• Title/Summary/Keyword: Phosphine

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Ligand Effect in Recycled CNT-Pd Heterogeneous Catalyst for Decarboxylative Coupling Reactions

  • Kim, Ji Dang;Pyo, Ayoung;Park, Kyungho;Kim, Gwui Cheol;Lee, Sunwoo;Choi, Hyun Chul
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2099-2104
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    • 2013
  • We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

A Study of Characteristics of lnxGa1-xP by Photoreflectance measurement (Photoreflectance 측정에 의한 InxGa1-xP의 특성 연구)

  • Kim D. L.;Yu J. I.
    • Laser Solutions
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    • v.8 no.3
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    • pp.5-10
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    • 2005
  • [ $InxGa_{1-x}P/GaAs$ ] structures were grown by chemical beam epitaxy(CBE), Pure phosphine($PH_3$) gases were used as group V sources. for the group III sources, TEGa, TmIn were used. $InxGa_{1-x}P$ epilayer was grown on SI-GaAs substrate and has a 1-${\mu}m$ thick. We have investigated the characteristics of $InxGa_{1-x}P$ by the photoreflectance(PR) spectroscopy, The PR spectrum of $InxGa_{1-x}P$ shows third-derivative feature whose Peaks Provide energy gap. The energy gap of $InxGa_{1-x}P$ has deduced composition x. From temperature dependance of PR spectra, temperature coefficient is $dEg/dT=-3.773{\times}10^{-4}$ eV/K, and Varshni coefficients $\alpha$ and $\beta$ values obtained $4{\times}10^4$ eV/K and 267 K respectively. Also, interaction $\alpha$B was 19.4 meV using the Bose-Einstein temperature relation, and $\Theta$ value related the average phonon frequency were 101.4 K. In particular, shoulder peak related to defects observed in PR signal that measured in temperature 82 K.

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Low Prewwure MOCVD Growth and Characterization of $Ga_xIn_{1-x}P$ Grown on (100) GaAs Substrates (저압 MOCVD법에 의한 (100)-GaAs 기판위의 $Ga_xIn_{1-x}P$ 성장과 특성)

  • 전성란;손성진;조금재;박순규;김영기
    • Journal of the Korean Vacuum Society
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    • v.3 no.1
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    • pp.94-102
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    • 1994
  • x- 0.51인 GaxIn1-x-P 에피층을 저압 MOCVD 성장법으로 TEGa(triethylgallium) TmIn(trimethylindium)등의 MO(metalorganic) 원료와 PH3(phosphine)를 사용하여 GaAs(100) 기판위에 성장하였다. 성장조건에 의한 표면 morphology 결정결함 성분비 PL spectra 운반자 농도와 이동도 및 DLTS spectra와 같은 성장층의 특성을 관찰하였다, $650^{\circ}C$의 성장온도와 V/III비, 즉 TEGa와 TMIn 두 원료의 유량에 대한 PH3 의유량변화에 아무런 영향을 받지 않음을 알 수 있었다. Ga0.51In0.49P에피층과 기판의 격자상수 차에 의한 격자 부정합 $\Delta$a /a0은 약 (3.7~8.9)x10-4 이었으며 실온과 5Kd서 에피층의 PL 피크 에너지는 각각 1.85eV와 1.9eV였다. 성장층의 운반자 농도와 이동도는 V/III 비에 따라 달라지 는데 그비가 120에서 220으로 증가함에 따라 농도는 1.8x1016cm-3에서 8.2x1016cm-3로 증가하였고 이동도 는 1010cm/V.sec에서 366cm/V.sec로 감소하였다.

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Determination of Mertansine in Rat Plasma Using Liquid Chromatography-Tandem Mass Spectrometry and Pharmacokinetics of Mertansine in Rats

  • Choi, Won-Gu;Kim, Ju-Hyun;Jang, Hyun-Joon;Lee, Hye Suk
    • Mass Spectrometry Letters
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    • v.11 no.3
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    • pp.59-64
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    • 2020
  • Mertansine, a thiol-containing maytansinoid, is a tubulin inhibitor used as the cytotoxic component of antibody-drug conjugates for the treatment of cancer. Liquid chromatography-tandem mass spectrometry was described for the determination of mertansine in rat plasma. 50-μL rat plasma sample was pretreated with 25 μL of 20 mM tris-(2-carboxyethyl)-phosphine, a reducing reagent, and further vortex-mixing with 50 μL of 50 mM N-ethylmaleimide for 3 min resulted in the alkylation of thiol group in mertansine. Alkylation reaction was stopped by addition of 100 μL of sildenafil in acetonitrile (200 ng/mL), and following centrifugation, aliquot of the supernatant was analyzed by the selected reaction monitoring mode. The standard curve was linear over the range of 1-1000 ng/mL in rat plasma with the lower limit of quantification level at 1 ng/mL. The intra- and inter-day accuracies and coefficient variations for mertansine at four quality control concentrations were 96.7-113.1% and 2.6-15.0%, respectively. Using this method, the pharmacokinetics of mertansine were evaluated after intravenous administration of mertansine at doses of 0.2, 0.5, and 1 mg/kg to female Sprague Dawley rats.

