the electromagnetic enhancement (or plasmonic) mechanism in relation to electron transfer, we compare graphene-on-Ga NP and Ga NP-on-graphene SERS platforms using the cationic dye rhodamine B, a drug model biomolecule, as the analyte.

Despite the large number of papers on the NH3 doping of graphene, the achievement of stable n-doped large area CVD (chemical vapor deposition) graphene, which is intrinsically p-doped, is still challenging. A control of the NH3 chemisorption and of the N-bond configuration is still needed. The feasibility of a room temperature high pressure NH3 treatment of CVD graphene to achieve n-type doping is shown here. We use and correlate data for (a) sheet resistance, R(sh), and the Hall coefficient, R(H), in van der Pauw configuration, acquired in real time during the NH3 doping of CVD-graphene on a glass substrate, (b) optical measurements of the effect of doping on the graphene Van Hove singularity point at 4.6 eV in the dielectric function spectra by spectroscopic ellipsometry, and of (c) N-bond configuration by XPS to better understand and, finally, control the NH3 doping of graphene. The discussion is focused on the thermal and time stability of the n-doping after air exposure. A chemical rationale is provided for the NH3 n-doping based on the interaction of (i) NH3 with intrinsic oxygen functionalities and defects of CVD graphene and of (ii) C-NH2 doping centers with acceptor species present in the air.

Gold nanoclusters are deposited directly on silicon by sputtering of a target of metallic gold using an argon plasma to provide a semiconductor-based plasmonic platform. The effects of annealing and substrate temperatures during the nanoparticles deposition and of the silicon surface energy on the shape of the nanoparticles and resulting surface plasmon resonance are investigated. The Au nanoparticles are characterized optically, structurally and morphologically using spectroscopic ellipsometry, transmission electron microscopy and atomic force microscopy to establish a correlation among the Au/Si interface reactivity, the Au nanoparticles shape and plasmonic resonance properties. It is found that post-growth annealing up to 600 degrees C of nanoparticles deposited at 60 degrees C causes aggregation of nanoparticles. Increasing the temperature of the substrate during the sputtering of gold on Si yields pancake-like nanoparticles with a large Si/Au interface reactivity forming a gold-silicides interface layer. The O2 plasma treatment of the Si surface forming a thin intentional SiO2 interface layer prevents the Au/Si interdiffusion yielding polyedrical nanoparticles whose plasmon resonance can be shifted down to 1.5 eV.

Understanding the chemical vapor deposition (CVD) kinetics of graphene growth is important for advancing graphene processing and achieving better control of graphene thickness and properties. In the perspective of improving large area graphene quality, we have investigated in real-time the CVD kinetics using CH(4)-H(2) precursors on both polycrystalline copper and nickel. We highlighted the role of hydrogen in differentiating the growth kinetics and thickness of graphene on copper and nickel. Specifically, the growth kinetics and mechanism is framed in the competitive dissociative chemisorption of H(2) and dehydrogenating chemisorption of CH(4), and in the competition of the in-diffusion of carbon and hydrogen, being hydrogen in-diffusion faster in copper than nickel, while carbon diffusion is faster in nickel than copper. It is shown that hydrogen acts as an inhibitor for the CH(4) dehydrogenation on copper, contributing to suppress deposition onto the copper substrate, and degrades quality of graphene. Additionally, the evidence of the role of hydrogen in forming C-H out of plane defects in CVD graphene on Cu is also provided. Conversely, resurfacing recombination of hydrogen aids CH(4) decomposition in the case of Ni. Understanding better and providing other elements to the kinetics of graphene growth is helpful to define the optimal CH(4)/H(2) ratio, which ultimately can contribute to improve graphene layer thickness uniformity even on polycrystalline substrates.

