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Kinetics and Mechanism of the Anilinolysis of Dibutyl Chlorophosphate in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.663-669
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    • 2012
  • The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse ($k_H/k_D$ = 0.86-0.97) with the strongly basic anilines while primary normal ($k_H/k_D$ = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine ($R_1O$)($R_2O$)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the $k_H/k_D$ values with X.

Optimal Determination of Loss Rate Functions by Runoff Modelling (유출 모델에 의한 손실함수의 결정)

  • Lee, Ja Hyung;Whang, Man Ha
    • KSCE Journal of Civil and Environmental Engineering Research
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    • v.5 no.4
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    • pp.57-64
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    • 1985
  • An optimization model is presented that can be used in the determination of a loss rate function and conceptual runoff models using observed rainfall and runoff data. In order to estimate the lumped parameters and to control inputs of the model, the differential equations, linear for underground flow and non-linear for overland flow, are transformed into state equations. Parameters of a loss rate function and runoff model under stationary assumption can be determined by the following procedures: optimization technique, linear control and non-linear curve fitting theory using several multiperiod storms simultaneously or using individual multiperiod storms. An infiltration equation that includes rainful intensity is used to dtermine the effective rainfall for a given rain of varying. The optimization model is applied to storms in Hyong Song watershed of Wonju area. The results of the new model are compared with earlier one.

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Fabrication of Nanoscale Reusable Quartz Master for Nano Injection Molding Process (재사용 가능한 100nm급 패턴의 퀄츠 마스터 제작 및 퀄츠 마스터를 사용한 사출성형실험)

  • Choi Doo-Sun;Lee Joon-Hyoung;Yoo Yeong-Eun;Je Tae-Jin;Whang Kyung-Hyun;Seo Young Ho
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.29 no.2 s.233
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    • pp.228-231
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    • 2005
  • In this paper, we present reusable quartz master fabricated by electron-beam lithography and dry etching process of quartz, and results of injection molding based on the reusable quartz master for the manufacturing of nano-scale information media. Since patterned structures of photoresist can be easily damaged by separation (demolding) process of nickel stamper and master, a master with photoresist cannot be reused in stamper fabrication process. In this work, we have made it possible of the repeated use of master by directly patterning on quart in nickel stamper fabrication process. We have designed and fabricated four different specimens including 100nm, 140nm 200nm and 400nm pit patterns. In addition, both intaglio and embossed carving patterns are fabricated for each specimen. In the preliminary test of injection molding, we have fabricated polycarbonate patterns with varying mold temperature. We have experimentally verified the fabrication process of the reusable quart master and possibility of quartz master as direct stamper.

Kinetics and Mechanism of the Anilinolysis of (2R,4R,5S)-(+)-2-Chloro-3,4-dimethyl -5-phenyl-1,3,2-oxazaphospholidine 2-Sulfide in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.1037-1041
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    • 2012
  • The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

Kinetics and Mechanism of the Pyridinolysis of (2R,4R,5S)-(+)-2-Chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-Sulfide in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.1047-1051
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    • 2012
  • The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide with X-pyridines are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The free energy relationships for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ac. Unusual positive $\rho_X$ (= +4.73) and negative ${\beta}_X$ (= -0.75) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=39.3^{\circ}C$. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater magnitudes of selectivity parameters ($\rho_X$ = -6.15 and ${\beta}_X$ = 1.11) with the strongly basic pyridines compared to those ($\rho_X$ = 4.73 and ${\beta}_X$ = -0.75) with the weakly basic pyridines.

Significant Substituent Effects on Pyridinolysis of Aryl Ethyl Chlorophosphates in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1460-1464
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    • 2014
  • The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.

Genomic identification and spatial expression analysis of Rab-5C-like gene identified from rock bream(Oplegnathus fasciatus)

  • Mothishri, M.S.;Umasuthan, Navaneethaiyer;Thulasitha, William Shanthakumar;Whang, Ilson;Lee, Jehee
    • Journal of fish pathology
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    • v.28 no.2
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    • pp.99-107
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    • 2015
  • Despite its economic importance as an aquaculture species, the molecular and genetic information regarding physiologically important elements in rock bream (Oplegnathus fasciatus) is not completely understood. Rab proteins play a vital role in cellular mechanisms and immunity as one of the key regulators of membrane trafficking. In this investigation, a Rab gene, named as RbRab-5C-like, was identified from Oplegnathus fasciatus. RbRab-5C-like protein exhibited high homology with Rab proteins of other species and possessed signature characteristics of Rab proteins with four conserved cysteine residues. Phylogenetic analysis showed that RbRab-5C-like clustered with other fish counterparts. The RbRab-5C-like genomic sequence possesses six exons and five introns. Transcriptional analysis revealed that RbRab-5C-like was ubiquitously expressed in all examined tissues with the highest expression occurring in the liver. While the structural and homologic characteristics of RbRab-5C-like suggest a strong conservation of this element in different species, its mRNA distribution implies a wide range of biological significance in rock bream.

