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Quan, De,Shin, Woon-Sup Korean Chemical Society 2004 Bulletin of the Korean Chemical Society Vol.25 No.6
DeniLite$^{TM}$ laccase immobilized platinum electrode was used for amperometric detection of hydroquinone (HQ) and homogentisic acid (HGA) by means of substrate recycling. In case of HQ, the obtained sensitivity is 280 nA/ ${\mu}$M with linear range of 0.2-35 ${\mu}$M ($r^2$ = 0.998) and detection limit (S/N = 3) of 50 nM. This high sensitivity can be attributed to chemical amplification due to the cycling of the substrate caused by enzymatic oxidation and following electrochemical regeneration. In case of HGA, the obtained sensitivity is 53 nA/ ${\mu}$M with linear range of 1-50 $[\mu}M\;(r^2$ = 0.999) and detection limit of 0.3 ${\mu}$M. The response times ($t_{90%}$) are about 2 seconds for the two substrates and the long-term stability is 60 days for HQ and around 40-50 days for HGA with retaining 80% of initial activities. The very fast response and the durable long-term stability are the principal advantages of this sensor. pH studies show that optimal pH of the sensor for HQ is 6.0 and that for HGA is 4.5-5.0. This shift of optimal pH towards acidic range for HGA can be attributed to the balance between enzyme activity and accessibility of the substrate to the active site of the enzyme.
Quan, De,Kim, You-Sung,Shin, Woon-Sup Korean Chemical Society 2004 Bulletin of the Korean Chemical Society Vol.25 No.8
Tyrosinase was covalently immobilized on platinum electrode according to the method we developed for laccase (Bull. Korean Chem. Soc. 2002, 23(7), 385) and p-chlorophenol, p-cresol, and phenol could be detected with sensitivities of 334, 139 and 122 nA/ ${\mu}M$ and the detection limits of 1.0, 2.0, and 2.5 ${\mu}M$, respectively. The response time ($t_{90\%}$) is 3 seconds for p-chlorophenol, and 5 seconds for p-cresol and phenol. The optimal pHs of the sensor are in the range of 5.0- 6.0. This sensor can tolerate at least 500 times repeated injections of p-chlorophenol with retaining 80% of initial activity. In case of tyrosinase and laccase co immobilized platinum electrode, the sensitivities are 560 nA/ ${\mu}M$ for p-phenylenediamine (PPD) and 195 nA/ ${\mu}M$ for p-chlorophenol, respectively. The sensitivity of the bi-enzyme sensor for PPD increases 70% compared to that of only laccase immobilized one, but the sensitivity for p-chlorophenol decreases 40% compared to that of only tyrosinase immobilized one. The sensitivity increase for the bi-enzyme sensor for PPD can be ascribed to the additional catalytic function of the co-immobilized tyrosinase. The sensitivity decrease for p-chlorophenol can be explained by the “blocking effect” of the co-immobilized laccase, which hinders the mass transport through the immobilized layer. If PPD was detected with the electrode that had been used for p-chlorophenol, the sensitivity decreased 20% compared to that of the electrode that had been used only for PPD. Similarly, if p-chlorophenol was detected with PPD detected electrode, the sensitivity also decreased 20%. The substrate-induced conformation changes of the enzymes in a confined layer may be responsible for the phenomena.
Quan De,Shin Woonsup The Korean Electrochemical Society 2004 한국전기화학회지 Vol.7 No.2
[ $DeniLite^{TM}$ ] laccase immobilized Pt electrode was used for amperometric detection of some catechol derivatives and o-aminophenol (OAP) derivative by means of substrate recycling. In case of catechol derivatives, the obtained sensitivities are 85, 79 and $57 nA/{\mu}M$ with linear ranges of $0.6\~30,\;0.6\~30\;and\; 1\~25 {\mu}M$ and detection limits (S/N=3) of 0.2, 0.2 and $0.3{\mu}M$ for 3,4-dihydroxycinnaminic acid (3,4-DHCA), 3,4-dihydroxybenzoic acid (3,4-DHBA) and 3,4-dihydroxyphenylacetic acid (3,4-DHPAA), respectively. In case of OAP derivative, the obtained sensitivity is $237 nA/{\mu}M$ with linear range of $0.2\~15{\mu}M$ and detection limit of 70 nM for 2-amino-4-chlorophenol (2-A-4-CP). The response time $(t_{90\%})$ is about 2 seconds for each substrate and the long-term stability is around 40-50days for catechol derivatives and 30 days for 2-A-4-CP with retaining $80\%$ of initial activity. The optimal pHs of the sensor for these substrates are in the range of 4.5-5.0, which indicates that stability of the enzymatically oxidized product plays a very important role in substrate recycling. The different sensitivity of the sensor for each substrate can be explained by the electronic effect of the sugstituent on the enzymatically oxidized form.
