• Journal of the Korean Chemical Society
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• v.51 no.4
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• pp.324-330
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• 2007

A new ion selective PVC membrane electrode is developed as a sensor for mercury(II) ions based on bis(benzoylacetone) propylenediimine (H2(BA)2PD) as an ionophore. The electrode shows good response characteristics and displays, a linear Emf vs. log[Hg2+] response over the concentration range of 1.0×10-6 to 1.0×10-1 M Hg(II) with a Nernstian slope of 29.8±0.75 mV per decade and with a detection limit of 2.2×10-7 M Hg(II) over the pH range of 2.5-11.5. Selectivity concentrations for Hg(II) relative to a number of potential interfering ions were also investigated. The sensor is highly selective for Hg(II) ions over a large number of cations with different charge. The sensor has been found to be chemically inert showing a fast response time of 60 s and was used over a period of 3 months with a good reproducibility (S = 0.27 mV). The electrode was successfully applied to determine mercury(II) in real samples with satisfactory results.

• Journal of the Korean Electrochemical Society
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• v.11 no.1
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• pp.59-63
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• 2008

Poly (vinylchloride) (PVC) membrane electrodes based on neutral carrier, tetracycline was prepared as an active sensor for Hg(II) ion, and tested in different contents of the potassium tetrakis (4-chlorophenyl) borate (KTpClPB) as lipophilic salt. Bis (2-ethylhexyl) sebacate (DOS), bis(l-butylpentyl) adipate (BBPA), 2-nitrophenyl octyl ether (NPOE) and dibutyl phthalate (DBP) were used as diverse plasticizing solvent mediators. This electrode shows excellent potentiometric response characteristics and display good linearity with log $[Hg^{+2}]$ versus EMF response, over a range of concentrations between $10^{-7}$ and $10^{-3}M$. With 30.8mV/decade Nernstian slope, the detection limit was $6.9{\times}10^{-9}M$ and the response time was less than 20s. The proposed electrode yields very good selectivity for mercury (II) ion over many cations such as alkali, alkaline earth, transition and heavy metal ions. And it shows a very stable potential values in a wide pH range. This reliable electrode prepared was kept at least a month without considerable alteration in their response to Hg (II) ion.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3707-3710
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• 2010

A chromo/fluorogenic $NO_2S_2$-macrocycle L functionalized with nitrobenzofurazan unit as a dual-signaling probe was synthesized and structurally characterized by single crystal X-ray analysis. In a cation-induced color change experiment, L exhibited excellent $Hg^{2+}$ ion selectivity by showing the color change from orange-red to yellow. However, this hypochromic shift by $Hg^{2+}$ was observed for the weaker coordinating anion system such as ${NO_3}^-$ and ${ClO_4}^-$ ions. The observed anion effect is due to the strong coordination of anions inhibits the bond formation between $Hg^{2+}$ and the macrocyclic tert-N atom, which is sensitive to induce the color change. In the fluorometric experiment, L showed chelate-enhanced fluorescence change effect only with $Hg^{2+}$ ion, together with a change from yellow to green emission. The sensing ability for $Hg^{2+}$ with the proposed chemosensor L is due to the stable complexation with 1:1 stoichiometry (metal-to-ligand).

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.223-229
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• 1992

Mechanistic studies on the metal-exchange reactions of sparteine copper(II) dichloride [$SpCuCl_2$] with Hg(II) ion and Hg(0) metal have been carried out with the aid of Cyclic Voltammetry and UV-visible spectrophotometry. The metal exchange reaction of $SpCuCl_2$ with both Hg(II) ion and Hg(0) metal follows pseudo-first order kinetics. Rate constants and activation parameters of metal exchange reaction have been evaluated and reported. Experimental results indicate that the rate determining step for the exchange reaction is the cleavage of Cu(II)-N bond in the transient binuclear complex of Cu(II) and mercury(II) bound to sparteine ligand.

• Applied Chemistry for Engineering
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• v.34 no.5
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• pp.556-565
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• 2023

Fast industrial and agricultural expansion result in the production of heavy metal ions (HMIs). These are exceedingly hazardous to both humans and the environment, and the necessity to eliminate them from aqueous systems prompts the development of novel materials. In the present study, a UIO-66 (COOH)₂ metal-organic framework (MOF) containing free carboxylic acid groups was post-synthetically modified with L-glutamic acid via the solid-solid reaction route. Pristine and glutamic acid-treated MOF materials were characterized in detail using several physicochemical techniques. Single-ion batch adsorption studies of Pb(II) and Hg(II) ions were carried out using pristine as well as amino acid-modified MOFs. We further examined parameters that influence removal efficiency, such as the initial concentration and contact time. The bare MOF had a higher ion adsorption capacity for Pb(II) (261.87 mg/g) than for Hg(II) ions (10.54 mg/g) at an initial concentration of 150 ppm. In contrast, an increased Hg(II) ion adsorption capacity was observed for the glutamic acid-modified MOF (80.6 mg/g) as compared to the bare MOF. The Hg(II) ion adsorption capacity increased by almost 87% after modification with glutamic acid. Fitting results of isotherm and kinetic data models indicated that the adsorption of Pb(II) on both pristine and glutamic acid-modified MOFs was due to surface complexation of Pb(II) ions with available -COOH groups (pyromellitic acid). Adsorption of Hg(II) on the glutamic acid-modified MOF was attributed to chelation, in which glutamic acid grafted onto the surface of the MOF formed chelates with Hg(II) ions.

