Daewoong Jung

Gold-Decorated Block Copolymer Microspheres with Controlled Surface Nanostructures

Gold-decorated block copolymer microspheres (BCP-microspheres) displaying various surface morphologies were prepared by the infiltration of Au precursors into polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) microspheres. The microspheres were fabricated by emulsifying the PS-b-P4VP polymers in chloroform into a surfactant solution in water, followed by the evaporation of chloroform. The selective swelling of the P4VP domains in the microspheres by the Au precursor under acidic conditions resulted in the formation of Au-decorated BCP-microspheres with various surface nanostructures. As evidenced by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) measurements, dotted surface patterns were formed when microspheres smaller than 800 nm were synthesized, whereas fingerprint-like surface patterns were observed with microspheres larger than 800 nm. Au nanoparticles (NPs) were located inside P4VP domains near the surfaces of the prepared microspheres, as confirmed by TEM. The optical properties of the BCP-microspheres were characterized using UV-vis absorption spectroscopy and fluorescence lifetime measurements. A maximum absorption peak was observed at approximately 580 nm, indicating that Au NPs are densely packed into P4VP domains on the microspheres. Our approach for creating Au-NP-hybrid BCP-microspheres can be extended to other NP systems such as iron-oxide or platinum NPs. These precursors can also be selectively incorporated into P4VP domains and induce the formation of hybrid BCP-microspheres with controlled surface nanostructures.

Multi-functionality of macroporous TiO2 spheres in dye-sensitized and hybrid heterojunction solar cells.

Micron-sized macroporous TiO2 spheres (MAC-TiO2) were synthesized using a colloidal templating process inside emulsions, which were then coated on a nanocrystalline TiO2 light absorption film to prepare a bilayered photoanode for liquid-based dye-sensitized solar cells (DSSC) and hybrid heterojunction solid-state solar cells. MAC-TiO2 layers can enhance light scattering as well as absorption, because their pore size and periodicity are comparable to light wavelength for unique multiple scattering and a porous surface can load dye more. Moreover, due to the bicontinuous nature of macropores and TiO2 walls, electrolyte could be transported much faster in between the TiO2 spheres rather than within the small TiO2 nonporous architectures. Electron transport was also facilitated along the interconnected TiO2 walls. In DSSCs with these MAC-TiO2 scattering layers, efficiency was higher than conventional DSSCs incorporating a commercial scattering layer. The unique geometry of MAC-TiO2 results in strong improvements in light scattering and infiltration of hole-transporting materials, thereby the MAC-TiO2-based solid-state device showed comparatively higher efficiency than the device with conventional nanocrystalline TiO2.

Highly Conductive Flexible Multi-Walled Carbon Nanotube Sheet Films for Transparent Touch Screen

Highly conductive and transparent thin films were prepared using highly purified multi-walled carbon nanotube (MWCNT) sheets. The electrical properties of the MWCNT sheet were remarkably improved by an acid treatment, resulting in densely packed MWCNTs. The morphology of the sheets reveals that continuous electrical pathways were formed by the acid treatment, greatly improving the sheet resistance all the while maintaining an excellent optical transmittance. These results encourage the use of these MWCNT sheets with low sheet resistance (450 Ω/sq) and high optical transmittance (90%) as a potential candidate for flexible display applications.

Flexible transparent conductive heater using multiwalled carbon nanotube sheet

This paper reports highly flexible, transparent, conducting heaters based on multiwalled carbon nanotube (MWCNT) sheets. The MWCNT sheets were spun directly from a well-aligned MWCNT forest. The fabrication of the MWCNT sheet heater was quite simple and suitable for mass production, requiring only a one-step transferring process, in which the MWCNT sheet is drawn onto the target substrates. This study examined the parameters that affect the heat generation of the MWCNT sheet-based heater; input power, surface area, and thermal conductivity of the substrate. In particular, more effort was focused on how to increase the surface area and contact points between the individual MWCNTs; simple acid treatment and added metal nanoparticles increased the heat performance of the heater dramatically. Moreover, the heaters exhibited durability and flexibility against many bending cycles. Therefore, the MWCNT sheet-based heater can be used for versatile applications requiring transparency, conduction, and flexibility.

Fast-Response Room Temperature Hydrogen Gas Sensors Using Platinum-Coated Spin-Capable Carbon Nanotubes

We report the properties of a hydrogen (H2) gas sensor based on platinum (Pt)-coated carbon nanotubes (CNTs) in this paper. To fabricate the Pt-CNT composite sensor, a highly aligned CNT sheet was prepared on a glass substrate from a spin-capable CNT forest, followed by electrobeam (e-beam) deposition of Pt layers onto the CNT sheet. To investigate the effect of Pt on the response of the sensor, Pt layers of different thicknesses were deposited on the CNT sheets. A Pt thickness of 6 nm yielded the highest response for H2 detection, whereas Pt layers thinner or thicker than 6 nm led to a reduction of the surface area for gas adsorption and, consequently, decreased response. The Pt-CNT composite sensor detects H2 concentrations of 3-33% at room temperature and shows reproducible behavior with fast response and recovery times.

