Extraction of Boron Nitride Nanotubes and Fabrication of Macroscopic Articles Using Chlorosulfonic Acid.

Due to recent advances in high-throughput synthesis, research on boron nitride nanotubes (BNNTs) is moving toward applications. One future goal is the assembly of macroscopic articles of high-aspect-ratio, pristine BNNTs. However, these articles are presently unattainable because of insufficient purification and fabrication methods. We introduce a solution process for extracting BNNTs from synthesis impurities without sonication or the use of surfactants and proceed to convert the extracted BNNTs into thin films. The solution process can also be used to convert as-synthesized material-which contains significant amounts of hexagonal boron nitride ( h-BN)-into mats and aerogels with controllable structure and dimension. The solution extraction method, combined with further advances in synthesis and purification, contributes to the development of all-BNNT macroscopic articles, such as fibers and 3-D structures.

Pore Diameter of Mesoporous Silica Modulates Oxidation of H2O2-Sensing Chromophore in a Porous Matrix.

Hydrogen peroxide (H2O2) is an attractive chemical because of its bleaching properties in paper and pulp industry and as a disinfectant in the food, water, and medical industries. However, it is important to monitor the residual H2O2 level after its usage and prevent any unintended health problems or chemical reactions. Most H2O2 sensors often utilize fluorophores or electrical circuitry that requires an additional irradiation or a digital display. To this end, this study presents a 3,3',5,5'-tetramethylbenzidine (TMB)/horseradish peroxidase (HRP)-loaded patch that alerts the presence of high H2O2 levels by generating a visible blue color. We hypothesized that water-insoluble TMB immobilized within mesoporous silica particles of proper pore diameter and structure would act as a colorimetric indicator through the H2O2-mediated oxidation within a cross-linked patch. We examined this hypothesis by immobilizing TMB molecules in mesoporous silica particles with 2 and 7 nm diameter cylindrical pores as well as on nonporous silica particles. Then, we loaded these TMB-silica particles and HRP in a porous alginate patch via sequential in situ cross-linking reaction and lyophilization. In the presence of 25-5000 µM H2O2, which simulate H2O2 concentrations found in residual disinfecting fluids, the patch loaded with TMB-mesoporous silica particles with 7 nm diameter pores generated a distinct blue color with varying intensities depending on the H2O2 concentration. The design principles demonstrated in this study should be applicable to a broad array of sensors to be integrated into a moldable, three-dimensional matrix.

Dissolution and Characterization of Boron Nitride Nanotubes in Superacid.

Boron nitride nanotubes (BNNTs) are of interest for their unique combination of high tensile strength, high electrical resistivity, high neutron cross section, and low reactivity. The fastest route to employing these properties in composites and macroscopic articles is through solution processing. However, dispersing BNNTs without functionalization or use of a surfactant is challenging. We show here by cryogenic transmission electron microscopy that BNNTs spontaneously dissolve in chlorosulfonic acid as disentangled individual molecules. Electron energy loss spectroscopy of BNNTs dried from the solution confirms preservation of the sp2 hybridization for boron and nitrogen, eliminating the possibility of BNNT functionalization or damage. The length and diameter of the BNNTs was statistically calculated to be ∼4.5 µm and ∼4 nm, respectively. Interestingly, bent or otherwise damaged BNNTs are filled by chlorosulfonic acid. Additionally, nanometer-sized synthesis byproducts, including boron nitride clusters, isolated single and multilayer hexagonal boron nitride, and boron particles, were identified. Dissolution in superacid provides a route for solution processing BNNTs without altering their chemical structure.

Liquid crystals of neat boron nitride nanotubes and their assembly into ordered macroscopic materials.

Boron nitride nanotubes (BNNTs) have attracted attention for their predicted extraordinary properties; yet, challenges in synthesis and processing have stifled progress on macroscopic materials. Recent advances have led to the production of highly pure BNNTs. Here we report that neat BNNTs dissolve in chlorosulfonic acid (CSA) and form birefringent liquid crystal domains at concentrations above 170 ppmw. These tactoidal domains merge into millimeter-sized regions upon light sonication in capillaries. Cryogenic electron microscopy directly shows nematic alignment of BNNTs in solution. BNNT liquid crystals can be processed into aligned films and extruded into neat BNNT fibers. This study of nematic liquid crystals of BNNTs demonstrates their ability to form macroscopic materials to be used in high-performance applications.