Engineering Characteristics and Reinforcement Program of Inclined Pre−stressed Concrete Pipe Piles
De-quan Zhou,Chen-xi Feng 대한토목학회 2019 KSCE JOURNAL OF CIVIL ENGINEERING Vol.23 No.9
When it comes to the deep soft soil foundation, improper construction, preloading, and excavation may result in the inclination of the pre−stressed concrete pipe (PCP) piles. Lack of understanding on deformation characteristics may lead to inaccurate reinforcement plan, thereby causing new engineering accidents. This study analyzes an engineering accident induced by the pile inclination, based on which the finite element method model is built. Deformation characteristics of the foundation incorporating inclined PCP piles are investigated, and the reinforcement program involving placement of the pile with opposite inclination is proposed and compared with the conventional reinforcement program using vertical piles. Findings of this study are two−folds: 1) A critical inclination angle affecting the vertical settlement exists, below which the pile inclination has limited effects upon the vertical load bearing capacity of the foundation. 2) The vertical subsidence, the lateral displacement and the bending moment of the reinforcement program based on the reversely inclined pile are all decreased, which helps bear the overburden load and improve stability. In the process of engineering accident treatment, the bearing capacity of PCP piles with small inclination angles can be first reduced according to their inclination angles, followed by judgement that whether these PCP piles meet the requirements on bearing capacity. The PCP piles with large inclination angles must be strengthened, and the reverse inclined PCP piles are recommended.
De Quan,신운섭 한국전기화학회 2004 한국전기화학회지 Vol.7 No.2
DeniLiteTM laccase immobilized Pt electrode was used for amperometric detection of some catechol derivatives and o-aminophenol (OAP) derivative by means of substrate recycling. In case of catechol derivatives, the obtained sensitivities are 85, 79 and 57 nA/M with linear ranges of 0.6~30, 0.6~30 and 1~25 M and detection limits (S/N=3) of 0.2, 0.2 and 0.3 M for 3,4-dihydroxycinnaminic acid (3,4-DHCA), 3,4-dihydroxybenzoic acid (3,4-DHBA) and 3,4-dihydroxyphenylacetic acid (3,4-DHPAA), respectively. In case of OAP derivative, the obtained sensitivity is 237 nA/M with linear range of 0.2~15 M and detection limit of 70 nM for 2-amino-4-chlorophenol (2-A-4-CP). The response time (t90%) is about 2 seconds for each substrate and the long-term stability is around 40~50 days for catechol derivatives and 30 days for 2-A-4-CP with retaining 80% of initial activity. The optimal pHs of the sensor for these substrates are in the range of 4.5~5.0, which indicates that stability of the enzymatically oxidized product plays a very important role in substrate recycling. The different sensitivity of the sensor for each substrate can be explained by the electronic effect of the substituent on the enzymatically oxidized form.
Assembly of Laccase over Platinum Oxide Surface and Application as an Amperometric Biosensor
Quan, De,Kim, You-sung,Yoon, Kyung-Byung,Shin, Woon-sup Korean Chemical Society 2002 Bulletin of the Korean Chemical Society Vol.23 No.3
Laccase could be successfully assembled on an amine-derivatized platinum electrode by glutaraldehyde coupling. The enzyme layer formed on the surface does not communicate electron directly with the electrode, but the enzymatic activity of the surf ace could be followed by electrochemical detection of enzymatically oxidized products. The well-known laccase substrates, ABTS (2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)) and PPD (p-phenylenediamine) were used. ABTS can be detected down to 0.5 ${\mu}M$ with linear response up to 15 ${\mu}M$ and current sensitivity of 75 nA/ ${\mu}M.$ PPD showed better response with detection limit of 0.05 ${\mu}M$, linear response up to 20 ${\mu}M$, and current sensitivity of 340 nA/ ${\mu}M$ with the same electrode. The sensor responses fit well to the Michaelis-Menten equation and apparent $K_M$ values are 0.16 mM for ABTS and 0.055 mM for PPD, which show the enzymatic reaction is the rate-determining step. The laccase electrode we developed is very stable and more than 80% of initial activity was still maintained after 2 months of uses.