Self-assembled monolayers (SAMs) derived of 4-methoxy-terphenyl-3'',5''-dimethanethiol (TPDMT) and 4-methoxyterphenyl-4''-methanethiol (TPMT) have been prepared by chemisorption from solution onto gold thin films and nanoparticles. The SAMs have been characterized by spectroscopic ellipsometry, Raman spectroscopy and atomic force microscopy to determine their optical properties, namely the refractive index and extinction coefficient, in an extended spectral range of 0.75-6.5 eV. From the analysis of the optical data, information on SAMs structural organization has been inferred. Comparison of SAMs generated from the above aromatic thiols to well-known SAMs generated from the alkanethiol dodecanethiol revealed that the former aromatic SAMs are densely packed and highly vertically oriented, with a slightly higher packing density and a absence of molecular inclination in TPMT/Au. The thermal behavior of SAMs has also been monitored using ellipsometry in the temperature range 25-500 degrees C. Gold nanoparticles functionalized by the same aromatic thiols have also been discussed for surface enhanced Raman spectroscopy applications. This study represents a step forward tailoring the optical and thermal behavior of surfaces as well as nanoparticles.

The transfer of two-dimensional materials from their growth substrate onto application wafers is a critical bottleneck in scaling-up devices based on such nanomaterials. Here, we present an innovative approach to achieve the automated and simultaneous transfer of arrays of graphene ribbons, with precise control over their orientation and alignment onto patterned wafers. The transfer is performed in a simple, yet efficient apparatus consisting of an array of glass columns, strategically shaped to control ribbon orientation and arranged to match the destination wafer, coupled to a dual inflow/outflow pumping system. This apparatus enables the transfer of a custom array of parallel graphene ribbons in a fraction of the time required with traditional methods. The quality of the transferred graphene was evaluated using optical imaging, scanning electron microscopy, hyperspectral Raman imaging, and electrical transport: all consistently indicating that the transferred graphene exhibits excellent quality, comparable to a manual transfer by an expert user. The proposed apparatus offers several competitive advantages, including ease of use, high transfer throughput, and reduced nanomaterial consumption. Moreover, it can be used repeatedly on the same wafer to assemble arrays of overlayed materials with controlled relative orientations. This approach thus opens promising opportunities for the large-scale fabrication of various heterostructures and devices based on vertical assemblies of 2D nanomaterials. [ABSTRACT FROM AUTHOR]

This study aims to examine the impact of carbon precursor materials, which are oil palm fiber (OPF) and waste polystyrene (PS), on friction and wear properties of paraffin base oil added with graphene-coated copper (Cu) additive. The graphene was synthesized on Cu particles via hydrogen-free chemical vapor deposition method. The graphene was characterized using Raman spectroscopy and transmission electron microscopy. The lubricity properties of 0.6 wt.% of synthesized graphene-coated Cu additive in paraffin base oil was analyzed based on its tribological behavior using a four-ball tribometer. From the quantitative and qualitative characterization analysis, graphene-coated Cu additive synthesized using 50 wt.% OPF carbon precursors has a good-quality graphene with minimal defects and a well-ordered lattice structure. From the tribological analysis, the paraffin base oil added with graphene-coated Cu additive synthesized using 50 wt.% OPF carbon precursor has the lowest coefficient of friction of 0.07 and wear rate of 1.6 × 10−5 mm3/min. Hence, it can be suggested that incorporating graphene-coated Cu particles, synthesized from a 50 wt.% OPF carbon precursor, into base oil shows great potential as an environmentally friendly additive, particularly in terms of enhancing lubrication performance. [ABSTRACT FROM AUTHOR]

A novel approach based on a molten multicomponent precursor source has been applied for the MOCVD fabrication of high-quality CaCu(3)Ti(4)O(12) (CCTO) thin films on various substrates. The adopted in situ strategy involves a molten mixture consisting of Ca(hfa)(2).tetraglyme, Ti(tmhd)(2)(O-iPr)(2), and Cu(tmhd)(2) [Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = 2,5,8,11,14-pentaoxapentadecane; Htmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = isopropoxide] precursors. Film structural and morphological characterizations have been carried out by several techniques [X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM)], and in particular the energy filtered TEM mapping and X-ray energy dispersive (EDX) analysis in TEM mode provided a suitable correlation between nanostructural properties of CCTO films and deposition conditions and/or the substrate nature. Correlation between the nanostructure and optical/dielectric properties has been investigated exploiting spectroscopic ellipsometry.

