Noncovalent Functionalization Research Articles

Propranolol chiral analysis using voltammetric sensor based on triterpenoid-graphene oxide hybrid material

Enantioselective sensors are potentially in demand at all stages of the production, storage and use of drugs, including identifying impurities of undesirable isomers and improving stereoselective synthesis methods. A key aspect for enantioselective sensors design is the development of appropriate molecular architectures that make it possible to create recognition sites with different affinities for enantiomers. This experimental work proposes a new chiral sensor based on glassy carbon electrode (GCE) modified by graphene oxide (GO) covalent functionalized with pentacyclic triterpenoid betulonic acid (BetA) for voltammetric recognition and determination of propranolol (Prop) enantiomers. Characterization of the materials was carried out using FTIR spectroscopy, scanning electron microscopy and cyclic voltammetry. Differential pulse voltammetry was used for Prop enantiomers recognition and quantification. The potential difference reached 30 mV along with enanitoselectivity coefficient ipS/ipR equal to 1.30. The calculated binding energy for S-Prop/GO-BetA complex is higher by 4.801 kcal moll−1 compared to R-Prop/GO-BetA indicating a more favorable mutual arrangement of molecules. The linear determination range was established as 5.0 × 10-6 ∼ 1.0 × 10-4 mol·L-1 and 1.0 × 10-4 ∼ 4.0 × 10-4 mol·L-1 for both enantiomers. The detection limits were determined to be 3.9⋅10-7 mol·L-1 and 5.0⋅10-7 mol·L-1 for S-Prop and R-Prop, respectively. The standard spike-recovery tests were carried out in human biological fluids with recoveries 97.3 % − 106.9 % for both enantiomers. The proposed sensor was used to determine the ratio of Prop enantiomers in mixture by regression analysis with projection to latent structures (PLS). The purpose was to build a PLS-model based on a calibration set containing a known number of Prop enantiomers and recognize a test set prepared independently. All samples of test set are correctly identified and the RSD did not exceed 8.7 %. GCE modified by covalent functionalized GO with BetA showed better stability compared with noncovalent functionalization in terms of electrode degradation.

Enhancement of oxygen evolution reaction by in situ growth PMo12@ZIF-67 on MWCNTs via perylene bisimide-based dispersant

The combination of metal organic frameworks (MOFs) and multi-walled carbon nanotubes (MWCNTs) can significantly improve their electrochemical performance. However, in most cases, chemical pre-treatment of MWCNTs is inevitable, which may compromise the ideal performance of the final composites. Herein, via a noncovalent functionalization method, PMo12@ZIF-67 was in situ grown on the surfaces of MWCNTs with the assistance of a new dispersant containing two triethylenetetramine (TETA) segments. In order to enhance the coordination of Co metal ions with the surface of MWCNTs, phenolic hydroxyl groups were incorporated into the dispersant through reaction with gallic acid (GA). After annealing, homogeneous CNT/Co6Mo6C2/Co composites were obtained, and they showed excellent performance on oxygen evolution reaction (OER). At a current density of 10 mA cm−2, the lowest overpotential is 263 mV, of which the performance is superior to that achieved by other in situ growth methods. The uniform distribution of coordination sites and subsequent in situ growth of MOFs on MWCNTs improved the electrical conductivity of the derivatives, thereby enhanced the utilization of catalytic active sites. This study presents a novel approach for synthesizing carbon-doped electrocatalytic materials, which demonstrates significant potential in various electrochemical applications.

Covalent vs. Non covalent chemical modification of multiwalled carbon nanotubes based-nanofluids: Stability and thermal conductivity steadiness over temperature

