• 제목/요약/키워드: charge transfer complex

검색결과 159건 처리시간 0.027초

(N-docosyl quinolinium)-TCNQ(1:2) 전하 이동 착물 Langmuir-Blodgett막의 전기적 특성 (Electrical Properties of (N-docosyl quinolinium)-TCNQ(1 :2) Charge Transfer Complex Langmuir-Blodgett Films)

  • 정순욱;정회걸
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 1999년도 추계학술대회 논문집
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    • pp.143-146
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    • 1999
  • In this study, Ultra-thin films of (N-ducosyl quinolinium)-TCNQ(1:2) complex were prepared on the hydrophilic substrate by Langmuir-Blodgett(LB) technique. By measure of UV-vis spectra and capacitance, deposition status was confirmed together with the thickness of natural oxidized aluminum film inside a device and dielectric constant of (N-docosyl quinolinium)-TCNQ(1:2) complex. The electrical properties of (N-docosyl 7uin7linium)-TCNQ(1:2) complex were investigated at room temperature. The conductivity of this film measured by the direction uf either vertical or horizontal axis is results in a quite different value.

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Synthesis and Characterization of the Mixed-valence $[Fe^{II}Fe^{III}BPLNP(OAc)_2](BPh_4)_2$ Complex As a Model for the Reduced Form of the Purple Acid Phosphatase

  • 이재승;;이호진;이강봉;허남회
    • Bulletin of the Korean Chemical Society
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    • 제21권10호
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    • pp.969-972
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    • 2000
  • [Fe II Fe III $BPLNP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)ami-no)methyl]-4-nitrophenol (HBPLNP) . Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electrochemical methods. Complex 1 exhibits two strong bands at 498 nm $(\varepsilon=$ 2.6 ${\times}10^3M-^1cm-^1)$ and 1363 nm $(\varepsilon=$ 5.7 ${\times}10^2M-^1cm-^1)$ in $CH_3CN.$ These are assigned to phenolate-to-FeIII and intervalence charge-transfer transitions, respectively. NMR spectrum of complex 1 exhibits sharp isotropically shifted resonances, which number is half of those expected for a valence-trapped species, indicating that electron transfer between FeⅡ and FeⅢ centers is faster than NMR time scale at room temperature. Complex 1 undergoes quasireversible one-electron redox processes. The $FeIII_2/FeIIFeIII$ and $FeIIFeIII/FeII_2$ redox couples are at 0.807 and 0.167 V ver-sus SCE, respectively. It has Kcomp = 5.9 ${\times}$10 1s(acetato) ligand combination sta-bilizes a mixed-valence FeIIFeIII complex in the air. Interestingly, complex 1 exhibits intense EPR signals at g = 8.56, 5.45, 4.30 corresponding to mononuclear high-spin FeⅢ species, which suggest a very weak magnetic coupling between the iron centers. Magnetic susceptibility study shows that there is a very weak antiferromag-netic coupling (J = $-0.78cm-^1$, H = $-2JS_1${\times}$S_2)$ between FeII and FeIII centers. Thus, we can suggest that complex 1 has a very weak antiferromagnetic coupling between the iron centers due to the electronic effect of the nitro group in the bridging phenolate ligand.

A New Model for the Reduced Form of Purple Acid Phosphatase: Structure and Properties of $[Fe_2BPLMP(OAc)_2](BPh_4)_2$

  • 임선화;이진호;이강봉;강성주;허남휘;Jang, Ho G.
    • Bulletin of the Korean Chemical Society
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    • 제19권6호
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    • pp.654-660
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    • 1998
  • $[Fe^{II}Fe^{III}BPLMP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)amino) methyl]-4-methylphenol (HBPLMP). Complex I has been characterized by X-ray diffraction method as having (μ-phenoxo)bis(acetato)diiron core. Complex 1 was crystallized in the monoclinic space group C2/c with the following cell parameters: a=41.620(6) Å, b=14.020(3) Å, c=27.007(4) Å, β=90.60(2)°, and Z=8. The iron centers in the complex 1 are ordered as indicated by the difference in the Fe-O bond lengths which match well with typical $Fe^{III}-O\; and\; Fe^{II}-O$ bond lengths. Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electochemical methods. Complex 1 exhibits strong bands at 592 nm, 1380 nm in $CH_3CN$ (ε = 1.0 × 103 , 3.0 × 102). These are assigned to $phenolate-to-Fe^{III}$ and intervalence charge-transfer transitions, respectively. Its NMR spectrum exhibits sharp isotropically shifted resonances, which number half of those expected for a valence-trapped species, indicating that electron transfer between $Fe^{II}\;and\;Fe^{III}$ centers is faster than NMR time scale. This complex undergoes quasireversible one-electron redox processes. The $Fe^{III}_2/Fe^{II}Fe^{III}\;and\;Fe^{II}Fe^{III}/Fe^{II}_2$ redox couples are at 0.655 and -0.085 V vs SCE, respectively. It has $K_{comp}=3.3{\times}10^{12}$ representing that BPLMP/bis(acetate) ligand combination stabilizes a mixed-valence $Fe^{II}Fe^{III}$ complex in the air. Complex 1 exhibits a broad EPR signal centered near g=1.55 which is a characteristic feature of the antiferromagnetically coupled high-spin $Fe^{II}Fe^{III}$ system $(S_{total}=1/2)$. This is consistent with the magnetic susceptibility study showing the weak antiferromagnetic coupling $(J= - 4.6\;cm^{-1},\; H= - 2JS_1{\cdot}S2)$ between $Fe^{II}\; and \;Fe^{III}$center.

