• Mass Spectrometry Letters
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• v.14 no.4
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• pp.153-159
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• 2023

The copper ion, Cu(II), binding sites for amyloid fragment Aβ1-16 (=Aβ16 ) were investigated to explain the biological activity difference in the Aβ16 aggregation process. The [M+Cu+(z-2)H]^z+ (z = 2, 3 and 4, M = Aβ16 monomer) and [D+Cu+(z-2)H]^z+ (z = 3 and 5, D = Aβ16 dimer) structures were investigated using electrospray ionization (ESI) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Fragment ions of the [M+Cu+(z-2)H]^z+ and [D+Cu+(z-2)H]^z+ complexes were observed using collision-induced dissociation MS/MS. Three different fragmentation patterns (fragment "a", "b", and "y" ion series) were observed in the MS/MS spectrum of the (Aβ16 monomer or dimer-Cu) complex, with the "b" and "y" ion series regularly observed. The "a" ion series was not observed in the MS/MS spectrum of the [M+Cu+2H]⁴⁺ complex. In the non-covalent bond dissociation process, the [D+Cu+3H]⁵⁺ complex separated into three components ([M+Cu+H]³⁺, M³⁺, and M²⁺), and the [M+Cu]²⁺ subunit was not observed. The {M + fragment ion of [M+Cu+H]³⁺} fragmentation pattern was observed during the covalent bond dissociation of the [D+Cu +3H]⁵⁺ complex. The {M + [M+Cu+H]³⁺} complex geometry was assumed to be stable in the [D+Cu+3H]⁵⁺ complex. The {M + fragment ion of [M+Cu]²⁺} fragmentation pattern was also observed in the MS/MS spectrum of the [D+Cu+H]³⁺ complex. The {M + [y₉+Cu]¹⁺} fragment ion was the characteristic fragment ion. The [D+Cu+H]³⁺ and [D+Cu+3H]⁵⁺ complexes were likely to form a monomer-monomer-Cu (M-M-Cu) structure instead of a monomer-Cu-monomer (M-Cu-M) structure.

• Textile Coloration and Finishing
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• v.8 no.6
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• pp.40-46
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• 1996

In order to investigate a practical application of fibrous absorbents to transition metals such as copper, nickel, cobalt, chrome, and iron, amidoximated fiber as a particular class of solid chelate agents were prepared from acrylic fibers treatment with hydroxylamine. The adsorption mechanisms of metal ions onto amidoximated acrylic fibers and their complexes were studied. Amidoximation of acrylic fiber with hydroxylamine is found to be first-order reaction, followed by the disappearance of infrared adsorption peaks due to nitrile groups of acrylic fibers. The uptake of metal ions onto amidoximated acrylic fiber is increased with temperature raising and the adsorption is also depended on pH of the soiutions. About 70% of metal ions can be recovered from aqueous solutions of Ni(II), Co(II), Cr(III), and Fe(II) on the concentration below 5x 10$^$^{-4}$ in the range of pH 2.1~10.0. Transition metals are adsorbed to form complex with amidoxime group by the ligand sites such as C=N, NH, NO, NHOH.OH.

• Journal of Powder Materials
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• v.26 no.3
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• pp.220-224
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• 2019

The aluminum (Al)/copper oxide (CuO) complex is known as the most promising material for thermite reactions, releasing a high heat and pressure through ignition or thermal heating. To improve the reaction rate and wettability for handling safety, nanosized primary particles are applied on Al/CuO composite for energetic materials in explosives or propellants. Herein, graphene oxide (GO) is adopted for the Al/CuO composites as the functional supporting materials, preventing a phase-separation between solvent and composites, leading to a significantly enhanced reactivity. The characterizations of Al/CuO decorated on GO(Al/CuO/GO) are performed through scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy mapping analysis. Moreover, the functional bridging between Al/CuO and GO is suggested by identifying the chemical bonding with GO in X-ray photoelectron spectroscopy analysis. The reactivity of Al/CuO/GO composites is evaluated by comparing the maximum pressure and rate of the pressure increase of Al/CuO and Al/CuO/GO. The composites with a specific concentration of GO (10 wt%) demonstrate a well-dispersed mixture in hexane solution without phase separation.

• Analytical Science and Technology
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• v.13 no.2
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• pp.173-178
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• 2000

A new open-chain ligand containing two phenol groups, 1, 14-Bis (2-hydroxybenzyl)-2, 6, 9, 12-tetraazatetradecane(bsated) was synthesized as its tetrahydrochloride salt and characterized by elemental analysis, mass, infrared and NMR. Its proton dissociation constants ($logK^n{_H}$) and stability constants ($logK_{ML}$) toward $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$ and $Zn^{2+}$ were determined at $25^{\circ}C$ and 0.10M($KNO_3$) ionic strength in aqueous solution by potentiometry. The X-ray structure of its copper (II) complex [Cu(bsated)]$(ClO_4)_2$ was reported: Monoclinic space group $P2_1/n$, $a=17.856(4){\AA}$, $b=17.709(1){\AA}$, $c=8.539(2){\AA}$, $V=2700(2){\AA}$ with Z=4. Electrochemical studies of [Cu(bsated)]$(ClO_4)_2$ complex in dimethyl sulfoxide (DMSO) solution containing tetrabutylammonium perchlorate (supporting electrolyte) were carried out by cyclic voltammograms (CV) and normal pulse voltammetry (NPV).

