Electronic structures and NIR-II optical properties of black phosphorus using first principles

Near infrared-II (NIR-II, 1 000—1 700 nm) imaging with high penetration tissue depth and signal-noise ratio has attracted wide interest in biomedicine. As a two-dimensional (2D) material with narrow band gap, the band structure of layered black phosphorus, as an important characteristic of electronic structure, determines the electronic transport and infrared optical properties, which show great potential in NIIR-II imaging. Here, the electronic structure and NIR-II optical properties of black phosphorus have been investigated in detail by employing the generalized gradient approximation + U (GGA+U) correction based on density functional theory (DFT). First, we performed the band structure and density of states for different layers of black phosphorus. From the electronic structures, the location of valence band maximum didn’t shift obviously, and the position of conduction band minimum shifted downward gradually, inducing the band gaps decreased gradually with the increasing layer number. While the layer number increased to 5, the behaviour of electronic structure was very similar to that of the bulk black phosphorus. Then, we calculated the NIR-II optical properties, and found the optical band gap of black phosphorus also showed layer dependent properties. From a single layer to 5 layers, the optical band gap changed from 1.71 eV to 0.92 eV. It is noting that black phosphorus also showed the significant optical absorption in NIR-IIa (1 300—1 400 nm) and NIR-IIb (1 500—1 700 nm) windows. Especially, the NIR-II optical absorption can be enhanced with increasing the layer number to 5, indicating promising photoresponse materials in NIR-II imaging.     

Single Atom-Engineered NIR-II Gold Clusters with Ultrahigh Brightness and Stability for Acute Kidney Injury

Near-infrared-II (NIR-II) imaging has shown great potential for monitoring the pathological progression and deep tissue imaging but is limited to present unmet NIR-II agent. Present fluorophores show a promising prospect for NIR-II imaging, but brightness and photostability are still highly challenging during real-time monitoring. In this work, atom-engineered NIR-II Au₂₄Cd₁ clusters with ultrahigh brightness, stability, and photostability are developed via single atomic Cd doping. Single atom Cd substitutions contribute to Cd 4d state in HOMO and redistribution of energy level near the gap, exhibiting 56-fold fluorescence enhancement of Au₂₄Cd₁ clusters. Meanwhile, single atomic Cd reinforces Cd Au bond energy, formation energy, and stabilized cluster structure, leading to persistent stability for up to 1 month without decay, as well as excellent photostability of 1 h without photobleaching, much longer than clinically approved indocyanine green (<5 min). In vivo imaging shows gold clusters can monitor acute kidney injury (AKI) even after 72 h of injury, enabling evaluating progression at a very long window. Meanwhile, the bioactive gold clusters can alleviate AKI-induced oxidative stress damage and acute neuroinflammation. Single atom-engineered gold clusters exhibit molecular tracking and diagnostic prospect in kidney-related diseases.