Interlocking Matrix and Filler for Enhanced Individualization and Reinforcement in Polymer-Single-Walled Carbon Nanotube Composites.

Poor individualization and interfacial adhesion prevent single-walled carbon nanotube (SWNT)-polymer composites from reaching outstanding mechanical properties. With much larger diameters, but common structural features (high aspect ratio and absence of functional groups for covalent or supramolecular attachment with the polymer), carbon fibers face similar problems, which are addressed by covering the fibers with a thin layer of polymer. This sizing strategy has allowed carbon fibers to become the filler of choice for the highest performing materials. Inspired by this, here we investigate the use of the mechanical bond to wrap SWNTs with a layer of polymeric material to produce SWNTs mechanically interlocked with a layer of polymer. We first validate the formation of mechanically interlocked nanotubes (MINTs) using mixtures of SWNTs of relatively large average diameter (1.6 ± 0.4 nm), which are commercially available at reasonable prices and therefore could be technologically relevant as polymer fillers. We then design and synthesize by ring-opening metathesis polymerization (ROMP) a polymer decorated with multiple U-shaped molecules, which are later ring-closed around the SWNTs using metathesis. The obtained hybrids contain a high degree of individualized SWNTs and exhibit significantly increased mechanical properties when compared to the matrix polymer. We envision that this strategy could be employed to produce SWNTs interlocked with polymer layers with various designs for polymer reinforcement.

Ultrasensitive detection of SARS-CoV-2 spike protein by graphene field-effect transistors.

COVID-19, caused by the severe acute respiratory syndrome-coronavirus 2 (SARS-CoV-2), originated a global health crisis, causing over 2 million casualties and altering human daily life all over the world. This pandemic emergency revealed the limitations of current diagnostic tests, highlighting the urgency to develop faster, more precise and sensitive sensors. Graphene field effect transistors (GFET) are analytical platforms that enclose all these requirements. However, the design of a sensitive and robust GFET is not a straightforward objective. In this work, we report a GFET array biosensor for the detection of SARS-CoV-2 spike protein using the human membrane protein involved in the virus internalisation: angiotensin-converting enzyme 2 (ACE2). By finely controlling the graphene functionalisation, by tuning the Debye length, and by deeply characterising the ACE2-spike protein interactions, we have been able to detect the target protein with an extremely low limit of detection (2.94 aM). This work set the basis for a new class of analytical platforms, based on human membrane proteins, with the potential to detect a broad variety of pathogens, even before their isolation, being a powerful tool in the fight against future pandemics.

Fabrication of devices featuring covalently linked MoS2-graphene heterostructures.

The most widespread method for the synthesis of 2D-2D heterostructures is the direct growth of one material on top of the other. Alternatively, flakes of different materials can be manually stacked on top of each other. Both methods typically involve stacking 2D layers through van der Waals forces-such that these materials are often referred to as van der Waals heterostructures-and are stacked one crystal or one device at a time. Here we describe the covalent grafting of 2H-MoS2 flakes onto graphene monolayers embedded in field-effect transistors. A bifunctional molecule featuring a maleimide and a diazonium functional group was used, known to connect to sulfide- and carbon-based materials, respectively. MoS2 flakes were exfoliated, functionalized by reaction with the maleimide moieties and then anchored to graphene by the diazonium groups. This approach enabled the simultaneous functionalization of several devices. The electronic properties of the resulting heterostructure are shown to be dominated by the MoS2-graphene interface.

A MoS2 platform and thionine-carbon nanodots for sensitive and selective detection of pathogens.

This work focuses on the combination of molybdenum disulfide (MoS2) and à la carte functionalized carbon nanodots (CNDs) for the development of DNA biosensors for selective and sensitive detection of pathogens. MoS2 flakes prepared through liquid-phase exfoliation, serves as platform for thiolated DNA probe immobilization, while thionine functionalized carbon nanodots (Thi-CNDs) are used as electrochemical indicator of the hybridization event. Spectroscopic and electrochemical studies confirmed the interaction of Thi-CNDs with DNA. As an illustration of the pathogen biosensor functioning, DNA sequences from InIA gen of Listeria monocytogenes bacteria and open reading frame sequence (ORF1ab) of SARS-CoV-2 virus were detected and quantified with a detection limit of 67.0 fM and 1.01 pM, respectively. Given the paradigmatic selectivity of the DNA hybridization, this approach allows pathogen detection in the presence of other pathogens, demonstrated by the detection of Listeria monocytogenes in presence of Escherichia coli. We note that this design is in principle amenable to any pathogen for which the DNA has been sequenced, including other viruses and bacteria. As example of the application of the method in real samples it has been used to directly detect Listeria monocytogenes in cultures without any DNA Polymerase Chain Reaction (PCR) amplification process.

Covalent Cross-Linking of 2H-MoS2 Nanosheets.

The combination of 2D materials opens a wide range of possibilities to create new-generation structures with multiple applications. Covalently cross-linked approaches are a ground-breaking strategy for the formation of homo or heterostructures made by design. However, the covalent assembly of transition metal dichalcogenides flakes is relatively underexplored. Here, a simple covalent cross-linking method to build 2H-MoS2 -MoS2 homostructures is described, using commercially available bismaleimides. These assemblies are mainly connected vertically, basal plane to basal plane, creating specific molecular sized spaces between MoS2 sheets. Therefore, this straightforward approach gives access to the controlled connection of sulfide-based 2D materials.

Mechanically Interlocked Carbon Nanotubes as a Stable Electrocatalytic Platform for Oxygen Reduction.

