• Title/Summary/Keyword: $S_N1$ mechanism

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Studies of Solvolyses of Di-n-butyl Phosphorochloridate by Extended Grunwald-Winstein Equation (확장된 Grunwald-Winstein 식에 의한 Di-n-butyl Phosphorochloridate의 가용매 분해반응 연구)

  • Kang, Min Sung;Kim, Cheul Ju;Kang, Suk Jin;Koh, Han Joong
    • Journal of the Korean Chemical Society
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    • v.59 no.5
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    • pp.373-378
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    • 2015
  • The solvolysis rate constants of di-n-butyl phosphorochloridate ((CH3CH2CH2CH2O)2POCI, 1) in 28 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivities values of 1.40 and 0.42 for l and m, respectively. These l and m values can be considered to support an SN2 reaction pathway. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH (8.0 to 15.9 kcal·mol−1 ) values and large negative ΔS (−25.8 to −53.1 cal·mol−1 ·K−1 ) values, the Kivinen’s n values (0.9~1.7), and the solvent kinetic isotope effect (1.62).

Studies on the Mechanism of 'Kresek' Induction of Rice Plant Caused by Xanthomonas oryzae (Uyeda & Ishiyama) Dowson (벼 위조형 흰빛잎마름병의 발병기작에 관한 연구)

  • Yu Y. H.;Cho Y. S.
    • Korean journal of applied entomology
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    • v.17 no.1 s.34
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    • pp.15-22
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    • 1978
  • The study has been carried out to investigate the mechanism of 'Kresek' induction caused by Xanthomonas oryzae (Uyeda & Ishiyama) Dowson. The results are summarized as follows: 1. K-isolate could always induce 'Kresek' symptom on susceptible varieties when the pathogenic bacteria were introduced either way through the leaves or roots, while N-isolate could not induce. 2. Milyang 23 which showed 'Kresek' symptom had significantly smaller diameter of vessel elements than those of other two varieties examined. 3. The bacterial number of It-isolates in the extract of Milyang 23 was higher than N-isolates but there was no difference in bacterial number between K-and N-isolates when they were grown in the extract of Tongil. 4. N and K-isolates reached to death phase after 3 days and 9 days, respectibly, when they were grown in the extract of Milyang 23. Both isolates, however, reached to death phase at the same time after 3 days of incubation in the extract of Tonsil. 5. Heavy precipitation was observed in the extract of Milyang 23 at PH 3.0-4.0 range, while only traceable precipitation could be observed in the extract of Tongil at the same pH range under room temperature.

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A New Chiral Stationary Phase Derived from Cyclohexylamide Derivative of (S)-Naproxen for the Liquid Chromatographic Resolution of Enantiomers

  • 현명호;이정배
    • Bulletin of the Korean Chemical Society
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    • v.16 no.10
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    • pp.977-980
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    • 1995
  • A new chiral stationary phase (CSP 2) derived from cyclohexylamide of (S)-naproxen has been prepared. CSP 2 has shown greater enantioselectivities for the two enantiomers of N-(3,5-dinitrobenzoyl)-a-amino esters and amides than the CSP derived from 3,5-dimethylanilide of (S)-naproxen (CSP 1) as expected from the reciprocity conception of chiral recognition. However, CSP 2 has been found to be worse than CSP 1 in resolving N-(3,5-dinitrobenzoyl)-a-arylalkylamines, supporting the previously proposed chiral recognition mechanism which utilizes the 3,5-dimethylphenyl group of CSP 1 as an alternative π-basic interaction site. In addition, CSP 2 has been found to be reasonably good in resolving the two enantiomers of a variety of other π-acidic racemates.

Preferred orientation of TiN thin films produced by Ion Beam Assist Deposition

  • Won, J.Y.;Kim, J.H.;Kang, H.J.;Baeg, C.H.;Park, S.Y.;Hong, J.W.;Wey, M.Y.
    • Journal of the Korean Vacuum Society
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    • v.6 no.S1
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    • pp.154-159
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    • 1997
  • The crystal structure properties of TiN thin films deposited on SKD61 steel and Si(100) substrates by Ion Beam Assisted Deposition have been studied to clarify the thin film growth mechanism by using XRD, RBS, SEM, and AFM. The preferred orientation of TiN thin films changes from (111) to (100) as increasing the assisted energy. This tendency is independent of the substrate structure. The TiN thin film grow with (100) direction having surface free energy minimum as the assisted energy increases.

