• 제목/요약/키워드: pH independent reaction

검색결과 62건 처리시간 0.021초

N-(5-phenyl-1,2,4-Oxadiazol-3-yl)-N'-arylformamidine의 Mononuclear Heterocyclic Rearrangement반응에 대한 반응속도론 (제1보) (Kinetics for Mononuclear Heterocyclic Rearrangement of N-(5-phenyl-1,2,4-oxadiazol-3-yl)-N'-arylformamidine (I))

  • 황정의;정종재;윤영주
    • 대한화학회지
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    • 제32권4호
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    • pp.301-310
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    • 1988
  • Dioxane/water (50 : 50, v/v) 용매 중에서 N-(5-phenyl-1,2,4-oxadiazol-3-yl)-N'-arylformamidine의 mononuclear heterocyclic rearrangement반응에 대한 속도를 분광광도법으로 측정하였다. pH에 따라 두가지의 다른 반응경로, 즉 pH에 무관한 경로와 pH에 의존하는 경로가 있음을 알았다. pH에 무관한 경로에서는 치환기효과를 IYT식으로 해석한 결과 질소-질소 결합의 형성이 우세하지만 질소-수소 결합도 약간 절단된 전이상태를 가진다고 결론지을 수 있었다. 한편 pH에 의존하는 경로에서는 위로 오목한 Hammett plot를 나타냈으며, 이는 전이상태에서 전자를 미는 치환기의 경우에는 질소-질소 결합의 형성이 질소-수소 결합의 절단보다 진전되어 있고 전자를 당기는 치환기의 경우에는 질소-수소 결합의 절단이 질소-질소 결합의 형성보다는 약간 더 진전되어 있기 때문으로 결론지을 수 있었다.

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Mechanism of DNA Cleavage Induced by Fe2+ Autoxidation

  • Kim, Jong-Moon;Kim, Seog-K.
    • Bulletin of the Korean Chemical Society
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    • 제32권3호
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    • pp.964-972
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    • 2011
  • This work investigated the difference between $Fe^{2+}$ autoxidation-induced and Fenton-type cleavage of pBR322 plasmid DNA. $^{\cdot}OH$ generation reactions in the absence and presence of $H_2O_2$ under various conditions were also investigated. Although both the $Fe^{2+}$ autoxidation and Fenton-type reactions showed DNA cleavage and $^{\cdot}OH$ generation, there were significant differences in their efficiencies and reaction rates. The rate and efficiency of the cleavage reaction were higher in the absence of 1.0 mM of $H_2O_2$ than in its presence in 20 mM phosphate buffer. In contrast, the $^{\cdot}OH$ generation reaction was more prominent in the presence of $H_2O_2$ and showed a pH-independent, fast initial reaction rate, but the rate was decreased in the absence of $H_2O_2$ at across the entire tested pH range. Studies using radical scavengers on DNA cleavage and $^{\cdot}OH$ generation reactions in both the absence and presence of $H_2O_2$ confirmed that both reactions spontaneously involved the active oxygen species $^{\cdot}OH$, ${O_2}^{\cdot-}$, $^1O_2$ and $H_2O_2$, indicating that a similar process may participate in both reactions. Based on the above observations, a new mechanism for the $Fe^{2+}$ autoxidation-induced DNA cleavage reaction is proposed.

Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology

  • Arachchi, Shanika Jeewantha Thewarapperuma;Kim, Ye-Joo;Kim, Dae-Wook;Oh, Sang-Chul;Lee, Yang-Bong
    • Preventive Nutrition and Food Science
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    • 제22권1호
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    • pp.37-44
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    • 2017
  • Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ${\Delta}E$ was consequently set as the fifth response factor. In the statistical analyses, determination coefficients ($R^2$) for their absorbance, Hunter's L, a, b values, and ${\Delta}E$ were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, $111^{\circ}C$ reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, $114^{\circ}C$ reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

사질토 지반에서 고강도 H-형강 말뚝의 수평거동 (Response of H-Pile under Lateral Load in Cohesionless Soils)