Mechanically interlocking redox-active anthraquinone onto single-walled carbon nanotubes (AQ-MINT) gives a new and advanced example of a noncovalent architecture for an electrochemical platform. Electrochemical studies of AQ-MINT as an electrode reveal enhanced electrochemical stability in both aqueous and organic solvents compared to physisorbed AQ-based electrodes. While maintaining the electrochemical properties of the parent anthraquinone molecules, we observe a stable oxygen reduction reaction to hydrogen peroxide (H2O2). Using such AQ-MINT electrodes, 7 and 2 µmol of H2O2 are produced over 8 h under basic and neutral conditions, while the control system of SWCNTs produces 2.2 and 0.5 µmol, respectively. These results reveal the potential of this rotaxane-type immobilization approach for heterogenized electrocatalysis.

Controlled Covalent Functionalization of 2 H-MoS2 with Molecular or Polymeric Adlayers.

Most air-stable 2D materials are relatively inert, which makes their chemical modification difficult. In particular, in the case of MoS2 , the semiconducting 2 H-MoS2 is much less reactive than its metallic counterpart, 1T-MoS2 . As a consequence, there are hardly any reliable methods for the covalent modification of 2 H-MoS2 . An ideal method for the chemical functionalization of such materials should be both mild, not requiring the introduction of a large number of defects, and versatile, allowing for the decoration with as many different functional groups as possible. Herein, a comprehensive study on the covalent functionalization of 2 H-MoS2 with maleimides is presented. The use of a base (Et3 N) leads to the in situ formation of a succinimide polymer layer, covalently connected to MoS2 . In contrast, in the absence of base, functionalization stops at the molecular level. Moreover, the functionalization protocol is mild (occurs at room temperature), fast (nearly complete in 1 h), and very flexible (11 different solvents and 10 different maleimides tested). In practical terms, the procedures described here allow for the chemist to manipulate 2 H-MoS2 in a very flexible way, decorating it with polymers or molecules, and with a wide range of functional groups for subsequent modification. Conceptually, the spurious formation of an organic polymer might be general to other methods of functionalization of 2D materials, where a large excess of molecular reagents is typically used.

Mild Covalent Functionalization of Transition Metal Dichalcogenides with Maleimides: A "Click" Reaction for 2H-MoS2 and WS2.

The physical properties of ultrathin transition metal dichalcogenides (2D-TMDCs) make them promising candidates as active nanomaterials for catalysis, optoelectronics, and biomedical applications. Chemical modification of TMDCs is expected to be key in modifying/adding new functions that will help make such promise a reality. We present a mild method for the modification of the basal planes of 2H-MoS2 and WS2. We exploit the soft nucleophilicity of sulfur to react it with maleimide derivatives, achieving covalent functionalization of 2H-TMDCs under very mild conditions. Extensive characterization proves that the reaction occurs through Michael addition. The orthogonality and versatility of the thiol-ene "click" chemistry is expected to allow the à la carte chemical manipulation of TMDCs.

Positive and negative regulation of carbon nanotube catalysts through encapsulation within macrocycles.

One of the most attractive applications of carbon nanomaterials is as catalysts, due to their extreme surface-to-volume ratio. The substitution of C with heteroatoms (typically B and N as p- and n-dopants) has been explored to enhance their catalytic activity. Here we show that encapsulation within weakly doping macrocycles can be used to modify the catalytic properties of the nanotubes towards the reduction of nitroarenes, either enhancing it (n-doping) or slowing it down (p-doping). This artificial regulation strategy presents a unique combination of features found in the natural regulation of enzymes: binding of the effectors (the macrocycles) is noncovalent, yet stable thanks to the mechanical link, and their effect is remote, but not allosteric, since it does not affect the structure of the active site. By careful design of the macrocycles' structure, we expect that this strategy will contribute to overcome the major hurdles in SWNT-based catalysts: activity, aggregation, and specificity.

Simultaneous assembly of van der Waals heterostructures into multiple nanodevices.

van der Waals heterostructures (vdWH) are made of different two-dimensional (2D) layers stacked on top of each other, forming a single material with unique properties that differ from those of the individual 2D constituent layers, and that can be modulated through the interlayer interaction. These hetero-materials can be artificially made by mechanical stamping, solution processing or epitaxial growth. Alternatively, franckeite has been recently described as an example of a naturally-occurring vdWH that can be exfoliated down to nanometer thicknesses. Research on vdWHs has so far been limited to manually exfoliated and stamped individual devices. Here, a scalable and fast method to fabricate vdWH nanodevices from liquid phase exfoliated nanoflakes is reported. The transport and positioning of the flakes into localized submicrometer structures is achieved simultaneously in multiple devices via a dielectrophoretic process. The complex vdWH is preserved after dielectrophoresis and the properties of the resulting field-effect transistors are equivalent to those fabricated via mechanical exfoliation and stamping. The combination of liquid phase exfoliation and dielectrophoretic assembly is particularly suited for the study of vdWHs and applications where large-scale fabrication is required.

Band-Gap Opening in Metallic Single-Walled Carbon Nanotubes by Encapsulation of an Organic Salt.

The encapsulation of viologen derivatives into metallic single-walled carbon nanotubes (SWNTs) results in the opening of a band gap, making the SWNTs semiconducting. Raman spectroscopy, thermogravimetric analysis, and aberration-corrected high-resolution transmission electron microscopy confirm the encapsulation process. Through the fabrication of field-effect transistor devices, the change of the electronic structure of the tubes from metallic to semiconducting upon the encapsulation is confirmed. The opening of a gap in the band structure of the tubes was not detected in supramolecular controls.