Thermal conductivity enhancement coupled to nanoparticle dispersion stability over time are the two main conflicting requirements to overcome to develop carbon nanomaterial-based nanofluids. Both covalent and non-covalent approaches, having their own advantages and disadvantages, are commonly used for carbon nanotube based nanofluids development. However, they are rarely compared regarding their impact on stability and thermal conductivity performances for the same kind of nanofluid. In this work, multiwalled carbon nanotubes have been chemically modified by both covalent and non-covalent functionalization. For the covalent functionalization, a simple oxidation method is applied. It consists of refluxing the powdered MWCNTs in H2SO4/HNO3 at 5 M concentration. For the non-covalent approach, both an anionic (sodium dodecyl sulfate) and a non-ionic (Pluronic P123, comprising poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) in an alternating linear fashion, PEO-PPO-PEO) surfactants were employed at a concentration of 1 wt%. Nanofluids were prepared with multiwalled carbon nanotubes at a fixed concentration of 0.2 wt% for both chemical modification approaches. The oxidation reaction occurs without significant structure damaging as shown by transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. UV–visible spectrophotometry analysis shows a remarkable stability with temperature in the 293.15–303.15 K range over one-week and for a longer period of 49 days for all the three types of nanofluids. Their thermal conductivity has been investigated in the same temperature range. For all the three nanofluid series prepared with a fixed concentration of carbon nanomaterials, a thermal conductivity enhancement compared to that of the base fluid has been observed. The thermal conductivity evolution with temperature is different for each type of nanofluid. The covalently oxidized multiwalled carbon nanotube based nanofluids showed the better thermal conductivity enhancement steadiness (around 7 %) with temperature. The discussion on the surfactant-based nanofluid behavior proposes the possible involved mechanisms as temperature increases for each surfactant.

Theoretical investigation on graphene induced self-alignment of donor-acceptor structures

Non-covalent functionalization of graphene (Gr) with conducting polymers (CPs) improves the electrical and mechanical properties of both materials owing to the noncovalent π-π stacking interaction between the surface and the aromatic rings in CPs. However, a comprehensive understanding of the self-organization and chain orientation of CPs on the Gr surface remains lacking, which may limit the engineering of CP-Gr complexes with optimized morphology for optoelectronic applications. This study focuses on the Density Functional Theory (DFT) calculations and homemade Python programming code to investigate the self-organization of donor (D)-acceptor (A) type molecules on the Gr surface, aiming to elucidate factors governing the direction of self-alignment. Specifically, basic structural parameters characterizing the aromatic D-A molecules, such as the intramolecular aromatic ring distances, are explored to determine the rules for the preferred alignment direction of the CP monomers on the Gr surface, either in armchair or zigzag paths. Additionally, the influence of Gr on the morphological properties of aromatic molecules, variations in interaction energies between Gr and D-A-D systems with changing A units, and the impact of Gr size on molecular fitting characteristics are examined. The accurate determination of chain alignment direction, which can be applied for all conjugated small molecules and polymers at 2D material interfaces is crucial for guiding experimental studies aimed at tailoring structures and enhanced properties, such as promoting the crystalline domains with high electrical conductivity.

Noncovalent Functionalization of Graphene Nanoplatelets and Their Applications in Supercapacitors.

We demonstrate a simple noncovalent functionalization technique, which involves graphite exfoliation and subsequent coating of the resulting graphene nanoplatelets (GNPs) with trimellitic anhydride (TMA), using a thermomechanical exfoliation process. TMA adsorbs on the surface of the GNPs, resulting in a reduction of the specific surface area to 312 ± 9 m2/g compared to 410 ± 12 m2/g for the unmodified GNPs. Detailed imaging, thermogravimetric, and X-ray diffraction analysis showed that the modified GNPs (TMA-GNPs) maintain similar structure to the unmodified GNPs. The presence of functional groups, confirmed by X-ray photoelectron spectroscopy analysis, caused an increase in the surface energy from 45.6 mJ/m2 for the GNPs to 57.9 mJ/m2 for TMA-GNPs. The resulting coated TMA-GNPs form stable dispersions in water while maintaining their inherent conductive properties, thus enabling applications, such as the manufacture of conductive films and supercapacitors. As a proof-of-concept, electrodes for supercapacitors are prepared from concentrated aqueous dispersions of the functionalized GNPs. Electrochemical characterization of the supercapacitors using electrochemical impedance spectroscopy, cyclic voltammetry and galvanostatic charge/discharge tests showed a specific capacitance of 22.2 F/cm3 at a scan rate of 1 mV/s from cyclic voltammetry and 17.3 F/cm3 at a current density of 1 A/g from galvanostatic charge/discharge tests, with a 90% capacitance retention after 10,000 cycles.