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.2981-2987
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• 2011

A comparative study of the photodynamic and antioxidant activities of methyl pheophorbide-a (MPa, 1) and its transition metal(II) complexes (2-5) is described. Four transition metal complexes (palladium(II): 2, zinc(II): 3, cobalt(II): 4 and copper(II): 5) of MPa were prepared by reaction between the corresponding transition metal and 1, respectively, and were characterized by $^1H$-NMR and UV-vis spectroscopic and mass spectrometric analyses. In vitro results show a photodynamic therapy (PDT) efficacy with A549 cells might be attributed to a heavy atom effect of the transition metal complexes of MPa. Among them, 4 and 5 showed higher photodynamic activity than that of 1 at the concentration of 5 ${\mu}M$ at 24 h incubation after photoirradiation. The images of morphological change for 2-5 show evidence for the PDT effect with A549 cells. And the all transition metal complexes of MPa showed higher antioxidant activity than that of MPa, in which 4 showed the highest antioxidant activity.

• Analytical Science and Technology
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• v.8 no.4
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• pp.511-517
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• 1995

A cationic water soluble porphyrin (5,10,15,20-tetrakis (l-methyl-pyridinium-4-yl)porphyrin, $H_2tmpyp^{4+}$) and its metalloporphyrins (MP) were easily extracted into acetonitrile separated by addition of sodium chloride ($4mol\;dm^{-3}$) in the presence of sodium perchlorate, where M denotes $Zn^{2+}$, $Cu^{2+}$, $Co^{3+}$, $Fe^{3+}$, and $Mn^{3+}$ and $P^{2-}$ is porphyrinate ion. The extracted ion-pair complexes were completely dissociated to $[MP(ClO_4)_3]^+$, and $[MP(ClO_4)_2]^{2+}$. The extraction and the dissociation constants were determined by taking into account of the partition constant of sodium perchlorate ($K_D=1.82{\pm}0.01$). The chemical properties of the separated acetonitrile phase as $E_{T(30)}$ and $D_{II,I}$ were determined and compared with other water miscible solvents (acetone, actonitrile, 1,4-dioxane, tetrahydrofuran, 1-propanol and 2-propanol). Furthermore, a sensitive and selective method was proposed for the determination of a subnanogram amount of copper(II) in natural water samples by using the present salting-out method and the porphyrins.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.1017-1021
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• 2011

Two new benzimidazolyl-containing complexes have been synthesized by reactions of $Cu^{II}$ salts and 1,2-bis(benzimidazolyl) benzene ($H_2bbbz$) with two different dicarboxylate ligands. When phthalate acid ($H_2pt$) was employed as secondary ligand, a 0D molecular complex Cu$(H_2bbbz)(pt){\cdot}(H_2pt)$ (1)was furnished and when the secondary ligand was instead by a linear bridging ligand of terephthalic acid ($H_2tp$) a 1D zipper-like coordination polymer $[Cu(H_2bbbz)(tp){\cdot}2(C_2H_5OH){\cdot}H_2O]_n$ (2) was obtained, suggesting the structure-direction effect of the secondary dicarbxylate ligand. The preliminary investigation on the spectral properties of the complexes was also presented.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.819-822
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• 2004

Protonation constants of calix[4]-cyclen-benzo-crown-6, L in 1X$10^{-2}$ M $Bu_4NCF_3SO_3$ in 40% $CH_2Cl_2/CH_3OH$ at $25^{\circ}C$ determined by potentiometric titration are log $K_1$ = 10.91, log $K_2$ = 10.30, log $K_3$ = 6.24 and log $K_4$ = 2.55. Stability constants for the receptor L complexes with Cu(II) and Zn(II) in 1X$10^{-2}$ M $Bu_4NCF_3SO_3$ in 40% $CH_2Cl_2/CH_3OH$ at $25^{\circ}C$ were determined by UV-VIS spectrometric titration. Stability constants of the CuL and ZnL complexes as log $\beta$ are 4.37 and 3.45, respectively. Stabilization energies for protonations of receptor L, derived from ab initio Hartree-Fock method with 6-31G basis set, are ${\Delta}E_1$ = -290.1, ${\Delta}E_2$ = -205.0, ${\Delta}E_3$ = -124.9 and ${\Delta}E_4$ = -26.9 kcal/mol and complexation energy of ZnL complex is -370.3 kcal/mol.

• 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.

• Bulletin of the Korean Chemical Society
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• v.25 no.8
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• pp.1137-1142
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• 2004

A spectrophotometric and first derivative spectrophotometric method was developed in aquatic Tween 80 micellar solutions for selective determination of nickel without using any pre-separation step. 1-(2-Pyridylazo)-2-naphthol (PAN), as a sensitive chromogenic complexing agent formed a red-colored Ni(II)-PAN complex in Tween 80 media with satisfactory solubility and stability. Conditions such as pH, PAN concentration, type and concentration of micellizing agent were optimized. Molar absorptivity of Ni-PAN complex was found $4.62\;{\times}\;10^4L\;cm^{?1}\;mol^{?1}$ at 569 nm, under the optimum condition. Calibration graphs were derived by zero, first and second derivative spectrophotometry at maximum wavelengths of 569, 578 and 571 nm with linear ranges of 30-1800, 20-2500 and 30-2000 ng $mL^{?1}$ , respectively. Precision as standard deviation as well as accuracy as recovery percent were in the range of 1-20 ng $mL^{?1}$, and 93.3-103.3%, respectively, for the entire of the linear ranges. Spectrophotometric detection limit was 3 ng $mL^{?1}$ and effects of diverse ions on the first derivative determination of nickel were studied to investigate selectivity of the method. Interferences of cobalt and copper on the nickel determination were prevented using o-phenanthroline as masking agent. The recommended procedures were applied to the various synthetic and stainless steel alloys, tea leaves and human hair, with satisfactory results.