• Title/Summary/Keyword: Osmium complex

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Synthesis of Several Osmium Redox Complexes and Their Electrochemical Characteristics in Biosensor (오스뮴 착물들의 합성 및 전기화학적인 특성에 관한 연구)

  • Kim, Hyug-Han;Choi, Young-Bong;Tae, Gun-Sik
    • Journal of the Korean Electrochemical Society
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    • v.11 no.3
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    • pp.176-183
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    • 2008
  • Redox complexes to transport electrodes from bioreactors to electrodes are very important part in electrochemical biosensor industry. A novel osmium redox complexes were synthesized by the coordinating pyridine group having different functional group at 4-position with osmium metal. Newly synthesized osmium complexes are described as ${[Os(dme-bpy)}_2{(ap-im)Cl]}^{+/2+}$, ${[Os(dme-bpy)}_2{(ap-im)Cl]}^{+/2+}$, ${[Os(dmo-bpy)}_2{(ap-im)Cl]}^{+/2+}$, ${[Os(dcl-bpy)}_2{(ap-im)Cl]}^{+/2+}$. We have been studied the electrochemical characteristics of these osmium complex with electrochemical techniques such as cyclic voltammetry and chronoamperommetry. Osmium redox complexes were immobilized on the screen printed carbon electrode(SPE) with deposited gold nanoparticles. The electrical signal converts the osmium redox films into an electrocatalyst for glucose oxidation. Each catalytic currents were related with the potentials of osmium complexes.

Synthesis of Osmium Redox Complex and Its Application for Biosensor Using an Electrochemical Method (오스뮴 착물 합성과 전기화학적인 방법을 이용한 바이오센서에 관한 연구)

  • Choi, Young-Bong;Kim, Hyug-Han
    • Journal of the Korean Electrochemical Society
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    • v.10 no.2
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    • pp.150-154
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    • 2007
  • Redox complexes to transport electrodes from biomaterial to electrodes are very important part in commercial biosensor industry. A novel osmium redox complex was synthesized by the coordinating pyridine group with osmium metal. A novel osmium complex is described as $[Os(dme-bpy)_2(ap-im)Cl]^{+/2+}$. We have been studied the electrochemical characteristics of this osmium complex with electrochemical techniques such as cyclic voltammetry and chronoamperommetry. In order to immobilize osmium redox complexes on the electrode, we deposited gold nano-particles on screen printed carbon electrode(SPE). The electrical signal converts the osmium redox films into an electrocatalyst for glucose oxidation. The catalytic currents were monitored that the catalytic currents were linearly increased from 1 mM to 5 mM concentrations of glucose.

Electrochemical Method for Detecting Hippuric Acid Using Osmium-antigen Conjugate on the Gold Nanoparticles Modified Screen-printed Carbon Electrodes

  • Choi, Young-Bong;Kim, Hyug-Han
    • Journal of Electrochemical Science and Technology
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    • v.2 no.1
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    • pp.57-61
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    • 2011
  • This paper describes an electrochemical immunoassay for simple, fast and quantitative detection of a urinary hippuric acid which is one of major biological indicator in toluene-exposed humans. The electrochemical system of immunoassay was based on the directly osmium complex conjugated with hippuric acid. With the competition between free hippuric acid (HA) and the osmium-hippuric acid conjugate (Os-HA) to bind with antibody hippuric acid (Anti-HA) coated onto gold nanoparticles, the electrical signals were proportional to urinary hippuric acid (HA) in the range of 0.01-5 mg/mL which is enough range to be used for in-field or point-of-care (POC) diagnosis. The proposed electrochemical method can be extended to the applications to detect a wide range of different small molecules in the field of health care.

Electrochemical behavior and Application of Osmium-Cupferron Complex (오스뮴-쿠페론의 전기화학적 행동 및 응용)

  • Kwon, Young-Soon;Chong, Mee-Young
    • Analytical Science and Technology
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    • v.16 no.3
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    • pp.198-205
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    • 2003
  • The ammonium salt of nitrosophenylhydroxylamine, called cupferron, has been used not only as the ligand but also as an oxidizing agent for adsorptive catalytic stripping voltammetry (AdCtSV). Cyclic voltammetry was used for elucidating the electrochemical behavior of Os-cupferron complex in 1 mM phosphate buffer. The optimal conditions for osmium analysis were found to be 1 mM phosphate buffer solution (pH 6.0) containing 0.1 mM cupferron at scan rate of 100 mV/s. By using the plot of reduction peak currents of linear scan voltammograms vs. osmium concentration, the detection limit was $1.0{\times}10^{-7}M$.