Drilling fluids are crucial for the safe and effective extraction of hydrocarbons from deep petroleum reserves. Lubricating, suspending, and conveying drilled cuttings to the surface are some of the functions of drilling fluids. Their performance depends on lubricity, fluid loss (FL) control, and rheology. Nanoparticles (NPs) have emerged in the oil and gas industry as an efficient fluid additive to modify and stabilize the properties of drilling fluids. NPs are thermally, chemically, and physically stable in drilling fluids; however, field data show they are inefficient at reducing drill string wear. Graphene nanoplatelets (GNPs) are now a useful drilling fluid agent because of their small particles with high specific surface area, good dispersion, high thermal and electrical stability, and their ability to lower stress and wear on the drill string. Thus, this study examined GNPs in drilling fluids, including surface modification methods and their effects on rheology, FL management, and lubricity. The unique properties of GNPs that make them a potential game-changer in drilling fluid are highlighted. The techniques used to modify GNP surfaces to improve drilling fluid compatibility, stability, and dispersion were also addressed. The broad study of laboratory GNP-modified drilling fluids is the central focus of this review. A scrutiny of the mechanisms by which GNPs influence the rheological behavior of drilling fluids and their impact on drilling efficiency and wellbore stability was also highlighted. Beyond laboratory tests, GNP's real-world applications and commercialization possibilities were examined, taking economic and environmental considerations into account. Comparative examination of methods and results helps optimize GNP-enhanced drilling fluids. Small concentrations of GNPs (0.1–2.5 g) increased the base fluid lubricity and rheology. They also reduced the FL by 40–89%. Due to hydroxyl groups on clay surfaces, GNP has a strong affinity for organophilic clays. The challenges and limitations of GNP-modified drilling fluids were highlighted, along with future research directions. Finally, using GNPs as a fluid modification agent may improve drilling fluid lubricity, FL control, and rheology. These attributes will improve oil and gas drilling safety and efficiency. This review consolidates information and lays the groundwork for this growing field's study and innovation. [ABSTRACT FROM AUTHOR]

Rare earth elements (REEs) are known as the "vitamin or nutrients" of metals. The addition of rare earth in a limited quantity can enhance the properties of materials. This article elucidates the effect of doping of rare earth oxide (0.9 wt.% Er2O3) on the mechanical and surface behavior of tungsten carbide (WC-10Co-4Cr) based coatings developed using high pressure high velocity oxygen fuel (HP-HVOF) thermal sprayed techniques on martensitic stainless steel (SS410). With the addition of rare earth oxides, the result shows that the hardness of the deposited coating (HV1261.17) is far higher than the substrate (HV193.47). The modulus of elasticity and flexural strength is enhanced for the coated sample as compared to the substrate. The porosity level of the coating is found to be less than 1% and the static water contact angle for coated surface (≈125.1°) shows the coated sample is hydrophobic in nature. The surface characterization was done using the scanning electron microscope attached with energy dispersive X-ray analysis which has identified the presence of various elements on the surface including rare earth. The surface of coated samples has various phases of rare earth oxides such as monoclinic and cubic rare earth oxides. Moreover, its compounds such as Co3W3C were confirmed by X-ray diffraction measurements. After comparing previous literature with current results can conclude that the addition of rare earth oxides (0.9 wt.% Er2O3) on carbide coatings enhanced the various properties of materials. [ABSTRACT FROM AUTHOR]

Monochalcogenides of groups III (GaS, GaSe) and VI (GeS, GeSe, SnS, and SnSe) are materials with interesting thickness-dependent characteristics, which have been applied in many areas. However, the stability of layered monochalcogenides (LMs) is a real problem in semiconductor devices that contain these materials. Therefore, it is an important issue that needs to be explored. This article presents a comprehensive study of the degradation mechanism in mechanically exfoliated monochalcogenides in ambient conditions using Raman and photoluminescence spectroscopy supported by structural methods. A higher stability (up to three weeks) was observed for GaS. The most reactive were Se-containing monochalcogenides. Surface protrusions appeared after the ambient exposure of GeSe was detected by scanning electron microscopy. In addition, the degradation of GeS and GeSe flakes was observed in the operando experiment in transmission electron microscopy. Additionally, the amorphization of the material progressed from the flake edges. The reported results and conclusions on the degradation of LMs are useful to understand surface oxidation, air stability, and to fabricate stable devices with monochalcogenides. The results indicate that LMs are more challenging for exfoliation and optical studies than transition metal dichalcogenides such as MoS2, MoSe2, WS2, or WSe2. [ABSTRACT FROM AUTHOR]

