Konstantin L. Firestein

Boron nitride nanotube growth via boron oxide-assisted chemical vapor transport-deposition process using LiNO3 as a promoter

High-purity straight and discrete multiwalled boron nitride nanotubes (BNNTs) were grown via a boron oxide vapor reaction with ammonia using LiNO3 as a promoter. Only a trace amount of boron oxide was detected as an impurity in the BNNTs by energy-dispersive X-ray (EDX) and Raman spectroscopies. Boron oxide vapor was generated from a mixture of B, FeO, and MgO powders heated to 1,150 °C, and it was transported to the reaction zone by flowing ammonia. Lithium nitrate was applied to the upper side of a BN bar from a water solution. The bar was placed along a temperature gradient zone in a horizontal tubular furnace. BNNTs with average diameters of 30–50 nm were mostly observed in a temperature range of 1,280–1,320 °C. At higher temperatures, curled polycrystalline BN fibers appeared. Above 1,320 °C, the number of BNNTs drastically decreased, whereas the quantity and diameter of the fibers increased. The mechanism of BNNT and fiber growth is proposed and discussed.

Effect of BN Nanoparticles Loaded with Doxorubicin on Tumor Cells with Multiple Drug Resistance

Herein we study the effect of doxorubicin-loaded BN nanoparticles (DOX-BNNPs) on cell lines that differ in the multidrug resistance (MDR), namely KB-3-1 and MDR KB-8-5 cervical carcinoma lines, and K562 and MDR i-S9 leukemia lines. We aim at revealing the possible differences in the cytotoxic effect of free DOX and DOX-BNNP nanoconjugates on these types of cells. The spectrophotometric measurements have demonstrated that the maximum amount of DOX in the DOX-BNNPs is obtained after saturation in alkaline solution (pH 8.4), indicating the high efficiency of BNNPs saturation with DOX. DOX release from DOX-BNNPs is a pH-dependent and DOX is more effectively released in acid medium (pH 4.0-5.0). Confocal laser scanning microscopy has shown that the DOX-BNNPs are internalized by neoplastic cells using endocytic pathway and distributed in cell cytoplasm near the nucleus. The cytotoxic studies have demonstrated a higher sensitivity of the leukemia lines to DOX-BNNPs compared with the carcinoma lines: IC50(DOX-BNNPs) is 1.13, 4.68, 0.025, and 0.14 μg/mL for the KB-3-1, MDR KB-8-5, K562, and MDR i-S9 cell lines, respectively. To uncover the mechanism of cytotoxic effect of nanocarriers on MDR cells, DOX distribution in both the nucleus and cytoplasm has been studied. The results indicate that the DOX-BNNP nanoconjugates significantly change the dynamics of DOX accumulation in the nuclei of both KB-3-1 and KB-8-5 cells. Unlike free DOX, the utilization of DOX-BNNPs nanoconjugates allows for maintaining a high and stable level of DOX in the nucleus of MDR KB-8-5 cells.

BN nanoparticle/Ag hybrids with enhanced catalytic activity: theory and experiments

Hexagonal boron nitride nanoparticles (BNNPs) with different amounts of boron oxide on their surfaces were used as catalyst carriers. BNNPs/Ag nanohybrids were produced via ultraviolet (UV) decomposition of AgNO3 in a mixture of polyethylene glycol and BNNPs. High temperature (1600 °C, 1.5 h) vacuum annealing of BNNPs promoted small size (5–10 nm) Ag nanoparticle (AgNPs) formation on BN surfaces with narrow size distribution, whereas using BNNPs in their as-produced state resulted in large AgNPs with various sizes. An increase in the B2O3 content on the BNNPs surfaces (up to a certain point) during BNNP pre-annealing in air led to larger amounts of AgNPs on their surfaces. Experimental results were confirmed by theoretical calculations of the adhesion energy of the (111)Ag with (0001)h-BN and (100)B2O3 surfaces. In contrast to the nonwettability of the h-BN surface by AgNPs, silver bound well to B2O3 with the formation of a covalent bond at the interface. Excessive fraction of B2O3, however, was not beneficial in terms of obtaining the optimal contents of AgNPs. Results of catalytic activity tests demonstrated that BNNPs/Ag nanohybrids synthesized using BNNPs with an optimized amount of B2O3 possess significantly enhanced catalytic activity compared to BNNPs without or with excess amounts of oxide. Finally, the catalytic activity of nanohybrids was theoretically analyzed using density functional theory (DFT) calculations.

