• Title/Summary/Keyword: Charge transfer complexes

Search Result 93, Processing Time 0.027 seconds

Electrocatalytic Effects for the Reduction of Thionyl Chloride in $Li/SOCl_2$ Cell Containing Schiff Base Metal(II) Complexes

  • Kim, Woo-Seong;Chung, Kwang-Il;Kim, Shin-Kook;Jeon, Seung-Won;Kim, Yeon-Hee;Sung, Yung-Eun;Choi, Yong-Kook
    • Bulletin of the Korean Chemical Society
    • /
    • v.21 no.6
    • /
    • pp.571-576
    • /
    • 2000
  • Electrocatalytic effects for the reduction of thionyl chloride in $LiAICI_4/SOCl_2$ electrolyte solution containing Schiff base M(II) (M; Co and Fe) complexes are evaluated by determining kinetic parameters with cyclic voltammetry and chronoamperometry at a glassy carbon electrode. The charge transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. The catalytic effects are demonstrated from both a shift of the reduction potential for the thionyl chloride toward a more positive direction and an increase in peak currents. Catalytic effects are larger in thionyl chloride solutions containing the binuclear [M(II) $_2$ (TSBP)] complex rather than mononuclear [M(II)(BSDT)] complexes. Significant improvements in the cell performance have been noted in terms of both thermodynamics and activation energy for the thionyl chloride reduction. The activation energy calculated from the Arrhenius plots is 4.5-5.9 kcal/mole at bare glassy carbon electrodes. The activation energy calculated for the catalyst containing solution is 3.3-4.9 kcalmole, depending on whether the temperature is lowered or rasied.

Synthesis and Characterization of Metal Complex Oxo Vanadium(Ⅳ) Complexes with Derivatives of Salicylaldoximes (옥심계 금속착물의 합성과 그 물성에 관한 연구 치환 살리실알데히드옥심의 바나듐(Ⅳ) 착물(1))

  • Lee, Kwang;Lee, Won Sik
    • Journal of the Korean Chemical Society
    • /
    • v.39 no.8
    • /
    • pp.611-616
    • /
    • 1995
  • Oxovanadium(IV) complexes with salicylaldoxime, o-vanilline oxime, 2-hydroxy-4-methoxybenzaldoxime, 2-hydroxy-5-methoxybenzaldoxime and 2-hydroxy-5-nitrobenzaldoxime were synthesized. The complexes have been characterized by elemental analysis, electric conductivity measurement, infrared spectrometry, electronic spectrometry, mass spectrometry, and thermal analysis. The results of elemental analysis were well coincided with the theoretical values. The values of molar conductance of the complexes in DMF implicated that the complexes were non-electrolyte. The characteristic stretching frequency of V=O appeared strong band in the range of $980{\pm}20\;cm^{-1}.$ All the complexes showed two d-d transition in visible spectra and two charge transfer transitions in ultraviolet spectra. Results of mass spectrometry of $VO(sal)_2\;and\;VO(van)_2$ indicated two peaks corresponding to vanadium containing ion(I) of 1 : 2(metal to ligand) chelate and a fragment ion(II) of 1 : 1 chelate due to loss of ligand radical from ion(I). The thermal analysis showed the endothermic peak due to the thermal decomposition.

  • PDF

EXCITED-STATE TWISTED INTRAMOLECLILAR CHARGE TRANSFER OF p-N,N-DIMETHYLAMINOBENZOIC ACID IN AQUEOUS CYCLODEXTRIN SOLUTIONS: TIME-RESOLVED FLUORESCENCE STUDY