Chemically Functionalized 2D Transition Metal Dichalcogenides for Sensors.

The goal of the sensor industry is to develop innovative, energy-efficient, and reliable devices to detect molecules relevant to economically important sectors such as clinical diagnoses, environmental monitoring, food safety, and wearables. The current demand for portable, fast, sensitive, and high-throughput platforms to detect a plethora of new analytes is continuously increasing. The 2D transition metal dichalcogenides (2D-TMDs) are excellent candidates to fully meet the stringent demands in the sensor industry; 2D-TMDs properties, such as atomic thickness, large surface area, and tailored electrical conductivity, match those descriptions of active sensor materials. However, the detection capability of 2D-TMDs is limited by their intrinsic tendency to aggregate and settle, which reduces the surface area available for detection, in addition to the weak interactions that pristine 2D-TMDs normally exhibit with analytes. Chemical functionalization has been proposed as a consensus solution to these limitations. Tailored surface modification of 2D-TMDs, either by covalent functionalization, non-covalent functionalization, or a mixture of both, allows for improved specificity of the surface-analyte interaction while reducing van der Waals forces between 2D-TMDs avoiding agglomeration and precipitation. From this perspective, we review the recent advances in improving the detection of biomolecules, heavy metals, and gases using chemically functionalized 2D-TMDs. Covalent and non-covalent functionalized 2D-TMDs are commonly used for the detection of biomolecules and metals, while 2D-TMDs functionalized with metal nanoparticles are used for gas and Raman sensors. Finally, we describe the limitations and further strategies that might pave the way for miniaturized, flexible, smart, and low-cost sensing devices.

Ternary (molybdenum disulfide/graphene)/carbon nanotube nanocomposites assembled via a facile colloidal electrostatic path as electrocatalysts for the oxygen reduction reaction: Composition and nitrogen-doping play a key role in their performance

Nanocomposites have garnered attention for their potential as catalysts in electrochemical reactions vital for technologies like fuel cells, water splitting, and metal-air batteries. This work focuses on developing three-dimensional (3D) nanocomposites through aqueous phase exfoliation, non-covalent functionalization of building blocks with surfactants and polymers, and electrostatic interactions in solution leading to the nanocomposites assembly and organization. By combining molybdenum disulfide (MoS2) layers with graphene nanoplatelets (GnPs) to form a binary 2D composite (MoS2/GnP), and subsequently incorporating multiwalled carbon nanotubes (MWNTs) to create ternary 3D composites, we explore their potential as catalysts for the oxygen reduction reaction (ORR) critical in fuel cells. Characterization techniques such as X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction elucidate material composition and structure. Our electrochemical studies reveal insights into the kinetics of the reactions and structure–activity relationships. Both the (MoS2/GnP)-to-MWNT mass ratio and nitrogen-doping of GnPs (N-GnPs) play a key role on the electrocatalytic ORR performance. Notably, the (MoS2/N-GnP)/MWNT material, with a 3:1 mass ratio, exhibits the most effective ORR activity. All catalysts demonstrate good long-term stability and methanol crossover tolerance. This facile fabrication method and observed trends offer avenues for optimizing composite electrocatalysts further.

Hyaluronic acid-functionalized graphene-based nanohybrids for targeted breast cancer chemo-photothermal therapy

Nanomaterials’ application in cancer therapy has been driven by their ability to encapsulate chemotherapeutic drugs as well as to reach the tumor site. Nevertheless, nanomedicines’ translation has been limited due to their lack of specificity towards cancer cells. Although the nanomaterials’ surface can be coated with targeting ligands, such has been mostly achieved through non-covalent functionalization strategies that are prone to premature detachment. Notwithstanding, cancer cells often establish resistance mechanisms that impair the effect of the loaded drugs. This bottleneck may be addressed by using near-infrared (NIR)-light responsive nanomaterials. The NIR-light triggered hyperthermic effect generated by these nanomaterials can cause irreversible damage to cancer cells or sensitize them to chemotherapeutics’ action. Herein, a novel covalently functionalized targeted NIR-absorbing nanomaterial for cancer chemo-photothermal therapy was developed. For such, dopamine-reduced graphene oxide nanomaterials were covalently bonded with hyaluronic acid, and then loaded with doxorubicin (DOX/HA-DOPA-rGO). The produced nanomaterials showed suitable physicochemical properties, high encapsulation efficiency, and photothermal capacity. The in vitro studies revealed that the nanomaterials are cytocompatible and that display an improved uptake by the CD44-overexpressing breast cancer cells. Importantly, the combination of DOX/HA-DOPA-rGO with NIR light reduced breast cancer cells’ viability to just 23 %, showcasing their potential chemo-photothermal therapy.

