• 제목/요약/키워드: Upward Reaction

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A LASER HOLOGRAPHIC STUDY ON THE INITIAL REACTION OF MAXILLOFACIAL COMPLEX TO MAXILLARY PROTRACTION (상악 전방견인시 악안면골의 초기반응에 관한 Laser Holography연구)

  • Kang, Hung Sok
    • The korean journal of orthodontics
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    • v.18 no.2
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    • pp.367-385
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    • 1988
  • In case of skeletal Class III malocclusion with underdeveloped maxilla, the extraoral orthopedic force for the stimulation of maxillary growth or anterior reposition of the maxilla has been used clinically for the improvement of facial skeletal relationship. The purpose of this investigation was to examine the initial reaction of maxillofacial complex to the maxillary protraction by using extraoral orthopedic force. The dried human skull was used and this investigation was done by means of double exposure holographic interferometry. The protraction forces placed on the canine or the first molar were parallel, $10^{\circ}$ downward, $20^{\circ}$ downward to the occlusal plane. Fringe pattern of each protraction condition was compared and analized. The results were as follows: 1. Each maxillofacial bone displaced saparately. 2. More displacement was shown at the area of the teeth and the alveolar bone. 3. A counterclockwise rotation of the maxilla wa decreased by downward protraction and especially 20 degree downward protraction from the canine showed least rotation. 4. On the zygomatic arch, outward bend was observed and this effect was decreased by downward protraction. 5. On the zygomatic bone, the counter clockwise rotation was increased by the downward protraction. 6. When maxillary expansion was applied at the same time, outward and upward displacement with counterclockwise rotation was observed on the maxilla. 7. The lateral pterygoid plate of sphenoid bone was affected by maxillary protraction.

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A Kinetic Study on Ethylaminolysis of Phenyl Y-Substituted-Phenyl Carbonates: Effect of Leaving-Group Substituents on Reactivity and Reaction Mechanism

  • Song, Yoon-Ju;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.6
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    • pp.1722-1726
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    • 2013
  • A kinetic study on nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5j) with ethylamine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of $k_{obsd}$ vs. [amine] are linear for the reactions of substrates possessing a strong electron-withdrawing group (EWG) but curve upward for those of substrates bearing a weak EWG, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. The reactions have been concluded to proceed through a stepwise mechanism with one or two intermediates (a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$) depending on the nature of the substituent Y. Analysis of Bronsted-type plots and dissection of $k_{obsd}$ into microscopic rate constants have revealed that the reactions of substrates possessing a strong EWG (e.g., 5a-5f) proceed through $T^{\pm}$ with its formation being the rate-determining step, while those of substrates bearing a weak EWG (e.g., 5g-5j) proceed through $T^{\pm}$ and $T^-$.

Disinfection of harmful organism for ballast water using electrolytic treatment system (전해처리를 통한 밸러스트수의 유해생물 살균처리)

  • 박상호;김인수
    • Proceedings of the Korean Institute of Navigation and Port Research Conference
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    • 2004.04a
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    • pp.227-232
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    • 2004
  • Ballast water from ship harmful microorganism sterilized use of electrolytic sterilization system. The experimental methods were use of peristaltic flow pump upward on electrode pole. Due to reaction time, HRT were unlike microorganism on flow rate. In electrolysis, dioxide iridium coated titanium(Ti/IrO$_2$) and stainless steel plate were used for anode and cathode respectively. Current density controls make use of D.C Power supply on 250V 100Amper. Experimental use of current density between 0.1 and 0.5A was able to disinfect microorganism at 5 seconds by the reaction time. This study shows that the electrolyzed water has a potential for the sterilization of ballast water.

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Kinetics and Mechanism of the Anilinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3355-3360
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    • 2011
  • The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $-15.0^{\circ}C$. The studied substrate of 1,2-phenylene phosphorochloridate is cyclic five-membered ring of phosphorus ester, and the anilinolysis rate of 1 is much faster than its acyclic analogue (4: ethyl phenyl chlorophosphate) because of extremely small magnitude of the entropy of activation of 1 compared to 4. The Hammett and Bronsted plots exhibit biphasic concave upwards for substituent X variations in the nucleophiles with a break point at X = 3-Me. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) change from secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines to primary normal ($k_H/k_D$ > 1) with the weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the transition state (TS) variation from a predominant backside attack to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. The primary normal DKIEs are substantiated by a hydrogen bonded, four-center-type TS.

Numerical Study on High Temperature CO-Shift Reactor in IGFC (고온수소 전환 반응기에 관한 수치해석적 연구)

  • SEO, DONG-KYUN;LEE, JIN-HYANG;CHI, JUN-HWA;HONG, JIN-PYO;OH, SUK-IN
    • Transactions of the Korean hydrogen and new energy society
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    • v.29 no.4
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    • pp.324-330
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    • 2018
  • In this study a numerical study was conducted to show flow, temperature and gas distributions in a high temperature CO shift reactor which was designed specially for energy saving and then evaluated with the related experiment. Mole fractions of syngas at the end of the catalyst bed were predicted with various assumed pre-exponential factors, were compared with the corresponding experimental results and $10^8$ was finally selected as the value. With the selection, a base case was examined. It was calculated that the inlet duct attached asymmetrically to the CO shift reactor affects on the distribution of the upward momentum (+z directional). In addition, CO conversion ratio is achieved up to 90% in the catalyst bed and especially it reached up to 70% at the initial part of catalyst bed.

