Search Results (24)

Carbon-based materials have emerged as promising biomaterials due to their biocompatibility and inherent antibacterial properties. Carbyne, a unique allotrope of carbon, characterized by sp-hybridized carbons forming alternating single and triple bonds, exhibits exceptional toughness. Herein, we explore the potential of carbyne-enriched plasma coatings for antibacterial applications in conjunction with micro- and nano-textured polymeric surfaces. We investigate and characterize carbyne-enriched plasma coatings onto superhydrophilic or superhydrophobic poly (methyl methacrylate) (PMMA) plasma micro-nanotextured surfaces. Our analysis evaluates the wetting properties and durability of these surfaces, particularly in liquid immersion conditions. The integration of carbyne-enriched plasma coatings serves a dual purpose: it enhances the chemical bactericidal action and protects surface micro-nanostructures from deformation due to capillary forces thanks to the material’s innate toughness. The results show that the micro-nanotextured and carbyne-enriched coated PMMA surfaces exhibit a significant bactericidal activity as expressed by a bactericidal index of approximately 50%, owing to the combined effect of both the surface topography and the plasma-deposited carbyne coating. Full article

Carbyne, a linear chain of carbon atoms, possesses extraordinary properties but has remained elusive due to its extreme instability. While encapsulation within carbon nanotubes stabilizes carbyne, a lack of synthetic control over its location has prevented practical use. Here, we introduce a spatially localized plasma jet technique that enables the guided spatially selective self-assembly of carbyne encapsulated within multiwalled carbon nanotube (carbyne@MWCNT) hybrids on graphite surfaces. This method uses intense, localized plasma energy to simultaneously grow nanotubes and synthesize carbyne within them, where the nanotube structure and carbyne encapsulation are governed by the localized heat flux distribution. Beyond confirming carbyne formation via its characteristic Raman mode, we discover its second-order vibrational spectrum, confirming anharmonic interactions between the chain and its nanotube container. This spatial control can be used to architect functional carbyne@MWCNT arrays, whose potential applications are discussed in detail. Full article

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. Full article

Anodic aluminum oxide (AAO) is a promising material for sensor applications due to its unique nanoporous structure and high surface area. This study investigates enhancing AAO’s sensing capabilities by incorporating carbyne-enriched nanomaterials. This research aimed to create a novel surface acoustic wave (SAW) sensor with improved performance characteristics. AAO films were fabricated using a two-step anodization process, followed by carbyne-enriched coating deposition via ion-assisted pulse-plasma deposition. The dielectric properties of the resulting composite material were characterized using impedance spectroscopy, while the sensing performance was evaluated by exposing the sensor to various ethanol concentrations. The results showed a significant increase in capacitance and dielectric permittivity for the carbyne-filled AAO compared to pristine AAO, along with a 5-fold improvement in sensitivity to ethanol vapor. The increased sensitivity is attributed to the synergistic combination of the AAO’s high surface area and the carbyne’s unique electrical properties. This work demonstrates the successful fabrication and characterization of a novel high-sensitivity gas sensor, highlighting the potential of carbyne-enriched AAO for advanced sensor applications. Full article

