• 제목/요약/키워드: reactive intermediate

검색결과 109건 처리시간 0.028초

Aminolysis of 2,4-Dinitrophenyl and 3,4-Dinitrophenyl 2-Thiophenecarboxylates: Effect of ortho-Nitro Group on Reactivity and Mechanism

  • Seo, Jin-A;Chun, Sun-Mee;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제29권8호
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    • pp.1459-1463
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    • 2008
  • Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

직류 반응성 sputtering법으로 제막된 ZnO:Al 박막의 물성에 미치는 증착조건 및 타겟의 영향 (Effect of sputtering parameters and targets on properties of ZnO:Al thin films prepared by reactive DC magnetron sputtering)

  • 유병석;오근호
    • 한국결정성장학회지
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    • 제8권4호
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    • pp.592-598
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    • 1998
  • ZnO($Al_2O_3\;2%$ 2% doped) 산화물 타겟과 금속 Zn(Al 2% doped) 타겟을 사용하여 반응성 직류 마그네트론 스퍼터링법으로 산소 가스 및 인가 전력을 조절하면서 AZO(Aluminum doped Zine Oxide) 막을 증착하였다. 비저항과 평균 투과율을 고려할 때 최적의 투명전도성을 보이는 조건은 산화물 타겟의 경우 산소가스의 비가 $0.5{\times}10^{-2}~1.0{\times}10^{-2}$범위이며, 금속 타겟의 경우 인가전력 0.6kW에서는 0.215~0.227, 1.0kW에서는 0.305~0.315이었다. 각 최적조건에서 제막된 AZO 막의 비저항은 $1.2~1.4{\times}10^{-3} {\Omega}{\cdot}cm$cm으로 타겟에 의한 차이는 없었다.

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육체운동에 의해 유발되는 화학물질에 대한 반응성의 변화 (Alteration in Response to Chemicals Induced by Physical Exercise)

  • 김영철
    • Toxicological Research
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    • 제18권3호
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    • pp.215-226
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    • 2002
  • Acute or repeated physical exercise affects a large number of physiological parameters including hemodynamics, respiration, pH, temperature, gastrointestinal function and biotransformation, which determine the pharmacokinetics of drugs and chemicals. The rate and the amount of a chemical reaching the active site are altered by physical exercise, which results in significant changes in pharmacolosical/toxicological activity of the chemical. This aspect of physical exercise has vast implication in therapeutics and in safety evaluation, particularly for chemicals that have a low margin of safety. However there appears to be a wide inter- and intraindividual variation in the effects of physical exercise depend-ing on the duration, intensity and type of exercise, and also on the properties of each chemical. It is suggested that more studies need to be done to determine which factor(s) plays a major role in the disposition of chemicals in human/animals performing physical exercise. Certain chemicals induce severe toxicity due to metabolic conversion to reactive intermediate metabolites. it is suggested that repeated exercise may enhance the free radical scavenging system by increasing the activity of antioxidant enzymes. This area of research remain to be explored to elucidate the interaction of exercise and chemical on the antioxidant system.

Kinetics and Mechanism for the Reaction of 4-Nitrophenyl 2-Thiophenecarboxylate with Secondary Alicyclic Amines

  • Um, Ik-Hwan;Lee, Eun-Ju;Lee, Jong-Pal
    • Bulletin of the Korean Chemical Society
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    • 제23권3호
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    • pp.381-384
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    • 2002
  • Second-order-rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a) with a series of secondary alicyclic amines in H2O containing 20 mole % DMSO at 25.0 $^{\circ}C$ . The ester 1a is less reactive than 4-nitrophenyl 2-furoate (1b) but more reactive than 4-nitrophenyl benzoate (1c) except towards piperazinium ion. The Brønsted-type plots for the aminolyses of 1a, 1b and 1c are linear with a $\beta$nuc value of 0.92, 0.84 and 0.85, respectively, indicating that the replacement of the CH=CH group by a sulfur or an oxygen atom in the benzoyl moiety of 1c does not cause any mechanism change. The reaction of piperidine with a series of substituted phenyl 2-thiophenecarboxylates gives a linear Hammett plot with a large $\rho^-$ value ($\rho^-$ = 3.11) when $\sigma^- $ constants are used. The linear Brønsted and Hammett plots with large $\beta$nuc and $\rho^-$ values suggest that the aminolysis of 1a proceeds via rate-determining break-down of the addition intermediate to the products.