Kinetics and Mechanism of the Pyridinolysis of O,O-Dimethyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2339-2344
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    • 2011
  • Kinetic studies for the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-pyridines have been carried out in dimethyl sulfoxide at 85.0 $^{\circ}C$. The Hammett and Br$\"{o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H, while those for substituent Z variations in the leaving groups are linear. The negative sign of the cross-interaction constant (${\rho}_{XZ}$) implies that the reaction proceeds through a concerted mechanism for both the strongly and weakly basic pyridines. The magnitude of ${\rho}_{XZ}$ (= -0.35) for the strongly basic pyridines is greater than that (${\rho}_{XZ}$ = -0.15) for the weakly basic pyridines, indicating a change of the nucleophilic attacking direction from frontside for the strongly basic pyridines to backside for the weakly basic pyridines. The early transition state is proposed on the basis of the absence of positive deviations from both the Hammett and Br$\"{o}$nsted plots for the strong ${\pi}$-acceptor, X = 4-Ac, and small values of ${\rho}_{XZ}$ and ${\beta}_X$.

Kinetic Study on Aminolysis of 4-Nitrophenyl Isonicotinate in Acetonitrile: Effect of Amine Basicity on Reactivity and Reaction Mechanism

  • Shin, Minah;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.2130-2134
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    • 2014
  • A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate (7) with a series of cyclic secondary amines in MeCN. The plots of $k_{obsd}$ vs. [amine] curve upward for the reactions with weakly basic amines (e.g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e.g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e.g., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i.e., the deprotonation process to yield $T^-$ from $T^{\pm}$ by a second amine molecule) is absent. The Br${\o}$nsted-type plots for $Kk_2$ and $Kk_3$ (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with ${\beta}_{nuc}$ = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail.

Characteristics of Vertical Acceleration at Center of Mass of the Body in Normal Gait (정상보행시 체중심의 수직 가속도 특성)

  • Yi, Jin-Bock;Kang, Sung-Jae;Kim, Young-Ho
    • Physical Therapy Korea
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    • v.9 no.3
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    • pp.39-46
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    • 2002
  • In this study, vertical acceleration of center of mass was observed along normal gait phases in 9 healthy male volunteers (aged $25.7{\pm}2.18$). The developed wireless accelerometric device was attached on the intervertebral space between L3 and L4 using a semi-elastic waist belt. A three-dimensional motion analysis system, synchronized with the accelerometry, was used for detecting gait phases. There was no significant correlation between the body weight and the acceleration. The first peak curve covered loading response phase. The second downward peak point was matched accurately with the opposite toe-off. In mid-stance and terminal stance, the acceleration curve highly resembled the vertical ground reaction force curve. There was no significant difference in timing between the final upward peak point and the initial contact. Therefore, the developed accelerometry system would be helpful in determining determine temporal gait pattems in patients with gait disorders.

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The Effect of Alkali Metal Ions on Reactions of 8-(5-Nitroquinolyl) 3-Furoate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Eum, Ik Hwan;Lee, Seong Eun;Min, Ji Suk
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.673-677
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    • 2001
  • Pseudo-first-order rate constants have been measured spectrophotometrically for the reactions of 8-(5-nitroquinolyl) 3-furoate with alkali metal ethoxides in anhydrous ethanol. The plot of kobs vs the concentration of alkali metal ethox ides is linear for the reactions performed in the presence of a complexing agent, 18-crown-6 ether, but exhibits upward curvatures for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions in this study behave as catalysts. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M + ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M + /kEtO-) was found to be 1.7, 3.4 and 2.5 for the reaction of 8-(5-nitroquinolyl) 3-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, 1.8, 3.7 and 2.4 for that of 8-(5-nitroquinolyl) benzoate, and 2.0, 9.8 and 9.3 for that of 8-(5-nitroquinolyl) 2-furoate with EtO- Li+ , EtO- Na+ and EtO- K+ , respectively. A 5-membered chelation at the leaving group is suggested to be responsible for the catalytic effect shown by alkali metal ions.

Aminolysis of Benzyl 4-Pyridyl Carbonate in Acetonitrile: Effect of Modification of Leaving Group from 2-Pyridyloxide to 4-Pyridyloxide on Reactivity and Reaction Mechanism

  • Bae, Ae-Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2719-2723
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    • 2012
  • A kinetic study is reported for nucleophilic substitution reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in MeCN. The plot of pseudo-first-order rate constant ($k_{obsd}$) vs. [amine] curves upward, which is typical for reactions reported previously to proceed through a stepwise mechanism with two intermediates (i.e., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). Dissection of $k_{obsd}$ into the second- and third-order rate constants (i.e., $Kk_2$ and $Kk_3$, respectively) reveals that $Kk_3$ is significantly larger than $Kk_2$, indicating that the reactions proceed mainly through the deprotonation pathway (i.e., the $k_3$ process) in a high [amine] region. This contrasts to the recent report that the corresponding aminolysis of benzyl 2-pyridyl carbonate 5 proceeds through a forced concerted mechanism. An intramolecular H-bonding interaction was suggested to force the reactions of 5 to proceed through a concerted mechanism, since it could accelerate the rate of leaving-group expulsion (i.e., an increase in $k_2$). However, such H-bonding interaction, which could increase $k_2$, is structurally impossible for the reactions of 6. Thus, presence or absence of an intramolecular H-bonding interaction has been suggested to be responsible for the contrasting reaction mechanisms (i.e., a forced concerted mechanism for the reaction of 5 vs. a stepwise mechanism with $T^{\pm}$ and $T^-$ as intermediates for that of 6).