• Macromolecular Research
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• 제17권5호
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• pp.325-331
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• 2009

The synthesis and the characterization of crosslinked ABC triblock copolymer, i.e. polystyrene-b-poly (hydroxyethyl methacrylate)-b-poly(styrene sulfonic acid), (PS-b-PHEMA-b-PSSA) is reported. PS-b-PHEMA-b-PSSA triblock copolymer at 20:10:70 wt% was sequentially synthesized via atom transfer radical polymerization (ATRP). The middle block was crosslinked by sulfosuccinic acid (SA) via the esterification reaction between -OH of PHEMA and -COOH of SA, as demonstrated by FTIR spectroscopy. As increasing amounts of SA, ion exchange capacity (IEC) continuously increased from 2.13 to 2.82 meq/g but water uptake decreased from 181.8 to 82.7%, resulting from the competitive effect between crosslinked structure and the increasing concentration of sulfonic acid group. A maximum proton conductivity of crosslinked triblock copolymer membrane at room temperature reached up to 0.198 S/cm at 3.8 w% of SA, which was more than two-fold higher than that of Nafion 117(0.08 S/cm). Transmission electron microscopy (TEM) analysis clearly showed that the PS-b-PHEMA-b-PSSA triblock copolymer is microphase-separated with a nanometer range and well developed to provide the connectivity of ionic PSSA domains. The membranes exhibited the good thermal properties up to $250^{\circ}C$ presumably resulting from the microphase-separated and crosslinked structure of the membranes, as revealed by thermal gravimetric analysis (TGA).

• 한국수소및신에너지학회논문집
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• 제25권1호
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• pp.28-38
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• 2014

The organic-inorganic composite membrane in polymer exchange membrane fuel cells (PEMFCs) have several fascinating technological advantages such as a proton conductivity, thermal stability and mechanical properties. As the inorganic filler, silicon carbide (SiC) fiber have been used in various fields due to its unique properties such as thermal stability, conductivity, and tensile strength. In this study, composite membrane was successfully fabricated by modified-silicon carbide fiber. Modified process, as a novel process in SiC, takes reaction by phosphoric acid after oxidation process (generated homogeniusly $SiO_2$ layer on SiC fiber). The mechanical property which was conducted by tensile test of the 5wt% modified-$SiO_2@SiCf$ composite membrane was better than that of Aquivion casting membrane as well as ion cxchange capacity(IEC) and proton conductivity. In addition, the single cell performance was observed that the 5wt% modified-$SiO_2@SiCf$ composite membrane was approximately $0.2A/cm^2$ higher than that of a Aquivion casting electrolyte membrane and electrochemical impedance was improved with the charge transfer resistance and membrane resistance.

• 한국음향학회지
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• 제23권7호
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• pp.497-502
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• 2004

Poly (sodium 4-styrenesulfonate) 수용액에 대한 3 MHz의 초음파 음속측정과 0.2-2.2 MHz의 범위에 대한 흡수계수를 측정하였다. 음속은 펄스법을 사용하여 농도 5-25 wt%, 온도 10-90 ℃에 대하여 측정한 결과, 농도 25, 20, 15, 10, 5 wt%에 대한음속의 최대치 온도는 각각 55, 59, 63, 67, 71 ℃이였다. 흡수계수측정은 광 회절 초음파공명법을 사용하여 농도 5-25 wt%, 20 ℃에서 행하였다. 그 결과, 200 kHz부근에서 고분자 chain의 부분운동에 의한 완화현상을, 1 MHz 부근에서는 술폰기 (SO₃)의 proton의 전이에 의한 완화현상을 각각 관측하였다. 흡수계수와 점성은 농도와 함께 증가하였으나 온도증가에 대해서는 감소하였다.