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Modulation of the Regioselectivity of a Thermotoga neapolitana $\beta$-Glucosidase by Site-Directed Mutagenesis

  • Choi, Ki-Won;Park, Kyung-Min;Jun, So-Young;Park, Cheon-Seok;Park, Kwan-Hwa;Cha, Jae-Ho
    • Journal of Microbiology and Biotechnology
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    • v.18 no.5
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    • pp.901-907
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    • 2008
  • Thermotoga neapolitana $\beta$-glucosidase (BglA) was subjected to site-directed mutagenesis in an effort to increase its ability to synthesize arbutin derivatives by transglycosylation. The transglycosylation reaction of the wild-type enzyme displays major ${\beta}(1,6)$ and minor ${\beta}(1,3)$ or ${\beta}(1,4)$ regioselectivity. The three mutants, N291T, F412S, and N291T/F412S, increased the ratio of transglycosylation/hydrolysis compared with the wild-type enzyme when pNPG and arbutin were used as a substrate and an acceptor, respectively. N291T and N219T/F412S had transglycosylation/hydrolysis ratios about 3- and 8-fold higher, respectively, than that of the wild-type enzyme. This is due to the decreased hydrolytic activity of the mutant rather than increased transglycosylation activity. Interestingly, N291T showed altered regioselectivity, as well as increased transglycosylation products. TLC analysis of the transglycosylation products indicated that N291T retained its ${\beta}(1,3)$ regioselectivity, but lost its ${\beta}(1,4)$ and ${\beta}(1,6)$ regioselectivity. The altered regioselectivity of N291T using two other acceptors, esculin and salicin, was also confirmed by TLC. The major transglycosylation products of the wild type and N291T mutant were clearly different. This result suggests that Asn-291 is highly involved in the catalytic mechanism by controlling the transglycosylation reaction.

Physiological and proteomic analysis of young rice leaves grown under nitrogen-starvation conditions

  • Kim, Sang-Gon;Wang, Yiming;Wu, Jingni;Kang, Kyu-Young;Kim, Sun-Tae
    • Plant Biotechnology Reports
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    • v.5 no.4
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    • pp.309-315
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    • 2011
  • Rice grown in anaerobic waterlogged soil accumulates ammonium as a major source of nitrogen (N). We have compared the physiological symptoms of rice seedlings subjected to N-starvation stress with those receiving sufficient N, based on measurements of shoot/root length and weight and an analysis of protein expression patterns. N starvation marginally increased root growth but notably decreased shoot biomass. N uptake was reduced by >50% in the roots and shoots of N-starved seedlings. To better understand the mechanism of N starvation in rice, we performed a comparative proteome analysis of proteins isolated from rice leaves. Twenty-five differentially expressed proteins were analyzed by matrixassisted laser desorption/ionization time-of-flight (TOF) mass spectrometry and electron spray ionization quadrupole TOF. Functional analysis of the N-starvation response proteins suggested their involvement in protein synthesis and fate, metabolism, and defense. These results indicate that these proteins may play important roles in regulating the plant's complex adaptation responses for N use during N starvation. The proteins may be useful for further characterization of protein function in plant N nutrition.

Solvolysis of 3-Chloro-1,2-benzisothiazole-1,1-dioxide (pseudosaccharin chloride (3-Chloro-1,2-benzisothiazole-1,1-dioxide (pseudosaccharin chloride)의 가용매 분해반응)

  • In-Sun Koo;Jeong-Ja Kim;Yong-Jin Yoon;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.296-300
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    • 1986
  • The pseudo-first order rate constants have been obtained for the solvolysis of pseudo-saccharinechloride in MeOH-$H_2O$, EtOH-$H_2O$, MeOH-MeCN and MeOH-$(Me)_2$CO solvents mixtures at various temperatures. Values of n and m in the Kivinen and Grunwald-Winstein plots, respectively, have been determined and the Taft's solvatochromic parameters were obtained; based on these solvent effect parameters as well as on the activation parameters it was concluded that reaction proceeds via an $S_N2$ mechanism.

