• Journal of the Korean Chemical Society
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• v.68 no.3
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• pp.139-145
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• 2024

This study aims to elucidate the mechanism involved in the hydrolysis of the hexacyanoferrate(III) complex ion (Fe(CN)₆^3-) and the mechanism leading to the formation of Prussian blue (Fe^III₄[Fe_II(CN)₆]₃·xH₂O, PB) in acidic aqueous solutions at moderately elevated temperatures. Hydrolysis constitutes a crucial step in generating PB through the widely used single-source or precursor method. Recent PB syntheses predominantly rely on the single-source method, where hexacyanoferrate(II/III) is the exclusive reactant, as opposed to the co-precipitation method employing bare metal ions and hexacyanometalate ions. Despite the widespread adoption of the single-source method, mechanistic exploration remains largely unexplored and speculative. Utilizing UV-vis spectrophotometry, negative-ion mode liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and a devised reaction, this study identifies crucial intermediates, including aqueous Fe^2+/3+ ions and hydrocyanic acid (HCN) in the solution. These two intermediates eventually combine to form thermodynamically stable PB. The findings presented in this research significantly contribute to understanding the fundamental mechanism underlying the acid-catalyzed hydrolysis of the hexacyanoferrate(III) complex ion and the subsequent formation of PB, as proposed in the sequential mechanism introduced herein. This finding might contribute to the cost-effective synthesis of PB by incorporating diverse metal ions and potassium cyanide.

• Journal of the Korean Chemical Society
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• v.56 no.6
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• pp.679-691
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• 2012

New series of metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Pd(II) and Pt(II) with 4-(p-chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide (HCPTS) have been synthesized and characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, $^1H$ NMR, mass and ESR) and thermal studies. The IR data suggest different coordination modes for HCPTS which behaves as a monobasic bidentate with all metal ions except Cu(II) and Zn(II) which acts as a monobasic tridentate. Based on the electronic and magnetic studies, Co(II), Cu(II), Pd(II) and Pt(II) complexes have square - planner, Ni(II) has mixed stereochemistry (tetrahedral + square planar), while Zn(II) is tetrahedral. Molar conductance in DMF solution indicates the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complex show $g_{\parallel}$ (2.2221) > $g_{\perp}$ (2.0899) > 2.0023 indicating square-planar structure and the presence of the unpaired electron in the $d_x2_{-y}2$ orbital with significant covalent bond character. The thermal stability and degradation kinetics of the ligand and its metal complexes were studied by TGA and DTA and the kinetic parameters were calculated using Coats-Redfern and Horowitz-Metzger methods. The complexes have more antibacterial activity against some bacteria than the free ligand. However, the ligand has high anticancer activities against HCT116 (human colon carcinoma cell line) and HEPG2 (human liver hepatocellular carcinoma cell line) compared with its complexes.

• Bulletin of the Korean Chemical Society
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• v.31 no.8
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• pp.2185-2189
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• 2010

Closely arranged CdSe and Zn doped CdSe vertical nanorod bundles were grown directly on FTO coated glass by using electrodeposition method. Structural analysis by XRD showed the hexagonal phase without any precipitates related to Zn. FE-SEM image showed end capped vertically aligned nanorods arranged closely. From the UV-vis transmittance spectra, band gap energy was found to vary between 1.94 and 1.98 eV due to the incorporation of Zn. Solar cell parameters were obtained by assembling photoelectrochemical cells using CdSe and CdSe:Zn photoanodes, Pt cathode and polysulfide (1M $Na_2S$ + 1M S + 1M NaOH) electrolyte. The efficiency was found to increase from 0.16 to 0.22 upon Zn doping. Electrochemical impedance spectra (EIS) indicate that the charge-transfer resistance on the FTO/CdSe/polysulfide interface was greater than on FTO/CdSe:Zn/polysulfide. Cyclic voltammetry results also indicate that the FTO/CdSe:Zn/polysulfide showed higher activity towards polysulfide redox reaction than that of FTO/CdSe/polysulfide.

