• Journal of the Korea Academia-Industrial cooperation Society
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• v.19 no.8
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• pp.378-384
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• 2018

$C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.

• Polymer(Korea)
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• v.25 no.6
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• pp.782-788
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• 2001

The $[Ru(v-bpy)_3]^{2+}$ and vinylbenzoic acid (vba) were electrochemically copolymerized to afford electrodes modified with dopamine to study their properties such as electropolymerization rate, redox process, and electron transfer. The optimum mole ratio of the monomers was 5:2, which gave $1.84{ imes}10^{-2}s^{-1}$ of rate constant for first order reaction, while the ratio of the substances on the copolymeric film produced was 5:1.68. The formal potential produced from the hydroquinone=quinone+$2H^+2e^-$reaction at the electrode of GC/p- $[Ru(v-bpy)_3]^{2+}$/vba-dopamine was 0.17 V in phosphate buffer (pH=7.10). The electrocatalytic rate was $2.58{ imes}10^5cms^{-1}$;2.41 times faster than that of non-modified one. The mass change measured by EQCM was $3.28{ imes}10^3$$gmol^{-1}$ which is larger than that of non-modified one.

• Bulletin of the Korean Chemical Society
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• v.24 no.4
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• pp.446-452
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• 2003

Some new nanohybrid materials have been synthesized by intercalating the oxotitanium(IV) meso-tetrakis(4- sulfonatophenyl) porphyrin$(O=Ti^{(IV)} TSPP)$ into the Zn/Al layered double hydroxides (LDHs), and their structures and photophysical properties have been investigated by various laser spectroscopic techniques. According to the XRD pattern of the synthesized nanohybrid materials, the macrocycle plane of $O=Ti^{(IV)}$ TSPP are grafted perpendicular to the LDH layers. The $O=Ti^{(IV)}$ TSPP-intercalated LDH exhibits band broadening of the absorption spectrum and a blue shift of Q-band as compared to that observed in solution. Resonance Raman spectral measurements demonstrate that the positively charged LDHs give rise to a slight decrease of the electronic density of the porphyrin ring accompanying a small change of the electronic distribution of the $O=Ti^{(IV)}$ TSPP. Consequently the LDH environment affects the energies of the two highest occupied molecular orbitals (HOMOs) of the $O=Ti^{(IV)}$) TSPP, $a_{1u}$ and $a_{2u}$, producing a mixed orbital character. Being consistent with these electronic structural changes of $O=Ti^{(IV)}$ TSPP in LDH, both the fluorescence spectral change and the fsdiffuse reflectance transient measurements imply that the photoexcitation of the $O=Ti^{(IV)}$ TSPP intercalated into LDH undergoes fast relaxation to the O=Ti(IV) $TSPP^+-LDH^- $charge transfer (CT) state within a few picoseconds, followed by a photoinduced electron transfer between the O=Ti(IV) TSPP and LDHs with a rate constant greater than %1×10^{10}S^{-1}$. No evidence is found for back electron transfer. In conclusion, the $O=Ti^{(IV)}$ TSPP intercalated LDH seems to be a possible candidate for an artificial reaction center for an efficient solar energy conversion system.

• Journal of the Korean Electrochemical Society
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• v.3 no.2
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• pp.121-126
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• 2000

The effect of electroless Ni and Cu plating on $LaNi_5$, $AB_5$ type hydrogen storage alloy was investigated by the various electrochemical techniques such as constant current charge-discharge test, cyclic voltammeoy, and a.c. impedance spectroscopy. Scanning electron microscopy and X-ray diffraction test were conducted for phenomenological logical analyses. Cyclic Voltammetry results show that activation characteristics, cycle life and reaction ,rate were improved through electroless Ni and Cu plating. Compared with bare $LaNi_5$ the charge transfer resistance of electrode was greatly reduced as charge-discharge cycle increases. Therefore, electroless Ni and Cu plating on $LaNi_5$ alloy tends to accelerate the early activation, increasing the cyclic lift of electrode.