This comprehensive study was dedicated to augmenting the sensing capabilities of Ni@GP_PEDOT@H2S through the strategic functionalization with nitrogen, phosphorus, and sulfur heteroatoms. Governed by density functional theory (DFT) computations at the gd3bj-B3LYP/def2svp level of theory, the investigation meticulously assessed the performance efficacy of electronically tailored nanocomposites in detecting H2S gas—a corrosive byproduct generated by sulfate reducing bacteria (SRB), bearing latent threats to infrastructure integrity especially in the oil and gas industry. Impressively, the analysed systems, comprising Ni@GP_PEDOT@H2S, N_Ni@GP_PEDOT@H2S, P_Ni@GP_PEDOT@H2S, and S_Ni@GP_PEDOT@H2S, unveiled both structural and electronic properties of noteworthy distinction, thereby substantiating their heightened reactivity. Results of adsorption studies revealed distinct adsorption energies (− 13.0887, − 10.1771, − 16.8166, and − 14.0955 eV) associated respectively with N_Ni@GP_PEDOT@H2S, P_Ni@GP_PEDOT@H2S, S_Ni@GP_PEDOT@H2S, and Ni@GP_PEDOT systems. These disparities vividly underscored the diverse strengths of the adsorbed H2S on the surfaces, significantly accentuating the robustness of S_Ni@GP_PEDOT@H2S as a premier adsorbent, fuelled by the notably strong sulfur-surface interactions. Fascinatingly, the sensor descriptor findings unveiled multifaceted facets pivotal for H2S detection. Ultimately, molecular dynamic simulations corroborated the cumulative findings, collectively underscoring the pivotal significance of this study in propelling the domain of H2S gas detection and sensor device innovation. [ABSTRACT FROM AUTHOR]

Gallium sulfides are wide-gap materials (band gap in the range of 2.85–3.05 eV) that have great potential for applications in optoelectronics, photovoltaics, nonlinear optics, and energy storage. In this study, thin films of gallium sulfide GaxS1−x were prepared for the first time by plasma-enhanced chemical vapor deposition using a transport reaction involving chlorine. High-purity elemental gallium and sulfur were directly used as starting materials. The non-equilibrium low-temperature plasma of the RF discharge (40.68 MHz) initiated chemical transformations. The effect of plasma power on the composition, structure, surface morphology, and optical properties of the films was studied. GaxS1−x films have sufficiently high transparency in the visible and near-IR ranges (up to 70%). [ABSTRACT FROM AUTHOR]

In this paper, stannic sulfide(SnS2) and gallium sulfide (GaS) crystals were grown by the chemical vapor transmission (CVT) method. Correlation analysis of X-ray diffraction, X-ray photoelectron spectroscopy and Raman vibrational modes of the two materials proved the high quality and purity of the sample growth. The absorption characteristics of the two materials were measured by spectrophotometer, and it was found that SnS2 and GaS crystals had absorption peaks at 390 nm and 460 nm, respectively. The corresponding band gap was calculated by the Tauc diagram. In addition, the dielectric response and optical properties of SnS2 and GaS crystal at wavelengths from 250 to 1000 nm were investigated by using ellipsometry and first-principles calculations. Similar broad and low absorption bands of both materials were found in the visible and infrared regions, and a high extinction coefficient was found in the ultraviolet region, which facilitates their use as corresponding photodetectors. These results are helpful for the study of the physical properties of SnS2 and GaS crystals and their related applications. [ABSTRACT FROM AUTHOR]