We conducted a joint synthetic, spectroscopic and computational study to explore the reactivity towards cyanide (from Bu₄NCN) of a series of dinuclear complexes based on the M₂Cp₂(CO)₃ scaffold (M = Fe, Ru; Cp = η⁵-C₅H₅), namely [M₂Cp₂(CO)₂(µ-CO){µ,η¹:η²-CH=C=CMe₂}]BF₄ (1Fe-Ru), [Ru₂Cp₂(CO)₂(µ-CO){µ,η¹:η²-C(Ph)=CHPh}]BF₄ (2Ru) and [M₂Cp₂(CO)₂(µ-CO){µ-CN(Me)(R)}]CF₃SO₃ (3Fe-Ru). While the reaction of 1Fe with Bu₄NCN resulted in prevalent allenyl deprotonation, preliminary CO-NCMe substitution in 1Ru enabled cyanide addition to both the allenyl ligand (resulting in the formation of a h¹:h²-allene derivative, 5A) and the two metal centers (affording 5B1 and 5B2). The mixture of 5B1-2 was rapidly converted into 5A in heptane solution at 100 °C, with 5A being isolated with a total yield of 60%. Following carbonyl-chloride substitution in 2Ru, CN⁻ was incorporated as a terminal ligand upon Cl⁻ displacement, to give the alkenyl complex 6 (84%). The reactivity of 3Fe and 3Ru is strongly influenced by both the metal element, M, and the aminocarbyne substituent, R. Thus, 7aRu was obtained with a 74% yield from cyanide attack on the carbyne in 3aRu (R = Cy, cyclohexyl), whereas the reaction involving the diiron counterpart 3aFe yielded an unclean mixture of the metastable 7aFe and the CO/CN⁻ substitution product 8aFe. The cyano-alkylidene complexes 7aRu (R = Cy) and 7bFe (R = Me) underwent CO loss and carbene to carbyne conversion in isopropanol at 60–80 °C, giving 8aRu (48%) and 8bFe (71%), respectively. The novel compounds 5A, 5B1-2, 6 and 7aRu were characterized by IR and NMR spectroscopy, with the structure of 7aRu further elucidated by single crystal X-ray diffraction analysis. Additionally, the DFT-optimized structures of potential isomers of 5A, 5B1-2 and 6 were calculated. Full article

The response characteristics of carbyne-enriched surface-acoustic-wave (SAW)-based gas sensors utilizing meander and rectangular microheater topologies were investigated to assess their desorption and recovery properties. Comparative analysis of contact resistance and interface capacitance before and after heating revealed minimal deviation in contact resistance, signifying strong thermal stability in the carbyne-enriched layer. However, the interface capacitance varied with the microheater size. Our analysis reveals that a small meander microheater configuration (line width: 300 µm) facilitates efficient sensor recovery at ethanol concentration measurements in the range of 180–680 ppm, maintaining a low deviation in time delay across different concentrations (~2.3%), resulting in a narrow hysteresis and linear sensor response. Conversely, the large meander microheater (line width: 450 µm) and rectangular dense microheater induce irreversible changes in the sensing structure, leading to a widened hysteresis at higher concentrations and increased power consumption. Recovery patterns display substantial deviations from initial values at different concentration levels. Higher concentrations exhibit broader hysteresis, while lower concentrations show narrower hysteresis loops, compared to the small meander microheater. The study offers insights into desorption rates, power consumption variations, and recovery behaviors related to different microheater configurations. It demonstrates the importance of microheater topology selection in tailoring recovery properties and response characteristics, contributing to the advancement of carbyne-based sensor technology. Full article

A convenient synthesis of [HB(HImMe)₃](PF₆)₂ (ImMe = N-methylimidazolyl) is decribed. This salt serves in situ as a precursor to the tris(imidazolylidenyl)borate Li[HB(ImMe)₃] pro-ligand upon deprotonation with ⁿBuLi. Reaction with [W(≡CC₆H₄Me-4)(CO)₂(pic)₂(Br)] (pic = 4-picoline) affords the carbyne complex [W(≡CC₆H₄Me-4)(CO)₂{HB(ImMe)₃}]. Interrogation of experimental and computational data for this compound allow a ranking of familiar tripodal and facially coordinating ligands according to steric (percentage buried volume) and electronic (ν_CO) properties. The reaction of [W(≡CC₆H₄Me-4)(CO)₂{HB(ImMe)₃}] with [AuCl(SMe₂)] affords the heterobimetallic semi-bridging carbyne complex [WAu(μ-CC₆H₄Me-4)(CO)₂(Cl){HB(ImMe)₃}]. Full article

Metallization for contacts in organic electronic nanodevices is of great importance for their performance. A lot of effects can appear at the contact/organic interface and modify the contact parameters, such as contact resistance, adhesive strength, and bonding ability. For novel materials, it is important to study the interactions with metal atoms to develop a suitable technology for contacts, fulfilling to the greatest extent the above-mentioned parameters. A novel material is carbyne, which is still under intensive research because of its great potential in electronics, especially for sensing applications. However, the most appropriate metallization strategy for carbyne-based devices is still unknown, so the interactions between carbyne and metal films should be studied to more precisely direct the development of the metallization technology, and to form contacts that are not limiting factors for device performance. Full article