Electrochemical Immobilization of Osmium Complex onto the Carbon Nano-Tube Electrodes and its Application for Glucose sensor (전기화학적인 방법을 이용한 탄소나노튜브 전극상의 오스뮴 착물의 고정화 및 혈당센서에 관한 응용)

  • Choi, Young-Bong;Jeon, Won-Yong;Kim, Hyug-Han
    • Journal of the Korean Electrochemical Society
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    • v.13 no.1
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    • pp.50-56
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    • 2010
  • The multi-wall carbon nano-tube composite mixed with carbon paste electrode presented more sensitive and selective amperometric signals in the oxidation of glucose than general screen-printed carbon electrodes(SPCEs). Redox mediators to transport electrodes from enzyme to electrodes are very important part in the biosensor. A novel osmium redox complex was synthesized by the coordinating pyridine group containing primary amines which were electrochemically immobilized onto the MWCNT-SPCEs surface. Electrochemical studies of osmium complexes were investigated by cyclic voltammetry, chronoamperometry. The surface coverage of osmium complexes on the modified carbon nano-tube electrodes were significantly increased at 100 time (${\tau}_0=2.0\;{\times}\;10^{-9}\;mole/cm^2$) compared to that of the unmodified carbon electrodes. It's practical application of the glucose biosensor demonstrated that it shows good linear response to the glucose concentration in the range of 0-10 mM.

Electrochemical Immunoassay for Detecting Hippuric Acid Based on the Interaction of Osmium-Antigen Conjugate Films with Antibody on Screen Printed Carbon Electrodes

  • Choi, Young-Bong;Jeon, Won-Yong;Kim, Hyug-Han
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1485-1490
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    • 2012
  • An electrochemical immunoassay based on osmium-hippuric acid (HA) conjugate films onto the electrode is presented for the detection of urinary HA. This is the first report on the use of the oxidative electropolymerization of 5-amino-1,10-phenanthroline (5-$NH_2$-phen) for immobilizing an antigen, osmium-conjugated HA. As a redox mediator, [Os(5-amino-1,10-phenanthroline)$_2$(4-aminomethylpyridine-HA)Cl]$^{+/2+}$ (Os-phen-HA) was successfully synthesized and electropolymerized onto the screen-printed carbon electrodes (SPCEs). The interaction between osmium-HA conjugate films and antibody-HA ($anti$-HA) was performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The electrical signals were linearly proportional to urinary HA in the range of 0.1-5.0 mg/mL, which is sufficient for use as an immunosensor using a cutoff concentration of 2.0 mg/mL in urine samples. The proposed electrochemical immunoassay method can be extended to various applications for detecting a wide range of different small antigens in the health care area.

Electrochemical Detection of Uric Acid using Three Osmium Hydrogels (세개의 오스뮴 고분자를 이용한 요산의 전기화학적 측정방법)

  • Jeon, Won-Yong;Choi, Young-Bong
    • Journal of the Korean Electrochemical Society
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    • v.19 no.2
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    • pp.29-38
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    • 2016
  • Screen printed carbon electrodes (SPCEs) with immobilized osmium-based hydrogel redox polymer, uricase and PEGDGE can be used to apply uric acid electrochemical detecting. The osmium redox complexes were synthesized by the coordinating pyridine group having different functional group at 4-position with osmium compounds. The synthesized poly-osmium hydrogel complexes are described as PAA-PVI-$[Os(dCl-bpy)_2Cl]^{+/2+}$, PAA-PVI-$[Os(dme-bpy)_2Cl]^{+/2+}$, PAA-PVI-$[Os(dmo-bpy)_2Cl]^{+/2+}$. The different concentrations of uric acid were measured by cyclic voltammetry technique using enzyme-immobilized SPCEs. The prepared SPCEs using PAA-PVI-$[Os(dme-bpy)_2Cl]^{+/2+}$ showed no interference from common physiologic interferents such as ascorbic acid (AA) or glucose. The resulting electrical currents at 0.33 V vs. Ag/AgCl displayed a good linear response with uric acid concentrations from 1.0 to 5.0 mM. Therefore, this approach allowed the development of a simple, point of care in the medical field, disposable electrochemical uric acid biosensor.

