Defect-Free, Few-Atomic-Layer Thin ZnO Nanosheets with Superior Excitonic Properties for Optoelectronic Devices.

Two-dimensional (2D) wide bandgap materials are gaining significant interest for next-generation optoelectronic devices. However, fabricating electronic-grade 2D nanosheets from non-van der Waals (n-vdW) oxide semiconductors poses a great challenge due to their stronger interlayer coupling compared with vdW crystals. This strong coupling typically introduces defects during exfoliation, impairing the optoelectronic properties. Herein, we report the liquid-phase exfoliation of few-atomic-layer thin, defect-free, free-standing ZnO nanosheets. These micron-sized, ultrathin ZnO structures exhibit three different orientations aligned along both the polar c-plane as well as the nonpolar a- and m-planes. The superior crystalline quality of the ZnO nanosheets is validated through comprehensive characterization techniques. This result is supported by density functional theory (DFT) calculations, which reveals that the formation of oxygen vacancies is energetically less favorable in 2D ZnO and that the c-plane loses its polarity upon exfoliation. Unlike bulk ZnO, which is typically dominated by defect-induced emission, the exfoliated nanosheets exhibit a strong, ambient-stable excitonic UV emission. We further demonstrate the utility of solution processing of ZnO nanosheets by their hybrid integration with organic components to produce stable light emitting diodes (LEDs) for display applications.

Reactive Oxygen Species Sequestration Induced Synthesis of ß-PbO and Its Polymorphic Transformation to α-PbO at Atomically Thin Regimes.

The emergence of attractive properties in materials at atomically thin regimes has seen an ongoing interest in two-dimensional (2D) materials. An aspect that has lacked focused attention is the effect of 2D material thickness on its crystal structure. As several layered materials naturally exist in mixed metastable phases, it raises an important question of whether a specific polymorph of these mixed-phase materials will be favored at atomically thin limits. This work attempts to address this issue by employing lead monoxide as a model 2D polymorphic system. We propose a reactive oxygen species (ROS) sequestration-mediated liquid-phase exfoliation (LPE) strategy for the facile synthesis of ultrathin PbO. This is followed by a suite of microscopic and spectroscopic analyses of the PbO nanosheets that reveals the polymorphic transformation of orthorhombic (ß) PbO to its tetragonal (α) analogue with reduction in nanosheet thickness. The transformation process reveals an interesting crystal structure of ultrathin 2D PbO where [001]-oriented domains of α-PbO coexist alongside [100]-oriented regions of ß-PbO. Density functional theory (DFT) calculations support our experimental data by revealing a higher thermodynamic stability of the tetragonal phase in PbO monolayers. These findings are likely to instigate interest in carefully evaluating the crystal structures of ultrathin 2D materials while promoting research in understanding the phase transformation across a range of 2D crystals.

Electrospun Nanodiamond-Silk Fibroin Membranes: A Multifunctional Platform for Biosensing and Wound-Healing Applications.

Next generation wound care technology capable of diagnosing wound parameters, promoting healthy cell growth, and reducing pathogenic infections noninvasively would provide patients with an improved standard of care and accelerated wound repair. Temperature is one of the indicating biomarkers specific to chronic wounds. This work reports a hybrid, multifunctional optical material platform-nanodiamond (ND)-silk membranes as biopolymer dressings capable of temperature sensing and promoting wound healing. The hybrid structure was fabricated through electrospinning, and 3D submicron fibrous membranes with high porosity were formed. Silk fibers are capable of compensating for the lack of an extracellular matrix at the wound site, supporting the wound-healing process. Negatively charged nitrogen vacancy (NV-) color centers in NDs exhibit optically detected magnetic resonance (ODMR) and act as nanoscale thermometers. This can be exploited to sense temperature variations associated with the presence of infection or inflammation in a wound, without physically removing the dressing. Our results show that the presence of NDs in the hybrid ND-silk membranes improves the thermal stability of silk fibers. NV- color centers in NDs embedded in silk fibers exhibit well-retained fluorescence and ODMR. Using the NV- centers as fluorescent nanoscale thermometers, we achieved temperature sensing in 25-50 °C, including the biologically relevant temperature window, for cell-grown ND-silk membranes. An enhancement (∼1.5× on average) in the temperature sensitivity of the NV- centers was observed for the hybrid materials. The hybrid membranes were further tested in vivo in a murine wound-healing model and demonstrated biocompatibility and equivalent wound closure rates as the control wounds. Additionally, the hybrid ND-silk membranes exhibited selective antifouling and biocidal propensity toward Gram-negative Pseudomonas aeruginosa and Escherichia coli, while no effect was observed on Gram-positive Staphylococcus aureus.

Photomodulated Spatially Confined Chemical Reactivity in a Single Silver Nanoprism.

Single-atom and single-particle catalysis is an area of considerable topical interest due to their potential in explaining important fundamental processes and applications across several areas. An interesting avenue in single-particle catalysis is spatial control of chemical reactivity within the particle by employing light as an external stimulus. To demonstrate this concept, we report galvanic replacement reactions (GRRs) as a spatial marker of subparticle chemical reactivity of a silver nanoprism with AuCl4- ions under optical excitation. The location of a GRR within a single Ag nanoprism can be spatially controlled depending on the plasmon mode excited. This leads to chemomorphological transformation of Ag nanoprisms into interesting Ag-Au structures. This spatial biasing effect is attributed to localized hot electron injection from the tips and edges of the silver nanoprisms to the adjacent reactants that correlate with excitation of different surface plasmon modes. The study also employs low-energy-loss EELS mapping to additionally probe the spatially confined redox reaction within a silver nanoprism. The findings presented here allow the visualization of a plasmon-driven subparticle chemical transformation with high resolution. The selective optical excitation of surface plasmon eigenmodes of anisotropic nanoparticles offers opportunities to spatially modulate chemical transformations mediated by hot electron transfer.

Antibacterial Properties of Graphene Oxide-Copper Oxide Nanoparticle Nanocomposites.

The resistance of pathogenic bacteria toward traditional biocidal treatment methods is a growing concern in various settings, including that of water treatment and in the medical industry. As such, advanced antibacterial technologies are needed to prevent infections, against which current antibiotics are failing. This study introduces copper oxide nanoparticles (CuONPs) doped in graphene oxide (GO) as a potential pathogenic bacterial treatment. The aim of the study was to evaluate the antibacterial properties of the GO-CuONP hybridized material against pathogenic Escherichia coli ATCC 8739 (E. coli) and Salmonella typhimurium ATCC 14028 (S. typhimurium). GO was synthesized using a modified Hummer's method and doped with 40% w/w CuONPs using a series of thermal chemical reactions. The resulting hybrids were then characterized using scanning electron microscopic (SEM) and spectroscopic studies. These studies revealed that the hybrid material was considerably altered by the inclusion of CuONPs. The live and dead bacteria attached to the GO-CuONP material were detected using confocal laser scanning microscopy (CLSM). The antibacterial activity assay of the GO-CuONP material was conducted using a standard plate count method. Importantly, the GO-CuONP nanocomposite was determined to be an effective antibacterial nanomaterial, significantly inhibiting the growth of both E. coli and S. typhimurium bacteria compared to that observed on the pristine GO material. This study suggests that GO-CuONP composites are a promising high-efficacy antibacterial nanomaterial.