  • Kim, Yong-Hee;Cho, Dae-Won;Yoon, Min-Joong
    • Journal of Photoscience
    • /
    • v.3 no.3
    • /
    • pp.153-158
    • /
    • 1996
  • The effects of $\alpha$- and $\beta$-cyclodextrins (CD) on the twisted intramolecular charge transfer (TICT) behavior of p-N,N'-dimethylaminobenzoic acid (DMABA) in buffered aqueous solution have been investigated by examining formation and decay behaviors of the TICT-typical dual fluorescence. The ratio of the TICT emission to the normal emission (I$_a$/I$_b$) increases linearly $\alpha$-CD concentration increases, while in the presence of $\beta$-CD it shows nonlinear dependences on the CD concentration. The analysis of the CD-dependent changes of the I$_a$/I$_b$ and absorption spectra demonstrates formation of 1:1 inclusion complexes between DMABA and CDs. The decay time of the normal emission (ca. 700 ps) is little affected by the formation of $\alpha$-CD inclusion complex, whereas it increases upto ca. 1.6 ns upon formation of $\beta$-CD inclusion complex. The TICT emission for the $\beta$-CD inclusion complex exhibits two decay components while it shows a single component for the $\alpha$-CD inclusion complex, indicating formation of one or two types of inclusion complex in the presence of $\alpha$-CD or $\beta$-CD, respectively. These results are attributed to the CD cavity size dependence on patterns of complexation between CDs and DMABA. The CD size dependences of the TICT fluorescence properties with the orientation of the guest molecule demonstrate that the specific hydrogen bonding between the carboxylic acid group and water plays an important role in the excited-state TICT.

  • PDF

Studies on the Cd(II)-Flavonoid Chelation Reactions (카드뮴(II)-플라보노이드 킬레이트 반응에 관한 연구)

  • Lee, Jeong-Ho;Shin, Sun-Woo;Baek, Seung-Hwa
    • YAKHAK HOEJI
    • /
    • v.54 no.1
    • /
    • pp.13-21
    • /
    • 2010
  • The interaction of cadmium (II) ion with quercetin, qurecitrin and (+)-catechin was investigated in aqueous solution at various pH. The flavonoid/cadmium stochiometries for cadmium (II) binding to flavonoid have been determined by UV-visible spectroscopy. 1:1 Cd(II)-Flavonoid complex had a maximum absorbance and showed the bathochromic shift of the long-wavelength band of the UV-vis spectra in the alkaline pH, that occurs upon complexation, is due to a ligand-tometal charge transfer. The optimal concentration of Cd(II)-flavonoid complexes showed that complexation reaction could be classified in the following way: 55.27 ${\mu}M$ catechin > 54.72 ${\mu}M$ quercetin > 53.52 ${\mu}M$ quercitrin at the chelating site level. These results suggest that Cd(II)-flavonoid complex has the optimal condition of chelation in 0.2 M $NH_3$ - 0.2 M $NH_4Cl$ (pH 8.0) solution.

Photoelectrochemical Water Oxidation and $CO_2$ Conversion for Artificial Photosynthesis

  • Park, Hyunwoong
    • Proceedings of the Korean Vacuum Society Conference
    • /
    • 2013.08a
    • /
    • pp.70-70
    • /
    • 2013
  • As the costs of carbon-footprinetd fuels grow continuously and simultaneously atmospheric carbon dioxide concentration increases, solar fuels are receiving growing attention as alternative clean energy carriers. These fuels include molecular hydrogen and hydrogen peroxide produced from water, and hydrocarbons converted from carbon dioxide. For high efficiency solar fuel production, not only light absorbers (oxide semiconductors, Si, inorganic complexes, etc) should absorb most sunlight, but also charge separation and interfacial charge transfers need to occur efficiently. With this in mind, this talk will introduce the fundamentals of solar fuel production and artificial photosynthesis, and then discuss in detail on photoelectrochemical (PEC) water splitting and CO2 conversion. This talk largely divides into two section: PEC water oxidation and PEC CO2 reduction. The former is very important for proton-coupled electron transfer to CO2. For this oxidation, a variety of oxide semiconductors have been tested including TiO2, ZnO, WO3, BiVO4, and Fe2O3. Although they are essentially capable of oxidizing water into molecular oxygen, the efficiency is very low primarily because of high overpotentials and slow kinetics. This challenge has been overcome by coupling with oxygen evolving catalysts (OECs) and/or doping donor elements. In the latter, surface-modified p-Si electrodes are fabricated to absorb visible light and catalyze the CO2 reduction. For modification, metal nanoparticles are electrodeposited on the p-Si and their PEC performance is compared.