폴리메틸벤젠과 할로겐 사이의 전하이동 착물생성에 관한 열역학적 연구 (제4보) (Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (IV))

  • 권오천;김정림;양제하
    • 대한화학회지
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    • 제26권5호
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    • pp.274-281
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    • 1982
  • 펜타메틸벤젠 및 헥사메틸벤젠과 요오드 및 일염화요오드와의 각계를 사염화 탄소용액에서 자외선 분광광도법에 의하여 연구한 결과 1:1 분자 착물이 형성됨을 알았다. 이들 착물 생성에 의한 흡수최대는 온도가 상승함에 따라 blue shift 되므로 이에 따른 각 온도에서의 평형상수를 구하였다. 이 값으로 부터 이들 착물 생성에 대한 열역학적 파라미터를 산출한 결과 각 온도에서 폴리메틸벤젠과 요오드 및 일염화요오드 사이에 생성된 착물의 상대적 안정도는 ICl이 $I_2$보다 크다는 것을 알 수 있다. 이 사실은 폴리메틸벤젠에 대한 그들의 상대적 산성도를 나타내며 할로겐 원자의 전기 음성도의 차이에 의하여 설명할 수 있다. 그리고 이 계열의 연구결과를 종합하면 벤젠에 치환된 메틸기의 수가 증가함에 따라 ${\lambda}_{max}$는 red shift 하였고 이들 착물의 상대적 안정도가 다음 순서로 증가함을 알 수 있었다.Benzene < Toluene < Xylene < Durene < Mesitylene < Pentamethylbenzene < Hexamethylbenzene. 이에 따른 결과에 대하여 고찰하였다.

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전하이동 착물형성에 의한 Ephedrine Alkaloids의 분석화학적 연구 (Spectrophotometric Determination of Ephedrine Alkaloids by Charge-Transfer Complexation)

  • 옥치완;백채선
    • 약학회지
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    • 제31권5호
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    • pp.330-337
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    • 1987
  • The weak UV absorbing ephedrine alkaloids such as ephedrine, pseudoephedrine, methylephedrine and norephedrine could be analyzed by charge-transfer spectrophotometric method. The results obtained are summarized as follows: (1) It was possible to determine a weak UV absorbing ephedrine alkaloids using the intense charge-transfer UV bands in chloroform. (2) This method was suitable for the spectrophotometric determination of ephedrine alkaloids in mixed pharmaceutical preparation. (3) Linear relationship was found between absorbance and concentration in the range of 1.0$\times$$10^{-5}M$~5$\times$$10^{-5}M$ of ephedrine ($\varepsilon$= 2.72$\times$$10^{4}LM^{-1}cm^{-1}$ and pseudoephedrine ($\varepsilon$=2.84$\times$$10^{4]LM^{-1}cm^{-1}$), 1.0$\times$$10^{-5}M$~5$\times$$10^{-5}$M of methylephdrine ($\varepsilon$=1.68$\times$$10^{4}LM^{-1}cm^{-1}$) and 1/3$\times$$10^{-4}M$~4/3$\times$$10^{-4}M$ of norephedrine ($\varepsilon$=0.74$\times$$10^{4}LM^{-1}cm^{-1}$. (4) CT- complex of ephedrine, pseudoephedrine and methylephedrine has absorption maxima at 293nm and norephedrine have absorption maximum at 253nm. (5) CT-complexes were formed in a 1:1 ratio between ephedrine alkaloids and iodine in chloroform. (6) By UV, IR, and $^1H$-NMR spectra, it could be inferred that CT-complexes were formed by interaction between the basic nitrogen of ephedrine alkaloids as electron (n) donor and iodine as electron ($\sigma$) acceptor.

