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J. Funct. Biomater. 2022, 13, 27 12 of 36 The flexibility and strength can be tuned by altering the in-plane bonding as well as the thickness of these materials, enabling each of them to be used in a particular applica- tion such as differentiation of stem cells, tissue engineering, monitoring intracranial brain injury and controlled drug delivery [62–64]. For instance, in a study clay-based 2DNMs were added to Poly(lactic-co-glycolide) (PLG) to result in enhanced fracture strength, toughness and elongation from 7% to 210%. Tuning the physical properties such as thick- ness and strain also plays an important role in controlling the other properties of 2DNMs such as their optical and electronic characteristics which enable them to be used in a vari- ety of therapeutics. 4.2. Electronic Properties It is well documented that 2DNMs have strong in-plane covalent bonds, however, their interlayer interactions are low or zero (i.e., single-layer nanosheets). Various classes of 2D materials show different electronic properties ranging from semimetals (i.e., gra- phene, which makes them an appropriate alternative for tissue engineering and biosens- ing applications such as prosthetic skins) to insulators (h-BN and clay-based nanomateri- als) and a variety of semiconductors (i.e., TMDs, TMOs and xenes) [65]. Tuning the con- ductivity of 2DNMs by controlling their structure results in a variety of biomedical appli- cations such as nanopore sequencing and FET-based biosensing, sequence-specific tran- sistors, biosensing, drug delivery, PDT and bioimaging [19]. Moreover, due to different extents of defects, doping or synthetic methods could also be applied to change the elec- tronic properties. Some of the most important aspects of 2DNMs such as energy level, scattering and excitation depend on external influences such as doping and thickness of the layer. Defects in general would cause lower conductivity since the free movement of electrons in a pristine plane of 2D materials is halted by adatoms. This change in electron- ics can be utilized in detecting signal molecules such as reducing agents or oxides. Under external stimulation (i.e., light excitation) electron movements in conducting and valence bands will change which can lead to a reaction of the active electrons with the ambient environment and impose oxidative stress. This feature of 2DNMs can be exhibited in their use in reactive oxygen species (ROS) generation and catalysis which can further be applied in photodynamic therapy (PDT) and biocatalysis [10]. Combining different properties of 2DNMs enables more efficient results than tuning an individual property. Coupling opti- cal and mechanical properties of 2DNMs with electronics leads to their versatile use in optoelectronic and piezoelectricity such as photodiodes, light emitting diodes, phototran- sistors, etc. [66]. 4.3. Optical Properties The optical properties of 2DNMs strongly depend on their absorption or emission of light which is in close relation to their electronic band structure. Spin-orbital interactions play an important role in modifying the optical properties of 2DNMs by changing the bandgap responsible for light absorption. Reduced dimensionality in some classes of 2DNMs shifts their indirect bandgap to a large direct bandgap (e.g., TMDs) which results in a significant change in optical properties. In fact, large bandgap results in both light absorbing and light emitting properties and small bandgaps can only possess light-ab- sorbing properties and are incapable of emitting light [67]. The ability to interact with light in a wide range of NIR to ultraviolet renders 2DNMs suitable for a plethora of applications such as bioimaging and biosensing. Semiconducting 2D (e.g., TMOs) nanomaterials can be used as photosensitizers due to their large optical absorption in UV regions to generate singlet oxygen that makes them ideal as PDT and photoacoustic imaging (PAI) agents for selective killing of both bacteria and cancer cells [68]. Tuning the structure such as building nanocomposites based on 2NMs expands their light response to a visible region by inhibiting their electron-hole pairPDF Image | Nanomaterials beyond Graphene for Biomedical Applications
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