• Journal of the Korean Electrochemical Society
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• v.18 no.4
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• pp.137-142
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• 2015

$Mn_{1+X}Co_{2-X}O_4$ solid solutions with various Mn/Co ratios were synthesized by a combustion method, and used as cathode catalysts for lithium/air secondary battery. Their electrochemical and physicochemical properties were investigated. The morphology was examined by transmission electron microscopy (TEM), and the crystallinity was confirmed by X-ray diffraction (XRD) analyses. For the measurement of electrochemical properties, charge and discharge measurements were carried out at a constant current density of $0.2mA/cm^2$, monitoring the voltage change. Electrochemical impedance spectroscopy (EIS) analyses were also employed to examine the change in charge transfer resistance during charge-discharge process. $Mn_{1+X}Co_{2-X}O_4$ solid solutions showed enhanced cycleability as a cathode of Li/air secondary battery, and the performance was found to be strongly dependent on Mn/Co ratio. Among synthesized catalysts, $Mn_{1.5}Co_{1.5}O_4$ exhibited the best performance and cycleability, due to high charge transfer rate.

• Polymer(Korea)
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• v.25 no.1
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• pp.6-14
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• 2001

The monomer N,N'-bis(3-pyrrol-1-yl-propyl)-4,4'-bipyridinium$(PF_6)_2$ was electrochemically polymerized on glassy carbon electrode surface. This polymer film electrode has electroactive sites on its bipyridinium ions distributed at the polymer strands. The formal potentials of the electrodes were -0.41V and -0.81V(vs. SSCE) for each step at phosphate buffer(pH=5.70). The diffusion coefficients of the dopants ions into the polymer matrix were $1.57{\times}10^{-4}$ and $4.35{\times}10^{-5}cm^2s^{-1}$ for first and second redox couple, respectively. The rate constants of electron transfer at $V^{2+/+}$ of the first step was a $57.53s^{-1}$, which was 22 times higher than $V^{+/0}$ one having $2.63s^{-1}$ in the solution. The charge transfer resistance of the polymer film was influenced by the dopant ion of the electrolyte. Thus the resistances were 22.63, 16.81, 12.44 and $11.36k{\Omega}$ for $LiClO_4,\;NaClO_4,\;KClO_4$, and phosphate buffer, respectively. The reaction order of the electropolymerization was first order and the rate constant of the polymerization was $1.31{\times}10^{-1}s^{-1}$ as determined by EQCM method. The G.C./p-BPB type electrode doped with phosphate ions showed a stability and reproducibility in CV procedure over 20 cycles.

• Rapid Communication in Photoscience
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• v.3 no.4
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• pp.70-72
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• 2014

Visible-light irradiation of MeCN solution containing di(hydroxo)metallo(tetraphenyl)porphyrin complex $(tppM(OH)_2$: 1a; $M=Sb(V)^+Br^-$, 1b; $M=P(V)^+Cl^-$, 1c; M=Ge(IV)) and 2-mercaptoethanol (2-ME) as a substrate under aerated condition gave bis(2-hydroxyethyl)disulfide (2-HEDS) as an oxidative product of 2-ME. It is indicated that the oxidation of 2-ME should proceed with a photocatalytic process by 1, because the turn over number (TON) for the formation of 2-HEDS was over unit. The TON was determined to be 642 as a maximum value when 1a was used as a sensitizer. The formation of 2-HDES was extremely slow under argon atmosphere. The fluorescence of 1 was not quenched by 2-ME at all, and the free energy change (${\Delta}G$) with electron transfer (ET) from 2-ME to excited triplet state of $1(^31^*)$ was estimated as a negative value. The quenching rate constant ($k_r$) of $^31^*$ by 2-ME, obtained by the kinetics for the formation of 2-HEDS, strongly depends on ${\Delta}G$. These findings indicate that 1-sensitized oxidation was initiated by photoinduced ET from 2-ME to $^31^*$ to generate both radical cation of 2-ME ($2-ME^{+\bulle}$) and porphyrin radical anion ($1^{-\bulle}$), resulting that the formation of 2-HEDS can be proceeded by the dimerization of $2-ME^{+\bulle}$, and through a catalytic cycle due to returning to 1 by the ET from $1^{-\bulle}$ to molecular oxygen.

