• Journal of the Korean Chemical Society
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• v.55 no.1
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• pp.38-45
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• 2011

The complexation behavior of the $\alpha$-ketostabilized phosphorus ylides $Ph_3P$=CHC(O) $C_6H_4-X$ (X=Br, Ph) towards the transition metal ions mercury (II) and Silver (I) was investigated. The mercury(II) complex {$HgX_2$ [Y]} 2 ($Y_1$=4-bromo benzoyl methylene triphenyl phosphorane; X=Cl(1), Br(2), I(3), $Y_2$=4-phenyl benzoyl methylene triphenyl phosphorane; X=Cl(4), Br(5), I(6)) have been prepared from the reaction of $Y_1$ and $Y_2$ with $HgX_2$ (X=Cl, Br, I) respectively. Silver complexes [$Ag(Y_2)_2]$ X(X=$BF_4$(7), OTf(8)) of the $\alpha$-keto-stabilized phosphorus ylides ($Y_2$) were obtained by reacting this ylide with AgX (X=$BF_4$, OTf) in $Me_2CO$. The crystal structure of complexes (1) and (4) was discussed. These reactions led to binuclear complexes C-coordination of ylide and trans-like structure of complexes $[Y_1HgCl_2]_2$. $CHCl_3$ (1) and $[Y_2HgCl_2]_2$ (4) is demonstrated by single crystal X-ray analyses. Not only all of complexes have been studied by IR, $^1H$ and $^{31}P$ NMR spectroscopy, but also complexes 1-3 have been characterized by $^{13}$CNMR.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.215-224
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• 1989

Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.2031-2035
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• 2010

A triple-probe channel type chemosensor based on an $NO_2S_2$-macrocycle functionalized with phenyltricyanovinyl group was synthesized and its sensing characteristics were examined. The pink-red solution of L changed selectively to pale yellow upon addition of $Hg^{2+}$. The selective fluorometric response of L to all the tested metal ions was studied. The results showed that a large enhancement of the fluorescence of L was observed only in the case of $Hg^{2+}$. In addition, L showed large anodic shift (~ 0.3 V) for the addition of excess $Hg^{2+}$. Through above three observed results by the different techniques, we confirmed that the proposed chemosensor acts as the multiple-probe channel sensing material. The crystal structure of mercury(II) nitrate complexs of L which shows a 1-D polymer network with a formula $[Hg_2(L)_2(NO_3)_2({\mu}-NO_3)_2]_n$ was also reported.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.545-552
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• 1991

A mercury ion-sensitive carbon-paste electrode (CPE) was constructed with l-sparteine. Mercury (II) ion was chemically deposited by the complexation with l-sparteine onto the CPE. The surface of CPEs was characterized by cyclic voltammetry and anodic stripping voltammetry in an acetate buffer solution, separately. Exposure of CPEs to acid solution could regenerate surface and reuse it for deposition. In 5 deposition/measurement/regeneration cycle, the response was reproducible and in licnear up to $2.0\;{\times}\;10^{-6}$ M with linear sweep voltammetry. In case of using the differential pulse technique, we have obtained the linear response up to $7.0 {\times}10^{-7}$ M with relative standard deviation of ${\pm}5.1$%. The detection limit was $5.0{\times}10^{-7}$ M for 20 minutes of the deposition. We have investigated the interference effect of various metal ions, which are expected to form the complex with ligand. Silver (I) ion of these has interfered with the analysis of Hg (II) ions. However, pretreatment of the silver (I) ion with potassium chloride led to no interference on the analysis of mercury ions in aqueous solution.

• Journal of Photoscience
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• v.1 no.1
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• pp.47-52
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• 1994

Effects of HgCl$_2$-treatment on electron transport, chlorophyll a fluorescence and its quenching were studied using isolated barley (Hordeum vulgare L. cv. Albori) chloroplasts. Depending on the concentration of HgCI$_2$, photosynthetic oxygen-evolving activities of photosystem II (PS II) were greatly inhibited, whereas those of photosystem I (PS I) were slightly decreased. The inhibitory effects of HgCl$_2$ on the oxygen-evolving activity was partially restored by the addition of hydroxyamine, suggesting the primary inhibition site by HgCl$_2$2-treatment is close to the oxidizing site of PS tl associated with water-splitting complex. Addition of 50 $\mu$M HgCI$_2$ decreased both photochemical and nonphotochemical quenching of chlorophyll fluorescence. Especially, energy dependent quenching (qE) was completely disappeared by HgCl$_2$-treatment as observed by NH$_4$CI treatment. In the presence of HgCI$_2$, F'o level during illumination was also increased. These results suggest that pH gradient across thylakoid membrane can not be formed in the presence of 0 $\mu$M HgCl$_2$. In addition, antenna pigment composition might be altered by HgCl$_2$-treatment.

• Bulletin of the Korean Chemical Society
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• v.34 no.5
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• pp.1429-1434
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• 2013

A synthesis and cation-induced fluorescent behavior of the carbazole-attached $NO_2S_2$-macrocycle (L) is described and structurally characterized by single crystal X-ray analysis. The photoluminescence spectrum of L in 80% $CH_3CN/CH_2Cl_2$ displays a peak maximum at 431 nm (blue emission). In the metal-induced fluorometric experiment, L showed a drastic chelation-enhanced fluorescence quenching (CHEQ) effect only with $Hg^{2+}$ and $Cu^{2+}$. In ESI-mass study, a 1:1 stoichiometry for complexation of L with $Hg^{2+}$ was confirmed, suggesting the unique sensing behavior of the proposed ligand L due to the selective complexation affinity for $Hg^{2+}$. The observed results indicate that L is a promising turn-off type fluoroionophore for $Hg^{2+}$ and $Cu^{2+}$ detections. Additionally, the $Ag^+$ complex of the precursor macrocycle was prepared and its solid structure was crystallographically characterized.

• Journal of the Korean Chemical Society
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• v.57 no.5
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• pp.568-573
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• 2013

A selective and sensitive method for simultaneous determination of copper in blood by adsorptive differential pulse cathodic stripping voltammetry is presented. The procedure involves an adsorptive accumulation of Cu(II)-ETSC (4- ethyl-3-thiosemicarbazide) on a hanging mercury drop electrode, followed by a stripping voltammetry measurement of reduction current of adsorbed complex at about -715 mV. The optimum conditions for the analysis of copper (II) ion are : pH 10.3, concentration of 4-ethyl-3-thiosemicarbazide $3.25{\times}10^{-6}$ M and an accumulation potential of -100 mV. The peak current is proportional to the concentration of copper over the range 0.003-125 ng/mL with a detection limit of 0.001 ng/mL and an accumulation time of 60 s. Moreover, with the use of the proposed method, there is a considerable improvement in the detection limit, the linear dynamic range and the deposition time, compared with the methods of adsorptive stripping voltammetry for the determination of copper. The developed method was validated by analysis of whole blood certified reference materials.