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Impedance Spectroscopy Studies on Corrosion Inhibition Behavior of Synthesized N,N’-bis(2,4-dihydroxyhydroxybenzaldehyde)-1,3-Propandiimine for API-5L-X65 Steel in HCl Solution

  • Danaee, I.;Bahramipanah, N.;Moradi, S.;Nikmanesh, S.
    • Journal of Electrochemical Science and Technology
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    • v.7 no.2
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    • pp.153-160
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    • 2016
  • The inhibition ability of N,N-bis(2,4-dihydroxyhydroxybenzaldehyde)-1,3-Propandiimine (DHBP) as a schiff base against the corrosion of API-5L-X65 steel in 1 M HCl solution was evaluated by electrochemical impedance spectroscopy, potentiodynamic polarization and scanning electron microscopy. Electrochemical impedance studies indicated that DHBP inhibited corrosion by blocking the active corrosion sites. The inhibition efficiency increased with increasing inhibitor concentrations. EIS data was analysed to equivalent circuit model and showed that the charge transfer resistance of steel increased with increasing inhibitor concentration whilst the double layer capacitance decreased. The adsorption of this compound obeyed the Langmuir adsorption isotherm. Gibbs free energy of adsorption was calculated and indicated that adsorption occurred through physical and spontaneous process. The corrosion inhibition mechanism was studied by potential of zero charge. Polarization studies indicated that DHBP retards both the cathodic and anodic reactions through adsorption on steel surface. Scanning electron microscopy was used to study the steel surface with and without inhibitor.

Testosterone-mediated Neuroprotection in NO Induced Cell Death of Motor Neuron Cells Expressing Wild Type or Mutant Cu/Zn Superoxide Dismutase (Cu/Zn Superoxide Dismutase 유전자 발현 운동신경세포주에서 NO 독성에 대한 Testosterone의 보호효과)

  • Kim, Nam Hee;Kim, Hyun Jung;Kim, Manho;Park, Kyung Seok;Lee, Kwang-Woo
    • Annals of Clinical Neurophysiology
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    • v.8 no.1
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    • pp.63-70
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    • 2006
  • Background: Testosterone is reported to have neuroprotective effect in various neurological diseases. Recently, the mechanism involved in nitric oxide (NO)-mediated motor neuron death is under extensive investigation. The Cu/Zn-superoxide dismutase (SOD1) mutations has been implicated in selective motor neuron death of amyotrophic lateral sclerosis (ALS) and it is said to play an important role in NO-mediated motor neuron death. However, neuroprotective effect of testosterone on motor neuron exposed to NO has rarely been studied. Methods: Motor neuron-neuroblastoma hybrid cells expressing wild-type or mutant (G93A or A4V) SOD gene were treated with $200{\mu}M$ S-nitrosoglutathione. After 24 hr, cell viability was measured by MTT assay. To see the neuroprotective effect of testosterone, pretreatment with 1 nM testosterone was done 1 hr before S-nitroglutathione treatment. To study the mechanism of protective effect, $20{\mu}M$ flutamide (androgen receptor antagonist) was also pretreated with testosterone 1 hr before S-nitroglutathione treatment. Results: S-nitrosoglutathione showed significant neurotoxic effect in all three cell lines. Percentage of cell death was somewhat different in each cell line. 1 nM testosterone showed neuroprotective effect in G93A and wild-type cell line. In A4V cell line, testosterone did not showed neuroprotective effect. The neuroprotective effect of testosterone was reversed by $20{\mu}M$ flutamide. Conclusions: These results indicate that testosterone induces neuroprotection in NO-mediated motor neuron death directly through the androgen receptor. This neuroprotective effect of testosterone varies according to the types of SOD1 gene mutation. These data suggest that testosterone may be of therapeutic value against ALS.

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A Non-coherent IR-UWB RF Transceiver for WBAN Applications in 0.18㎛ CMOS (0.18㎛ CMOS 공정을 이용한 WBAN용 비동기식 IR-UWB RF 송수신기)

  • Park, Myung Chul;Chang, Won Il;Ha, Jong Ok;Eo, Yun Seong
    • Journal of the Institute of Electronics and Information Engineers
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    • v.53 no.2
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    • pp.36-44
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    • 2016
  • In this paper, an Impulse Radio-Ultra Wide band RF Transceiver for WBAN applications is implemented in $0.18{\mu}m$ CMOS technology. The designed RF transceiver support 3-5GHz UWB low band and employs OOK(On-Off Keying) modulation. The receiver employs non-coherent energy detection architecture to reduce complexity and power consumption. For the rejection of the undesired interferers and improvement of the receiver sensitivity, RF active notch filter is integrated. The VCO based transmitter employs the switch mechanism. As adapt the switch mechanism, power consumption and VCO leakage can be reduced. Also, the spectrum mask is always same at each center frequency. The measured sensitivity of the receiver is -84.1 dBm at 3.5 GHz with 1.579 Mbps. The power consumption of the transmitter and receiver are 0.3nJ/bit and 41 mW respectively.