Hydrogenation of trans-Cinnamaldehyde with Hydrido-Carbonyl Osmium(II) Complexes of Chelating Phosphine Ligands

  • 정민교;허성;이원용;전무진
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.806-810
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    • 1997
  • A series of new hydridocarbonyl osmium(Ⅱ) complexes, OsHCl(CO)(PPh3)(L-L)[L-L=Ph2P(CH2)nPPh2 (n=1 (1), 2 (2), 3 (3), cis-Ph2PCH=CHPPh2 (4), and Fe(η5-C5H4PPh2)2 (5)] has been synthesized from OsHCl(CO)(PPh3)3 and chelating diphosphines. These complexes have been characterized by IR, 1H NMR and elemental analysis. The catalytic activities of these complexes both for the transfer hydrogenation of trans-cinnamaldehyde with 2-propanol as the hydrogen donor, and for the selective hydrogenation of trans-cinnamaldehyde with H2, have been examined. Complexes (1)-(5) were shown to have higher selectivities for the transfer hydrogenation of the C=O bond of aldehyde than for the transfer hydrogenation of the C=C bond of aldehyde. The selectivities for the transfer hydrogenation with 2-propanol as well as for the hydrogenation with H2 have been found to decrease in the order 3 > 5 > 2 > 4 > 1. Complex (3) has shown to possess almost 90% of the selectivity to cinnamyl alcohol for transfer hydrogenation. It is also found that there is a correlation between the ν(CO) of each complex and the hydrogenation, of the C=O bond of trans-cinnamaldehyde. Overall, the selectivities with the complexes (1)-(5) are greater for the transfer hydrogenation with 2-propanol than for the hydrogenation with H2.

Synthesis of a New Cathode Redox Polymer for High Performance in Biofuel Cells

  • Choi, Young-Bong;Lee, Jung-Min;Kim, Hyug-Han
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2803-2808
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    • 2014
  • High potential and fast electron transfer of a cathode mediator are significant factors for improving the performance of biofuel cells. This paper reports the first synthesis of a cathode redox polymer that is a coordination complex of poly (acrylic acid-vinylpyridine-acryl amide) (PAA-PVP-PAA) and [Os(4,4'-dicarboxylic acid-2,2'-bipyridine)$_2Cl_2]^{/+}$ ($E^{\circ}=0.48V$ versus Ag/AgCl). Bilirubin oxidase can be easily incorporated into this polymer matrix, which carried out the four-electron oxygen under typical physiological conditions (pH 7.2, 0.14 M NaCl, and $37^{\circ}C$). This new polymer showed an approximately 0.1 V higher redox potential than existing cathode mediators such as PAA-PVI-$[Os(dCl-bpy)_2Cl]^{+/2+}$. In addition, we suggest increasing the polymer solubility with two hydrophilic groups present in the polymer skeleton to further improve fast electron transfer within the active sites of the enzyme. The maximum power density achieved was 60% higher than that of PAA-PVI-$[Os(dCl-bpy)_2Cl]^{+/2+}$. Furthermore, high current density and electrode stability were confirmed for this osmium polymer, which makes it a promising candidate for high-efficiency biofuel cells.

A Density Functional Theory Investigation on Intramolecular Hydrogen Transfer of the [Os3(CO)11P(OMe)3(Ru(η5-C5H5))2] Cluster

  • Buntem, Radchada;Punyain, Kraiwan;Tantirungrotechai, Yuthana;Raithby, Paul R.;Lewis, Jack
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.934-940
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    • 2010
  • The reduction of [$Os_3(CO)_{11}P(OMe)_3$] and subsequent ionic coupling of the reduced species with $[Ru({\eta}^5-C_5H_5)(CH_3CN)_3]^+$ resulted in the formation of [$Os_3(CO)_{11}P(OMe)_3(Ru({\eta}^5-C_5H_5))_2$] which can be converted to spiked tetrahedral cluster, [$HOs_3(CO)_{11}P(OMe)_3Ru_2({\eta}^5-C_5H_5)(C_5H_4)$] via the intramolecular hydrogen transfer. Due to the unavailability of a suitable single crystal, the PW91/SDD and LDA/SDD density functional methods were used to predict possible structures and the available spectroscopic information (IR, NMR) of [$Os_3(CO)_{11}P(OMe)_3(Ru({\eta}^5-C_5H_5))_2$]. The most probable geometry found by constrained search is the isomer (a2) in which the phosphite, $P(OMe)_3$, occupies an axial position on one of the two osmium atoms that is edge bridged by the $Ru(CO)_2({\eta}^5-C_5H_5)$ unit. By using the most probably geometry, the predicted infrared frequencies and $^1H$, $^{13}C$ and $^{31}P$ NMR chemical shifts of the compound are in the same range as the experimental values. For this type of complex, the LDA/SDD method is appropriate for IR predictions whereas the OPBE/IGLO-II method is appropriate for NMR predictions. The activation energy and reaction energy of the intramolecular hydrogen transfer coupled with the structural change of the transition metal framework were estimated at the PW91/SDD level to be 110.32 and -0.14 kcal/mol respectively.