• 대한화학회지
• /
• 제43권1호
• /
• pp.85-91
• /
• 1999

Phenyl N,N-diethyl-P-benzylphonamidate 및 그 유도체들의 염기성 가수분해 반응속도 상수를 분광 광도법으로 측정하였다. 속도 상수로부터 열역학적 파라메타(Ea, ${\Delta}H^{\neq}$,${\Delta}S^{\neq}$)를 구하였고, 이탈기의 치환기 효과는 Hammett 식을 이용하여 얻었다. 이들 실험 자료에 의하면 가수분해 반응은 활성화 엔트로피가 양의 값이나 작은 음의 값을 갖고 카르보음이온 생성이 수반되는 해리반응 보다는 이중피라미드 중간체 또는 전이 상태를 경유하는 회합 메카니즘을 강력히 암시하고 있다. 반응속도론적 연구 결과에 의하면 치환 pheny N,N-diethyl-P-benzylphosphonamidates의 가수분해 반응은 회합성 메카니즘으로 진행됨을 알 수 있었다.

• 대한환경공학회지
• /
• 제27권11호
• /
• pp.1238-1243
• /
• 2005

본 연구에서는 해안가에서 자생하는 두 종의 해조류(Laminaria japonica와 Kjellmaniella crassifolia)를 생체흡착제로 사용하여 용액중의 중금속(납) 제거 실험을 통해 생체흡착제의 납의 흡착속도와 흡착평형 특성을 연구하였다. 두 종의 해조류을 사용한 납의 생체흡착은 흡착초기 2시간 이내에 평형에 도달하였다. 흡착속도는 유사 2차 흡착속도식에 의해 거의 정확한 모사가 가능하였으며, 여기에서 산출된 속도상수, $k_{2,ad.}$는 각각 $0.883{\times}10^{-3}$와 $0.628{\times}10^{-3}\;g/mg/min$이었다. 흡착평형은 Langmuir, Redlich-Peterson 및 Koble-Corrigan (Langmuir-Freundlich) 모델식에 의해 잘 모사되었다. 또한, L. japonica와 K. crassifolia의 4가지 중금속에 대한 선택성은 Pb>Cd>Cr>Cu와 Pb>Cu>Cd>Cr순으로 나타났다. 본 실험에 사용된 L. japonica는 pH의 증가에 따라 납의 흡착량도 증가되었다.

• 한국수산과학회지
• /
• 제17권3호
• /
• pp.191-196
• /
• 1984

색광에 대한 말쥐치 Navodon modestus의 행동을 조사하기 위하여, 2가지씩의 서로 다른 색광을 조합하여 수조의 양단에서 동시에 광자극을 가했을 때의 반응을 주간과 야간으로 구분 조사한 결과는 다음과 갈다. 1. 수조내에서의 말쥐치의 구간별분포곡선은 양단 구간에 다소 많이 모여 대체로 U 자형이 되었다. 2. 양색선원쪽에서의 평균분포차는 $10.65\%(4.59{\sim}19.16\%)$였고, 주간($13.20\%$)보다 야간($8.09\%$) 에 적었다. 3. 말쥐치가 잘 모이는 색광은 주간과 야간의 구별없이 청색, 백색, 황색, 적색의 순으로 나타났다. 4. 조명시간의 경과에 따른 집어율의 변화는 일정한 증감추세를 보이지 않고 계속 불안정하게 변동했다. 5. 두가지 색광에 대한 집어율의 차는 비교적 뚜렸하지 않았는데 야간보다 주간에 그 차가 심했다.

• KSBB Journal
• /
• 제32권2호
• /
• pp.117-123
• /
• 2017

Maple tree is a useful medical plant for obtaining bioactive materials such as pharmaceutics, cosmetics, food additive, etc., and there are 16 species of native maple trees in Korea. In this study, we evaluated the antioxidant activity of sap and crude extracts of Acer mono Max, a representative maple species. The crude extracts were obtained by solvent extraction (water, ethanol, and ethyl acetate) from its branches (bark and xylem). The phenolic contents and radical scavenging capacities of the extracts and the sap were evaluated in terms of half maximal effective concentration ($EC_{50}$) and kinetics by 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. The ethanol extracts showed the highest extraction yield, phenolic contents and antioxidant activity, and bark extracts showed better antioxidant activity than xylem extracts. The antioxidant activity of the sap was very low, but the $EC_{50}$ of ethanol and ethyl acetate extracts ranged from 68 to $79{\mu}g/mL$, similar to that ($60{\mu}g/mL$) of the control, butylated hydroxytoluene (BHT). The DPPH radical scavenging rate ($220{\sim}760{\mu}M/min$) and the second-order reaction rate constant ($6.48{\sim}7.04L/g{\cdot}min$) of these extracts were better than those of BHT ($55{\sim}370{\mu}M/min$ and $3.60L/g{\cdot}min$). These results suggest that A. mono Max. is one of the useful bioresources for obtaining antioxidant biologically active substances, and it is possible to obtain physiologically active substances from by-product of its pruning while minimizing the effect on the growth of the tree.