Silicon sub-bandgap near-infrared (NIR) (λ > 1100 nm) photovoltaic (PV) response by plasmon-enhanced internal photoemission was investigated. The Si sub-bandgap NIR PV response, which remains unexploited in Schottky junction-like solar cell device, was examined using nanometer sized Au/Al2O3/n-Si junction arrays. This kind of metal–insulator–semiconductor structure was similar in functionality to Schottky junction in NIR absorption, photo-induced charge separation and collection. It showed that NIR absorption increased steadily with increasing volume of Au nanoparticles (NPs) till a saturation was reached. Simulation results indicated the formation of localized surface plasmon on the surfaces of Au NPs, which was correlated well with the observed NIR absorption. On the other hand, the NIR PV response was found sensitive to the amount and size of Au NPs and thickness of Al2O3. Chemical and field-effect passivation of n-Si by using Al2O3 and SiO2 were used to optimize the NIR PV response. In the current configuration, the best PV conversion efficiency was 0.034% at λ = 1319 nm under illumination power of 0.1 W/cm2. [ABSTRACT FROM AUTHOR]

Hyphaene thebaica fruits were used for the fabrication of spherical erbium oxide nanoparticles (HT-Er2O3 NPS) using a one-step simple bioreduction process. XRD pattern revealed a highly crystalline and pure phase with crystallite size of ~ 7.5 nm, whereas, the W–H plot revealed crystallite size of 11 nm. FTIR spectra revealed characteristic Er-O atomic vibrations in the fingerprint region. Bandgap was obtained as 5.25 eV using K-M function. The physicochemical and morphological nature was established using Raman spectroscopy, reflectance spectroscopy, SAED and HR-TEM. HT-Er2O3 NPS were further evaluated for antidiabetic potential in mice using in-vivo and in-vitro bioassays. The synthesized HT-Er2O3 NPS were screened for in vitro anti-diabetic potentials against α-glucosidase enzyme and α-amylase enzyme and their antioxidant potential was evaluated using DPPH free radical assay. A dose dependent inhibition was obtained against α-glucosidase (IC50 12 μg/mL) and α-amylase (IC50 78 μg/mL) while good DPPH free radical scavenging potential (IC50 78 μg mL−1) is reported. At 1000 μg/mL, the HT-Er2O3 NPS revealed 90.30% and 92.30% inhibition of α-amylase and α-glucosidase enzymes. HT-Er2O3 NPs treated groups were observed to have better glycemic control in diabetic animals (503.66 ± 5.92*** on day 0 and 185.66 ± 2.60*** on day 21) when compared with positive control glibenclamide treated group. Further, HT-Er2O3 NPS therapy for 21 days caused a considerable effect on serum total lipids, cholesterol, triglycerides, HDL and LDL as compared to untreated diabetic group. In conclusion, our preliminary findings on HT-Er2O3 NPS revealed considerable antidiabetic potential and thus can be an effective candidate for controlling the post-prandial hyperglycemia. However, further studies are encouraged especially taking into consideration the toxicity aspects of the nanomaterial. [ABSTRACT FROM AUTHOR]

This paper reports the synthesis method by sputtered technique for Silicon and Au different thicknesses layers onto glass/FTO substrate, after that the thermal annealing, and then using sol–gel method producing AuNPs@TiO2 plasmonic structure to produce four sample groups: Glass/FTO/AuNPs; glass/FTO/AuNPs/AuNPs@TiO2, glass/FTO/a-Si/AuNPs, and dual combined glass/FTO/a-Si/Au NPs/AuNPs@TiO2 configurations. After thermal annealing, the sputtered Si layer on glass/FTO has amorphous phase (a-Si), sputtered Au layer has crystallized phase in (111) direction and TiO2 has anatase phase. Some optical measurements have investigated such as the transmission, reflection and the absorption measurements were carried out for different sample groups in comparison for choosing the sample group having the highest optical absorption spectrum aiming for application in the modified plasmonic solar cell. The optical absorption of the dual combined glass/FTO/a-Si/AuNPs/AuNPs@TiO2 configuration were significantly enhanced in ultraviolet, visible and near infrared regions with plasmonic resonance peaks shifted depending on Au NPs sizes and a-Si layer thicknesses. This result can be explained by the effects of the dual combined plasmonic structure where the partial /a-Si/Au NPs plasmonic structure has plasmonic resonance around 610 nm with enhanced tail cover to 800 nm, and the partial AuNPs@TiO2 plasmonic structure has plasmonic resonance around 510 nm. The dual combined glass/FTO/a–Si/Au NPs/Au NPs@TiO2 configuration with enhanced absorption spectrum in a wide range that is proposed for applying in the modified plasmonic solar cell for performance enhancement. [ABSTRACT FROM AUTHOR]