  • PDF

Spectrophotometric Determination of Nizatidine and Ranitidine Through Charge Transfer Complex Formation

  • Walash, M.;Din, M.-Sharaf-EI;Metwalli, M.E.S.;RedaShabana, M.
    • Archives of Pharmacal Research
    • /
    • v.27 no.7
    • /
    • pp.720-726
    • /
    • 2004
  • Two Spectrophotometric procedures are presented for the determination of two commonly used H2-receptor antagonists, nizatidine (I) and ranitidine hydrochloride (II). The methods are based mainly on charge transfer complexation reaction of these drugs with either ${\rho}-chloranilic$ acid (${\rho}-CA$) or 2, 3 dichloro-5, 6-dicyanoquinone (DDQ). The produced colored products are quantified spectrophotometrically at 515 and 467 nm in chloranilic acid and 000 methods, respectively. The molar ratios for the reaction products and the optimum assay conditions were studied. The methods determine the cited drugs in concentration ranges of 20-200 and $20-160\;\mu\textrm{g}/mL$ for nizatidine and ranges of 20-240 and $20-140\;\mu\textrm{g}/mL$ for ranitidine with chloranilic acid and DDQ methods, respectively. A more detailed investigation of the complexes formed was made with respect to their composition, association constant, molar absorptivity and free energy change. The proposed procedures were successfully utilized in the determination of the drugs in pharmaceutical preparations. The standard addition method was applied by adding nizatidine and ranitidine to the previously analyzed tablets or capsules. The recovery of each drug was calculated by comparing the concentration obtained from the spiked mixtures with those of the pure drug. The results of analysis of commercial tablets and the recovery study (standard addition method) of the cited drugs suggested that there is no interference from any excipients, which are present in tablets or capsules. Statistical comparison of the results was performed with regard to accuracy and precision using student's t-test and F-ratio at 95% confidence level. There is no significant difference between the reported and proposed methods with regard to accuracy and precision.

$3{\beta}$[L-Lysinamide-Carbamoyl] Cholesterol Cationic Lipid as a Biocompatible Vector for Efficient Gene Transfer

  • Choi, Joon-Sig;Lee, Eun-Jung;Jang, Hyung-Suk;Park, Jong-Sang
    • BMB Reports
    • /
    • v.33 no.6
    • /
    • pp.476-482
    • /
    • 2000
  • In this paper, we report a new cationic lipid composed of L-lysinamide and cholesterol as a potent gene delivery vector. $3{\beta}$[L-Lysinamide-carbamoyl] cholesterol could self-assemble with plasmid DNA forming discrete lipoplexes. From atomic force microscopic images of the complexes, the size distribution was observed to range from 100 to 150 nm in diameter. The transfection efficiency of this amphiphile on different cell lines was evaluated as a micellar solution in the absence of the fusogenic helper lipid, dioleoyl phosphatidyletbanolamine (DOPE). Transfection experiments were performed as a function of charge ratio (lipid/DNA) and transfection time. Cytotoxicity and in vitro transfection efficiency of the amphiphile was demonstrated and compared with those of commercially available Lipofectin and polyethylenimine (PEI).

  • PDF

Binding Modes of New Bis-Ru(II) Complexes to DNA: Effect of the Length of the Linker