Pulsed Laser Deposition (PLD) is a highly flexible experimental methodology for the growth of thin films of a broad variety of materials, based on the generation of laser-induced plasmas (LIP) with material ablated from a solid target and on the transfer of the ablated material to a substrate. This review is focused on carbon-based materials—specifically, diamond-like carbon (DLC), graphene and carbyne—and will both discuss the influence of the most critical experimental parameters on the obtained materials and present the experimental developments proposed in the recent literature to tailor the properties of the deposited films and optimize the standard PLD technique for production of various carbon-based materials. Full article

We report a broad theoretical study on [(PMe₃)₃MER]⁺ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = Ar^Mes, Tbb, (Ar^Mes = 2,6-dimesitylphenyl; Tbb = C₆H₂-2,6-[CH(SiMe₃)₂]₂-4-^tBu). A few years ago, our group succeeded in obtaining heavier homologues of cationic group 10 carbyne complexes via halide abstraction of the tetrylidene complexes [(PMe₃)₃M=E(X)R] (X = Cl, Br) using a halide scavenger. The electronic structure and the M-E bonds of the [(PMe₃)₃MER]⁺ complexes were analyzed utilizing quantum-chemical tools, such as the Pipek–Mezey orbital localization method, the energy decomposition analysis (EDA), and the extended-transition state method with natural orbitals of chemical valence (ETS-NOCV). The carbyne, silylidyne complexes, and the germylidyne complex [(PMe₃)₃NiGeAr^Mes]⁺ are suggested to be tetrylidyne complexes featuring donor–acceptor metal tetrel triple bonds, which are composed of two strong π(M→E) and one weaker σ(E→M) interaction. In comparison, the complexes with M = Pd, Pt; E = Sn, Pb; and R = Ar^Mes are best described as metallotetrylenes and exhibit considerable M−E−C bending, a strong σ(M→E) bond, weakened M−E π-components, and lone pair density at the tetrel atoms. Furthermore, bond cleavage energy (BCE) and bond dissociation energy (BDE) reveal preferred splitting into [M(PMe₃)₃]⁺ and [ER] fragments for most complex cations in the range of 293.3–618.3 kJ·mol⁻¹ and 230.4–461.6 kJ·mol⁻¹, respectively. Finally, an extensive study of the potential energy hypersurface varying the M−E−C angle indicates the presence of isomers with M−E−C bond angles of around 95°. Interestingly, these isomers are energetically favored for M = Pd, Pt; E = Sn, Pb; and R = Ar^Mes over the less-bent structures by 13–29 kJ·mol⁻¹. Full article

Transistors made up of carbon nanotube CNT have demonstrated excellent current–voltage characteristics which outperform some high-grade silicon-based transistors. A continuously tunable energy barrier across semiconductor interfaces is desired to make the CNT-based transistors more robust. Despite that the direct band gap of the carbyne inside a CNT can be widely tuned by strain, the size of the carbyne cannot be controlled easily. The production of a monoatomic chain with more than 6000 carbon atoms is an enormous technological challenge. To predict the optimal chain length of a carbyne in different molecular environments, we have developed a Monte Carlo model in which a finite-length carbyne with a size of 4000–15,000 atoms is encapsulated by a CNT at finite temperatures. Our simulation shows that the stability of the carbyne@nanotube is strongly influenced by the nature and porosity of the CNT, the external pressure, the temperature, and the chain length. We have observed an initiation of the chain-breaking process in a compressed carbyne@nanotube. Our work provides much-needed input for optimizing the carbyne length to produce carbon chains much longer than 6000 atoms at ~300 K. Design rules are proposed for synthesizing ~1% strained carbyne@(6,5)CNT as a component in CNT-based transistors to tune the energy barriers continuously. Full article