  • 박영호;정현식;이영생;정종홍
    • 한국지반공학회:학술대회논문집
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    • 한국지반공학회 2000년도 가을 학술발표회 논문집
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    • pp.237-244
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    • 2000
  • Piles are often subjected to both axial and lateral loads. The nonlinear subgrade reaction method is widely used for the design of laterally loaded piles and in this approach the soil reaction is replaced with a series of independent nonlinear Winkler springs. In this study, Laterally loaded high strength H-piles were analyzed using a finite difference solution, and three p-y curve models with different k values(the coefficient of horizontal subgrade reaction, [FL$\^$-3/]) were evaluated using data obtained from various field tests, and another analysis method using Q$\sub$g/ - y$\sub$g/ curve was developed. The results of this analysis were compared with the measured values to assess their applicability.

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만니톨의 효소 가수분해 반응 조건 최적화 (Optimization for Enzymatic Hydrolysis of Mannitol)

  • 박은영;김용진;정승미;이동훈
    • KSBB Journal
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    • 제28권2호
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    • pp.65-73
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    • 2013
  • This study aimed to investigate the enzymatic hydrolysis of mannitol using Viscozyme$^{(R)}$ L, Celluclast$^{(R)}$ 1.5 L, Saczyme$^{(R)}$, Novozym$^{(R)}$, Fungamyl$^{(R)}$ 800 L, Driselase$^{(R)}$ Basidiomycetes sp., and Alginate Lyase, and to optimize of reaction conditions for production of reducing sugar. Response surface methodology (RSM) based on central composite rotatable design was used to study effects of the independent variables such as enzyme (1-9% v/w), reaction time (10-30 h), pH (3.0-7.0) and reaction temperature ($30-70^{\circ}C$) on production of reducing sugar from mannitol. The coefficient of determination ($R^2$) of $Y_1$ (yield of reducing sugar by Viscozyme$^{(R)}$ L) and $Y_3$ (yield of reducing sugar by Saczyme$^{(R)}$) for the dependent variable regression equation was analyzed as 0.985 and 0.814. And the p-value of $Y_1$ and $Y_3$ showing 0.000 and 0.001 within 1% (p < 0.01), respectively, was very significant. The optimum conditions for production of reducing sugar with Viscozyme$^{(R)}$ L were 9.0 % (v/w) amount of enzyme, 30.0 hours of reaction time, pH 4.5 and $30.0^{\circ}C$ of reaction temperature, and those with Saczyme$^{(R)}$ were 9.0% (v/w) of amount of enzyme dosage, 30.0 h of reaction time, pH 7.0 and $30.0^{\circ}C$ of reaction temperature, consequently, the predicted reducing sugar yields were 22.5 and 27.9 mg/g-mannitol, respectively.

생쥐 정자의 첨체반응에 미치는 Dimethyl Amiloride의 영향 (Effect of Dimethyl Amiloride on the Acrosome Reaction in Mouse Epididymal Sperm in vitro)

  • 계명찬
    • 한국발생생물학회지:발생과생식
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    • 제3권1호
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    • pp.87-93
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    • 1999
  • 생쥐 정자의 수정능력획득과 첨체반응에 작용하는 $Na^{+}$/H$^{+}$ antiporter의 역할을 조사하고자 하였다. $Na^{+}$/H$^{+}$ antiporter를 특이적으로 억제하는 dimethyl amiloride는 정자의 자발적인 첨체반응을 농도 의존적으로 억제한 반면 난포액 및 calcium ionophore인 A23l87에 의해 유도된 첨체반응은 억제하지 못하였다. 이러한 결과는 정자내 $Na^{+}$/H$^{+}$ antiporter에 의한 1가이온의 출입과 이에 따른 세포질내 pH 조절이 정자의 수정능력 획득과 자발적인 첨체반응에 조절요인으로 작용함을 암시한다. 수정능력을 획득한 정자에서 난포액 등의 agonist 또는 A23l87에 의해 유도되는 첨체반응은 $Na^{+}$/H$^{+}$ antiporter와는 무관하게 진행되는 것으로 사료된다.