Anodic voltage performance of conducting polymer-functionalized boron nitride nanosheets: a DFT assessment.

The search for low-diffusion barriers and high-capacity anode materials is considered a key step in boosting the efficiency of metal-ion batteries. Herein, we investigate the impact of a series of conducting polymers (CPs), namely, polyacetylene (PA), polypyrrole (PP), poly-p-phenylene (PPPh), and polythiophene (PT), on enhancing the material design and anodic performance of boron nitride nanosheet (BNNS)-based Li-ion and Na-ion batteries. For this purpose, first principle DFT simulations, utilizing both clustered and periodic models, are systematically performed to assess the stability of such nanostructures and their electronic behavior as potential anodic materials. It is revealed that frontier molecular orbitals calculated for BNNSs are stabilized upon association with the series of CPs, resulting in a reduction in the energy gaps of CP-BNNSs by nearly 50%, which in turn improves the charge transfer properties and cell reaction kinetics. A remarkable improvement in the cell voltage is predicted for PP and PT functionalized BNNSs, reaching approximately 3.5 V for Li+ and 3.0 V for Na+ ions. The outcome of the study emphasizes the influence of the size of metal ions, whether mono- or di-valent, and the nature of adsorbed conducting polymers. Manipulating the electronic features of boron nitride nanostructured surfaces through non-covalent functionalization with conducting polymers could pave the way for the design of highly efficient energy storage anodic CP-BNNS-based systems.

Supramolecular complexation of C60 with branched polyethylene.

Fullerene C60 is a ubiquitous material for application in organic electronics and nanotechnology, due to its desirable optoelectronic properties including good molecular orbital alignment with electron-rich donor materials, as well as high and isotropic charge carrier mobility. However, C60 possesses two limitations that hinder its integration into large-scale devices: (1) poor solubility in common organic solvents leading to expensive device processing, and (2) poor optical absorbance in the visible portion of the spectrum. Covalent functionalization has long been the standard for introducing structural tunability into molecular design, but non-covalent interactions have emerged as an alternative strategy to tailor C60-based materials, offering a versatile and tuneable alternative to novel functional materials and applications. In this work, we report a straightforward non-covalent functionalization of C60 with a branched polyethylene (BPE), which occurs spontaneously in dilute chloroform solution under ambient conditions. A detailed characterization strategy, based on UV-vis spectroscopy and size-exclusion chromatography was performed to verify and investigate the structure of the C60+BPE complex. Among others, our work reveals that the supramolecular complex has an order of magnitude higher molecular weight than its C60 and BPE constituents and points towards oxidation as the driving force behind complexation. The C60+BPE complex also possesses significantly broadened optical absorbance compared to unfunctionalized C60, extending further into the visible portion of the spectrum. This non-covalent approach presents an inexpensive route to address the shortcomings of C60 for electronic applications, situating the C60+BPE complex as a promising candidate for further investigation in organic electronic devices.

Label-Free Electrochemical Sensing Using Glassy Carbon Electrodes Modified with Multiwalled-Carbon Nanotubes Non-Covalently Functionalized with Human Immunoglobulin G

