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Biomedical subjects

Kilwon Cho

Publications and source records attributed to Kilwon Cho.

At least 19 recordsLinked to original sources

Photoreversibly switchable superhydrophobic surface with erasable and rewritable pattern.

We report the facile fabrication of a functional nanoporous multilayer film with wettability that is reversibly tunable between superhydrophobicity and superhydrophilicity with UV/visible irradiation. Our approach controls surface roughness with an electrostatic self-assembly process and makes use of the photoresponsive molecular switching of fluorinated azobenzene molecules. Selective UV irradiation onto the nanostructured substrate was used to realize substrates with erasable and rewritable patterns of extreme wetting properties. Our findings will open up new avenues for external stimuli-responsive smart surfaces.

Journal Article↗

Controlled one-dimensional nanostructures in poly(3-hexylthiophene) thin film for high-performance organic field-effect transistors.

With the aim of improving the field-effect mobilities in poly(3-hexylthiophene) (P3HT) thin film transistors, we controlled the nanostructures of P3HT thin film by changing the solvent vapor pressure in a spin-coating chamber during solidification. The transistors with P3HT thin films spin-coated under a high solvent vapor pressure (56.5 KPa), showing the one-dimensional nanowire morphologies, resulted in the relatively high field-effect mobilities (0.02 cm2/(V.s)) that are typically more than 1 order of magnitude higher than those prepared under ambient conditions, showing the featureless morphologies. This can be attributed to the higher solvent vapor pressure during film formation, providing the solvent is allowed to evaporate slowly and the degree of ordering within the P3HT crystalline domains is dramatically improved.

Membranes, Artificial↗

Two modes of transformation of amorphous calcium carbonate films in air.

Large-area amorphous calcium carbonate (ACC) films in air are shown to be transformed into crystalline calcium carbonate (CaCO(3)) films via two modes-dissolution-recrystallization and solid-solid phase transition-depending on the relative humidity of the air and the temperature. Moisture in the air promotes the transformation of ACC into crystalline forms via a dissolution-recrystallization process. Increasing the humidity increases the rate of ACC crystallization and gives rise to films with numerous large pores. As the temperature is increased, the effect of moisture in the air is reduced and solid-solid transition by thermal activation becomes the dominant transformation mechanism. At 100 and 120 degrees C, ACC films are transformed into predominantly (110) oriented crystalline films. Collectively, the results show that calcium carbonate films with different morphologies, crystal phases, and structures can be obtained by controlling the humidity and temperature. This ability to control the transformation of ACC should assist in clarifying the role of ACC in the biomineralization of CaCO(3) and should open new avenues for preparing CaCO(3) films with oriented and fine structure.

Air↗

Stable superhydrophobic organic-inorganic hybrid films by electrostatic self-assembly.

Organic-inorganic hybrid films were prepared through layer-by-layer (LBL) deposition of poly(allylamine hydrochloride) (PAH) and ZrO(2) nanoparticles coated with poly(acrylic acid) (PAA), allowing facile control of surface roughness and hydrophobicity. Superhydrophobic behavior was observed after deposition of silica nanoparticles and a simple fluorination of the surface. The structure of films was controlled by the number of deposition cycles using PAA-coated 100 nm ZrO(2) nanoparticles, the particle size, and the prelayer with PAH and PAA. The change in the apparent water contact angle of (PAH/PAA-coated ZrO(2)n surfaces without fluorination of the surface agrees with Cassie and Baxter's model for nonwetted surfaces even though the outermost surface itself is hydrophilic. Superhydrophobic surfaces were then successfully developed by the deposition of hydrophilic silica nanoparticles on a 10 bilayer surface of PAH/PAA-coated ZrO(2), and a simple fluorination. Moreover, the chemical stability of the film was greatly increased by heat-induced cross-linking of the film. The incorporation of ZrO(2) nanoparticles in superhydrophobic films promises better mechanical properties than the organic film.

Acrylic Resins↗

Measurements of the thickness compressibility of an n-octadecyltriethoxysilane monolayer self-assembled on mica.