Kinetic Studies on the Structure-Reactivity of Aryl Dithiomethylacetates

  • Oh, Hyuck-Keun;Park, Jie-Eun;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.25 no.7
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    • pp.1041-1045
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    • 2004
  • Kinetic studies of the pyridinolysis $(XC_5H_4N)$ of aryl dithiomethylacetates $(CH_3CH_2C(=S)SC_6H_4Z,\;1)$ are carried out in acetonitrile at $60.0^{\circ}C$. A biphasic Bronsted plot is obtained with a change in slope from a large $({\beta}X\;{\cong}\;0.8)$ to a small $({\beta}X\;{\cong}\;0.2)$ value at $pK_a^{\circ}$ = 5.2, which is attributed to a change in the rate limiting step from breakdown to formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in reaction path as the basicity of the pyridine nucleophile increases. This mechanism is supported by the change of the cross-interaction constant ${\rho}xz$ from a large positive ( ${\rho}xz$ = +1.36) for the weakly basic pyridines to a small negative ( ${\rho}_xz$ = -0.22) value for the strongly basic pyridines. The magnitudes of ${\rho}z$ and activation parameters are also consistent with the proposed mechanism.

Pupil Data Measurement and Social Emotion Inference Technology by using Smart Glasses (스마트 글래스를 활용한 동공 데이터 수집과 사회감성 추정 기술)

  • Lee, Dong Won;Mun, Sungchul;Park, Sangin;Kim, Hwan-jin;Whang, Mincheol
    • Proceedings of the Korean Society of Broadcast Engineers Conference
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    • 2019.11a
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    • pp.1-4
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    • 2019
  • 본 연구에서는 적외선 카메라 기반의 비접촉식 측정 방법을 이용하여 동공 반응 데이터를 수집하여 공감의 사회감성을 객관적이고 정량적으로 추정하는데 그 목적이 있다. 실험에는 10명(남 6명, 여 4명, M ± SD = 24.17 ± 2.16세)의 피험자가 참여하였다. 30초의 참조 데이터 측정 후, 공감 유무에 따라 과제는 얼굴 표정 모방 과제와 얼굴 표정 자발적 표현 과제로 구분되어 두 사람은 표정으로 상호작용하였고, 2번씩 반복 진행하며 적외선 카메라를 통해 동공을 촬영하였다. 이진화 및 원형 윤곽선 검출법의 영상처리를 활용하여 동공 데이터를 수집하였고, 이동 평균 기법을 활용해 눈깜빡임 노이즈를 제거하고 동공 크기 개인차로 데이터 표준화를 진행하였다. 공감 유무에 따른 동공 크기 데이터는 정규성 검증 및 독립표본 t검정을 통해 통계적 유의성을 확인하였다. 분석결과, 공감하는 경우(M ± SD = 0.508 ± 1.278)와 공감하지 않은 경우(M ± SD = 1.681 ± 0.968) 동공 크기가 통계적으로 유의미한 차이를 보였다(t(18) = -2.313, p = 0.033). 판별분석을 통해 동공 크기에 따른 공감의 유무를 추정하는 규칙을 정의하였다. 본 연구에서 제안한 동공 크기 데이터를 이용한 공감의 사회감성 추정 기술은 비접촉식 카메라 기반의 기술로 스마트 글래스와 접목되어 다양한 분야에 활용도가 높을 것으로 기대된다.

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Influence upon Machining Accuracy of Micro-Pattern Roll Mold Processed by Temperature Variation (미세 패턴 롤 금형 가공시스템의 온도변화가 가공정밀도에 미치는 영향 연구)

  • Je, T.J.;Park, S.C.;Lee, K.W.;Noh, J.S.;Choi, D.S.;Whang, K.H.
    • Transactions of Materials Processing
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    • v.18 no.2
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    • pp.107-111
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    • 2009
  • Temperature variation happens in micro prism roll mold processing system during machining the prism pattern roll mold using manufacturing optical films of LCD (liquid crystal display). This temperature variation induces pitch errors of the prism patterns. The temperature variation displaces the positions of the diamond cutting tool on the roll which was coated by the copper. In order to prevent the pitch errors, the stabilizing the temperature of machining environment is needed. Therefore, the researching on the temperature variation of the ultra-precision roll mold processing system on the machining of micro prism rot 1 mold is needed. In this paper, the temperature variation of micro prism roll mold processing system is researched, the influence is analyzed, and the study for reducing the pitch errors carried out.