• 제목/요약/키워드: Complex formation constant

검색결과 130건 처리시간 0.023초

토양 혼합여재를 이용한 질소산화물 제거특성 (Removal Characteristics of NOx Using a Mixed Soil-Biofilter)

  • 조기철;신은상;황경철;조일형;이내현;여현구
    • 환경위생공학
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    • 제21권3호
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    • pp.15-26
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    • 2006
  • As traffic in city-centre around the world continues to increase, so levels of atmospheric pollutants continue to rise. High concentrations of NOx can have negative effects on human health, and we must find new ways to reduce their levels in the air we breathe. Nitrogen oxide gas (NOx), consisting of nitrogen monoxide (NO) and nitrogen dioxide $(NO_2)$ produced using $O_3$ oxidation, at a low concentration corresponding to that on roads as a result of exhaust from automobiles, was carried out to evaluate the removal characteristics of NOx through a laboratory-scale biofilter packed with soil as a packing material. A mixture media (yellow soil (30%): soil (40%): compost (10%): a used briquet (20%)) was applied. After about 1day of operation, the removal efficiency for $NO_2$ in all experiments with a constant condition ($25^{\circ}C$ and water humidity (60%)) was over 98%. The retention times of the section between phase I and phase II for formation and reduction of $NO_3$ NO and $NO_2$ on the initial $NO_3$ concentration was 50min $(O_3:195\;ppb),\;55min\;(O_3:925\;ppb),\;65min\;(O_3:1743\;ppb),\;70min\;(O_3:2616\;ppb),\;75min\;(O_3:3500\;ppb)$, respectively The soil biofilter system is a unique technology that purifies urban air by utilizing the natural processes that take place in the soil. Although some of the processes are quite complex, they can broadly be summarized as adsorption onto soil particles, dissolution into soil pore water, and biochemical.

Effects of Acute Lymphoblastic Leukemia on Ceruloplasmin Oxidase, Copper and Several Markers of Oxidative Damage, in Children

  • Mehdi, Wesen Adel;Yusof, Faridah;Mehde, Atheer Awad;Zainulabdeen, Jwan Abdulmohsin;Raus, Raha Ahmed;Abdulbari, Alaa Shawqi
    • Asian Pacific Journal of Cancer Prevention
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    • 제16권13호
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    • pp.5205-5210
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    • 2015
  • Background: Acute leukaemia is characterized by fast growth of abnormal clones of haemopoietic precursor cells inside bone marrow leading to undue accumulation in the bone marrow. Acute lymphoblastic leukemia (ALL) is the most common form of childhood cancer. Materials and Methods: The study concerned 50 children diagnosed with ALL (mean age, $8.55{\pm}2.54$) compared to 40 healthy controls (mean age, $8.00{\pm}1.85$). The Hb, serum copper, ceruloplasmin oxidase, advanced oxidation protein products (AOPPs), total antioxidant activity (TAA) and protein were measured in all groups.One proteinous component was isolated by gel filtration chromatography from the precipitate produced by polyethylene glycol. Results: Significantly higher levels of AOPP, copper and decrease in total antioxidant activity were noted in the cases. Statistical analysis also showed a significant increase (p<0.01) in the activity of serum ceruloplasmin oxidase in patients with ALL compared to normal subjects .The maximum velocity (Vmax) and Michaelis constant had values of 104.2 U/L and 11.7 mM, respectively. The ${\Delta}H^*$ values for ceruloplasmin oxidase in ALL patients were positive, confirming the reaction to be endothermic. Conclusions: The results from this study showed a significant increase in AOPP, ceruloplasmine oxidase and decrease in total antioxidant activity .These parameters may play a role in development of DNA damage in childhood patients with acute lymphoblastic leukemia (ALL).The ${\Delta}S^*$ and ${\Delta}G^*$ values were negative, these refer that the reaction of ES formation is spontaneous, but needs energy in a so-called endergonic reaction. Also the negative ${\Delta}S^*$ value of ceruloplasmin oxidase indicates that the complex [$ES^*$] is further modulated through increasing structure arrangement.