The surface forces apparatus technique and the Johnson-Kendall-Roberts theory were used to study the elastic properties of an n-octadecyltriethoxysilane self-assembled monolayer (OTE-SAM) on both untreated and plasma-treated mica. Our aim was to measure the thickness compressibilities of OTE monolayers on untreated and plasma-treated mica and to estimate their surface densities and phase-states from the film compressibility. The compressibility moduli of OTE are (0.96 +/- 0.02) x 10(8) N/m(2) on untreated mica and (1.24 +/- 0.06) x 10(8) N/m(2) on plasma-treated mica. This work suggests that the OTE phase-state is pseudocrystalline. In addition, the results from the compressibility measurements in water vapor suggest that the OTE-SAM on both untreated and plasma-treated mica is not homogeneous but rather contains both crystalline polymerized OTE domains and somewhat hydrophilic gaseous regions.

Journal Article↗

Conducting AFM and 2D GIXD studies on pentacene thin films.

Among all organic semiconductors, pentacene has been shown to have the highest thin film mobility reported to date. The crystalline structure of the first few pentacene layers deposited on a dielectric substrate is strongly dependent on the dielectric surface properties, directly affecting the charge mobility of pentacene thin film OTFTs. Herein, we report that there is a direct correlation between the crystalline structure of the initial submonolayer of a pentacene film and the mobility of the corresponding 60-nm-thick films showing terrace-like structure, as confirmed by 2D grazing-incidence X-ray diffraction and atomic force microscopy. Specifically, multilayered pentacene films, grown from single crystal-like faceted islands on HMDS-treated surface, have shown much higher charge mobility (mu = 3.4 +/- 0.5 cm2/Vs) than those with polycrystalline dendritic islands (mu = 0.5 +/- 0.15 cm2/Vs) on OTS-treated ones.

Crystallization↗

Quantitative equivalence between polymer nanocomposites and thin polymer films.

The thermomechanical responses of polymers, which provide limitations to their practical use, are favourably altered by the addition of trace amounts of a nanofiller. However, the resulting changes in polymer properties are poorly understood, primarily due to the non-uniform spatial distribution of nanoparticles. Here we show that the thermomechanical properties of 'polymer nanocomposites' are quantitatively equivalent to the well-documented case of planar polymer films. We quantify this equivalence by drawing a direct analogy between film thickness and an appropriate experimental interparticle spacing. We show that the changes in glass-transition temperature with decreasing interparticle spacing for two filler surface treatments are quantitatively equivalent to the corresponding thin-film data with a non-wetting and a wetting polymer-particle interface. Our results offer new insights into the role of confinement on the glass transition, and we conclude that the mere presence of regions of modified mobility in the vicinity of the particle surfaces, that is, a simple two-layer model, is insufficient to explain our results. Rather, we conjecture that the glass-transition process requires that the interphase regions surrounding different particles interact.

Elasticity↗

Diverse access to artificial superhydrophobic surfaces using block copolymers.

The creation of an artificial superhydrophobic surface with micro- and nanostructures has been demonstrated using a block copolymer micelle solution and silica nanoparticles. The unique technique of a nanoparticle-supported micelle stabilization together with changes in the solvent power guarantees the precise morphology control of certain block copolymer-mediated surfaces. The approaches presented here provide a new strategy for the fabrication of a wettability-controlled organic-inorganic hybrid or organic coatings.

Journal Article↗

Temperature-dependent intermolecular force measurement of poly(N-isopropylacrylamide) grafted surface with protein.

We have investigated the temperature dependence of the intermolecular force between poly(N-isopropylacrylamide) (PNiPAM) grafted surface and bovine serum albumin (BSA) in phosphate buffer (pH 7.4) using atomic force microscopy at the nanonewton scale. These observations show that the interaction force is nearly zero below the phase transition temperature of PNiPAM and that it increases steeply during the phase transition. Since the PNiPAM chains are grafted onto the aminosilane (gamma-aminopropyltriethoxysilane)-treated silicon wafer, we measured the force-distance curve of BSA-immobilized tips for the bare and the aminosilane-treated silicon wafer. These surfaces show no temperature dependence and their values are different from those of the PNiPAM-grafted surfaces at 30 degrees C. The results indicate that the measured adhesion force is between the PNiPAM-grafted surface and the BSA-immobilized tip. Our studies on the intermolecular force between other surfaces (CH(3)- and COOH-terminated self-assembled monolayers) and the BSA-immobilized tip indicate that the variation in the intermolecular force between the PNiPAM surface and BSA with temperature can be attributed to the changes in the properties of the PNiPAM chains. From consideration of the PNiPAM phase transition mechanism, it is speculated that the intermolecular force between the PNiPAM-grafted surface and BSA would be affected by changes in the arrangement of the bound water molecules around the PNiPAM chain and by changes in the conformation (i.e., in the chain mobility) of the PNiPAM chain during the phase transition.