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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
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    • 제27권7호
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    • pp.720-726
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    • 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.

Silver Colloidal Effects on Excited-State Structure and Intramolecular Charge Transfer of p-N,N-dimethylaminobenzoic Acid Aqueous Cyclodextrin Solutions

  • 최정관;김양희;윤민중;이승준;김관;정새채
    • Bulletin of the Korean Chemical Society
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    • 제22권2호
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    • pp.219-227
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    • 2001
  • The silver colloidal effects on the excited-state structure and intramolecular charge transfer (ICT) of p-N,N-dimethylaminobenzoic acid (DMABA) in aqueous cyclodextrin (CD) solutions have been investigated by UV-VIS absorption, steady-state and time-resolved fluorescence, and transient Raman spectroscopy. As the concentration of silver colloids increases, the ratio of the ICT emission to the normal emission (Ia /Ib) of DMABA in the aqueous $\alpha-CD$ solutions are greatly decreased while the Ia /Ib values in the aqueous B-CD solutions are significantly enhanced. It is also noteworthy that the ICT emission maxima are red-shifted by 15-40 nm upon addition of silver colloids, implying that DMABA encapsulated in $\alpha-CD$ or B-CD cavity is exposed to more polar environment. The transient resonance Raman spectra of DMABA in silver colloidal solutions demonstrate that DMABA in the excited-state is desorbed from silver colloidal surfaces as demonstrated by the disappearance of νs (CO2-)(1380 cm-1 ) with appearance of ν(C-OH)(1280 cm -1) band, respectively. Thus, in the aqueous B-CD solutions the carboxylic acid group of DMABA in the excited-state can be readily hydrogen-bonded with the secondary hydroxyl group of B-CD while in aqueous and $\alpha-CD$ solutions the carboxylic acid group of DMABA has the hydrogen-bonding interaction with water. Consequently, in the aqueous B-CD solutions the enhancement of the Ia /Ia value arises from the intermolecular hydrogen-bonding interaction between DMABA and the secondary hydroxyl group of B-CD as well as the lower polarity of the rim of the B-CD cavity compared to bulk water. This is also supported by the increase of the association constant for DMABA/ B-CD complex in the presence of silver colloids.

Photochemical Studies of Schiff Base Cu(II) Complex: (1) UV-Irradiation of N,$N^{\prime}$-bis(salicylidene)ethylenediamine copper(II)

  • 안병태
    • Bulletin of the Korean Chemical Society
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    • 제16권3호
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    • pp.202-204
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    • 1995
  • The ultraviolet photochemistry of N,N'-bis(salicylidene)ethylenediamine copper(II), Cu(sal)2en, was investigated with low pressure mercury lamp. Redution of Cu(Ⅱ) and formation of Cl- were shown on 254 nm irradiation both for aerated and deaerated chlorinated hydrocarbon solvent such as CH2Cl2, chloroform, and 1,2-dichloroethane. Relatively long lived $({\tau}=100{\mu}sec)$ intermediate was detected by flash photolysis. Overall photo-process can be described as the formation of Cl- and new copper complex, product(1) by chlorohydrocarbon mediation, photoinduced reduction by abstraction of halogen from solvent, followed by redox induced substitution of axial ligand with chlorine. Product(1) is possibly Cu(III) chlorosalicylaldeimido complex and cyclic -CH2CH2- moiety is absent in the structure. 247nm band of Cu(sal)2en should contain ligand to metal charge transfer character.

발효조중의 발효이동에 미치는 phenol 유도체 및 Catechol 유도체의 영향

  • 이경희;이근태
    • 한국미생물생명공학회:학술대회논문집
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    • 한국미생물생명공학회 1978년도 춘계학술대회
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    • pp.98.2-98
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    • 1978
  • 호기성 발효에 있어서, 산소와 charge transfer complex를 형성할 수 있는 phenol 유도체인 guai-acol, vanillin, O-v-anillin 등과 catechol 유도체인 resorcine, adrenaline, dopamin 등이 산소와의 반응에 의하여 효과적인 산소공급 촉진제로서 이용될 수 있는가를 알아보기 위하여 합성배지중에서 나타내는 산소이동계수(KLQ)를 측정 비교하여 발효공학에의 응용가능성을 검토하였다.

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