• Bulletin of the Korean Chemical Society
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• 제29권10호
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• pp.1911-1914
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• 2008

Second-order rate constants (kN) have been measured for Michael-type addition reactions of a series of alicyclic secondary amines to 1-phenyl-2-propyn-1-one (2) in MeCN at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. All the amines studied are less reactive in MeCN than in $H_2O$ although they are more basic in the aprotic solvent by 7-9 p$K_a$ units. The Bronsted-type plot is linear with $\beta_{nuc}$ = 0.40, which is slightly larger than that reported previously for the corresponding reactions in $H_2O$ ($\beta_{nuc}$ = 0.27). Product analysis has shown that only E-isomer is produced. Kinetic isotope effect is absent for the reactions of 2 with morpholine and deuterated morpholine (i.e., $k^H/k^D$ = 1.0). Thus, the reaction has been concluded to proceed through a stepwise mechanism, in which proton transfer occurs after the rate-determining step. The reaction has been suggested to proceed through a tighter transition state in MeCN than in H2O on the basis of the larger $\beta_{nuc}$ in the aprotic solvent. The nature of the transition state has been proposed to be responsible for the decreased reactivity in the aprotic solvent.

• Bulletin of the Korean Chemical Society
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• 제27권5호
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• pp.733-738
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• 2006

Nucleophilic addition reactions of p-substitutedbenzylamines $(XC _6H_4CH _2NH _2)$ to $\alpha$-phenyl-$\beta$-thiophenyl-acrylonitriles ($YC _4SH _2CH=C(CN)C_6H_4$Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 ${^{\circ}C}$. The reactions take place in single step in which the $C_\beta$ -N bond formation and proton transfer to $C_\alpha$ of $\alpha$-phenyl-$\beta$-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative $\rho$x and large positive $\rho$Y' values and also large magnitude of $\rho$X, (ii) the negative sign and large magnitude of the cross-interaction constants ($\rho$XY), (iii) the normal kinetic isotope effects ($k_H/k_D$ > 1.0), and (iv) relatively low $\Delta H ^\neq$ and large negative $\Delta S ^\neq$ values.

• 대한화학회지
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• 제34권4호
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• pp.319-324
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• 1990

비스(아세틸아세토네이토)옥소바나듐(Ⅳ) 착물(VO (acac)$_2$)에서 하나의 아세틸아세톤(acac) 배위자가 디벤조일메탄(dbm)에 의해 치환되는 반응속도를 여러 가지 용매에서 분광광도법으로 측정했다. 반응조건을 [VO (acac)$_2$] 》[Hdbm]으로 했을 때 치환반응의 속도식은 다음과 같다. 속도 = k$_2$K[VO(acac)$_2$] [Hdbm] / (1 ＋ K[VO(acac)$_2$])여기에서 평형상수 K는 [VO (acac)$_2$dbmH] / [VO(acac)$_2$][Hdbm]이며, 반응속도상수 k$_2$는 dbmH착물내에서 Hdbm으로부터 acac-로의 양성자 이동속도에 해당하는 값이다.

• Bulletin of the Korean Chemical Society
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• 제26권6호
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• pp.935-938
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• 2005

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to $\alpha-cyano-\beta$-phenylacrylamides (CPA; $YC_6H_4CH=C(CN)CONH_2$) have been investigated in acetonitrile at 25.0 ${^{\circ}C}$. The rate is first order with respect to BA and CPA and no base catalysis is observed. The addition of BA to CPA occurs in a single step in which the addition of BA to $C_{\beta}$ of CPA and proton transfer from BA to $C_{\alpha}$ of CPA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($\rho_X$) and Bronsted ($\beta_X$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the crossinteraction constant, $\rho_XY$ (= −D0.26), is comparable to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($k_H/k_D\;{\gt}$ 1.0) and relatively low ${\Delta}H^{\neq}$ and large negative ${\Delta}S^{\neq}$ values are also consistent with the mechanism proposed.

• 멤브레인
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• 제27권3호
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• pp.205-215
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• 2017