Acrylamides↗

Combined effect of chain length and phase state on adhesion/friction behavior of self-assembled monolayers.

The combined effects of phase state and chain length on the adhesion and friction behavior of self-assembled monolayers (SAMs) are demonstrated using atomic force microscopy (AFM). The phase state of n-alkyltrichlorosilane monolayers of varying chain length (C-8, C-12, and C-18) was controlled by adjusting the preparation temperature. The adhesion forces and friction coefficients were observed to increase dramatically around the phase-transition temperature of each monolayer. The phase state effect was more prominent for the longer chain SAMs, which is attributed to the larger deformation volume associated with disordered monolayers. The adhesion/friction diagram for chain length effect with a wide range of phase states is successfully presented. This study reveals that the chain length effect on adhesion/friction can be correctly evaluated by examining the phase-state dependence of adhesion/friction behind the chain length effect.

Adhesiveness↗

Deposition of amorphous calcium carbonate hemispheres on substrates.

The amorphous calcium carbonate (ACC) hemispheres were deposited on the mica and poly(diallyldimethylammonium chloride) modified surface. The form of the ACC deposit on the substrates can be controlled by modifying the substrate surface, the introduction of additives, or both. It demonstrated that substrates (insoluble matrix) and additives (soluble macromolecules) have significant influence on the crystallization of CaCO(3).

Journal Article↗

Surface-induced conformational changes in poly(3-hexylthiophene) monolayer films.

With the aim of elucidating the surface-induced molecular ordering in regioregular poly(3-hexylthiophene) (P3HT) monolayer films, we have controlled the intermolecular interactions at the interface between P3HT and the insulator substrate by using self-assembled monolayers (SAMs) functionalized with two kinds of groups (-NH2 and -CH3). We have found that, depending on the surface properties of such modified insulator substrates, the P3HT chains in the monolayer films can adopt two different conformations (edge-on and face-on). This surprising variation in chain conformation arises because of the specific interactions of the P3HT chains with the modified insulator substrates, which can be explained in terms of the following factors: the unshared electron pairs of the SAM end groups (in the -NH2 system), the pi-H interactions between the thienyl backbone bearing pi systems and the H (hydrogen) atoms of the SAM end groups, and interdigitation between the alkyl chains of P3HT and the alkyl chains of the SAMs (in the -NH2 system).

Letter↗

Exploiting poly(dimethylsiloxane)-modified tips to evaluate frictional behavior by friction force microscopy.

With the aim of investigating the effect of the surface properties on the friction behavior of self-assembled monolayers, we have modified tipless atomic force microscopy (AFM) cantilevers with a poly(dimethylsiloxane) (PDMS) lens. The friction coefficient using the silicon tip is strongly influenced by the mechanical properties of the substrate monolayer because hard, sharp silicon tips penetrate the surface of organic monolayers. However, the friction coefficient obtained for the PDMS-modified AFM cantilever is mostly due to the surface properties of the monolayer functional end group, rather than the viscoelastic deformation of the monolayer. The use of the PDMS tip was demonstrated as a novel means to investigate the effect of surface properties on the frictional behavior of self-assembled monolayers with various functional groups with less mechanical deformation.

Journal Article↗

Evaluation of the adhesion properties of inorganic materials with high surface energies.