Study on the Inclusion Behavior of Sulfobutylether-β-Cyclodextrin with Perphenazine by Flow Injection Chemiluminescence

  • Shen, Minxia;Lv, Hairu;Song, Zhenghua
    • Bulletin of the Korean Chemical Society
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    • 제34권11호
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    • pp.3199-3205
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    • 2013
  • The inclusion behavior of sulfobutylether-${\beta}$-cyclodextrin (SBE-${\beta}$-CD) with perphenazine (PPH) was first studied by flow injection (FI)-chemiluminescence (CL) analysis with proposed $lg[(I_0-I_s)/I_s]=lgK_{P-CD}+nlg[C_{PPH}]$ model and molecular docking. Results showed that a 1:1 complex of SBE-${\beta}$-CD/PPH could online form, with the formation constant $K_{P-CD}$ of $2.57{\times}10^7Lmol^{-1}$ at 298 K. The thermodynamic parameters showed that the inclusion behavior of SBE-${\beta}$-CD/PPH was a spontaneous process by hydrophobic interaction. The molecular docking results revealed PPH entered into the larger cavity of SBE-${\beta}$-CD with two hydrogen bonds. Based on the linear relationship of the decrement of luminol/SBE-${\beta}$-CD/PPH CL intensity against the logarithm of PPH concentration ranging from 0.03 to 30.0 ng $mL^{-1}$, the present FI-CL analysis using luminol/SBE-${\beta}$-CD/PPH system was successfully applied to PPH determination in biological fluids and tablets with recoveries from 94.5 to 105.6% and RSDs less than 2.6% (n = 5).

The Mechanism of the Decomposition of a Bronchodilator, S-Nitroso-N-acetyl-D,L-penicillamine (SNAP), by a Bronchoconstrictor, Aqueous Sulfite: Detection of the N-Nitrosohydroxylamine-N-sulfonate ion

  • Holder, Alvin A.;Marshall, Sophia C.;Wang, Peng George;Kwak, Chee-Hun
    • Bulletin of the Korean Chemical Society
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    • 제24권3호
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    • pp.350-356
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    • 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)].

수용액에서의 Eu(Ⅲ) 착물의 형광스펙트럼에 영향을 미치는 온도 및 리간드 효과에 관한 연구 (Temperature and Ligand Effects on the Eu(Ⅲ) Emission Spectra in the Aqueous Solution)

  • 이인숙;김건
    • 대한화학회지
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    • 제34권6호
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    • pp.548-554
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    • 1990
  • Eu(III)이온과 간단한 리간드 사이의 착물형성에 대한 온도와 리간드의 영향을 형광방출 스펙트럼을 이용하여 연구하였다. 온도와 리간드에 따라 hypersensitive 전이($^5D0\; {\to}\;^7F_2$)와 nonhypersensitive 전이($^5D0\; {\to}\;^7F_1$)의 상대적 세기는 온도와 리간드의 영향을 크게 받는다. 이러한 상대적 세기변화를 내부권 착물 형성에 의한 평형상수의 변화로 해석하여 $Eu(H_2O)_X^{3+}$ 에서 EuL(H$_2O)_{X-1}^{2+}$로의 내부권 착물 형성시의 열역학적 함수들을 계산하는데 사용하였다. EuCl(H$_2O)_{X-1}^{2+}$의 내부권 착물 형성시의 $\Delta{H}$는 대략 15 kJ/mol이고 온도에 따라 거의 영향을 받지 않는다. 그러나, EuNO$_3(H_2O)_{X-1}^{2+}$의 내부권 착물 형성시의 $\Delta{H}$는 온도에 따라 25$^{\circ}C$에서는 -11 kJ/mol 그리고 250$^{\circ}C$에서는 47 kJ/mol로 증가하였다.