CPN의 관리 모델과 망 엑세스 흐름/혼잡 제어 (CPN Management Model and Network Access Flow/Congestion Control in ATM Network)

  • 김양섭;권혁인;김영찬
    • 한국통신학회논문지
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    • 제23권8호
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    • pp.2096-2105
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    • 1998
  • ATM 망에서는 어느 한 순간에 다수의 연결에서 동시에 발생하는 버스트가 일어날 수 있으며, 이는 혼잡을 야기 할 수 있다. 따라서, 사용자의 QoS를 보장하기 위해서는 반작용적인(Reactive) 흐름 제어 기법들이 필요하다. 그러나, ATM망은 고속통신망이기 때문에 중간노드에서의 혼잡에 대해서 반작용적으로 소스의 전송률을 제어하기란 쉽지 않다. 그러므로, CPN(Customer Premise Network)에서의 흐름 제어가 종단-대-종단 흐름 제어보다 더 효율적일 수 있다. 본 논문에서는 CPN에서의 흐름 제어를 위한 관리 모델을 제시하고 가상 경로 연결(VPC)을 효율적으로 이용하기 위한 새로운 망 엑세스 흐름/혼잡 제어(NAPC: Network Access Flow/Congestion Control) 기법을 제안한다.

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Aminolyses of 2,4-Dinitrophenyl 2-Furoate and Benzoate: Effect of Nonleaving Group on Reactivity and Mechanism

  • Um, Ik-Hwan;Chun, Sun-Mee;Akhtar, Kalsoom
    • Bulletin of the Korean Chemical Society
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    • 제28권2호
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    • pp.220-224
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    • 2007
  • Second-order rate constants (kN) have been determined spectrophotometrically for reactions of 2,4-dintrophenyl 2-furoate (2) with a series of alicyclic secondary amines in 80 mol % H2O/20 mol % dimethyl sulfoxide (DMSO) at 25.0 oC. The furoate 2 is more reactive than 2,4-dintrophenyl benzoate (1) toward all the amines studied. The higher acidity of 2-furoic acid (pKa = 3.16) compared with benzoic acid (pKa = 4.20) has been suggested to be responsible for the reactivity order, at least in part. The Brønsted-type plots for the reactions of 1 and 2 are curved downwardly, indicating that the aminolyses of both 1 and 2 proceed through a zwitterionic tetrahedral intermediate (T±) with a change in the rate-determining step on changing the amine basicity. Dissection of the kN values into their microscopic rate constants has revealed that the pKao and k2/k-1 ratios for the reactions of 1 and 2 are identical, indicating that the nature of the nonleaving group (i.e., benzoyl and 2-furoyl) does not affect the reaction mechanism. The k1 values have been found to be larger for the reactions of 2 than for those of 1, which is fully responsible for the fact that the former is more reactive than the latter.

Continuous Viewing Angle Distribution Control of Liquid Crystal Displays Using Polarization-Dependent Prism Array Film Stacked on Directional Backlight Unit

  • Park, Min-Kyu;Park, Heewon;Joo, Kyung-Il;Jeong, Hee-Dong;Choi, Jun-Chan;Kim, Hak-Rin
    • Journal of the Optical Society of Korea
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    • 제20권6호
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    • pp.799-806
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    • 2016
  • We present a polarization-dependent prism array film for controlling the viewing angle distribution of liquid crystal (LC) display panels without loss of light efficiency. On a directional backlight unit, our polarization-dependent prism array film, made into a stacked bilayer with a well-aligned liquid crystalline reactive mesogen (RM) layer on the UV-imprinted prism structure, can continuously control the light refraction function of the prism array by electrically switching incident polarization states of a polarization-controlling layer prepared by a twisted nematic LC mode. The viewing angle control properties of the polarization-dependent prism array film are analyzed under different prism angle and refractive index conditions of the RM layer. A simple analytic model is also presented to describe the intermediate viewing angle distributions with continuously varying applied voltages and incident polarization states.