With the aim of checking the validity of methods for characterizing the adhesion between inorganic materials with high surface energies, the properties of the adhesion between an inorganic material (indium tin oxide (ITO)) and model surfaces with various surface energies (Cl-, NH2-, CH(3)-, and CF3-functionalized surfaces) were evaluated using atomic force microscopy (AFM) and the Johnson-Kendall-Roberts (JKR) apparatus. For this purpose, the AFM tip and the JKR lens were modified with ITO using radio frequency (rf) magnetron sputtering. The work of adhesion between the ITO coating and each model surface was estimated using AFM and the JKR apparatus and compared with the result obtained from contact angle measurements. The adhesion forces determined from the force-displacement curves (AFM) were found to agree with the predictions of the Derjaguin-Muller-Toporov (DMT) theory. The JKR equation used in the interpretation of the JKR experiments was modified by taking into account the differences between the surface and bulk moduli of the ITO-coated poly(dimethylsiloxane) (PDMS) lens. The ratio of the surface modulus to the bulk modulus we used in this modified JKR equation was obtained by determining the slope of the attracting part of the force-displacement curve. The values of the work of adhesion calculated using the modified JKR equation were also found to agree with the values obtained from contact angle measurements. We conclude that the two methods using AFM and the JKR apparatus can be used in the evaluation of the work of adhesion between inorganic materials with high surface energies such as metal and metal oxide surfaces.

Journal Article↗

Phase state effect on adhesion behavior of self-assembled monolayers.

The effect of phase state of self-assembled monolayers (SAMs) on adhesion behavior was studied using a combination of atomic force microscopy (AFM) and Johnson-Kendall-Roberts (JKR) methods. The phase state of SAMs was controlled by adjusting the reaction temperature. Order-to-disorder structural transitions in monolayers of n-alkyltrichlorosilanes resulted in dramatic increases in adhesion force and adhesion hysteresis, which represents the first report of alterations in adhesion properties due to phase changes of monolayers without any effect of chain length and surface heterogeneity. This increase in mechanical deformation of the disordered monolayer is understood to be caused by increases in (1) molecular contact between the AFM tip and a disordered monolayer due to the more deformable state of the latter and (2) monolayer deformation during unloading by the JKR probe lens. Adhesion hysteresis was found to have greater sensitivity toward the unloading rate for disordered monolayers. The occurrence of maximum hysteresis at faster rates proves that monolayer chain mobility increases with structural disorder, resulting in increased mechanical deformation.

Adhesiveness↗

Fabrication of superhydrophobic surface from a supramolecular organosilane with quadruple hydrogen bonding.

A supramolecular organosilane, 2-(3-(triethoxysilyl)propylaminocarbonylamino)-6-methyl-4[1H]pyrimidinone comprising quadruple hydrogen bonds has been synthesized in one step from commercially available starting materials. The synthesized supramolecular organosilane can be stabilized and phase-separated by dimerization via the linear array of quadruple hydrogen bonds in solution. This property of the supramolecular organosilane has been exploited to fabricate structuring materials having a superhydrophobic surface property. We have successfully generated the interconnected granular structure with adequate roughness for superhydrophobicity via sol-gel process.

Journal Article↗

Incorporation and release behavior of hydrophobic drug in functionalized poly(D,L-lactide)-block-poly(ethylene oxide) micelles.

The poly(ethylene oxide)-poly(lactide) (PEO-PLA) block copolymers containing a small quantity of carboxylic acid in the PLA block were synthesized. The microscopic characteristics of nanoparticles with carboxylic acid content in the copolymer were analyzed, and the effect of specific interactions between the copolymer and the model drug on the drug loading capacity and the release behavior were investigated systematically. The sizes of nanoparticles prepared by a dialysis method are within the range of 30-40 nm. The nanoparticles prepared from functionalized block copolymers have a very low critical micelle concentration (CMC) value as low as approximately 10(-3) mg/ml, which indicates a good stability of the nanoparticles in spite of the presence of carboxylic acid. The drug loading efficiency of nanoparticles dramatically increased when carboxylic acid content was increased in the block copolymer. This result may be attributed to the increase of interactions between the copolymer and the drug. The release rate of the drug was much slower from nanoparticles containing higher amounts of carboxylic acid in the copolymer, which might be associated with the enhanced interaction between the carboxylic group of copolymers and the drug. These experimental results suggest that the nanoparticles prepared from functionalized PEO-PLA block copolymers could be a good candidate for an injectable drug delivery carrier.

Hydrophobic and Hydrophilic Interactions↗