Hanhan Xie

Ultrasmall Black Phosphorus Quantum Dots: Synthesis and Use as Photothermal Agents

Black phosphorus quantum dots (BPQDs) were synthesized using a liquid exfoliation method that combined probe sonication and bath sonication. With a lateral size of approximately 2.6 nm and a thickness of about 1.5 nm, the ultrasmall BPQDs exhibited an excellent NIR photothermal performance with a large extinction coefficient of 14.8 L g(-1) cm(-1) at 808 nm, a photothermal conversion efficiency of 28.4%, as well as good photostability. After PEG conjugation, the BPQDs showed enhanced stability in physiological medium, and there was no observable toxicity to different types of cells. NIR photoexcitation of the BPQDs in the presence of C6 and MCF7 cancer cells led to significant cell death, suggesting that the nanoparticles have large potential as photothermal agents.

Biodegradable black phosphorus-based nanospheres for in vivo photothermal cancer therapy

Photothermal therapy (PTT) offers many advantages such as high efficiency and minimal invasiveness, but clinical adoption of PTT nanoagents have been stifled by unresolved concerns such as the biodegradability as well as long-term toxicity. Herein, poly (lactic-co-glycolic acid) (PLGA) loaded with black phosphorus quantum dots (BPQDs) is processed by an emulsion method to produce biodegradable BPQDs/PLGA nanospheres. The hydrophobic PLGA not only isolates the interior BPQDs from oxygen and water to enhance the photothermal stability, but also control the degradation rate of the BPQDs. The in vitro and in vivo experiments demonstrate that the BPQDs/PLGA nanospheres have inappreciable toxicity and good biocompatibility, and possess excellent PTT efficiency and tumour targeting ability as evidenced by highly efficient tumour ablation under near infrared (NIR) laser illumination. These BP-based nanospheres combine biodegradability and biocompatibility with high PTT efficiency, thus promising high clinical potential.

Surface Coordination of Black Phosphorus for Robust Air and Water Stability

A titanium sulfonate ligand is synthesized for surface coordination of black phosphorus (BP). In contrast to serious degradation observed from the bare BP, the BP after surface coordination exhibits excellent stability during dispersion in water and exposure to air for a long period of time, thereby significantly extending the lifetime and spurring broader application of BP.

Metabolizable Ultrathin Bi2Se3 Nanosheets in Imaging-Guided Photothermal Therapy

Poly(vinylpyrrolidone)-encapsulated Bi2 Se3 nanosheets with a thickness of 1.7 nm and diameter of 31.4 nm are prepared by a solution method. Possessing an extinction coefficient of 11.5 L g(-1) cm(-1) at 808 nm, the ultrathin Bi2 Se3 nanosheets boast a high photothermal conversion efficiency of 34.6% and excellent photoacoustic performance. After systemic administration, the Bi2 Se3 nanosheets with the proper size and surface properties accumulate passively in tumors enabling efficient photoacoustic imaging of the entire tumors to facilitate photothermal cancer therapy. In vivo biodistribution studies reveal that they are expelled from the body efficiently after 30 d. The ultrathin Bi2 Se3 nanosheets have large clinical potential as metabolizable near-infrared-triggered theranostic agents.

Black Phosphorus Based Photocathodes in Wideband Bifacial Dye-Sensitized Solar Cells

Ultrasmall black phosphorus quantum dots (BPQDs) serve as the near-infrared light absorber and charge transfer layer in the photocathode of a bifacial n-type dye sensitized solar cell. Wideband light absorption and ≈20% enhancement in the light-to-electron efficiency are accomplished due to the fast carrier transfer and complementary light absorption by the BPQDs demonstrating that BP has large potential in photovoltaics.

Synthesis of bright upconversion submicrocrystals for high-contrast imaging of latent-fingerprints with cyanoacrylate fuming

Upconversion particles (UCPs) as a new generation of imaging agent are gaining prominence due to their unique optical properties. Herein, we report the synthesis of bright UCPs for high-contrast imaging of latent-fingerprints with cyanoacrylate-fuming (CA-fuming). The hexagonal-phase and rod-shaped NaYF4:Yb,Er/Ce submicrocrystals (0.5 × 1.0 μm in dimension) coated with polyethylenimine (PEI) are synthesized using a dopant-controlled strategy and exhibit much stronger UC fluorescence than their nanosized analogues. The appropriate particle size and good surface properties of the UCPs make them easily come into the holes formed on fibrous layers of fingerprint ridges after fuming by CA. Compared with downconversion fluorescent materials, the UCPs exhibit the ability to suppress background fluorescence interference for obtaining high-contrast fingerprint images under near-infrared (NIR) light irradiation. Our results indicate that this strategy can successfully be applied to detect latent-fingerprints on various surfaces including non-porous and porous surfaces, and the fingerprints from different people can be identified. All of these benefits ensure this strategy is an important tool in fingerprint detection and will find wide-ranging applications in forensic investigations and medical diagnostics.