This work reports new analytical applications of glassy carbon electrodes (GCE) modified with a nanohybrid obtained by non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with human immunoglobulin G (IgG) (GCE/MWCNT-IgG). We report the label-free and non-amplified breast cancer 1 gen (BRCA1) biosensing based on the facilitated adsorption of the DNA probe at the nanohybrid modified GCE and the impedimetric detection of the hybridization event in the presence of the redox marker benzoquinone/hydroquinone. The resulting genosensor made the fast, highly selective, and sensitive quantification of BRCA1 gene possible, with a linear range between 1.0 fM and 10.0 nM, a sensitivity of (3.0 ± 0.1) × 102 Ω M−1 (R2 = 0.9990), a detection limit of 0.3 fM, and excellent discrimination of fully non-complementary and mismatch DNA sequences. The detection of BRCA1 in enriched samples of diluted human blood serum showed a recovery percentage of 94.6%. Another interesting analytical application of MWCNT-IgG-modified GCE based on the catalytic activity of the exfoliated MWCNTs is also reported for the simultaneous quantification of dopamine and uric acid in the presence of ascorbic acid, with detection limits at submicromolar levels for both compounds.

Quantitative Rapid Magnetic Immunoassay for Sensitive Toxin Detection in Food: Non-Covalent Functionalization of Nanolabels vs. Covalent Immobilization.

In this study, we present a novel and ultrasensitive magnetic lateral flow immunoassay (LFIA) tailored for the precise detection of zearalenone, a mycotoxin with significant implications for human and animal health. A versatile and straightforward method for creating non-covalent magnetic labels is proposed and comprehensively compared with a covalent immobilization strategy. We employ the magnetic particle quantification (MPQ) technique for precise detection of the labels and characterization of their functionality, including measuring the antibody sorption density on the particle surface. Through kinetic studies using the label-free spectral phase interferometry, the rate and equilibrium constants for the binding of monoclonal antibodies with free (not bound with carrier protein) zearalenone were determined to be kon = 3.42 × 105 M-1s-1, koff = 7.05 × 10-4 s-1, and KD = 2.06 × 10-9 M. The proposed MPQ-LFIA method exhibits detection limits of 2.3 pg/mL and 7.6 pg/mL when employing magnetic labels based on covalent immobilization and non-covalent sorption, with dynamic ranges of 5.5 and 5 orders, correspondingly. We have successfully demonstrated the effective determination of zearalenone in barley flour samples contaminated with Fusarium graminearum. The ease of use and effectiveness of developed test systems further enhances their value as practical tools for addressing mycotoxin contamination challenges.

Non-Covalent Functionalization of Graphene Oxide with POSS to Improve the Mechanical Properties of Epoxy Composites.

Phenyl polyhedral oligomeric silsesquioxane (POSS) is modified onto the GO surface by using the strong π-π coupling between a large number of benzene rings at the end of the phenyl POSS structure and the graphite structure in the GO sheet, realizing the non-covalent functionalization of GO (POSS-GO). The POSS-GO-reinforced EP (POSS-GO/EP) composite material is prepared using the casting molding process. The surface morphology of GO before and after modification and its peel dispersion in EP are examined. Furthermore, the mechanical properties, cross-sectional morphology, and reinforcement mechanism of POSS-GO/EP are thoroughly examined. The results show that the cage-like skeleton structure of POSS is embedded between the GO layers, increasing the spacing between the GO layers and leading to a steric hindrance effect, which effectively prevents their stacking and aggregation and improves the dispersion performance of GO. In particular, the 0.4 phr POSS-GO/EP sample shows the best mechanical properties. This is because, on the one hand, POSS-GO is uniformly dispersed in the EP matrix, which can more efficiently induce crack deflection and bifurcation and can also cause certain plastic deformations in the EP matrix. On the other hand, the POSS-GO/EP fracture cross-section with a stepped morphology of interlaced "canine teeth" shape is rougher and more uneven, leading to more complex crack propagation paths and greater energy consumption. Moreover, the mechanical meshing effect between the rough POSS-GO surface and the EP matrix is stronger, which is conducive to the transfer of interfacial stress and the strengthening and toughening effects of POSS-GO.

