Yuho Min

Metabolizable Bi2Se3 Nanoplates: Biodistribution, Toxicity, and Uses for Cancer Radiation Therapy and Imaging

Bi, a high atomic number element, has a high photoelectric absorption coefficient, and Se has anticancer activity. Hence, their compound chalcogenide (Bi2Se3) deserves a thorough investigation for biomedical applications. This study reveals that Bi2Se3 nanoplates (54 nm wide) protected with poly(vinylpyrollidone) (PVP) could be presumed to have low toxicity even at a high dose of 20 mg/kg in mice. This conclusion is made through studies on the biodistribution and 90-day long term in vivo clearance of the nanoplates. The liver and spleen are dominant organs for accumulation of the nanoplates, which is mainly due to RES absorption. 93% of the nanoplates are cleared after 90 days of treatment. Concentrations of Bi and Se in tumor tissue continuously increased until 72 h after intraperitoneal injection into mice. Such selective accumulation of Bi is utilized to enhance the contrast of X-ray computerized tomography (CT) images. Bi element concentrated in a tumor leads to damage on the tumor cells when exposed to gamma radiation. Growth of the tumor is significantly delayed and stopped in 16 days after the tumor is treated by radiation with Bi2Se3 nanoplates. This work clearly shows that Bi2Se3 nanoplates may be used for cancer radiation therapy and CT imaging. The nanoplates deserve further study for biological and medical applications.

Surfactant‐Free Scalable Synthesis of Bi2Te3 and Bi2Se3 Nanoflakes and Enhanced Thermoelectric Properties of Their Nanocomposites

Surfactant-free nanoflakes of n-type Bi2 Te3 and Bi2 Se3 are synthesized in high yields. Their suspensions are mixed to create nanocomposites with heterostructured nanograins. A maximum ZT (0.7 at 400 K) is achieved with a broad content of 10-15% Bi2 Se3 in the nanocomposites.

Quick, Controlled Synthesis of Ultrathin Bi2Se3 Nanodiscs and Nanosheets

Ultrathin (4-6 nm) single-crystal Bi(2)Se(3) nanodiscs and nanosheets were synthesized through a simple and quick solution process. The growth mechanism was investigated in detail. Crystal seeds grew via 2D self-attachment of small nanoparticles followed by epitaxial recrystallization into single crystals. The lateral dimension of the nanodiscs increased and their shape changed from circles to hexagons as the reaction temperature increased. Positively charged polymer surfactants greatly enlarged the lateral dimension to produce nanosheets with uniform thickness.

Solution-based synthesis of anisotropic metal chalcogenide nanocrystals and their applications

This article reviews recent advances in solution phase synthesis to generate 1-D and 2-D anisotropic metal chalcogenide (MC) nanostructures with a focus on using different growth mechanisms to control the shapes of the MCs. Four different synthetic approaches have been reviewed: naturally favoured growth due to its intrinsically anisotropic crystal structure, modified anisotropic growth by changing surface energies or utilizing organic templates, oriented attachment of small nanocrystal building blocks to form nanowires or nanosheets, and chemical transformation from existing nanostructures into new species. We discuss current understanding of the thermodynamic and kinetic aspects associated with the mechanisms of forming these anisotropic MC nanostructures. We provide examples of representative applications of anisotropic chalcogenide nanomaterials that are expected to be practically meaningful in the near future. The applications include electrodes for lithium ion batteries, photodetectors, thermoelectric devices, and solar cells. A brief review of other potential applications (oxygen reduction reaction, localized surface plasmon resonance, topological insulator, superconductor) is provided as well. This review ends with discussions on the challenges to be investigated thoroughly in the solution-based synthesis of anisotropic nanomaterials, which includes surface energy control, correcting the nucleation & growth mechanism, removal of the organic surfactant, kinetic study on the chemical transformation, scale-up of production, and eco-friendly synthesis.

Synthesis of Multishell Nanoplates by Consecutive Epitaxial Growth of Bi2Se3 and Bi2Te3 Nanoplates and Enhanced Thermoelectric Properties

We herein demonstrate the successive epitaxial growth of Bi2Te3 and Bi2Se3 on seed nanoplates for the scalable synthesis of heterostructured nanoplates (Bi2Se3@Bi2Te3) and multishell nanoplates (Bi2Se3@Bi2Te3@Bi2Se3, Bi2Se3@Bi2Te3@Bi2Se3@Bi2Te3). The relative dimensions of the constituting layers are controllable via the molar ratios of the precursors added to the seed nanoplate solution. Reduction of the precursors produces nanoparticles that attach preferentially to the sides of the seed nanoplates. Once attached, the nanoparticles reorganize epitaxially on the seed crystal lattices to form single-crystalline core-shell nanoplates. The nanoplates, initially 100 nm wide, grew laterally to 620 nm in the multishell structure, while their thickness increased more moderately, from 5 to 20 nm. The nanoplates were pelletized into bulk samples by spark plasma sintering and their thermoelectric properties are compared. A peak thermoelectric figure of merit (ZT) ∼0.71 was obtained at 450 K for the bulk of Bi2Se3@Bi2Te3 nanoplates by simultaneous modulation of electronic and thermal transport in the presence of highly dense grain and phase boundaries.

Surfactant-free CuInSe 2 nanocrystals transformed from In 2 Se 3 nanoparticles and their application for a flexible UV photodetector

In(2)Se(3) nanoparticles were synthesized in an aqueous solution without using any surfactant and then chemically transformed into CuInSe(2) nanocrystals. The transformation was thermodynamically favorable and fast. The 93% production yield in mild reaction conditions allowed mass production of the CuInSe(2) nanocrystals. By the virtue of the surface charges, the CuInSe(2) nanocrystals were well dispersed in polar solvents. The surfactant-free nanocrystals enabled the formation of semiconducting CuInSe(2) films on a flexible polymer substrate without any thermal treatment. We took advantage of this to fabricate a flexible UV photodetector. The current and sensitivity of the devices could be improved by utilizing CuInSe(2) nanocrystals annealed at 160 °C in the reaction batch. On bending test, the detection sensitivity remained the same until the bending radius was reduced down to 4 mm. The dynamic response of the film device was stable and reproducible during light illumination (350 nm).