• Applied Chemistry for Engineering
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• v.35 no.4
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• pp.352-359
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• 2024

Environmental pollution from heavy metal ions (HMIs) is a global concern. Recently, biosorption methods using cellulose sorbents have gained popularity. The objective of this study was to assess the removal efficiency of Cu(II), Pb(II), and Hg(II) ions at low concentration levels (100-700 ppb) from aqueous solutions using three different cellulose fiber-based filter media. Sample A was pure cellulose fiber, Sample B was 10% activated carbon-cellulose fiber, and Sample C was cellulose fiber-glass fiber-30% activated carbon-20% amorphous titanium silicate (ATS). The samples were characterized by several physicochemical techniques. The porosity measurements using N₂ sorption isotherms revealed that Samples A and B are nonporous or macroporous materials, whereas the addition of 50% filler materials into the cellulose resulted in a microporous material. The Brunauer-Emmett-Teller (BET) surface area and pore volume of Sample C were found to be 320.34 m²/g and 0.162 cm³/g, respectively. The single ion batch adsorption experiments reveal that at 700 ppb initial metal ion concentration, Sample A had removal efficiencies of 7.5, 11.5, and 13.7% for Cu(II), Pb(II), and Hg(II) ions, respectively. Sample B effectively eliminated 99.6% of Cu(II) ions compared to Pb(II) (14.2%) and Hg(II) (31.9%) ions. Cu(II) (99.37%) and Pb(II) (96.3%) ions are more efficiently removed by Sample C than Hg(II) (68.2%) ions. The X-ray photoelectron spectroscopy (XPS) wild survey spectrum revealed the presence of Cu(II), Pb(II), and Hg(II) ions in HMI-adsorbed filter media. The high-resolution C1s spectra of Samples A and B reveal the presence of -C-OH and -COOH groups on their surface, which are essential for HMIs adsorption via complexation reactions. Additionally, the ATS in Sample C facilitates the adsorption of Pb(II) and Hg(II) ions through ion exchange.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.346-350
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• 2002

A glassy carbon electrode (GCE) modified with 2,2':6':2”-terpyridine (2,2':6':2”-TPR) using a spin coating method was applied for the highly selective and sensitive analysis of a trace amount of $Hg_2^{2+}$ ions. Various experimental parameters, which influenced the response of the 2,2':6':2”-TPR modified electrode to $Hg_2^{2+}$ ions, were optimized. The linear sweep and differential pulse voltammograms for the 2,2':6':2”-TPR modified electrode deposited with Hg show a well-defined anodic peak at +0.65 V (vs. Ag|AgCl). After a 25 min preconcentration time in an $Hg_2^{2+}$ ion solution (0.1 M acetate buffer, pH 5.0), differential pulse voltammetry(DPV) with 2,2':6':2”-TPR modified electrode shows a linear response between $1.0\;{\times}\;10^{-6}M\;and\;2.0\;{\times}\;10^{-7}M$. The least-square treatment of these data produce an equation of I[${\mu}A$] = 0.031 + 0.005C with r = 0.980(n = 5). The detection limit of this electrode with linear sweep voltammetry and differential pulse anodic voltammetry were $2.0\;{\times}\;10^{-6}M\;and\;8.0\;{\times}\;10^{-8}M$, respectively. The presence of Pb, Fe, Cd, Ti, Ni, Co, Mg, Al, Mn, and Zn did not interfere in the analysis of the $Hg_2^{2+}$ ion. The 2,2':6':2”-TPR modified GCE has been successfully applied in determination trace amounts of Hg in a human urine sample.

• Proceeding of EDISON Challenge
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• 2014.03a
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• pp.275-285
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• 2014

Dipyrene-based fluorescent chemosensor(분자 1)가 개발되었다. 분자 1은 여러 금속이온 중 $Cu^{2+}$와 $Hg^{2+}$의 fluorescent chemosensor로서 센싱할 수 있고, excimer-switch off mechanism에 따라 $Cu^{2+}$와 $Hg^{2+}$ 금속이온을 감지한다. Ground state와 excited state에 대한 DFT와 TD-DFT 방법을 통해 분자 1의 $Hg^{2+}$에 대한 형광 turn on/off을 확인하고, 구조변화에 따른 molecular orbital을 계산하였다. 계산결과 분자 1은 excited state에서 excimer를 형성할 수 있으나 $1+Hg^{2+}$는 excimer를 형성하지 못함을 알 수 있었다. 여기서 우리는 분자 1과 $Hg^{2+}$ 금속이온 결합에 대하여 실험값과 비교 분석하여 그 메커니즘 조사하였다.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.687-691
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• 1993

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.

• Bulletin of the Korean Chemical Society
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• v.31 no.1
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• pp.230-233
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• 2010