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Quenching of Ofloxacin and Flumequine Fluorescence by Divalent Transition Metal Cations

  • Park, Hyoung-Ryun;Oh, Chu-Ha;Lee, Hyeong-Chul;Choi, Jae-Gyu;Jung, Beung-In;Bark, Ki-Min
    • Bulletin of the Korean Chemical Society
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    • 제27권12호
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    • pp.2002-2010
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    • 2006
  • This study examined the quenching of ofloxacin (OFL) and flumequine (FLU) fluorescence by $Cuj^{2+}$, $Ni^{2+}$, $Co^{2+}$ and $Mn^{2+}$ in an aqueous solution. The change in the fluorescence intensity and lifetime was measured at various temperatures as a function of the quencher concentration. According to the Stern-Volmer plots, the fluorescence emission was quenched by both collisions (dynamic quenching) and complex formation (static quenching) with the same quencher but the effect of static quenching was larger than that of dynamic quenching. Large static and dynamic quenching constants for both OFL and FLU support significant ion-dipole and orbital-orbital interactions between fluorophore and quencher. For both molecules, the static and dynamic quenching constants by $Cu^{2+}$ were the largest among all the metal quenchers examined in this study. In addition, both the static and dynamic quenching mechanisms by $Cu^{2+}$ were somewhat different from the quenching caused by other metals. Between $Ni^{2+}$ and FLU, a different form of chemical interaction was observed compared with the interaction by other metals. The change in the absorption spectra as a result of the addition of a quencher provided information on static quenching. With all these metals, the static quenching constant of FLU was larger than those of OFL. The fluorescence of OFL was quite insensitive to both the dynamic and static quenching compared with FLU. This property of OFL can be explained by the twisted intramolecular charge transfer in the excited state.

Metal Ion Catalysis in Nucleophilic Displacement Reactions of 2-Pyridyl X-Substituted Benzoates with Potassium Ethoxide in Anhydrous Ethanol

  • Lee, Jae-In;Kang, Ji-Sun;Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제31권12호
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    • pp.3543-3548
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    • 2010
  • A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.

투명한 폴리이미드 공중합체 필름의 합성과 특성 연구 (I) (Synthesis and Characterization of Transparent Copolyimide Films (I))

  • 박종수;장진해
    • 폴리머
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    • 제32권6호
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    • pp.580-586
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    • 2008
  • 4,4'-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) 와 1,3-bis (3-aminophenoxy) benzene(BAPB)의 조성에 2,2-bis [4-(4-aminophenoxy)phenyl] hexafluoropropane (BAPP)를 다양한 몰 비에 따른 폴리이미드(PI) 공중합체를 합성하였다. PI 공중합체 필름들은 여러 열처리 과정을 통하여 용액 캐스팅 (solution casting)된 폴리아믹산(PAA)으로부터 얻었다. 퓨리에 변환 적외선 분광기(FT-IR), 넓은 각 X-선 회절(XRD), 전계 방사형 주사 전자 현미경(FE-SEM) 시차 주사 열량계(DSC)와 열 중량 분석기(TGA), 만능 인장 시험기 (UTM) 그리고 자외선-가시광선 흡광도기 (UV-Vis. spectrometer) 등을 사용하여 PI 공중합체 필름의 열적 기계적 성질, 모폴로지 및 광학 투명도를 측정하였다. PI 공중합체 필름의 유리전이온도 및 최종 강도와 초기 탄성률은 BAPP의 몰 비가 증가할수록 증가하였으나, 초기분해온도는 BAPP의 몰 비 증가에 무관하게 일정하였다. BAPP가 charge transfer complex를 형성하는 이유로 BAPP 농도가 증가함에 따라 PI 공중합체 필름의 투명도는 약간씩 감소하였다.

Spectrophotometric Determination of Nizatidine and Ranitidine Through Charge Transfer Complex Formation