Glucose Biosensors - State of the Art and Prospects

Rapid glucose concentration detection in technical and biological systems is an important scientific and technical task of modern chemistry, engineering and technology. The article provides an overview of the last technical solutions in this area. The issues of developing first generation biosensors are considered. However, the main disadvantage of such systems was the significant influence of ascorbic and uric acids on the generated signal, which significantly reduced their selectivity and accuracy. To solve this problem, it is possible to use ion-selective membranes such as Nafion and polycarbonate. The second generation of glucose biosensors uses artificial mediators to facilitate electron transfer between the enzyme and the electrode. These mediators can be immobilized directly by the enzyme or introduced into an enzyme-modified electrode. Suitable mediators include conducting organic salts, ferrocene, quinone compounds, ferricyanide, transition metal complexes, phenothiazine and foxazine compounds. Effective interactions between enzymes and mediators are critical for efficient electron transport. Various approaches have been proposed to tailor mediators, such as the use of Os complexes, noncovalent functionalization of carbon nanotubes, and stabilization of artificial mediators. The third generation of enzyme glucose biosensors uses direct electron transfer to perform electrochemical reduction. Various approaches have been considered, including reassembling apoproteins on cofactor-modified enzymes and electrically coupling enzymes to electrode surfaces using redox polymers or nanomaterials such as gold nanoparticles. Such approaches ensure the formation of an effective enzyme-electrode bond. In addition, the thickness of the enzymatic layer can affect the performance of the biosensor. External factors such as temperature, pH and humidity can have a significant impact on the performance of such electrodes.

A new strategy to build electrochemical enzymatic biosensors using a nanohybrid material based on carbon nanotubes and a rationally designed schiff base containing boronic acid

We report a nanohybrid material obtained by non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with the new ligand (((1E,1′E)-(naphthalene-2,3-diylbis(azaneylylidene))bis(methaneylylidenedene)) bis(4-hydroxy-3,1-phenylene))diboronic acid (SB-dBA), rationally designed to mimic some recognition properties of biomolecules like concanavalin A, for the development of electrochemical biosensors based on the use of glycobiomolecules as biorecognition element. We present, as a proof-of-concept, a hydrogen peroxide biosensor obtained by anchoring horseradish peroxidase (HRP) at a glassy carbon electrode (GCE) modified with the nanohybrid prepared by sonication of 2.0 mg mL−1 MWCNTs and 0.50 mg mL−1 SB-dBA in N,N-dimethyl formamide (DMF) for 30 min. The hydrogen peroxide biosensing was performed at −0.050 V in the presence of 5.0 × 10−4 M hydroquinone. The analytical characteristics of the resulting biosensor are the following: linear range between 0.175 μM and 6.12 μM, detection limit of 58 nM, and reproducibility of 2.0 % using the same nanohybrid (6 biosensors), and 9.0 % using three different nanohybrids. The sensor was successfully used to quantify hydrogen peroxide in enriched milk and human blood serum samples and in a commercial disinfector.

Evaluation of Multiwalled Carbon Nanotube-Silver Nanocomposite: A Fluorescence Spectroscopic Approach.

Silver nanoparticles (AgNPs) have been extensively utilized in various fields due to their excellent physical and chemical properties. The green synthetic routes for the synthesis of AgNPs have been adopted to eliminate the impact of the chemicals over the environment. These methods are more cost-effective, eco-friendly and simple. The association of AgNPs on to the surface of functionalized multi-walled carbon nanotubes (f-MWCNTs) produces nanocomposites with unique properties. This can be achieved by different methods such as covalent functionalization, non-covalent functionalization and so on.In the current study, AgNPs are synthesized by biochemical method and they are anchored on to the surface of functionalized MWCNTs is carried out via a non-covalent interaction. The fluorescence studies are done on the nanocomposites in the presence of a suitable external probe i.e., MB. Here fluorescence and UV-Visible spectroscopy are used.

Graphene nanocomposites for real-time electrochemical sensing of nitric oxide in biological systems.