• Advanced Composite Materials
• /
• 제18권2호
• /
• pp.187-195
• /
• 2009

Much attention has been paid to the processing of inorganic whisker, especially calcium carbonate whisker, which can be used as reinforcement materials of polymer composite due to its low price. Unfortunately, the present synthesis technique of calcium carbonate whisker starts from calcinations of limestone, which involves high energy consumption and furthermore is a highly environment polluting reaction. In this report, needle-like aragonite was synthesized with a reversible solution reaction from limestone without calcination. Optical microscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques were used to characterize the morphology and crystal structure of intermediates as well as that of the product, aragonite. GCC (grinding calcium carbonate) powder was dissolved in an aqueous solution of magnesium sulfate with reflux and air flush. EDTA titration was used to evaluate reaction rate of the dissolution. A kinetics equation of the dissolution reaction was constructed, which displayed second-order kinetics with respect to the concentration of magnesium sulfate. A rate constant of $0.0015\;l^{-3}{\cdot}mol^{-1}{\cdot}h^{-1}$ was obtained. The dissolution reaction gave fiber-like magnesium hydroxide sulfate and gypsum crystal. Then needle-like aragonite with a length of $9.13\;{\pm}\;1.02\;{\mu}m$ and an aspect ratio of $5.64\;{\pm}\;1.37$ was synthesized from the dissolution product with $CO_2$ bubbling at $70^{\circ}C$.

• Bulletin of the Korean Chemical Society
• /
• 제35권7호
• /
• pp.2135-2138
• /
• 2014

A kinetic study is reported for the SNAr reaction of 1-Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1h) with OH- in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The second-order rate constant ($k_{OH^-}$) increases as the substituent Y in the leaving group changes from an electron-donating group (EDG) to an electronwithdrawing group (EWG). The Br${\o}$nsted-type plot for the reactions of 1a-1h is linear with ${\beta}_{lg}$ = -0.16, indicating that the reactivity of substrates 1a-1h is little affected by the leaving-group basicity. A linear Br${\o}$nsted-type plot with ${\beta}_{lg}=-0.3{\pm}0.1$ is typical for reactions reported previously to proceed through a stepwise mechanism in which formation of a Meisenheimer complex is the rate-determining step (RDS). The Hammett plot correlated with ${\sigma}_Y{^{\circ}}$ constants results in a much better correlation than that correlated with ${\sigma}_Y{^-}$constants, implyng that no negative charge is developing on the O atom of the leaving group (or expulsion of the leaving group is not advanced at all in the TS). This excludes a possibility that the $S_NAr$ reaction of 1a-1h with $OH^-$ proceeds through a concerted mechanism or via a stepwise pathway with expulsion of the leaving group being the RDS. Thus, the current reactions have been concluded to proceed through a stepwise mechanism in which expulsion of the leaving group occurs rapidly after the RDS.

• Bulletin of the Korean Chemical Society
• /
• 제24권3호
• /
• pp.350-356
• /
• 2003

The mechanism of the decomposition of a bronchodilator, S-nitroso-N-acetyl-D,L-penicillamine (SNAP) by a bronchoconstrictor, aqueous sulfite, has been investigated in detail. The decomposition was studied using a conventional spectrophotometer at 336 nm over the ranges: 0.010 ≤ $[S^{IV}]_T$ ≤ 0.045 mol $dm^{-3}$, 3.96 ≤ pH ≤ 6.80 and 15.0 ≤ θ≤ 30.0 ℃, 0.60 ≤ I ≤ 1.00 mol $dm^{-3}$, and at ionic strength 1.00 mol $dm^{-3}$ (NaCl). The rate of reaction is dependent on the total sulfite concentration and pH in a complex manner, i.e., $k_{obs}\;=\;k_1K_2[S^{IV}]_T/ ([H^+]\;+\;K_2)$. At 25.0 ℃, the second order rate constant, $k_1$, was determined as $12.5\;{\pm}\;0.15\;mol^{-1}\;dm^3\;s^{-1}$. ${\Delta}H^{neq}\;=\;+32\;{\pm}\;3 kJ\;mol^{-1}\;and\;{\Delta}S^{\neq}\;=\;-138\;{\pm}\;13\;J\;mol^{-1}K^{-1}$. The N-nitrosohydroxylamine-N-sulfonate ion was detected as an intermediate before the formation of any of the by-products, namely, N-acetyl-D,L-penicillamine. The effect of concentration of aqueous copper(Ⅱ) ions on this reaction was also examined at pH 4.75, but there was no dependence on $[Cu^{2+}]$. In addition, the $pK_a$ of SNAP was determined as 3.51 ± 0.06 at 25.4 ℃ [I = 1.0 mol $dm^{-3}$ (NaCl)].