  • Walash, M.;Din, M.-Sharaf-EI;Metwalli, M.E.S.;RedaShabana, M.
    • Archives of Pharmacal Research
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    • 제27권7호
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    • pp.720-726
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    • 2004
  • Two Spectrophotometric procedures are presented for the determination of two commonly used H2-receptor antagonists, nizatidine (I) and ranitidine hydrochloride (II). The methods are based mainly on charge transfer complexation reaction of these drugs with either ${\rho}-chloranilic$ acid (${\rho}-CA$) or 2, 3 dichloro-5, 6-dicyanoquinone (DDQ). The produced colored products are quantified spectrophotometrically at 515 and 467 nm in chloranilic acid and 000 methods, respectively. The molar ratios for the reaction products and the optimum assay conditions were studied. The methods determine the cited drugs in concentration ranges of 20-200 and $20-160\;\mu\textrm{g}/mL$ for nizatidine and ranges of 20-240 and $20-140\;\mu\textrm{g}/mL$ for ranitidine with chloranilic acid and DDQ methods, respectively. A more detailed investigation of the complexes formed was made with respect to their composition, association constant, molar absorptivity and free energy change. The proposed procedures were successfully utilized in the determination of the drugs in pharmaceutical preparations. The standard addition method was applied by adding nizatidine and ranitidine to the previously analyzed tablets or capsules. The recovery of each drug was calculated by comparing the concentration obtained from the spiked mixtures with those of the pure drug. The results of analysis of commercial tablets and the recovery study (standard addition method) of the cited drugs suggested that there is no interference from any excipients, which are present in tablets or capsules. Statistical comparison of the results was performed with regard to accuracy and precision using student's t-test and F-ratio at 95% confidence level. There is no significant difference between the reported and proposed methods with regard to accuracy and precision.

Ni(II)-거대고리 리간드 착이온 ($NiL_m{^{2+}}$) 과 $CN^-$ 이온간의 반응성 (Chemical Reactivity between Ni(II)-Macrocycle Complex Ions ($NiL_m{^{2+}}$) and $CN^-$)

  • 박유철;변종철
    • 대한화학회지
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    • 제31권4호
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    • pp.334-343
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    • 1987
  • $NiL_m{^{2+}}$착이온 {$Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}$}과 $CN^-$이온 사이의 화학반응은 분광광도법으로 연구하였다. $NiL_m{^{2+}}$착이온과 $CN^-$이온으로부터 1:1착이온, $[NiLm(CN)]^+$생성반응의 평형상수$(K_1)$는 3 ~ $25^{\circ}C$ 범위에서 결정되었다. $NiL_m{^{2+}}$착이온이 $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+}$, 그리고 $Ni(meso-[14]-decane)^{2+}$일때 평형상수($K_1$)은 $15^{\circ}C$에서 각각 4.7, 5.3, 6.2, 7.5, 9.4, 및 9.8이었다. $K_1$값은 온도가 증가함에 따라 감소하였다. $K_1$에 대한 온도영향으로 부터 열역학적 파라메터 $({\Delta}G^{\circ},\;{\Delta}H^{\circ},\;{\Delta}S^{\circ})$를 계산하였으며, 이 결과 $[NiLm(CN)]^+$ 생성반응은 모두 발열반응으로 나타났다. $NiL_m{^{2+}}$ 착이온과 $CN^-$이온은 반응하여 Ni(CN)_4{^{2-}}$이온과 거대고리 리간드 (Lm)가 생성된다. $[CN^-],\;[HCN],\;and\;[OH^-]$ 변화에 따라 $Ni(CN)_4{^{2-}}$이온의 생성속도는 0.5M $NaClO_4$, 온도 3∼$25^{\circ}C$ 범위에서 연구되었다. $[CN^-]$가 일정할 때 [HCN]가 증가하면 $k_{obs}/[CN^-]^2$값은 선형으로 증가하였다. $OH^-$ 이온이 과량으로 존재할 때 [$OH^-$]에 따라 역시 $k_{obs}/[CN^-]^2$ 값은 선형으로 증가하였다. $NiL_m{^{2+}}$ 착이온과 $CN^-$이온 반응의 속도상수($k_{obs}$)에 대한 온도영향으로 부터 활성화 파라메터$({\Delta}H^{\neq},\;{\Delta}S^{\neq})$를 결정하였다. $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+}$, 그리고 $Ni(meso-[14]-decane)^{2+}$ 순서로 d-d 전이에너지, $ν(cm^{-1})$가 감소할수록, ${\Delta}H^{\neq}$도 점차적으로 감소하였다. 그리고 5가지의 $NiL_m{^{2+}}$ 착이온과 $CN^-$이온 사이의 반응은 동일한 경로로 반응이 진행되었다.

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