BN/Ag hybrid nanomaterials with petal-like surfaces as catalysts and antibacterial agents

BN/Ag hybrid nanomaterials (HNMs) and their possible applications as novel active catalysts and antibacterial agents are investigated. BN/Ag nanoparticle (NP) hybrids were fabricated using two methods: (i) chemical vapour deposition (CVD) of BN NPs in the presence of Ag vapours, and (ii) ultraviolet (UV) decomposition of AgNO3 in a suspension of BN NPs. The hybrid microstructures were studied by high-resolution transmission electron microscopy (HRTEM), high-angular dark field scanning TEM imaging paired with energy dispersion X-ray (EDX) mapping, X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy (FTIR). They were also characterized in terms of thermal stability, Ag+ ion release, catalytic and antibacterial activities. The materials synthesized via UV decomposition of AgNO3 demonstrated a much better catalytic activity in comparison to those prepared using the CVD method. The best catalytic characteristics (100% methanol conversion at 350 °C) were achieved using the UV BN/Ag HNMs without preliminary annealing at 600 °C in an oxidizing atmosphere. Both types of the BN/Ag HNMs possess a profound antibacterial effect against Escherichia coli K-261 bacteria.

Optical and Optoelectronic Property Analysis of Nanomaterials inside Transmission Electron Microscope

In situ transmission electron microscopy (TEM) allows one to investigate nanostructures at high spatial resolution in response to external stimuli, such as heat, electrical current, mechanical force and light. This review exclusively focuses on the optical, optoelectronic and photocatalytic studies inside TEM. With the development of TEMs and specialized TEM holders that include in situ illumination and light collection optics, it is possible to perform optical spectroscopies and diverse optoelectronic experiments inside TEM with simultaneous high resolution imaging of nanostructures. Optical TEM holders combining the capability of a scanning tunneling microscopy probe have enabled nanomaterial bending/stretching and electrical measurements in tandem with illumination. Hence, deep insights into the optoelectronic property versus true structure and its dynamics could be established at the nanometer-range precision thus evaluating the suitability of a nanostructure for advanced light driven technologies. This report highlights systems for in situ illumination of TEM samples and recent research work based on the relevant methods, including nanomaterial cathodoluminescence, photoluminescence, photocatalysis, photodeposition, photoconductivity and piezophototronics.

Fabrication and application of BN nanoparticles, nanosheets and their nanohybrids

Smart implementation of novel advanced nanomaterials is the key for the solution of many complex problems of modern science. In recent years, there has been a great interest in the synthesis and application of boron nitride (BN) nanotubes because of their unique physical, chemical, and mechanical properties. By contrast, the synthesis, characterization and exploration of other morphological types of BN nanostructure - BN nanoparticles and BN nanosheets - have received less attention. However, the detailed investigations on advantages of every morphological BN type for specific applications have only recently been started. One of the promising directions is the utilization of BN-based nanohybrids. This review is dedicated to the in-depth analysis of recently published works on the fabrication and application of BN nanoparticles, nanosheets, and their nanohybrids. It covers a variety of developed synthetic methods toward fabrication of such nanostructures, and their specific application potentials in catalysis, drug delivery, tribology and structural materials. Finally, the review focuses on the theoretical aspects of this quickly emerging field.

Photocatalysis with Pt–Au–ZnO and Au–ZnO Hybrids: Effect of Charge Accumulation and Discharge Properties of Metal Nanoparticles

Metal-semiconductor hybrid nanomaterials are becoming increasingly popular for photocatalytic degradation of organic pollutants. Herein, a seed-assisted photodeposition approach is put forward for the site-specific growth of Pt on Au-ZnO particles (Pt-Au-ZnO). A similar approach was also utilized to enlarge the Au nanoparticles at epitaxial Au-ZnO particles (Au@Au-ZnO). An epitaxial connection at the Au-ZnO interface was found to be critical for the site-specific deposition of Pt or Au. Light on-off photocatalysis tests, utilizing a thiazine dye (toluidine blue) as a model organic compound, were conducted and confirmed the superior photodegradation properties of Pt-Au-ZnO hybrids compared to Au-ZnO. In contrast, Au-ZnO type hybrids were more effective toward photoreduction of toluidine blue to leuco-toluidine blue. It was deemed that photoexcited electrons of Au-ZnO (Au, ∼5 nm) possessed high reducing power owing to electron accumulation and negative shift in Fermi level/redox potential; however, exciton recombination due to possible Fermi-level equilibration slowed down the complete degradation of toluidine blue. In the case of Au@Au-ZnO (Au, ∼15 nm), the photodegradation efficiency was enhanced and the photoreduction rate reduced compared to Au-ZnO. Pt-Au-ZnO hybrids showed better photodegradation and mineralization properties compared to both Au-ZnO and Au@Au-ZnO owing to a fast electron discharge (i.e. better electron-hole seperation). However, photoexcited electrons lacked the reducing power for the photoreduction of toluidine blue. The ultimate photodegradation efficiencies of Pt-Au-ZnO, Au@Au-ZnO, and Au-ZnO were 84, 66, and 39%, respectively. In the interest of effective metal-semiconductor type photocatalysts, the present study points out the importance of choosing the right metal, depending on whether a photoreduction and/or photodegradation process is desired.