Diatom Microbubbler for Active Biofilm Removal in Confined Spaces.

Bacterial biofilms form on and within many living tissues, medical devices, and engineered materials, threatening human health and sustainability. Removing biofilms remains a grand challenge despite tremendous efforts made so far, particularly when they are formed in confined spaces. One primary cause is the limited transport of antibacterial agents into extracellular polymeric substances (EPS) of the biofilm. In this study, we hypothesized that a microparticle engineered to be self-locomotive with microbubbles would clean a structure fouled by biofilm by fracturing the EPS and subsequently improving transports of the antiseptic reagent. We examined this hypothesis by doping a hollow cylinder-shaped diatom biosilica with manganese oxide (MnO2) nanosheets. In an antiseptic H2O2 solution, the diatoms doped by MnO2 nanosheets, denoted as diatom bubbler, discharged oxygen gas bubbles continuously and became self-motile. Subsequently, the diatoms infiltrated the bacterial biofilm formed on either flat or microgrooved silicon substrates and continued to generate microbubbles. The resulting microbubbles merged and converted surface energy to mechanical energy high enough to fracture the matrix of biofilm. Consequently, H2O2 molecules diffused into the biofilm and killed most bacterial cells. Overall, this study provides a unique and powerful tool that can significantly impact current efforts to clean a wide array of biofouled products and devices.

Cobalt oxide hollow nanoparticles derived by bio-templating.

We present here the first fabrication of hollow cobalt oxide nanoparticles produced by a protein-regulated site-specific reconstitution process in aqueous solution and describe the metal growth mechanism in the ferritin interior.

Electron exchange between Fe(II)-horse spleen ferritin and Co(III)/Mn(III) reconstituted horse spleen and Azotobacter vinelandii ferritins.

Azotobacter vinelandii bacterioferritin (AvBF) containing 800-1500 Co or Mn atoms as Co(III) and Mn(III) oxyhydroxide cores (Co-AvBF, Mn-AvBF) was synthesized by the same procedure used previously for horse spleen ferritin (HoSF). The kinetics of reduction of Co-AvBF and Mn-AvBF by ascorbic acid are first-order in each reactant. The rate constant for the reduction of Mn-AvBF (8.52 M(-1) min(-1)) is approximately 12 times larger than that for Co-AvBF (0.72 M(-1) min(-1)), which is consistent with a previous observation that Mn-HoSF is reduced approximately 10-fold faster than Co-HoSF [Zhang, B. et al. (2005) Inorg. Chem. 44, 3738-3745]. The rates of reduction of M-AvBF (M = Co and Mn) are more than twice that for the reduction of the corresponding M-HoSF. HoSF containing reduced Fe(II) cores (Fe(II)-HoSF), prepared by methyl viologen and CO, also reduces M-HoSF and M-AvBF species, with both cores remaining within ferritin, suggesting that electrons transfer through the ferritin shell. Electron transfer from Fe(II)-HoSF to Co-AvBF occurs at a rate approximately 3 times faster than that to Co-HoSF, indicating that the Co cores in AvBF are more accessible to reduction than the Co cores in HoSF. The presence of nonconductive (SiO2) or conductive (gold) surfaces known to bind ferritins enhances the rate of electron transfer. A more than approximately 4-fold increase in the apparent reaction rate is observed in the presence of gold. Although both surfaces (SiO2 and gold) enhance reaction by providing binding sites for molecular interaction, results show that ferritins with different mineral cores bound to a gold surface transfer electrons through the gold substrate so that direct contact of the reacting molecules is not required.

Kinetic and thermodynamic characterization of the cobalt and manganese oxyhydroxide cores formed in horse spleen ferritin.

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05 +/- 0.10 e/M forming a stable M(OH)(2) mineral core. At pH 9.0, ascorbic acid (AH(2)), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH(2) shifted the reaction to completion with a M(3+)/AH(2) stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(O)OH and excess AH(2) was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74 M(-1) min(-1), respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH(2) concentration, equilibrium constants at pH 9.0 of 5.0 +/- 1.9 for Co-HoSF and 2.9 +/- 0.9 for Mn-HoSF were calculated for 2M(O)OH + AH(2) = 2M(OH)(2) + D, where AH(2) and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH(2). Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.