Nonstoichiometric nucleation and growth of multicomponent nanocrystals in solution.

The ability to assemble nanoscale functional building blocks is a useful and modular way for scientists to design valuable materials with specific physical and chemical properties. Chemists expect multicomponent, heterostructured nanocrystals to show unique electrical, thermal, and optical properties not seen in homogeneous, single-phase nanocrystals. Although researchers have made remarkable advances in heterogeneous nucleation and growth, design of synthetic conditions for obtaining nanocrystals with a target composition and shape is still a big challenge. There are several outstanding issues that chemists need to address before they can successfully carry out the design-based synthesis of multicomponent nanocrystals. For instance, small changes in the reaction parameters, such as the precursor, solvent, surfactant, reducing agent, and the reaction temperature, often result in changes in the structure and chemical composition of the final product. Although scientists do not fully understand the mechanisms underlying the nucleation and growth processes involved in the synthesis of these multicomponent nanocrystals, recent progress in understanding of the thermodynamic and kinetic factors have improved our control over their final structure and chemical composition. In this Account, we summarize our recent advances in understanding of the nucleation and growth mechanisms involved in the solution-based synthesis of multicomponent nanocrystals. We also discuss the various challenges encountered in their synthesis, emphasizing what still needs special consideration. We first discuss the three different nucleation paths from a thermodynamics perspective: amorphous nucleation, crystalline nucleation, and two-step nucleation. Amorphous nucleation and two-step nucleation involve the generation of nonstoichiometric nuclei. We initiate this process mainly by introducing an imbalance in the concentrations of the reduced elements. When the nonstoichiometric nuclei grow, we can add secondary elements to the growing nonstoichiometric nuclei. This leads to either the physical deposition or atomic mixture formation through the diffusion and rearrangement of constituents. The processes of mixture formation and the physical deposition of the secondary constituent element also compete and determine the shape and chemical composition of the final product. If the free energy change by mixture formation is positive (ΔGAB ≥ 0), physical deposition takes place predominantly, and the spreading coefficient (S) determines the structure of the nanocrystals. However, when mixture formation is highly spontaneous (ΔGAB < -ξ), the chemical composition of the final product is usually stoichiometric, and its shape then depends on the size of the primary nanocrystals. When the mixture formation and physical deposition are in competition (-ξ ≤ ΔGAB < 0), as commonly seen for many nanoalloy systems, both the chemical composition and the structure are determined by the size of the primary nanocrystals as well as the degree of mixture formation at the interface of the constituent components. Finally, we discuss the challenges and caveats that one needs to take into account when synthesizing multicomponent nanocrystals.

Understanding the epitaxial growth of SexTey@Te core-shell nanorods and the generation of periodic defects.

This study demonstrates solution-processed epitaxial growth of Te on Se(x)Te(y) nanorods and the generation of periodic defects in the core. We investigated Se(x)Te(y)@Te core-shell nanorods with a diameter of 40-50 nm and a length of 600-700 nm. In spite of a large lattice mismatch between the Se(x)Te(y) core and the Te shell, the soft character of the core and the shell at a high reaction temperature allowed epitaxial growth of Te on the Se(x)Te(y) nanorods. During the cooling process to room temperature (below the glass transition temperatures), the lattice mismatch between the core and the shell led to homogeneous stress along the epitaxial interface so that periodic defects were generated in the core.

Original ArticleCatalytic topological insulator Bi2Se3 nanoparticles for in vivo protection against ionizing radiation

Bi2Se3 nanoparticles (NPs) have attracted wide interests in biological and medical applications. Layer-like Bi2Se3 with high active surface area is promising for free radical scavenging. Here, we extended the medical applications of Bi2Se3 NPs further to in vivo protection against ionizing radiation based on their superior antioxidant activities and electrocatalytic properties. It was found that Bi2Se3 NPs can significantly increase the surviving fraction of mice after exposure of high-energy radiation of gamma ray. Additionally, the Bi2Se3 NPs can help to recover radiation-lowered red blood cell counts, white blood cell counts and platelet levels. Further investigations revealed that Bi2Se3 NPs behaved as functional free radical scavengers and significantly decreased the level of methylenedioxyamphetamine. In vivo toxicity studies showed that Bi2Se3 NPs did not cause significant side effects in panels of blood chemistry, clinical biochemistry and pathology.

The effect of Se doping on the growth of Te nanorods

In this study, we successfully conducted a series of computationally-assisted experiments, regarding the morphology control and chemical transformation of Te nanorods. The morphology of Te nanorods is controlled by introducing a minute amount of isovalent Se dopant. Density-functional theory calculations predicted the Gibbs surface free energy change due to the adsorbent Se on the major facets of Te nanorods. Encouraged by the theoretical prediction, we conducted experiments on Te nanorod growth and did find significant variation of the morphology of Te nanorods due to Se injection. Furthermore, we demonstrated the chemical transformation of the shape-controlled Te nanorods to binary thermoelectric compounds such as PbTe and Bi2Te3 without losing the tailored morphology. The transformed PbTe and Bi2Te3 have nanoscale grain boundaries as seen from the cross-section HRTEM image. We emphasize that the robust production of morphology-controlled thermoelectric nanorods can be an optimal approach to develop an advanced thermoelectric composite material, by which the multiscale phonon scattering effect can be maximized.