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Fluorescamine을 이용한 sulfonamide의 형광 분석법 (Spectrofluometry of sulfonamides using fluorescamine)

  • 임재영;한수남;이문한;박종명
    • 대한수의학회지
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    • 제30권1호
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    • pp.41-49
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    • 1990
  • These experiments were carried out to develop a novel, simple, and rapid method to determine urinary sulfonamides using fluorescamine by spectrofluorometry. To get optimal conditions for the sulfonamide-fluorescamine reaction, sulfonamides such as sulfamethazine, sulfamerazine, sulfadimethoxine and sulfamonomethoxine, dissolved in buffers with various pH ranges were reacted with various concentrations of fluorescamine. and then, the fluorescence intensity and stability of the fluorophore were measured. To eliminate the interfering substances in urine, the fluorophore in buffers and urine with a definite pH range was extracted with some organic solvents. After then the fluorescence intensity was measured in organic and aquous phases. The results obtained were summarized as follows: 1. The maximal fluorescence of sulfonamides was presented in acidic state, pH 4.5~5.0, at 30 minutes after reaction. 2. The optimal concentration ratio of sulfamethazine and ffuorescamine was more than 1 : 40 in mole. 3. In pH 4.0, the intensity was maximal but was time-dependent, whereas in pH 8.0, the intensity was time-independent. 4. Sulfamethazine-fluorescamine conjugate could be dissolved in some of organic solvents in acidic state such as chloroform, n-butanol, and ethylacetate. 5. Sulfamethazine-flnorescamine conjugate in swine urine coule be extracted with ethylacetate in acidic state, pH 4.0~5.0.

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Iron Oxide Coated Sand(ICS)의 중금속 흡착제거 특성

  • 최형진;양재규;장윤영
    • 한국지하수토양환경학회:학술대회논문집
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    • 한국지하수토양환경학회 2003년도 추계학술발표회
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    • pp.379-381
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    • 2003
  • Metal sorption onto the ICS (Iron oxide coated sand) was studied in batch experiments. Heavy metal cations such as Cd, Pb, and Cu, and a metal anion, As, which sporadically exist in mine sites, were tested for the sorptive removal by ICS. In low pH conditions As showed the highest removal efficiency compared to the other metal cations. And the sorption removal of As was apparently pH-independent reaction. However, removal of metal cations increased with pH and above pH 7 most metal cations showed very low soluble concentrations after treatment. Such a high removal ratio of metal cations above the neutral pH appeared predominantly due to precipitation.

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등온적정열량계를 이용한 BaCl2와 EDTA 킬레이션 결합 반응의 pH 영향 (Influence of pH on Chelation of BaCl2 and EDTA Using Isothermal Titration Calorimetry)

  • 육가은;장지웅
    • 공업화학
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    • 제34권3호
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    • pp.279-284
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    • 2023
  • 등온 적정 열량계는 리간드-수용체 사이의 킬레이션 결합 반응의 엔탈피, 깁스에너지, 엔트로피, 화학양론 등 포함한 모든 열역학적 정보를 측정하는데 유용한 기술이다. 단일독립결합모델을 이용하여 Tricine과 HEPES 완충용엑에서의 BaCl2 와 ethylenediaminetetraacetic acid (EDTA)의 킬레이션 결합에서의 열역학적 정보를 획득하였다. 등온 적정 열량계를 이용하여 pH 7~11 영역에서의 킬레이션 결합의 메커니즘과 최적의 결합 조건을 확인하였다. BaCl2와 EDTA의 결합은 자발적인 발열반응이며 pH가 증가할수록 엔트로피적 영향이 높아진다. 1:1로 결합하는 pH 영역은 pH 9.0 근처에서 매우 좁은 영역에서 나타난다.

Interaction Metal Ions with NADH Model Compounds. Cupric Ion Oxidation of Dihydronicotinamides

  • Park, Joon-Woo;Yun, Sung-Hoe;Koh Park, Kwang-Hee
    • Bulletin of the Korean Chemical Society
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    • 제9권5호
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    • pp.298-303
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    • 1988
  • Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.