Dong June Ahn

Total alignment of calcite at acidic polydiacetylene films: Cooperativity at the organic-inorganic interface

Biological matrices can direct the absolute alignment of inorganic crystals such as calcite. Cooperative effects at an organic-inorganic interface resulted in similar co-alignment of calcite at polymeric Langmuir-Schaefer films of 10,12-pentacosadiynoic acid (p-PDA). The films nucleated calcite at the (012) face, and the crystals were co-aligned with respect to the polymers conjugated backbone. At the same time, the p-PDA alkyl side chains reorganized to optimize the stereochemical fit to the calcite structure, as visualized by changes in the optical spectrum of the polymer. These results indicate the kinds of interactions that may occur in biological systems where large arrays of crystals are co-aligned.

Immobilization of poly(ethylene glycol) or its sulfonate onto polymer surfaces by ozone oxidation

A novel surface modification method has been developed to improve biocompatibility of polymeric biomaterials. This approach involves ozonation and then followed by graft polymerization with acrylates containing PEG, sulfonated PEG or by coupling of PEG derivatives. All the reactions were confirmed by ATR FT-IR and ESCA. The degree of ozonation measured by the iodide method was dependent on the ozone permeability of the polymers used. Surface hydrophilicity was investigated by measuring the contact angles. Ozonation itself yielded a slight increase in hydrophilicity and a decrease in platelet adhesion, but PEG immobilization showed a significant effect on surface hydrophilicity and platelet adhesion to confirm well-known PEGs passivity which minimize the adhesion of blood components on polymer surfaces. Both graft polymerization and coupling were effective for PU. In contrast, only grafting gave enough yields for PMMA and silicone. Platelet adhesion results demonstrated that all PEG modified surfaces adsorbed lower platelet adhesion than untreated or ozonated ones. Polymers coupled with sulfonated PEG exhibited the lowest platelet adhesion when compared with control and PEG coupled ones by virtue of the synergistic effect of non-adhesive PEG and negatively charged SO3 groups. This PEG or sulfonated PEG immobilization technology using ozonation is relatively simple for introducing uniform surface modification and therefore very useful for practical application of blood contacting medical devices.

Spreading of an Inkjet Droplet on a Solid Surface with a Controlled Contact Angle at Low Weber and Reynolds Numbers

Even though the inkjet technology has been recognized as one of the most promising technologies for electronic and bio industries, the full understanding of the dynamics of an inkjet droplet at its operating conditions is still lacking. In this study, the normal impact of water droplets on solid substrates was investigated experimentally. The size of water droplets studied here was 46 microm and was much smaller than the most of the previous studies on drop impact. The Weber number (We) and Reynolds number (Re) were 0.05-2 and 10-100, respectively, and the Ohnesorge number was fixed at 0.017. The wettability of the solid substrate was varied by adsorbing a self-assembled monolayer of octadecyltrichlorosilane followed by the exposure to UV-ozone plasma. The impact scenarios for low We impacts were found to be qualitatively different from the high to moderate We impacts. Neither the development of a thin film and lamella under the traveling sphere nor the entrapment of small bubbles was observed. The dynamics of droplet impact at the conditions studied here is found to proceed under the combined influences of inertia, surface tension, and viscosity without being dominated by one specific mechanism. The maximum spreading factor (beta), the ratio of the diameter of the wetted surface and the drop diameter before impact, was correlated well with the relationship ln beta=0.090 ln We/(fs-cos theta)+0.151 for three decades of We/(fs-cos theta), where theta is the equilibrium contact angle, and fs is the ratio between the surface areas contacting the air and the solid substrate. The result implies that the final shape of the droplet is determined by the surface phenomenon rather than fluid mechanical effects.

Electrical transport through 60 base pairs of poly(dG)-poly(dC) DNA molecules

We report electrical transport through 60 base pairs of poly~dG!-poly~dC! DNA molecules. The DNA solution is dropped on two metal electrodes with the gap of 20 nm. The current‐voltage characteristics measured between the electrodes exhibits clear staircases, which are reproducible over repeated measurements. The size of the observed staircases is consistent with the energy gap obtained from a tight binding calculation.

FT-IR and Isotherm Study on Anion Adsorption onto Novel Chelating Fibers

A new chelating fiber, poly(acrylo-amidino diethylenediamine), was synthesized based on polyacrylonitrile fibers in diethylenetriamine with the aid of AlCl 3 . Complex formation with CrO 4 2- was strongly pH-dependent, as complexes formed only in the presence of NH 3 + and NH 2 + . In the medium pH region, both ionic and hydrogen bonds were formed between poly(acrylo-amidino diethylenediamine) and the chromate ion, as was confirmed by means of FT-IR spectroscopy.

Effect of phospholipid insertion on arrayed polydiacetylene biosensors

Micro-arrayed polydiacetylene (PDA) vesicles mixed with phospholipids on glass slides were prepared for label-free detection of Escherichia coli. When E. coli bound to its antibodies chemically attached to polydiacetylene, the fluorescence of the vesicles was dramatically increased. The insertion of dimyristoyl phosphatidylcholine (DMPC) in the vesicles drastically reduced the response time for the fluorescence changes. Vesicles with 20-30% DMPC provided optimal results for bacterial detection. Fourier transform infrared (FTIR) spectra analysis suggested that DMPC insertion decreased the strength of hydrogen bonding among the amide and carboxylic acid groups of the polydiacetylene vesicles. Reduced bonding strength resulted in less rigid structure of the polydiacetylene polymer, allowing more rapid detection upon molecular recognition.