A laboratory course experiment is described that combines traditional semiconductor fabrication techniques with the application of a nanotechnology‐relevant material, graphene. Sensor devices made with graphene are integrated with a microfluidic device in order to introduce students to new applications of this technology in biology and medicine. The fabrication and test process for a pH sensor is used as a tangible example, exhibiting a changing resistance across graphene strips immersed in different pH buffer solutions. The processing and test equipment required is available in many Si device fabrication educational laboratories. [ABSTRACT FROM AUTHOR]

Graphene (G) has been a game-changer for conductive optical devices and has shown promising aspects for its implementation in the power industry due to its diverse structures. Graphene has played an essential role as electrodes, hole transport layers (HTLs), electron transport layers (ETLs), and a chemical modulator for perovskite layers in perovskite solar cells (PSCs) over the past decade. Nitrogen-doped graphene (N-DG) derivatives are frequently evaluated among the existing derivatives of graphene because of their versatility of design, easy synthesis process, and high throughput. This review presents a state-of-the-art overview of N-DG preparation methods, including wet chemical process, bombardment, and high thermal treatment methods. Furthermore, it focuses on different structures of N-DG derivatives and their various applications in PSC applications. Finally, the challenges and opportunities for N-DG derivatives for the continuous performance improvement of PSCs have been highlighted. [ABSTRACT FROM AUTHOR]

The electric heaters used in wearable electronic devices require mechanical and thermal stability against deformation and flexibility. In this study, we fabricated a film heater by coating a flexible substrate with a network of silver nanowires coated with chemical-vapour-deposited graphene (denoted as GPonAgNWs) and observed the effect of the number of graphene layers on the heating performance and stability. As the number of graphene layers increased, the maximum temperature and bending cycles that the GPonAgNW network could withstand increased upon repeated bending deformation. Silver nanowire networks coated with two and four graphene layers could, respectively, withstand temperatures of 58 and 70 °C for 18,000 bending cycles at a strain of 15%, whereas a graphene-free silver nanowire network failed at 51 °C after 180 cycles. Moreover, a real-time analysis during cyclic bending deformation of the silver nanowire network coated with four-layer graphene showed a stable temperature variation within 2 °C despite the doubling of resistance for 180,000 cycles. Structural analysis and Monte Carlo simulation demonstrated that the graphene-induced reduction of the contact resistance between the two nanowires could suppress the hotspots generated at the contact, thereby providing an extended heater lifetime and stable heater performance in the GPonAgNW network. Thus, we suggest that flexible heaters made of GPonAgNW networks, exhibiting high reliability upon repeated deformation, can be used in wearable devices. [ABSTRACT FROM AUTHOR]

(Sun)Light is an abundantly available sustainable source of energy that has been used in catalyzing chemical reactions for several decades now. In particular, studies related to the interaction of light with plasmonic nanostructures have been receiving increased attention. These structures display the unique property of localized surface plasmon resonance, which converts light of a specific wavelength range into hot charge carriers, along with strong local electromagnetic fields, and/or heat, which may all enhance the reaction efficiency in their own way. These unique properties of plasmonic nanoparticles can be conveniently tuned by varying the metal type, size, shape, and dielectric environment, thus prompting a research focus on rationally designed plasmonic hybrid nanostructures. In this review, the term “hybrid” implies nanomaterials that consist of multiple plasmonic or non-plasmonic materials, forming complex configurations in the geometry and/or at the atomic level. We discuss the synthetic techniques and evolution of such hybrid plasmonic nanostructures giving rise to a wide variety of material and geometric configurations. Bimetallic alloys, which result in a new set of opto-physical parameters, are compared with core–shell configurations. For the latter, the use of metal, semiconductor, and polymer shells is reviewed. Also, more complex structures such as Janus and antenna reactor composites are discussed. This review further summarizes the studies exploiting plasmonic hybrids to elucidate the plasmonic-photocatalytic mechanism. Finally, we review the implementation of these plasmonic hybrids in different photocatalytic application domains such as H2 generation, CO2 reduction, water purification, air purification, and disinfection. [ABSTRACT FROM AUTHOR]

