Graphene Amination towards Its Grafting by Antibodies for Biosensing Applications.

The facile synthesis of biografted 2D derivatives complemented by a nuanced understanding of their properties are keystones for advancements in biosensing technologies. Herein, we thoroughly examine the feasibility of aminated graphene as a platform for the covalent conjugation of monoclonal antibodies towards human IgG immunoglobulins. Applying core-level spectroscopy methods, namely X-ray photoelectron and absorption spectroscopies, we delve into the chemistry and its effect on the electronic structure of the aminated graphene prior to and after the immobilization of monoclonal antibodies. Furthermore, the alterations in the morphology of the graphene layers upon the applied derivatization protocols are assessed by electron microscopy techniques. Chemiresistive biosensors composed of the aerosol-deposited layers of the aminated graphene with the conjugated antibodies are fabricated and tested, demonstrating a selective response towards IgM immunoglobulins with a limit of detection as low as 10 pg/mL. Taken together, these findings advance and outline graphene derivatives' application in biosensing as well as hint at the features of the alterations of graphene morphology and physics upon its functionalization and further covalent grafting by biomolecules.

Toward On-Chip Multisensor Arrays for Selective Methanol and Ethanol Detection at Room Temperature: Capitalizing the Graphene Carbonylation.

The artificial olfaction units (or e-noses) capable of room-temperature operation are highly demanded to meet the requests of society in numerous vital applications and developing Internet-of-Things. Derivatized 2D crystals are considered as sensing elements of choice in this regard, unlocking the potential of the advanced e-nose technologies limited by the current semiconductor technologies. Herein, we consider fabrication and gas-sensing properties of On-chip multisensor arrays based on a hole-matrixed carbonylated (C-ny) graphene film with a gradually changed thickness and concentration of ketone groups of up to 12.5 at.%. The enhanced chemiresistive response of C-ny graphene toward methanol and ethanol, of hundred ppm concentration when mixing with air to match permissible exposure OSHA limits, at room-temperature operation is signified. Following thorough characterization via core-level techniques and density functional theory, the predominant role of the C-ny graphene-perforated structure and abundance of ketone groups in advancing the chemiresistive effect is established. Advancing practice applications, selective discrimination of the studied alcohols is approached by linear discriminant analysis employing a multisensor array's vector signal, and the fabricated chip's long-term performance is shown.

Template-Directed Polymerization Strategy for Producing rGO/UHMWPE Composite Aerogels with Tunable Properties.

In this paper, we suggest a previously unknown template-directed polymerization strategy for producing graphene/polymer aerogels with elevated mechanical properties, preservation of the nanoscale pore structure, an extraordinary crystallite structure, as well as tunable electrical and hydrophobic properties. The suggested approach is studied using the reduced graphene oxide (rGO)/ultrahigh molecular weight polyethylene (UHMWPE) system as an example. We also develop a novel method of ethylene polymerization with formation of UHMWPE directly on the surface of rGO sheets prestructured as the aerogel template. At a UHMWPE content smaller than 20 wt %, composite materials demonstrate completely reversible deformation and good conductivity. An ultrahigh polymer content (more than 80 wt %) results in materials with pronounced plasticity, improved hydrophobic properties, and a Young's modulus that is more than 200 times larger than that of pure rGO aerogel. Variation of the polymer content makes it possible to tune the electro-conductive properties of the aerogel in the range from 4.8 × 10-6 to 4.9 × 10-1 S/m and adjust its hydrophobic properties. The developed approach would make it possible to create composite materials with highly developed nanostructural morphology and advanced properties controlled by the thickness of the polymer layer on the surface of graphene sheets.

A Blueprint for the Synthesis and Characterization of Thiolated Graphene.

Graphene derivatization to either engineer its physical and chemical properties or overcome the problem of the facile synthesis of nanographenes is a subject of significant attention in the nanomaterials research community. In this paper, we propose a facile and scalable method for the synthesis of thiolated graphene via a two-step liquid-phase treatment of graphene oxide (GO). Employing the core-level methods, the introduction of up to 5.1 at.% of thiols is indicated with the simultaneous rise of the C/O ratio to 16.8. The crumpling of the graphene layer upon thiolation without its perforation is pointed out by microscopic and Raman studies. The conductance of thiolated graphene is revealed to be driven by the Mott hopping mechanism with the sheet resistance values of 2.15 kΩ/sq and dependable on the environment. The preliminary results on the chemiresistive effect of these films upon exposure to ethanol vapors in the mix with dry and humid air are shown. Finally, the work function value and valence band structure of thiolated graphene are analyzed. Taken together, the developed method and findings of the morphology and physics of the thiolated graphene guide the further application of this derivative in energy storage, sensing devices, and smart materials.

Cationic Magnetite Nanoparticles for Increasing siRNA Hybridization Rates.

An investigation of the interaction principles of nucleic acids and nanoparticles is a priority for the development of theoretical and methodological approaches to creating bionanocomposite structures, which determines the area and boundaries of biomedical use of developed nanoscale devices. «Nucleic acid-magnetic nanoparticle¼ type constructs are being developed to carry out the highly efficient detection of pathogens, create express systems for genotyping and sequencing, and detect siRNA. However, the data available on the impact of nanoparticles on the behavior of siRNA are insufficient. In this work, using nanoparticles of two classical oxides of inorganic chemistry (magnetite (Fe3O4) and silica (SiO2) nanoparticles), and widely used gold nanoparticles, we show their effect on the rate of siRNA hybridization. It has been determined that magnetite nanoparticles with a positive charge on the surface increase the rate of siRNA hybridization, while negatively charged magnetite and silica nanoparticles, or positively charged gold nanoparticles, do not affect hybridization rates (HR).