Complexation of $Cd^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions with four cryptands were studied by potentiometry and solution calorimetry in various weight percent methanol-aqueous solvent at 25${\circ}$C under $CO_2$free nitrogen atmosphere. The stabilities of the complexes were dependent on the cavity size of macrocycles. The $Hg^{2+}$ ion stability constants are higher than those of $Cd^{2+}\;and\;Pb^{2+}$ ion. All the cryptands formed complexes having 1 : 1 (metal to ligand) mole-ratio except for $Hg^{2+}-L_1$ (cryptand 1,2b: 3,5-benzo-9,14,17-trioxa-1,7-diazabicyclo-(8,5,5) heptadecane) and $Cd^{2+}-L_2$ (cryptand 2,2b: 3,5-benzo-10,13,18,21-tetraoxa-1,7-diazabicyclo (8,5,5) eicosane) complexes. $Hg^{2+}-L_1$ complex was a sandwitch type, and the $Cd^{2+}-L_2$ complex showed two stepwise reactions. Thermodynamic parameters of the $Cd^{2+}-L_2$ complex were $6.08(log\;K_1)$, -7.28 Kcal/mol $({\Delta}H_1)$, and $4.78\;(log\;K_2)$, -4.62 Kcal/mol $({\Delta}H_2)$, respectively, for 1 : 1 and 2: 1 mole-ratio. The sequences of the selectivity were increased in the order of $Hg^{2+}\;>Pb^{2+}\;>Cd^{2+}$ ion for $L_3\;and\;L_4$ macrocycles, and the $L_2$-macrocycle has a selectivity for $Cd^{2+}$ ion relative to $Zn^{2+},\;Ni^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions. Thus, it is expected that the $L_2$ can be used as carrier for seperation of the post transition metals by macrocycles-mediated liquid membrane because $L_2$ is not soluble in water, and the difference of stability constants of the metal complexes with $L_2$ are large as compared with the other transition metal complexes. The $^1H\;and\;^{13}C-NMR studies indicated that the nitrogen atoms of cryptands have greater affinity to the post transition metal ions than the oxygen atoms, and that the planarities of the macrocycles were lost by complexation with the metal ions because of the perturbation of ring current of benzene molecule attached to macrocycles and counter-anions.
Proceedings of the Materials Research Society of Korea Conference
/
2011.05a
/
pp.244.2-244.2
/
2011
We introduce a novel and robust method for the preparation of nanocomposite multilayers, which allows the excellent photoluminescent (PL) properties as well as the accurate control over the composition and dimensions of multilayers. By exchanging the oleic acid stabilizers of CdSe@ZnS quantum dots (QDs) synthesized in organic solvent with 2-bromo-2-methylpropionic acid (BMPA) in the same solvent, these nanoparticles were be alternately deposited by nucleophilic substitution reaction with highly branched poly(amidoamine) dendrimer (PAMA) through layer-by-layer (LbL) assembly process. Our approach does not need to be transformed into the water-dispersible nanoparticles with electrostatic or hydrogen-bonding groups, which can deteriorate their inherent properties, for the built-up of multilayers. The nanocomposite multilayers including QDs exhibited the strong PL properties achieving densely packed surface coverage as well as long-term PL stability under atmospheric conditions in comparison with those of conventional LbL multilayers based on electrostatic interaction. Furthermore, we demonstrate that the flexible multilayer films with optical properties can be easily prepared using nucleophilic substitution reaction between bromo and amino groups in organic media. This robust and tailored method opens a new route for the design of functional film devices based on nanocomposite multilayers.
A new rhodamine-based sensor 1 was designed and synthesized by incorporating rhodamine B and benzimidazole moieties. Sensor 1 exhibits high selectivity and sensitivity to $Cu^{2+}$ in $CH_3CN$-water solution (HEPES buffer, pH = 7.0) with an obvious color change from colorless to pink. Other metal ions such as $Hg^{2+}$, $Ag^+$, $Pb^{2+}$, $Sr^{2+}$, $Ba^{2+}$, $Cd^{2+}$, $Ni^{2+}$, $Co^{2+}$, $Fe^{2+}$, $Mn^{2+}$, $Cu^{2+}$, $Zn^{2+}$, $Ce^{3+}$, $Mg^{2+}$, $K^+$ and $Na^+$ had no such color change and have no significant influence on $Cu^{2+}$ recognition process. The interaction of $Cu^{2+}$ and sensor 1 was proven to adopt a 1:1 binding stoichiometry and the recognition process is reversible.
An investigation of grain size, organic compounds and metal distribution in 23 sediment samples of the Geum-River basin (Korea) was conducted in two seasons of 2012 (dry season and rainy season). The samples of sediment were collected from the basin and investigated for concentrations of some metal and general indexes containing grain size. Concentrations of Pb, Zn, Cu, Cr, Ni, As, Cd, Hg, Al and Li have been determined by inductively coupled plasma spectrometer (ICP) and the sediments organic matter content was determined by the loss on ignition, and sediments were fractionated with three different nylon sieves. Correlation analysis was made for grain size, organic material and metal concentrations, and the Pearson correlation coefficients between their concentrations were determined. As a result, the higher metal concentrations were found in the period of the dry season than in another season. The metal concentrations showed high correlation with that of organic material (COD and TOC). Thereby, the high distribution of metal concentrations in sediment containing high organic compound is suggesting an interaction with organic matter.
