• Journal of the Korean Vacuum Society
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• v.19 no.2
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• pp.81-90
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• 2010

We introduce a novel and versatile approach for preparing self-assembled nanoporous multilayered films with antireflective properties. Protonated polystyrene-block-poly (4-vinylpyrine) (PS-b-P4VP) and anionic polystyrene-block-poly (acrylic acid) (PS-b-PAA) block copolymer micelles (BCM) were used as building blocks for the layer-by-layer assembly of BCM multilayer films. BCM film growth is governed by electrostatic and hydrogen-bonding interactions between the oppositely BCMs. Both film porosity and film thickness are dependent upon the charge density of the micelles, with the porosity of the film controlled by the solution pH and the molecular weight (Mw) of the constituents. PS7K-b-P4VP28K/PS2K-b-PAA8K films prepared at pH 4 (for PS7K-b-P4VP28K) and pH 6 (for PS2K-b-PAA8K) are highly nanoporous and antireflective. In contrast, PS7K-b-P4VP28K/PS2K-b-PAA8K films assembled at pH 4/4 show a relatively dense surface morphology due to the decreased charge density of PS2K-b-PAA8K. Films formed from BCMs with increased PS block and decreased hydrophilic block (P4VP or PAA) size (e.g., PS36K-b-P4VP12K/PS16K-b-PAA4K at pH 4/4) were also nanoporous. Furthermore, we demonstrate that the nanostructured electrochemical sensors based on patterning methods show the electrochemical activities. Anionic poly(styrene sulfonate) (PSS) layers were selectively and uniformly deposited onto the catalase (CAT)-coated surface using the micro-contact printing method. The pH-induced charge reversal of catalase can provide the selective deposition of consecutive PE multilayers onto patterned PSS layers by causing the electrostatic repulsion between next PE layer and catalase. Based on this patterning method, the hybrid patterned multilayers composed of platinum nanoparticles (PtNP) and catalase were prepared and then their electrochemical properties were investigated from sensing $H_2O_2$ and NO gas. This study was based on the papers reported by our group. (J. Am. Chem. Soc. 128, 9935 (2006); Adv. Mater. 19, 4364 (2007); Electro. Mater. Lett. 3, 163 (2007)).

• Applied Biological Chemistry
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• v.26 no.2
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• pp.125-131
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• 1983

Formal net charges, bond populations, atomic orbital coefficients, energy components and conformation of dimethyl-2,2-dichlorovinylphosphate have been studied theoretically by using the CNDO/2 molecular orbital calculation method in attempt to describe the reactivity and the stability of the molecule. From the analysis of rate equation, molecular orbital calculations and identification of the hydrolysis products, 2,2-dichloroacetaldehyde and dimethylphosphoric acid, a mechanism of the hydrolysis of dimethyl-2,2-dichlorovinylphosphate(DDVP) has been proposed. The hydrolysis of DDVP proceeds through the mechanism of nucleophilic addition, typical Micheal reaction in basic media. Therefore, it appears probable that the attack by strong nucleophile, hydroxide ion occurs at the increased positive charge $C_2({\alpha})$ atom of a staggered conformation due to the inductive effect (-)I>(+)R of 2,2-dichlorovinyl, electron-attracting group. And then, the hydrolytic scission involves the $C_2({\alpha})-O_3$, ${\pi}-anti-bonding\;orbital({\pi}^*)$ in the subsequent reaction in aqueous solution.