A study of electrochemical kinetics of lithium ion in organic electrolytes

Limiting current densities equivalent to the transport-controlling step of lithium ions in organic electrolytes were measured by using a rotating disk electrode (RDE). The diffusion coefficients of lithium ion in the electrolyte of PC/LiClO4, EC : DEC/LiPF6 and EC : DMC/LiPF6 were determined by the limiting current density data according to the Levich equation. The diffusion coefficients increased in the order of PC/LiClO4<EC : DEC/LiPF6<EC : DMC/ LiPF6 with respect to molar concentration of lithium salt. The maximum value of diffusivity was 1.39x10-5cm2/s for 1M LiPF6 in EC : DMC=1 : 1. Exchange current densities and transfer coefficients of each electrolyte were determined according to the Butler-Volmer equation.

Interactions of charged Langmuir monolayers with dissolved ions

Dissociation of protons from fatty acid Langmuir monolayers causes competitive adsorption of other counterions and partial charge neutralization. A new equilibrium model incorporating surface electrochemical and thermodynamic features is presented. The Stern–Gouy–Chapman equations are used, along with a modified Langmuir isotherm in which ion activities in the mixed surface monolayer instead of concentrations are employed. A two‐dimensional lattice model with Flory–Huggins interaction parameters χij is invoked to obtain the activities of the ions in the monolayer. The competitive adsorption of ions to fatty acid monolayers is either ‘‘ideal’’ (χij=0), or nonideal, depending on the ions mixing behavior with protons. Previous electrochemical models apply only for ideal adsorption, which appears to occur for Cd2+ and Ca2+. The nonideal adsorption is characterized successfully by the use of the above interaction parameters. Ba2+ ions show negative deviations from ideal adsorption, i.e., they adsorb less than ...

Surface Characteristics and Fibroblast Adhesion Behavior of RGD-Immobilized Biodegradable PLLA Films

The interactions between the surface of scaffolds and specific cells play an important role in tissue engineering applications. Some cell adhesive ligand peptides including Arg-Gly-Asp (RGD) have been grafted into polymeric scaffolds to improve specific cell attachment. In order to make cell adhesive scaffolds for tissue regeneration, biodegradable nonporous poly(l-lactic acid) (PLLA) films were prepared by using a solvent casting technique with chloroform. The hydrophobic PLLA films were surface-modified by Argon plasma treatment andin situ direct acrylic acid (AA) grafting to get hydrophilic PLLA-g-PAA. The obtained carboxylic groups of PLLA-g-PAA were coupled with the amine groups of Gly-Arg-Asp-Gly (GRDG, control) and GRGD as a ligand peptide to get PLLAg-g-GRDG and PLLA-g-GRGD, respectively. The surface properties of the modified PLLA films were examined by various surface analyses. The surface structures of the PLLA films were confirmed by ATR-FTIR and ESCA, whereas the immobilized amounts of the ligand peptides were 138–145 pmol/cm2. The PLLA surfaces were more hydrophilic after AA and/or RGD grafting but their surface morphologies showed still relatively smoothness. Fibroblast adhesion to the PLLA surfaces was improved in the order of PLLA control < PLLA-g-PAA=PLLA-g-GRDG < PLLA-g-GRGD, indicating that PLLA-g-GRGD has the highest cell adhesive property.

Biodegradable poly(L-lactide) composites by oligolactide-grafted magnesium hydroxide for mechanical reinforcement and reduced inflammation

Biodegradable polymers, such as poly(l-lactide) (PLLA), are very useful in many biomedical applications. However, their degradation by-products have been much of a concern as they are the sources of inflammatory reactions in the body. In this work, we suggest a novel composite system composed of PLLA and oligolactide-grafted magnesium hydroxide (Mg-OLA) that can overcome drawbacks caused by poor mechanical properties and inflammatory response of PLLA for biomedical applications. Mg-OLAs were synthesized by ring opening polymerization and the structure, morphology, pH change, thermal, and mechanical properties were analyzed using FTIR, SEM, pH meter, TGA, and UTM. In particular, the tensile strength and modulus of PLLA/Mg80-OLA20 (0-20 wt%) were higher than those of PLLA/magnesium hydroxide. The PLLA/Mg80-OLA20 composite was also very effective in neutralizing the acidic environment caused by the degradable by-product of the PLLA matrix. In vitro cell viability and the expression levels of COX-2 and IL-6 proteins in the PLLA composites were also evaluated. Cell viability increased to around 100% with increasing the amount of Mg80-OLA20 from 0 to 20 wt%. The expression levels of IL-6 and COX-2 were reduced dramatically when increasing the proportion of Mg80-OLA20 from 0 to 50 wt%. As a result, the incorporation of Mg-OLAs into the PLLA matrix could reinforce the mechanical properties as well as reduce the inflammatory response of the hybrid PLLA. Therefore, this hybrid composite system blending oligomer-grafted magnesium hydroxide in biodegradable polymers would be a promising strategy for avoiding current fatal problems in biomedical applications.