The Effect of Polarizability on Rate and Reaction Mechanism: Reactions of S-Aryl Substituted Thiobenzoates with $HO-$ and Aryloxide Ions

  • Ik-Hwan Um;Sang-Eun Chun;Dong-Sook Kwon
    • Bulletin of the Korean Chemical Society
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    • 제12권5호
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    • pp.510-514
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    • 1991
  • Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.

C-reactive Protein Concentration Is Associated With a Higher Risk of Mortality in a Rural Korean Population

  • Lee, Jung Hyun;Yeom, Hyungseon;Kim, Hyeon Chang;Suh, Il;Kim, Mi Kyung;Shin, Min-Ho;Shin, Dong Hoon;Koh, Sang-Baek;Ahn, Song Vogue;Lee, Tae-Yong;Ryu, So Yeon;Song, Jae-Sok;Choe, Hong-Soon;Lee, Young-Hoon;Choi, Bo Youl
    • Journal of Preventive Medicine and Public Health
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    • 제49권5호
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    • pp.275-287
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    • 2016
  • Objectives: C-reactive protein (CRP), an inflammatory biomarker, has been widely used as a preclinical marker predictive of morbidity and mortality. Although many studies have reported a positive association between CRP and mortality, uncertainty still remains about this association in various populations, especially in rural Korea. Methods: A total of 23 233 middle-aged participants (8862 men and 14 371 women) who were free from cardiovascular disease, cancer, and acute inflammation (defined by a CRP level ${\geq}10mg/L$) were drawn from 11 rural communities in Korea between 2005 and 2011. Blood CRP concentration was analyzed as a categorical variable (low: 0.0-0.9 mg/L; intermediate: 1.0-3.0 mg/L; high: 3.1-9.9 mg/L) as well as a continuous variable. Each participant's vital status through December 2013 was confirmed by death statistics from the National Statistical Office. Cox proportional hazard models were used to assess the independent association between CRP and mortality after adjusting for other risk factors. Results: The total quantity of observed person-years was 57 975 for men and 95 146 for women, and the number of deaths was 649 among men and 367 among women. Compared to the low-CRP group, the adjusted hazard ratio for all-cause mortality of the intermediate group was 1.17 (95% confidence interval [CI], 0.98 to 1.40) for men and 1.27 (95% CI, 1.01 to 1.61) for women, and the corresponding values for the high-CRP group were 1.98 (95% CI, 1.61 to 2.42) for men and 1.41 (95% CI, 1.03 to 1.95) for women. Similar trends were found for CRP evaluated as a continuous variable and for cardiovascular mortality. Conclusions: Higher CRP concentrations were associated with higher mortality in a rural Korean population, and this association was more prominent in men than in women.

층간금속층에 따른 ITO 박막의 메탄올 검출민감도 개선 효과 (Effect of Intermediate Metal on the Methanol Gas Sensitivity of ITO Thin Films)

  • 이학민;허성보;공영민;김대일
    • 한국진공학회지
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    • 제20권3호
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    • pp.195-199
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    • 2011
  • RF 마그네트론 스퍼터와 DC 마그네트론 스퍼터를 병행하여 ITO/Au/ITO, ITO/Cu/ITO, 그리고 ITO/Ni/ITO 박막을 유리기판 위에 증착하였다. 증착 후 진공열처리를 통하여 층간 금속 층이 ITO박막의 메탄올 검출 민감도에 미치는 영향을 분석하였다. 모든 박막센서의 두께는 100 nm로 동일하게 ITO 50 nm/metal 10 nm/ITO 40 nm로 제작되었고 메탄올 농도는 100에서 1,000 ppm까지 달리하였다. ITO/Au/ITO 박막센서가 가장 높은 민감도를 보임으로써 ITO/Au/ITO 다층박막이 기존의 ITO메탄올 센서를 대체할 수 있는 센서임을 확인하였다.