고분자 분리막은 가격이 저렴하고, 쉽게 제조가 가능하며, 투과도와 선택도가 우수하여 수처리 분야뿐만 아니라 기체분리에서도 중요한 역할을 한다. 하지만, 고분자 분리막은 일반적으로 투과도와 선택도의 역상관 관계를 나타내는 단점이 있다; 즉, 투과도가 높으면 선택도가 낮고, 선택도가 높으면 투과도가 높다. 이러한 단점을 극복하기 위한 방안 중의 하나가 촉진수송이다. 지난 수십 년간 촉진수송 이론은 촉진수송 분리막 제조에 있어 매우 중요하고 다양한 모델을 제시하는 데에 핵심적인 역할을 하였다. 한편, 촉진수송에서 주된 역할을 하는 운반체의 특성, 매질의 유동성 및 고분자 복합체의 물리화학적 성질 등을 이해하는 것은 중요하다. 운반체의 유동성에 따라 촉진수송 분리막의 종류를 3가지로 나눌 수 있다; 즉, 이동상 운반체 분리막, 준이동상 운반체 분리막, 고정상 운반체 분리막. 또한 촉진 운반체가 특정물질과 상호작용하는 데에는 4가지 종류의 가역반응으로 나눌 수 있다; 즉, 수소원자 전달 반응, 친핵성 첨가반응, 파이-착체 반응, 그리고 전기화학 반응. 이러한 촉진수송 분리막은 이산화탄소, 산소, 올레핀(프로필렌, 에틸렌)의 투과도를 선택적으로 향상시키는 역할을 한다. 이와 같이 본 총설에서는 다양한 촉진수송 분리막에 관련된 주요 연구내용과 이러한 연구를 수행하는 대표적인 전략들을 소개하고자 한다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.91-91
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• 2013

Imagine a world where we could biomanufacture hybrid nanomaterials having atomic-scale resolution over functionality and architecture. Toward this vision, a fundamental challenge in materials science is how to design and synthesize protein-like material that can be fully self-assembled and exhibit information-specific process. In an ongoing effort to extend the fundamental understanding of protein structure to non-natural systems, we have designed a class of short peptides to fold like proteins and assemble into defined nanostructures. In this talk, I will talk about new strategies to drive the self-assembled structures designing sequence of peptide. I will also discuss about the specific interaction between proteins and inorganics that can be used for the development of new hybrid solar energy devices. Splitting water into hydrogen and oxygen is one of the promising pathways for solar to energy convertsion and storage system. The oxygen evolution reaction (OER) has been regarded as a major bottleneck in the overall water splitting process due to the slow transfer rate of four electrons and the high activation energy barrier for O-O bond formation. In nature, there is a water oxidation complex (WOC) in photosystem II (PSII) comprised of the earthabundant elements Mn and Ca. The WOC in photosystem II, in the form of a cubical CaMn4O5 cluster, efficiently catalyzes water oxidation under neutral conditions with extremely low overpotential (~160 mV) and a high TOF number. The cluster is stabilized by a surrounding redox-active peptide ligand, and undergo successive changes in oxidation state by PCET (proton-coupled electron transfer) reaction with the peptide ligand. It is fundamental challenge to achieve a level of structural complexity and functionality that rivals that seen in the cubane Mn4CaO5 cluster and surrounding peptide in nature. In this presentation, I will present a new strategy to mimic the natural photosystem. The approach is based on the atomically defined assembly based on the short redox-active peptide sequences. Additionally, I will show a newly identified manganese based compound that is very close to manganese clusters in photosystem II.

• 미생물학회지
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• 제32권4호
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• pp.315-321
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• 1994

Pleurotus ostreatus로부터 glyoxalase I(S-lactoyl-glutathione methylglyoxal lyase, EC 4.4.1.5)이 S-hexylglutathione affinity chromatography, Sephadex G-150 gel permeation chromatography, DEA-sepharose A-50 CL-6B ion exchange chromatography를 통해 순수 분리되었다. 이 결과, 전체 활성도의 21.7% fmf 수확하였으며, 분리 배수는 2,294 배 이었다. Gel filtration chromatography로 측정한 효소의 분자량은 34 kDa이며, SDS-PAGE 결과 본 효소는 분자량 17 kDa인 동일한 소단위체 두 개로 구성된 이합체라고 생각된다. Methylglyoxal과 phenylglyoxal에 대한 $K_m$ 값은 각각 0.39 mM 과 0.22 mM 이며 L-xylosone과 hydroxypyruvaldehyde에 대해서도 강한 친화력을 보여주었고, pH 6.5~7.5, $35~45^{\circ}C$에서 활성도가 가장 높았다. 이 효소의 반응 과정을 핵자기공 명분광법으로 분석한 결과, 분자내의 양성자 전달과정이 뚜렷이 관찰되었다.