  • Kwon, Byung-Hyang;Choi, Byung-Hoon;Lee, Hyun-Mee;Jang, Yoon-Jung;Lee, Jae-Cheol;Kim, Seog-K.
    • Bulletin of the Korean Chemical Society
    • /
    • v.31 no.6
    • /
    • pp.1615-1620
    • /
    • 2010
  • Bis-[dipyrido[3,2-$\alpha$:2',3'-c]phenazine)$_2$(1,10-phenanthroline)$_2Ru_2$]$^{2+}$ complexes (bis-Ru(II) complexes) tethered by linkers of various lengths were synthesized and their binding properties to DNA investigated by normal absorption and linear dichroism spectra, and fluorescence techniques in this study. Upon binding to DNA, the bis-Ru(II) complex with the longest linker (1,3-bis-(4-pyridyl)-propane), exhibited a negative $LD^r$ signal whose intensity was as large as that in the DNA absorption region, followed by a complicate $LD^r$ signal in the metal-to-ligand charge transfer region. The luminescence intensity of this bis-Ru(II) complex was enhanced. The observed $LD^r$ and luminescence results resembled that of the [Ru(1,10-phenanthroline)$_2$ dipyrido[3,2-$\alpha$:2',3'-c]phenazine]$^{2+}$ complex, whose dipyrido[3,2-$\alpha$:2',3'-c]phenazine (dppz) ligand has been known to intercalate between DNA bases. Hence, it is conclusive that both dppz ligands of the bis-Ru(II) complex intercalate. The binding stoichiometry, however, was a single intercalated dppz per ~ 2.3 bases, which violates the "nearest binding site exclusion" model for intercalation. The length between the two Ru(II) complexes may be barely long enough to accommodate one DNA base between the two dppz ligands, but not for two DNA bases. When the linker was shorter (4,4'-bipyridine or 1,2-bis-(4-pyridyl)-ethane), the magnitude of the LD in the dppz absorption region, as well as the luminescence intensity of both bis-Ru(II) complexes, was half that of the bis-Ru(II) complex bearing a long linker. This observation can be elucidated by a model whereby one of the dppz ligands intercalates while the other is exposed to the aqueous environment.

Synthesis and Characterization of Molybdenum(V)-Iminodiaceticacid Derivatives Complexes (몰리브덴(V)와 이미노디아세틱액시드계 착물 합성과 그 성질)

  • Sang-Oh Oh;Sik-Young Choi
    • Journal of the Korean Chemical Society
    • /
    • v.31 no.6
    • /
    • pp.520-526
    • /
    • 1987
  • A new series of $dioxo-di-\mu-oxo-dimolybdate(V)$, has been prepared by reaction of pyridinum oxoisothiocyantomolybdate (V) with iminodiacetic acid derivatives containing amine carboxyl groups. The properties and possible molecular structure of these complexes were discussed by elemental analysis, spectroscopic studies and magnetic susceptibility measurements. The infrared spectra of these complexes all show two strong $Mo=O_t$ stretching bands in the 900∼$980cm^{-1}$, $MoO_2Mo$ very prominent strectching bands at around 410~425 and 735~$750cm^{-1}$ to symmetrical and asymmetrical O-bridge stretching, a coordinated $coo^-$ asymmetrical band in the 1585∼$1,640cm^{-1}$. Also, d-d transition of molybdenyl complexes corresponding to $^2B_2{\to}^2B_1$ occured in the 24,800~$28,000cm^{-1}$ region, charge transfer transition corresponding to ligand-to-molybdenum in the 32,500~33,800, 42,000~$47,500cm^{-1}$ region. The complexes synthesized were yellow or orange and diamagnetic.

  • PDF

Light-Induced Electron Transfer Reactions in FeⅡ-CoⅢ Binuclear Complexes ($Fe^{II}-Co^{III}$이핵착물의 광유발 전자이동반응)

  • Lee, Gyu Hwan
    • Journal of the Korean Chemical Society
    • /
    • v.38 no.8
    • /
    • pp.598-602
    • /
    • 1994
  • Light-induced electron transfer reaction within binuclear complex $(NC)_5FeII-L-CoIII(NH_3)_5$ was studied with steady-state photolysis and the rate constants were measured for various bridging lignands. klight and quantum yields for BP, PHEN, DAP having conjugation between metal binding sites were about $3{\times}10^{-2} sec^{-1}$ and 1, and for BPEA having no conjugation were about $2{\times}10^{-4} sec^{-1}$ and 0.03. Light-induced electron transfer reaction within binuclear complex was proved to be the chemical mechanism which had charge transfer excited state MLCT*.

  • PDF