Stretchable and bendable carbon nanotube on PDMS super-lyophobic sheet for liquid metal manipulation

We report a vertically-aligned carbon nanotube (CNT) forest on polydimethylsiloxane (PDMS) sheet as a novel widely stretchable and bendable anti-wetting super-lyophobic surface for naturally oxidized gallium-based liquid metals. The vertically-aligned CNT has inherent chemical inertness and a hierarchical texture combining micro/nanoscale roughness; these two characters render the developed sheet as a super-lyophobic substrate against gallium-based liquid metals. The vertically-aligned CNT forest was first grown on Si substrate and then transferred onto a PDMS sheet by imprinting. It was found that the transferred CNT on the PDMS sheet maintained its vertically-aligned nature as well as hierarchical micro/nano surface morphology. It was found that the static contact angles of the gallium-based liquid metal droplet on the CNT on Si and on the CNT on PDMS were both greater than 155° and the contact angle hysteresis on the CNT on Si was 4° and that on the transferred CNT on PDMS was 19°. These measurement results showed that the surface retains a super-lyophobic property before and after the CNT transfer onto PDMS. We tested the CNT on PDMS sheet for its mechanical flexibility using stretching (50% and 100%) and bending (curvature of 0.1 and 0.4 mm−1). We carried out a bouncing test and a rolling test on the stretched/bent CNT on the PDMS sheet and the results confirmed that the flexible sheet maintains anti-wetting characteristics under bending or stretching conditions.

Effect of hydrogen pretreatment on the spin-capability of a multiwalled carbon nanotube forest

The authors report the effect of hydrogen (H2) pretreatment on the spin capability of vertically aligned multiwalled carbon nanotubes (MWCNTs) grown on an iron (Fe) catalyst by using a chemical vapor deposition system. Variations in H2 pretreatment time had significant effects on the distribution, morphology, diameter, and height of MWCNTs. A longer H2 pretreatment time to the Fe film increased the number of large Fe particles as well as crystallization of Fe3O4 phase. As a result, the areal density of carbon nanotubes (CNTs) was largely reduced, whereas the mean CNT diameter slightly increased. This worsened the alignment of the CNTs and reduced the spin-capability of MWCNTs.

Effect of Carrier Gas on the Growth and Characteristics of Spin-Capable Multiwalled Carbon Nanotubes

Multiwalled carbon nanotube (MWCNT) sheets that can be spun directly from a spin-capable MWCNT forest promise novel applications that utilize the unique and outstanding characteristics of this material. The growth of spin-capable MWCNT forests will be achieved through the understanding of the important factors affecting the forest growth, since the precise conditions necessary for effective spin-capability are extremely sensitive. In this paper, we discuss the effect of carrier gas, the initial catalyst thickness, and the roles of the hydrogen. These factors were investigated in order to assess and understand these critical parameters and thereby develop a repeatable and reliable spin-capable MWCNT growth process.

Facilitated Ion Diffusion in Multiscale Porous Particles: Application in Battery Separators

Polyethylene (PE) separators have been the most popular option for commercial Li-ion batteries because of their uniform pore size, high tensile strength, low cost, and electrochemical stability. Unfortunately, PE separators generally suffer from significant dimensional changes at high temperatures, which frequently results in serious safety problems. In this regard, the integration of inorganic nanoparticles with PE separators has been considered to be a promising approach. Here, inorganic nanoparticles with a hierarchical pore structure were coated on a conventional polymer separator. The resultant composite separator exhibited superior Li ion transportation compared with separators coated with mesopore-only nanoparticles or conventional nonporous nanoparticles. The mesopores and macropores act synergistically to improve the electrolyte uptake and ionic conductivity of the inorganic nanoparticles, while other positive aspects such as their thermal and mechanical properties are still maintained.

Zwitterionic mesoporous nanoparticles with a bioresponsive gatekeeper for cancer therapy.

UNLABELLED To enhance cellular uptake and site-specific drug release in the tumor microenvironment, zwitterionic mesoporous silica nanoparticles (Z-MSN) were prepared by introducing a bioresponsive gatekeeper composed of negatively charged carboxylic groups and positively charged quaternary amine groups. When these Z-MSN encountered a mildly acidic environment, their surface charge readily switched from negative to positive by cleavage of an acid-labile maleic amide linkage, thus allowing for effective cellular uptake into tumor tissue. Doxorubicin (DOX) encapsulated in Z-MSN was not significantly released in physiological conditions (pH 7.4), whereas the release rate of DOX remarkably increased in mildly acidic conditions through disintegration of the gatekeeper. The antitumor efficacy of DOX-loaded Z-MSN (DOX-Z-MSN) was evaluated after their systemic administration to tumor-bearing mice. Compared to free DOX and DOX-loaded MSN without the gatekeeper, DOX-Z-MSN exhibited much higher antitumor efficacy in vivo. Overall, these results demonstrated that the hydrophilic negative surface of Z-MSN, with their closed gate, allowed for their effective accumulation in tumor tissue after systemic administration, and that their charge-swapping and gate-opening in the tumor environment enhanced their cellular uptake and drug release rate simultaneously, implying a highly promising potential for development of Z-MSN as a drug carrier for cancer therapy. STATEMENT OF SIGNIFICANCE In an attempt to address the issues of enhanced cellular uptake and site-specific drug release of nanoparticles, we herein report on zwitterionic MSN (Z-MSN) with a pH-responsive gatekeeper which can be internalized into cancer cells via switching their surface charge from negative, in physiological conditions, to positive, in the tumor microenvironment. We hypothesized that the hydrophilic negative surface of Z-MSN with a closed gate allows for their accumulation into tumor tissue after systemic administration, whereas their charge-swapping and gate-opening in the tumor environment enhance cellular uptake and drug release rate simultaneously. Overall, Z-MSN constitute a promising drug delivery carrier for cancer therapy.