• Title/Summary/Keyword: Biphasic

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Effects of Sodium Fluoride on the Water Transport in Leaves of Barley and Rice under Salt Stress in the Light

  • Hwang, Hong-Jin;Oh, Kwang-Hoon;Park, Phun-Bum;Lee, Choon-Hwan
    • Journal of Photoscience
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    • v.11 no.1
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    • pp.25-28
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    • 2004
  • The kinetics of the loss of leaf fresh weight during incubation of barley and rice leaves in 9% or 15% NaCl solutions were biphasic, indicating the existence of a controlling mechanism for water transport. The first rapid phases reached their plateaus within 1 and 2 h in the case of rice and barley leaves, respectively. When barley leaves were fed with sodium fluoride, an inhibitor of phosphatase inhibitor, through their epicotyls for 3 h in darkness, prior to the treatment of NaCl, the biphasic pattern shown during NaCl treatment was disappeared resulting in linear decreases in the relative fresh weights. The results suggest that NaF accelerates salt-induced water efflux from plant cells, possibly by inhibiting the protection mechanism that may act in NaF-untreated leaves. The linear water loss can be explained in terms of phosphorylation of aquaporin by blocking its dephosphorylation in the presence of the phosphatase inhibitor to keep aquaporin in a phosphorylated form. However, the effect of NaF shown in barley leaves were not observed in rice. These results suggest that the regulation of water transport depends on plant species, and the mechanism for the controlling water transport in rice is different from that of barley.

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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.

Kinetics and Mechanism of the Pyridinolysis of Diphenyl Phosphinic and Thiophosphinic Chlorides in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Dey, Nilay Kumar;Guha, Arun Kanti;Kim, Chan-Kyung;Lee, Bon-Su;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.28 no.10
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    • pp.1797-1802
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    • 2007
  • The kinetics and mechanism of the nucleophilic substitution reactions of diphenyl phosphinic (1) and thiophosphinic (2) chlorides with substituted X-pyridines are investigated kinetically in acetonitrile at 35.0 and 55.0 oC, respectively. A concerted mechanism with backside nucleophilic attack is proposed for the pyridinolysis of 1, on the basis of the linear Bronsted plot with the βX value of 0.68. In the case of the pyridinolysis of 2, the Hammett and Bronsted plots are biphasic concave upwards with the break point at 3- phenyl pyridine. These results indicate a change in mechanism from a concerted SN2(P) process with direct backside nucleophilic attack for less basic nucleophiles (X = 3-CN-3-Ph) to a stepwise process with frontside attack for more basic nucleophiles (X = 4-MeO-3-Ph). Apparent secondary inverse kinetic isotope effects with deuterated pyridine (C5D5N), kH/kD < 1, are observed for the pyridinolysis of 1 and 2.

Kinetics and Mechanism of the Pyridinolysis of Aryl Phenyl Isothiocyanophosphate in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai-Whang;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.24 no.8
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    • pp.1135-1140
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    • 2003
  • The kinetics and mechanism of the pyridinolysis $(XC_5H_4N)$ of Y-aryl phenyl isothiocyanophosphates (1;$(YC_6H_4O)\;(C_6H_5O)$P(=O)NCS) are investigated in acetonitrile at 55.0 ℃. The Hammett plots for substituent (Y) variations in the substrate (log k₂ vs σY) exhibit a convex upward biphasic type with breaks at Y = H. For electron-donating Y groups the Hammett coefficients, ρY, are positive and cross-interaction constant ρXY is negative, while those for electron-withdrawing Y groups ρY values are negative with a positive ρXY. These results are interpreted to indicate mechanistic change at the breakpoint (σY = 0) from a concerted to a stepwise mechanism with rate-limiting expulsion of the $^-NCS$ group from a trigonal bipyramidal pentacoordinated (TBP-5C) intermediate. Biphasic plots of log k₂ vs σX or $pK_a$(X) with steeper slopes for the more basic nucleophiles are obtained suggesting an equatorial nucleophilic attack in contrast to an apical attack for the less basic nucleophiles with smaller magnitude of ρX or βx.

A Study on the Change of Body Temperature according to Menstrual Cycle (월경주기에 따른 체온변화 관찰)

  • Park, Dae-Soon;Cho, Jung-Hoon;Jang, Jun-Bock;Lee, Kyung-Sub
    • Journal of Oriental Medical Thermology
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    • v.2 no.1
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    • pp.6-10
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    • 2003
  • Purpose : Man is a homoiothermal animal. But by various causes, body temperature can be changed to $1^{\circ}C$. Basal temperature is a very useful method in many fields of OB&GY area. So we observed the change of body temperature according to menstrual cycle. Materials and Methods : We observed 3 female who have very regular 30 days menstrual cycle. The Observation started before the onset of menstruation and body temperature was checked in the same time (11:00 am) of a day. To evaluate the change of body temperature, we examined three points of body. And to observe the body temperature we used the D.I.T.I(Dorex, Inc., USA). Results : On this study we couldn't find the typical biphasic change of body temperature but most of the materials showed the elevation of body temperature on the 14th day. Between the examined three points, the lowest point was showed more typical biphasic change of body temperature.

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Dual Substituent Effects on Anilinolysis of Bis(aryl) Chlorothiophosphates

  • Barai, Hasi Rani;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3597-3601
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    • 2013
  • The reactions of bis(Y-aryl) chlorothiophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett plots for substituent Y variations in the substrates show biphasic concave upwards with a break point at Y = H. The cross-interaction constants (${\rho}_{XY}$) are positive for both electron-donating and electron-withdrawing Y substituents. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1. The effect of the cross-interaction between Y and Y on the rate changes from negative role with electron-donating Y substituents to positive role with electron-withdrawing Y substituents, resulting in biphasic concave upward free energy correlation with Y. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate involving a predominant frontside attack hydrogen bonded, four-center-type transition state is proposed based on the positive sign of ${\rho}_{XY}$ and primary normal deuterium kinetic isotope effects.