Low impact development (LID) facilities are established for the purpose of restoring the natural hydrologic cycle as well as the removal of pollutants from stormwater runoff. Improved efficiency of LID facilities can be obtained through the optimized interaction of their major components (i.e., plant, soil, filter media, microorganisms, etc.). Therefore, this study was performed to evaluate the performances of LID facilities in terms of runoff and pollutant reduction and also to provide an optimal maintenance method. The monitoring was conducted on four LID technologies (e.g., bioretention, small wetlands, rain garden and tree box filter). The optimal SA/CA (facility surface area / catchment area) ratio for runoff reduction greater than 40% is determined to be 1 - 5%. Since runoff reduction affects the pollutant removal efficiency in LID facilities, SA/CA ratio is derived as an important factor in designing LID facilities. The LID facilities that are found to be effective in reducing stormwater runoff are in the following order: rain garden > tree box filter > bioretention> small wetland. Meanwhile, in terms of removal of particulate matter (TSS), the effectiveness of the facilities are in the following order: rain garden > tree box filter > small wetland > bioretention; rain gardens > tree box filter > bioretention > small wetland were determined for the removal of organic matter (COD, TOC), nutrients (TN, TP) and heavy metals (Cu, Pb, Cd, Zn). These results can be used as an important material for the design of LID facilities in runoff volume and pollutant reduction.
This experiment was carrid out to investigate the interaction between boilelr strains and nutrition levels, and the performances of four broiler strains such as Han Hyup 603, Hubbard, Anak and Filch when they were fed by four different nutrition levels (High Protein and energy; HP. HE., Medium Protein and energy; MP. ME., Low Protein ana energy; LP. LE., and low protein and energy; LLP. LLE.). The data used in this study were obtained from a total of 1200 broiler type chicks in Poultry Testing Station, Korean Poultry Association from June 16, to August 11, 1978. Differences of all characters among four nutrition levels were significant except viability and carcass rate. HP. HE and MP. ME treatments showed nearly the same performances in body weight, feed efficiency and point, spread but they were significantly superior to those of LP. LE and LLP. LLE. There were not significant differences among four strains in feed efficiency and viability but other characters, body weight, point spread and carcass rate were observed that the performance of the best strain B was significantly superior to strain D but it was not recognized significance compared with strain A, C in tile result of statisticel analysis. In the interaction between strains and nutrition levels, body weight at high and levels showed significantly differences but at low and low nutrition levels were nearly same among four strains. Therefore this study demonstrated that comparision of body weights between strains should be performed at medium nutrition level or above. Also point spread calculated as index of body weight and feed efficiency was observed that strain B at low nutrition level is excellently higher than other strains and there were little differences at low nutrition level among all strains. It was found that ]it tie differences between performances of high arid medium levels seemed to be as the reason of high fat addition for energy source to high mutrition feed, and in general superior strain showed good performance at all the nutrition levels in$.$all characters but in body weight and point spread there were significantly different responses with different nutrition level, The most superior strain B among four strains earned the most profit per bird, Although performances of high and medium nutrition levels were nearly the same, medium nutrition level also showed the most profit because the feed cost of high nutrition level was higher than that of medium nutrition level.
Park Yeong-Chul;Park Hae-Mo;Ko Seong-Gyu;Lee Sun-Dong;Park Hong-Duok
Journal of Environmental Health Sciences
/
v.32
no.3
/
pp.199-206
/
2006
Various heavy metals have been known for causing ischemic stroke. In order to describe the causative relationship between the blood levels of various heavy metals and stroke patients, 116 patients with stroke and 111 patients without stroke were selected from one Oriental medical hospital in Wonju, Korea. Total of 9 kinds of metals such as As, Cd, Co, Cu, Hg, Mn, Ni, Pb, and Zn were analyzed in blood from patients with and without stroke. There were no significant differences in the means of metal concentrations between the stroke and nonstroke patients except for the mean of Co concentration. In the case of Co, the means for stroke and non-stroke patients were 0.44 ug/l and 0.40 ug/l showing a significant difference at the level of p-value=0.05. The odds ratios for each metal ranged from 0.96 to 2.86. Most odds ratios were not significant but the odds ratio for Co, $2.86{\pm}1.49$ was significant, indicating that Co increases the risk of stroke by 2.86 times. In order to identify the specific risk level of stroke increased by a multiple interaction of metals, regression coefficients and odds ratio for a pair or multiple pair of metals were reanalyzed. However, all of regression coefficients and odds ratios were not significant. In conclusion, Co showed the significant level in blood from patients with stroke. In addition, the odds ratio of stroke was significantly different from other metals. Thus, it is considered that Co among various metals analyzed in this study is the important metal for increasing the risk of stroke.