Using laser-induced vaporisation to evaporate and ionise a source of curved polyaromatic hydrocarbons (carbon nanobelts), we show collision impacts between species cause mass loss and the resultant ions are catalogued via mass-spectrometry. These data are interpreted via a series of “in-silico”-simulated systematic hydrogen-loss studies using density functional theory modelling, sequentially removing hydrogen atoms using thermodynamic stability as a selection for subsequent dehydrogenation. Initial hydrogen loss results in the formation of carbyne chains and pentagon-chains while the nanobelt rings are maintained, giving rise to new circular strained dehydrobenzoannulene species. The chains subsequently break, releasing CH and C₂. Alternative routes towards the formation of closed-cages (fullerenes) are identified but shown to be less stable than chain formation, and are not observed experimentally. The results provide important information on collision degradation routes of curved molecular carbon species, and notably serve as a useful guide to high-energy impact conditions observed in some astrochemical environments. Full article

Due to the unique combination of physicochemical and structural properties of carbyne-enriched nanocoatings, they can be used for the development of high-end electronic devices. We propose using it for the development of sensor platforms based on silicon bulk micromachined membranes that serve as a part of microcapacitors with flexible electrodes, with various sizes and topologies. The carbyne-enriched nanocoating was grown using the ion-assisted pulse-plasma deposition method in the form of 2D-ordered linear-chain carbon with interchain spacing in the range of approximately 4.8–5.03 Å. The main characteristics of the fabricated sensors, such as dynamic range, sensitivity, linearity, response, and recovery times, were measured as a function of the ethanol concentration and compared for the different sizes of the micromembranes and for the different surface states, such as patterned and non-patterned. The obtained results are the first step in the further optimization of these sensor platforms to reach more precise detection of volatile organic compounds for the needs of the healthcare, air monitoring, and other relevant fields of human health. Full article

The application of carbyne-enriched nanomaterials opens unique possibilities for enhancing the functional properties of several nanomaterials and unlocking their full potential for practical applications in high-end devices. We studied the ethanol-vapor-sensing performance of a carbyne-enriched nanocoating deposited onto surface acoustic wave (SAW) composite substrates with various electrode topologies. The carbyne-enriched nanocoating was grown using the ion-assisted pulse-plasma deposition technique. Such carbon nanostructured metamaterials were named 2D-ordered linear-chain carbon, where they represented a two-dimensionally packed hexagonal array of carbon chains held by the van der Waals forces, with the interchain spacing approximately being between 4.8 and 5.03 Å. The main characteristics of the sensing device, such as dynamic range, linearity, sensitivity, and response and recovery times, were measured as a function of the ethanol concentration. To the authors’ knowledge, this was the first time demonstration of the detection ability of carbyne-enriched material to ethanol vapors. The results may pave the path for optimization of these sensor architectures for the precise detection of volatile organic compounds, with applications in the fields of medicine, healthcare, and air composition monitoring. Full article

Background: Due to the aging of the world population, the number of joint diseases, along with the number of arthroplasties, has increased, simultaneously increasing the amount of complications, including periprosthetic joint infection (PPI). In this study, to combat a PPI, we investigated the antimicrobial properties of the new composite cover for titanium implants, silver-doped carbyne-like carbon (S-CLC) film. Methods: The first assay investigated the antimicrobial activity against Pseudomonas aeruginosa and releasing of silver ions from S-CLC films into growth media covered with S-CLC with a thickness of 1, 2, and 4 mm. The second assay determined the direct antibacterial properties of the S-CLC film’s surface against Staphylococcus aureus, Enterococcus faecalis, or P. aeruginosa. The third assay studied the formation of microbial biofilms of S. aureus or P. aeruginosa on the S-CLC coating. Silver-doped carbyne-like carbon (S-CLC)-covered or titanium plates alone were used as controls. Results: S-CLC films, compared to controls, prevented P. aeruginosa growth on 1 mm thickness agar; had direct antimicrobial properties against S. aureus, E. faecalis, and P. aeruginosa; and could prevent P. aeruginosa biofilm formation. Conclusions: S-CLC films on the Ti surface could successfully fight the most common infectious agent in PPI, and prevented biofilm formation. Full article