Mass Transfer of Citric and Acetic Acid by Reactive Extractant in Batch Extractor (회분식 추출기에서 반응추출제에 의한 구연산과 초산의 물질이동)

  • Lee, Han-Seob
    • Applied Chemistry for Engineering
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    • v.5 no.2
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    • pp.223-229
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    • 1994
  • The effect of agitation speed on mass transfer coefficient in the extraction of citric acid from mixed aqueous solutions of citric and acetic acid with n-butylacetate solutions of di-isotridecylamine(DITDA) and 50% mixture of tri-n-octyl and try-n-hexyl phosphine oxide(MOHPO), were studied in batch extractor. Experimental results showed that the degree of extraction was higher with increasing agitation speed, and was best at 200rpm and 30 minutes in batch extractor. The higher degree of extraction was obtained in mixed solution of citric-acetic acid by using DITDA than MOHPO as an carrier. Mass transfer coefficient was proportional to the degree of extraction, and $K_r=1.254{\times}10^{-3}Re^{0.536}$ was found for she extraction of citric acid by DITDA.

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Effects of Irradiation and Fumigation on Physicochemical Properties of Red Pepper during Storage (감마선과 훈증처리가 건고추의 저장 중 이화학적 특성에 미치는 영향)

  • Kim, Byeong-Keun;Kwon, Joong-Ho
    • Journal of the Korean Society of Food Culture
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    • v.19 no.5
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    • pp.491-498
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    • 2004
  • In order to study the quarantine and sanitization methods for dried red pepper, comparative effects of commercial fumigation (methyl bromide/MeBr, $phosphine gas/PH_{3}$ and gamma irradiation (5, 10 kGy) were investigated in terms of its physicochemical properties. There were no noticeable chances in pH and soluble solids among the untreated control, irradiated and fumigated samples soon after treatments, but some decrease was found in stored samples (especially soluble solid in fumigated samples) for 8 months under room temperature. Total sugar content was influenced by storage time rather than both treatments. Immediately after treatments, reducing sugar content was significantly reduced in the samples including pericarp when exposed to fumigants (p<0.05), while an apparent decrease was observed in the stored samples including seeds with negligible differences among treatment groups. The electron donating ability (EDA) of the extracts was high in the order of pericarp, whole pepper, powdered pepper and seeds, which was reduced during storage for 8 months particularly in the samples containing seeds. The EDA of irradiated samples during storage was equal to that of the control sample, whereas that of fumigated samples was relatively low (p<0.05).

Kinetic Studies on the Mechanism of Hydrolysis of Styryldiphenylphosphine Oxide (Styryldiphenylphosphine Oxide의 가수분해 반응 메카니즘에 관한 반응속도론적 연구)

  • Kim, Tae Rin;Shin, Gap Cheol;Pyun, Sang Yong;Lee, Seok Hee
    • Journal of the Korean Chemical Society
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    • v.44 no.5
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    • pp.429-434
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    • 2000
  • The rate constants for the hydrolysis of styryldiphossphine oxide(SDPO) were deter-mined by ultraviolet visible spectrophotometric method and rate equation which can be applied over wide pH ranges was obtained. On the basis of pH-rate profile, hydrolysis product analysis, general base catalysis and substituent effect, a plausible hydrolysis mechanism is proposed : Below pH 4.5, the hydrolysis reaction is pro-ceeded by the attack of water to carbocation after protonaticentration of hydroxide ion.

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Cu Catalyst System with Phosphorous Containing Bidendate Ligand for Living Radical Polymerization of MMA

  • Hong Sung Chul;Shin Ki Eun;Noh Seok Kyun;Lyoo Won Seok
    • Macromolecular Research
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    • v.13 no.5
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    • pp.391-396
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    • 2005
  • The polymerization of methyl methacrylate (MMA) was carried out using CuBr/bidentate phosphorus ligand catalyst systems. MMA polymerization with CuBr/phosphine-phosphinidene (PP) exhibited high conversion ($\~80\%$) in 5 h at $90^{\circ}C$ along with a linear increase of ln($[M]_0/[M]$) versus time, indicating constant concentration of the propagating radicals during the polymerization. The molecular weight of the prepared PMMA tended to increase with conversion, suggesting the living polymerization characteristic of the system. On the other hand, a large difference between the measured and theoretical molecular weight and a broad molecular weight distribution were observed, implicating possible incomplete control over the polymerization. This may have been caused by the low deactivation rate constant ($\kappa_{deact}$) of the system. The low $\kappa_{deact}$, would result in irreversible generation of radicals instead of reversible activation/deactivation process of ATRP. Polymerizations performed at different ligand to CuBr ratios and different monomer to initiator ratios did not afford better control over the polymerization, suggesting that the controllability of CuBr/phosphorus ligand system for ATRP is inherently limited.

Effect of Gamma Irradiation and Fumigation on the Biological Qualities of Green, Black, and Oolong Teas

  • Kwon, Joong-Ho;Kausar, Tusneem;Kwon, Yong-Jung;Kim, Jung-Ae;Huh, Eun-Youp;Lee, Kyeong-Yeoll;Saeed, Shafqat
    • Food Science and Biotechnology
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    • v.15 no.1
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    • pp.1-4
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    • 2006
  • The biological qualities of green, black, and oolong teas were monitored by observing their microbial decontamination and insect disinfestation following gamma irradiation (0-10 kGy) and fumigation (MeBr or $PH_3$) during 6-month storage at room temperature. Plodia interpunctella Hubner was found as an important quarantine pest in teas used. In a comparative study, both treatments were found to be effective in disinfecting the stored samples. An irradiation dose of 5 kGy was sufficient to control all microorganisms related to the quality of teas, while fumigation with methyl bromide and phosphine showed no appreciable decontamination effect on the microorganisms. As a result, irradiation was found an effective alternative to fumigants for the improvement of biological tea qualities during storage.

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.