• Membrane and Water Treatment
• /
• 제10권6호
• /
• pp.471-484
• /
• 2019

The complex combination of organic contaminants in the wastewater made water treatment challenging; hence, organic matter in water bodies is usually measured in terms of organic carbon. Since it is important to identify the types of compounds when deciding suitable treatment methods, this study implemented a quantitative and qualitative analysis of the organic matter content in an actual graywater sample from Ulsan, Republic of Korea using mass spectroscopy (MS). The graywater was treated using adsorption to remove the organic contaminants. Using orbitrap MS, the organic matter content between an untreated graywater and the treated effluent were compared which yielded a significant formula count difference for the samples. It was revealed that CHON formula has the highest removal count. Isotherm studies found that the Freundlich equation was the best fit with a coefficient of determination ($R^2$) of 0.9705 indicating a heterogenous GAC surface with a multilayer characteristic. Kinetics experiments fit the pseudo-second order equation with an $R^2$ of 0.9998 implying that chemisorption is the rate-determining step between the organic compounds and GAC at rate constant of $52.53g/mg{\cdot}h$. At low temperatures, the reaction between GAC and organic compounds were found to be spontaneous and exothermic. The conditions for optimization were set to achieve a maximum DOC and TN removal which yielded removal percentages of 94.59% and 80.75% for the DOC and TN, respectively. The optimum parameter values are the following: pH 6.3, 2.46 g of GAC for every 30 mL of graywater sample, 23.39 hrs contact time and $38.6^{\circ}C$.

• BMB Reports
• /
• 제28권2호
• /
• pp.112-117
• /
• 1995

Succinic semialdehyde reductase was inactivated by o-phthalaldehyde. The inactivation followed pseudo-first order kinetics, and the second-order rate constant for the inactivation process was 28 $M^{-1}s^{-1}$ at pH 7.4 and $25^{\circ}C$. The absorption spectrum ($\lambda_{max}$ 337 nm) and fluorescence excitation ($\lambda_{max}$ 340 nm) and fluorescence emission spectra ($\lambda_{max}$ 409 nm) were consistent with the formation of an isoindole derivative in the catalytic site between a cysteine and a lysine residue approximately about 3 $\AA$ apart. The substrate, succinic semialdehyde, did not protect enzymatic activity against inactivation, whereas the coenzyme NADPH protected against o-phthaladehyde induced inactivation of the enzyme. About 1 isoindole group per mol of the enzyme was formed following complete loss of enzymatic activity. These results suggest that the amino acid residues of the enzyme participating in a reaction with o-phthalaldehyde are cysteinyl and lysyl residues at or near the NADPH binding site.

• 한국환경과학회지
• /
• 제20권2호
• /
• pp.241-249
• /
• 2011

In this research, equilibrium of adsorption and kinetics of As(V) removal were investigated. The coal mine drainage sludge(CMDS) was used as adsorbent. To find out the physical and chemical properties of CMDS, XRD (X-ray diffraction), XRF (X-ray fluorescence spectrometer) analysis were carried out. The CMDS was consist of 70% of goethite and 30% of calcite. From the results, an adsorption mechanism of As(V) with CMDS was dominated by iron oxides. Langmuir adsorption isotherm model was fitted well more than Freundlich isotherm adsorption model. Adsorption capacities of CMDS 1 was not different with CMDS 2 on aspect of amounts of arsenic adsorbed. The maximum adsorption amount of two CMDS were respectively 40.816, 39.682 mg/g. However, the kinetic of two CMDS was different. The kinetic was followed pseudo second order model than pseudo first order model. Concentrations of arsenic in all segments of the polymer in CMDS 2 does not have a constant value, but the rate was greater than the value of CMDS 1. Therefore, CMDS 2, which is containing polymer, is more effective for adsorbent to remove As(V).