• Journal of the Korean Chemical Society
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• v.54 no.4
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• pp.402-410
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• 2010

New complexes cis-[$Mo_2O_5(Hapdhba)_2$], trans-[$UO_2(Hapdhba)_2$], [Pd(Hapdhba)Cl($H_2O$)], [Pd(bpy)(Hapdhba)]Cl, [Ag(bpy)(Hapdhba)], [$Ru(Hapdhba)_2(H_2O)_2$], [$Rh(Hapdhba)_2Cl(H_2O)$] and [Au(Hapdhba)$Cl_2$] are reported, where $H_2$apdhba is the Schiff-base derived from 2-aminopyrimidine and 2,4-dihydroxy benzaldehyde. The complexes were characterized by IR, electronic, $^1H$ NMR and mass spectra, conductivity, magnetic and thermal measurements. The inhibitive effect of $H_2$apdhba for the corrosion of copper in 0.5 M HCl was also determined by potentiodynamic polarization measurements.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.44-50
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• 1992

The ability to account for magnetic and spectra properties of complexes was investigated for the splitting of the degenerate d-orbitals and with nonaqueous solution by UV/vis-spectrophotometric method. The correlation of the magnetitude of 10Dq obtained from the spectra, the pairing energy, and the spin state of the complexes. The electrochemical behavior of complexes were investigated by the use of cyclic voltammetry in aprotic media. These reduction peak of $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$ and $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$ were irreversible one-electron processes at peak $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$ and $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$ of these complexes vs. Ag/AgCl, but nickel complexes were not to be reducible.

• Bulletin of the Korean Chemical Society
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• v.11 no.3
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• pp.206-208
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• 1990

Cu(II) hexaazamacrotricyclic complexes $[Cu(L)](ClO_4)_2$ and $[(Cu(L)Cl]ClO_4$, where L = 1,3,6,9,11,14-hexaazatricyclo$[12.2.1.1^{6,9}]octadecane(L_1)$ or 1,3,6,10,12,15-hexaazatricyclo$[13.3.1.1^{6,10}]eicosane(L_2)$, have been prepared by the simple template condensation reactions of triamines, diethylenetriamine for $L_1$, and N-(2-aminoethyl)-1,3-propanediamine for $L_2$, with formaldehyde in the presence of $Cu(OAc)_2\;or\;CuCl_2$. The Cu(II) complexes of $L_1$ contain two 1,3-diazacyclopentane ring moieties and those of $L_2$ contain two 1,3-diazacyclohexane ring moieties that are fused to the 14-membered macrocyclic framework. Spectra indicate that complexes $[Cu(L)](ClO_4)_2\;and\;[Cu(L)Cl]ClO_4$ have square-planar and square-pyramidal chromophores, respectively. square-planar $[Cu(L)](ClO_4)_2$ are remarkably stable against ligand dissociation in acidic aqueous solutions. Square-pyramidal $[Cu(L)Cl]ClO_4$ complexes dissociate their axial Cl-ligands easily in aqueous solutions to form $[Cu(L)H_2O]^{2+}$ species. Infrared and UV/vis absorption spectra of the Cu(II) complexes reveal that Cu-N interactions and the ligand field strengths are significantly weaker in the complexes of $L_2$ than in the complexes of $L_1$.

• Analytical Science and Technology
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• v.12 no.6
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• pp.498-503
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• 1999

Co(II), Ni(II), and Cu(II) complexes with tetradentate schiff base-$NOTDH_2$, were synthesized. The structures of these complexes were characterized by elemental analysis, IR, UV-visible, NMR spectra, and thermogravimetric analysis. The mole ratio of schiff base($NOTDH_2$) to the metal(II) at complexes was found to be 1:1. Cu(II) complexes were four-coordinated configuration, while Co(II) and Ni(II) complexes were hexacoordinated configuration containing two water molecules and all complexes were non-ionic compounds.