Novel $CO_2$-soluble 8-hydroxyquinoline (8-HQ) chelating agents were synthesized and evaluated for solubility and metal ion extraction ability in supercritical $CO_2\;(Sc-CO_2)$. Among them, secondary amide-containing 8- HQ derivatives cannot be dispersed well into Sc-$CO_2$, but tertiary amide-containing derivatives can dissolve completely in Sc-$CO_2$ even at low CO2 pressures, perhaps owing to the predominant intermolecular interaction between the chelating agent and the $CO_2$ molecule. Based on 8-HQ chelating agent solubility data, we investigated the extraction of metal ions ($Co^{2+}$, $Cu^{2+}$, $Sr^{2+}$, $Cd^{2+}$, and $Zn^{2+}$) using two highly $CO_2$-soluble 8-HQ derivatives (4d, 4e) in Sc-$CO_2$. The extraction efficiency of tertiary amide-containing 8-HQ ligands, both fluorinated and non-fluorinated forms, was dramatically increased in the presence of diethyl amine (organic base). We suggest that diethyl amine could play an important synergistic role in the stronger metal binding ability of 8-HQ through an in situ deprotonation reaction in Sc-$CO_2$ medium.
Moon-Hwan Cho;Hea-Suk Chun;Jin-Ho Kim;Chang-Hwan Rhee;Si-Joong Kim
Bulletin of the Korean Chemical Society
/
v.12
no.5
/
pp.474-477
/
1991
The preferential transport phenomena of neutral cation-anion moieties in neutral macrocycle-facilitated emulsion liquid membrane were described in this study. Emulsion membrane systems consisting of (1) aqueous source phase containing 0.001 M M($NO_3$)$_2(M=Mn^{2+},\;Co^{2+},\;Ni^{2+},\;Cu^{2+},\;Zn^{2+},\;Sr^{2+},\;Cd^{2+},\;and\;Pb^{2+})$ (2) a toluene membrane containing 0.01 M ligand $(DBN_3O_2$, DA18C6, DT18C6, TT18C6, HT18C6) and the surfactant span 80 (sorbitan monooleate) (3% v/v) and (3) an aqueous receiving phase containing $Na_2S_2O_3$ or $NaNO_3$ were studied with respect to the disappearence of transition metal ions from the source phase as a function of time. Cation transports for various two component or three component equimolar mixture of transition metal and $Cu^{2+}$ in a emulsion membrane system incorporating macrocyclic ligand (HT18C6) as carrier were determinded. $Cu^{2+}$ was transported higher rates than the other $M^{2+}$ in the mixture solution. Equilibrium constants for cation-source phase co-anion, cation macrocycle and cation-receiving phase reagent interaction are examined as parameters for the prediction of cation transport selectivities.
Proceedings of the Botanical Society of Korea Conference
/
1987.07a
/
pp.133-148
/
1987
Gibberellin(GA) 3-$\beta$ hydroxylation is very important for the shoot elogation in the higher plants, since only 3$\beta$-hydryoxylated GAs promote shoot elogation in several plants. Fluctuation of 3$\beta$-hydryoxylase activity was examined during seed maturation using two cultivars of , P. vulgaris, Kentucky Wonder (normal) and Masterpiece (dwarf). Very immature seeds of both cultivars contain high level of 3$\beta$-hydroxylase activity (per mg protein). Both cultivars showed maximum of enzyme activity (per seed) in the middle of their maturation process. Gibberellin 3$\beta$-hydroxylase catalyzing the hydroxylation of GA20 to GA1 was purified 313-fold from very early immature seeds of P. vulgaris. Crude soluble enzyme extracts were purified by 15% methanol precipitation, hydrophobic interaction chromatogrphy, DEAE ion exchange column chromatography and gel filtration HPLC. The 3$\beta$-hydroxylase activity was unstable and lost much of its activity duting the purification. The molecular weight of purified enzyme was extimated to be 42, 000 by gel filtration HPLC and SDS-PAGE. The enzyme exhibited maximum activity at pH 7.7. The Km values for [2.3-3H] GA20 and [2.3-3H]GA9 were 0.29 $\mu$M and 0.33 $\mu$M, respectively. The enzyme requires 2-oxoglutarate as a cosubstrate; the Km value for 2-oxoglutarate was 250 $\mu$M using 3H GA20 as a substrate. Fe2+ and ascorbate significantly activated the enzyme at all purification steps, while catalase and BSA activated the purified enzyme only. The enzyme was inhibited by divalent cations Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+. Effects of several GAs and GA anaogues on the putrified 3$\beta$-hydroxylase were examined using [3H]GA9 and GA20 as a substrates. Among them, GA5, GA9, GA15, GA20 and GA44 inhibited the enzyme activity. [13C, 3H] GA20 was converted by the partially purified enzyme preparation to [13C, 3H]GA1, GA5 and GA6, which were identified by GC-MS, GA9 was converted only GA4, GA15 and GA44 were converted to GA37 and GA38, respectively. GA5 was epoxidized to GA6 by the preparation. This suggests that 3$\beta$-hydroxylation of GA20 and epoxidation of GA5 are catalyzed by the same enzyme in P, vulgaris.
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