Nitric oxide (NO) signaling plays many pivotal roles impacting almost every organ function in mammalian physiology, most notably in cardiovascular homeostasis, inflammation, and neurological regulation. Consequently, the ability to make real-time and continuous measurements of NO is a prerequisite research tool to understand fundamental biology in health and disease. Despite considerable success in the electrochemical sensing of NO, challenges remain to optimize rapid and highly sensitive detection, without interference from other species, in both cultured cells and in vivo. Achieving these goals depends on the choice of electrode material and the electrode surface modification, with graphene nanostructures recently reported to enhance the electrocatalytic detection of NO. Due to its single-atom thickness, high specific surface area, and highest electron mobility, graphene holds promise for electrochemical sensing of NO with unprecedented sensitivity and specificity even at sub-nanomolar concentrations. The non-covalent functionalization of graphene through supermolecular interactions, including π-π stacking and electrostatic interaction, facilitates the successful immobilization of other high electrolytic materials and heme biomolecules on graphene while maintaining the structural integrity and morphology of graphene sheets. Such nanocomposites have been optimized for the highly sensitive and specific detection of NO under physiologically relevant conditions. In this review, we examine the building blocks of these graphene-based electrochemical sensors, including the conjugation of different electrolytic materials and biomolecules on graphene, and sensing mechanisms, by reflecting on the recent developments in materials and engineering for real-time detection of NO in biological systems.

A Prato Tour on Carbon Nanotubes: Raman Insights.

The functionalisation of carbon nanotubes has been instrumental in broadening its application field, allowing especially its use in biological studies. Although numerous covalent and non-covalent functionalisation methods have been described, the characterisation of the final materials has always been an added challenge. Among the various techniques available, Raman spectroscopy is one of the most widely used to determine the covalent functionalisation of these species. However, Raman spectroscopy is not a quantitative technique, and no studies are reported comparing its performance when the same number of functional groups are added but using completely different reactions. In this work, we have experimentally and theoretically studied the functionalisation of carbon nanotubes using two of the most commonly used reactions: 1,3-dipolar cycloaddition of azomethylene ylides and diazonium-based radical addition. The number of groups introduced onto the tubes by these reactions has been determined by different characterisation techniques. The results of this study support the idea that data obtained by Raman spectra are only helpful for comparing functionalisations produced using the same type of reaction. However, they should be carefully analysed when comparing functionalisations produced using different reaction types.

Non-covalent functionalization of surfactant-assisted graphene oxide with silver nanocomposites for highly efficient photocatalysis and anti-biofilm applications

This study presents a comprehensive investigation on the synthesis and characterization of surfactant-assisted graphene oxide non-covalent functionalized silver nanocomposites (rGS-AgNPs) for achieving remarkable photocatalytic and anti-biofilm properties. The approach involves using an anionic surfactant (sodium lauryl sulfate (SLS)), silver nitrate (AgNO3), and reduced graphene oxide (rGO) as stabilizing/reducing agents, metal precursors, and supporting materials, respectively. Different composites were prepared by varying the concentration of AgNO3, resulting in rGS-AgNPs composites with concentrations of 0.9 × 10−3 mM, 1.8 × 10−3 mM, and 2.7 × 10−3 mM. Characterization techniques including XRD, FTIR, SEM, and TEM/EDS analysis confirmed the formation of face-centered cubic AgNPs and amorphous rGO structures. The composites exhibited a firm binding of the surfactant and AgNPs on the surface of rGO nanosheets, resulting in efficient anti-biofilm and photocatalytic activity. The size of the supported AgNPs on rGO/SL was found to be 8–10 nm. The rGS-AgNPs composites displayed significantly improved anti-biofilm and photocatalytic performance, attributed to the increased surface area of AgNPs. Moreover, the photocatalytic efficiency of the rGS-AgNPs composites reached 96.48 % within 60 min, outperforming pure AgNPs. The synthetic producre and practical applications will be utilized for biosensors, food packing technology, biomedical and pharmaceutically valuable reactions.

Highly Conductive Robust Carbon Nanotube Networks for Strong Buckypapers and Transparent Electrodes

AbstractWhile individual single‐wall carbon nanotubes (SWCNTs) have remarkable strength and electrical conductivity, SWCNT networks fabricated from dispersions have inferior properties due to nanotube bundling, limiting the potential applications of SWCNT materials. Herein, a common dye molecule (purpurin) is used to exfoliate SWCNTs via noncovalent functionalization and to fabricate SWCNT materials by a simple solution‐based process. The advantageous noncovalent interactions result in efficient exfoliation and metallic SWCNT enrichment, affording SWCNT materials with high mechanical robustness and electrical conductivity. This method is used to prepare mechanically robust SWCNT films and flexible transparent conductive electrodes.