• Journal of the Korean Society of Food Science and Nutrition
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• v.30 no.4
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• pp.732-738
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• 2001

This study was attempted to isolate and identify the anticancer compounds from Eucommia ulmoides leaves using a human colon cancer cell line HCT-116. The petroleum ether extracts with anticancer activity was chromatographed on silica gel TLC and finally anticancer compounds was purified by HPLC. Their chemical structures were roughly elucidate by UV-VIS absorption spectral data HPLC elution pattern and FAM/MS spectroscopy. From this study these compounds were suspected to be pheophytin a formed by the removal of $Mg^{2+}$ from chlorophyll a and pyropheophytina formed by the removal of acetate group from pheophytin a respectively. To confirm the anticancer effects against HCT-116 cancer cell petroleum ether extract fractions of column chromatography and fractions separated on TLC were tested. All samples tested including the extract of petroleum ether fractions of column chromatograph and three bands (0.13,0.19,0.25) of TLC appeared to inhibit the growth of HCT-116 cancer cell however especially 0.19 and 0.25 fractions separated on TLC plate revealed the strongest effect. These results suggest that chlorophyll derivatives in Eucommia ulmoides may be potential anticancer agents against a human colon cancer cell HCT-116.

• Korean Journal of Materials Research
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• v.18 no.2
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• pp.84-91
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• 2008

The effects of the deposition and annealing temperature on the structural, electrical and optical properties of Ag doped ZnO (ZnO : Ag) thin films were investigated. All of the films were deposited with a 2wt% $Ag_2O-doped$ ZnO target using an e-beam evaporator. The substrate temperature varied from room temperature (RT) to $250^{\circ}C$. An undoped ZnO thin film was also fabricated at $150^{\circ}C$ as a reference. The as-grown films were annealed in temperatures ranging from 350 to $650^{\circ}C$ for 5 h in air. The Ag content in the film decreased as the deposition and the post-annealing temperature increased due to the evaporation of the Ag in the film. During the annealing process, grain growth occurred, as confirmed from XRD and SEM results. The as-grown film deposited at RT showed n-type conduction; however, the films deposited at higher temperatures showed p-type conduction. The films fabricated at $150^{\circ}C$ revealed the highest hole concentration of $3.98{\times}1019\;cm^{-3}$ and a resistivity of $0.347\;{\Omega}{\cdot}cm$. The RT PL spectra of the as-grown ZnO : Ag films exhibited very weak emission intensity compared to undoped ZnO; moreover, the emission intensities became stronger as the annealing temperature increased with two main emission bands of near band-edge UV and defect-related green luminescence exhibited. The film deposited at $150^{\circ}C$ and annealed at $350^{\circ}C$ exhibited the lowest value of $I_{vis}/I_{uv}$ of 0.05.

• Polymer(Korea)
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• v.27 no.5
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• pp.464-469
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• 2003

In this work, the fragrant oil release behavior of poly($\varepsilon$-caprolactone) (PCL) microcapsules containing SiO$_2$ was investigated. The SiO$_2$ was chemically treated in 10, 20, and 30 wt% hydrochloric acid and sodium hydroxide. The acid and base values were determined by Boehm's titration technique and $N_2$/77 K adsorption isotherm characteristics, the specific surface area and total pore volume were studied by BET. The PCL microcapsules containing SiO$_2$ and fragrant oil were prepared by oil-in-water (o/w) emulsion solvent evaporation method. The shape and surface of PCL microcapsules were observed using image analyzer and scanning electron microscope (SEM). The fragrant oil release behavior of PCL microcapsules was characterized using UV/vis. spectra. The average diameters of PCL microcapsules were decreased from 35 to 21 $\mu$m with increasing stirring rate. It was found that in the case of acidic treatment the fragrant oil adsorption capacity and release rate were increased due to the increase of specific surface area and acid value. In the case of basic treatment, the fragrant oil adsorption capacity and release rate were decreased due to the decrease of sp ecific surface area and the increase of acid-base interactions between SiO$_2$-NaOH and fragrant oil with increasing base value of SiO$_2$.