In the present work, ZnO nanorods have been grown, by hydrothermal method, on glass substrate coated with sputtered ZnO thin film seed layer. The effect of the zinc precursor salt concentration is varied to investigate its effect on the grown nanorod properties. X rays diffraction (XRD), scanning electron microscopy (SEM) technique have been used to analyze the nanorods crystalline structure and morphology. UV–visible optical transmittance and photoluminescence (PL) were used to characterize the nanorods’ optical properties and electronic defects. The XRD analysis reveals the high texturation along the (002) direction indicating the well alignment of the grown nanorods confirmed by the SEM observation. Increasing the salt solution leads to ZnO nanorods with larger diameter and dense ZnO nanorods array. The nanorods optical transmission is characterized by a non-common linear decreasing with wavelength reduction. An explanation model of this behavior is addressed. The PL result analysis suggests that the synthetized ZnO nanorods are formed with Zn-termination polar face. [ABSTRACT FROM AUTHOR]

A label-free immunosensor was constructed in oxidation and reduction dual channel mode for the trace detection of cancer antigen 125 (CA125) in serum. The gold–vertical graphene/titanium dioxide (Au–VG/TiO2) electrode was used as the signal-amplification platform, and cytosine and dopamine were used as probes in the oxidation and reduction channels, respectively. VG nanosheets were synthesized on a TiO2 nanotube array via chemical vapor deposition (CVD), and Au nanoparticles were deeply embedded on the surface and in the root of the VG nanosheets via electrodeposition. The CA125 antibody was then directly immobilized onto the electrode surface, benefitting from its natural affinity for Au nanoparticles. In the oxidation and reduction channels the CA125 antibody–Au–VG/TiO2 immune electrode had the same response concentration range (0.01–1000 mU∙mL−1) for the determination of the CA125 antigen. However, the oxidation channel had a higher sensitivity (14.82 μA•(log(mU•mL−1))−1 at a working potential of ~ 1.25 V vs. SCE), lower detection limit (0.0001 mU∙mL−1), higher stability, and lower performance deviation than the reduction channel. This immunosensor was successfully used for CA125 detection in human serum. The recoveries of spiked serum samples ranged from 99.8 ± 0.5 to 100 ± 0.4%. The study on the difference in the sensing performance between oxidation and reduction channels provides a preliminary experimental reference for exploring dual-channel synchronous detection immunosensors and verifying the accuracy of the assay based on dual-channel data, which will promote the development of reliable electrochemical immunosensor technology. [ABSTRACT FROM AUTHOR]

The past decade has witnessed a rapid growth of graphene plasmonics and their applications in different fields. Compared with conventional plasmonic materials, graphene enables highly confined plasmons with much longer lifetimes. Moreover, graphene plasmons work in an extended wavelength range, i.e., mid-infrared and terahertz regime, overlapping with the fingerprints of most organic and biomolecules, and have broadened their applications towards plasmonic biological and chemical sensors. In this review, we discuss intrinsic plasmonic properties of graphene and strategies both for tuning graphene plasmons as well as achieving higher performance by integrating graphene with plasmonic nanostructures. Next, we survey applications of graphene and graphene-hybrid materials in biosensors, chemical sensors, optical sensors, and sensors in other fields. Lastly, we conclude this review by providing a brief outlook and challenges of the field. Through this review, we aim to provide an overall picture of graphene plasmonic sensing and to suggest future trends of development of graphene plasmonics. [ABSTRACT FROM AUTHOR]