• Journal of Microbiology and Biotechnology
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• v.28 no.9
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• pp.1482-1492
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• 2018

Fusarium oxysporum trypsin (FOT) is a fungal serine protease similar to mammal trypsin. The FOT could be successfully expressed in Pichiapastoris by engineering the natural propeptide APQEIPN. In this study, we constructed two recombinant enzymes with engineered amino acid sequences added to the N-terminus of FOT and expressed in P. pastoris. The N-terminal residues had various effects on the structural and functional properties of trypsin. The FOT, and the recombinants TE (with peptide YVEF) and TS (with peptide YV) displayed the same optimum temperature ($40^{\circ}C$) and pH (8.0). However, the combinants TE and TS showed significantly increased thermal stability at $40^{\circ}C$ and $50^{\circ}C$. Moreover, the combinants TE and TS also showed enhanced tolerance of alkaline pH conditions. Compared with those of wild-type FOT, the intramolecular hydrogen bonds and the cation ${\pi}$-interactions of the recombinants TE and TS were significantly increased. The recombinants TE and TS also had significantly increased catalytic efficiencies (referring to the specificity constant, $k_{cat}/K_m$), 1.75-fold and 1.23-fold than wild-type FOT. In silico modeling analysis uncovered that the introduction of the peptides YVEF and YV resulted in shorter distances between the substrate binding pocket (D174, G198, and G208) and catalytic triad (His42, Asp102, and Ser180), which would improve the electron transfer rate and catalytic efficiency. In addition, N-terminal residues modification described here may be a useful approach for improving the catalytic efficiencies and characteristics of other target enzymes.

• Journal of the Korean Electrochemical Society
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• v.10 no.1
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• pp.1-6
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• 2007

Mercaptopropionic acid(mpa) has been used to make self-assembled monolayer(SAMs) on the surface of graphite electrode incorporating gold nano particles, which are subsequently modified with dopamine(dopa). Such modified electrodes haying types of Gr(Au)/mpa-dopa were employed in the electrocatalytic oxidation of NADH. The responses of such modified electrodes were studied in terms of electron transfer kinetics and reaction procedure in the reaction. The reaction of the surface immobilized dopa with NADH was studied using the rotating disk electrode technique and a value of $5.06{\times}10^5M^{-1}s^{-1}$ was obtained for the second-order rate constant in 0.1 M phosphate buffer(pH=7.0), which was a $EC_{cat}$ and kinetic controlled procedure. But, the modified electrodes were diffusion controlled reaction having $4.64{\times}10^{-4}cm^2s^{-1}$ of the coefficient within $10^{-3}s$ after starting the reaction.

• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.177-182
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• 2011

A diketo-type ligand was synthesized by the Knoevenagel condensation reaction of thiophene-2-aldehyde with acetylacetone, subsequently its transition metal complexes with Cu(II), Ni(II), and Co(II) chlorides were also prepared. All the complexes were characterized by various physico-chemical methods. The molar conductivity data reveals ionic nature for the complexes. The electronic spectrum and the EPR values suggest square planar geometry for the Cu(II) ion. Interaction of the Cu(II) complex with CTDNA (calf thymus DNA) was studied by absorption spectral method and cyclic voltammetry. The $k_{obs}$ values versus [DNA] gave a linear plot suggesting psuedo-first order reaction kinetics. The cyclic voltammogram of the Cu(II) complex reveals a quasi-reversible wave attributed to Cu(II)/Cu(I) redox couple for one electron transfer with $E_{1/2}$ values -0.240 V and -0.194 V. respectively. On addition of CTDNA, there is a shift in the $E_{1/2}$ values 168 mV and 18 mV respectively and decrease in Ep values. The shift in $E_{1/2}$ values in the presence of CTDNA suggests strong binding of Cu(II) complex to the CTDNA.