Different-sized black phosphorus nanosheets with good cytocompatibility and high photothermal performance

As a new kind of two-dimensional (2D) material, black phosphorus (BP) has attracted explosive interest in biomedical applications. It is well-recognized that the biomedical performances of nanoparticles depend not only on their properties, but also on their structures and dimensions. Here in this study, we successfully prepared three kinds of BP nanosheets with different sizes, then systematically investigated their cytocompatibility and photothermal effects to ablate cancer cells. It is evident from various assays that all the three BP samples have excellent cytocompatibility, and the BP nanosheets with a large size have better photothermal efficiency for cancer cell ablation. Our findings may provide a new insight into the fundamental cyto-performances of BP.

Competitive Reaction Pathway for Site‐Selective Conjugation of Raman Dyes to Hotspots on Gold Nanorods for Greatly Enhanced SERS Performance

Common methods to prepare SERS (surface-enhanced Raman scattering) probes rely on random conjugation of Raman dyes onto metal nanostructures, but most of the Raman dyes are not located at Raman-intense electromagnetic hotspots thus not contributing to SERS enhancement substantially. Herein, a competitive reaction between transverse gold overgrowth and dye conjugation is described to achieve site selective conjugation of Raman dyes to the hotspots (ends) on gold nanorods (GNRs). The preferential overgrowth on the nanorod side surface creates a barrier to prevent the Raman dyes from binding to the side surface except the ends of the GNRs, where the highest SERS enhancement factors are expected. The SERS enhancement observed from this special structure is dozens of times larger than that from conjugates synthesized by conventional methods. This simple and powerful strategy to prepare SERS probes can be extended to different anisotropic metal nanostructures with electromagnetic hotspots and has immense potential in in-depth SERS-based biological imaging and single-molecule detection.

Black-Phosphorus-Incorporated Hydrogel as a Sprayable and Biodegradable Photothermal Platform for Postsurgical Treatment of Cancer

Abstract Photothermal therapy (PTT) is a fledgling therapeutic strategy for cancer treatment with minimal invasiveness but clinical adoption has been stifled by concerns such as insufficient biodegradability of the PTT agents and lack of an efficient delivery system. Here, black phosphorus (BP) nanosheets are incorporated with a thermosensitive hydrogel [poly(d,l‐lactide)‐poly(ethylene glycol)‐poly(d,l‐lactide) (PDLLA‐PEG‐PDLLA: PLEL)] to produce a new PTT system for postoperative treatment of cancer. The BP@PLEL hydrogel exhibits excellent near infrared (NIR) photothermal performance and a rapid NIR‐induced sol–gel transition as well as good biodegradability and biocompatibility in vitro and in vivo. Based on these merits, an in vivo PTT postoperative treatment strategy is established. Under NIR irradiation, the sprayed BP@PLEL hydrogel enables rapid gelation forming a gelled membrane on wounds and offers high PTT efficacy to eliminate residual tumor tissues after tumor removal surgery. Furthermore, the good photothermal antibacterial performance prevents infection and this efficient and biodegradable PTT system is very promising in postoperative treatment of cancer.

Near-infrared light-triggered drug delivery system based on black phosphorus for in vivo bone regeneration

A near-infrared (NIR) light-triggered drug delivery platform is produced by incorporating SrCl2 and BP nanosheets (BPs) into poly(lactic-co-glycolic acid) (PLGA) for bone regeneration. The fabricated BP-SrCl2/PLGA microspheres show efficient NIR absorption and photothermal effects due to the BPs. The NIR-triggered release behavior of Sr2+ by flawing the PLGA shells is investigated and the microspheres exhibit excellent cell viability and biodegradability. Implantation of the BP-SrCl2/PLGA microspheres into a rat femoral defect demonstrates good tissue compatibility and excellent bone regeneration capacity under NIR light irradiation. Our study indicates that local release of Sr2+ at optimal time periods controlled by NIR irradiation improves bone regeneration significantly and this NIR-triggered drug delivery system composed of BPs is suitable for therapies requiring precise control at specific time.