• Title/Summary/Keyword: Phosphonium

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Conductivity and Surface Tension Behavior for Binary Mixtures over a Various Concentration of TTAB

  • Ahn, Beom-Shu
    • Journal of the Korean Applied Science and Technology
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    • v.23 no.2
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    • pp.160-168
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    • 2006
  • The conductances of trimethyltetradecylammonium bromide (TTAB) plus triphenyltetradecyl phosphonium bromide (TTPB) and TTAB plus trimethylhexadecylammonium bromide (HTAB) over the entire mole fraction range of TTAB were measured in water and in cyclodextrin plus water mixtures at fixed 4 and 8 mM of cyclodextrin at $30^{\circ}C$. The conductivity plot for both binary mixtures shows a single break from which the mixed critical micelle concentration and degree of micelle ionization were computed. From the slope of the conductivity curve, the equivalent ionic conductivities of the monomeric, associated, and the micelle states were calculated and discussed with respect to the surfactant-cyclodextrin complexation in the whole mole fraction range of both surfactant binary mixtures. The association constant K between the respective monomeric surfactant and cyclodextrin cavity of fixed 4 mM cyclodextrin was computed by considering 1:1 association from the surface tension measurement. A comparison among the K values for HTAB-cyclodetrin, TTAB-cyclodextrin, and TTPB-cyclodextrin shows that the former complexation is significantly stronger in comparison to the other ones due to the longer hydrophobic tail.

Synthesis and Reactivity of Dinuclear Ni(II) Azido Complexes Containing Bithienylene or Terthienylene Bridging Ligands

  • Kim, Yong-Joo;Lee, Hyuck-Hee;Zheng, Zhen Nu;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3239-3244
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    • 2011
  • Dinuclear Ni(II)-thiophene halides, which contain linear bridging thienylenes, trans,trans-[$(PR_3)_2$(X)Ni-Y-Ni(X)$(PR_3)_2$] {X = Cl, Br; $H_2Y$ = 5,5'-dichloro-2,2'-bithiophene ($H_2bth$); $H_2tth$ = 5,5"-dichloro-2,2':5',2''-terthiophene ($H_2tth$)} were prepared by the oxidative addition of dihalobithiophene ($H_2bth$) or dihaloterthiophene ($H_2tth$) to [$Ni(COD)_2$] in the presence of tertiary phosphines. Subsequent reactions of $NaN_3$ with the dinuclear Ni(II)-thiophene chlorides gave the corresponding Ni(II)-azido complexes, trans,trans-[$(PR_3)_2(N_3)$Ni-Y-Ni$(N_3)(PR_3)_2$], whose reactivity toward trimethylsilyl pseudohalides such as trimethylsilyl isothiocyanates and cyanides was investigated. In addition, the reaction of trans-[$BrNi(PEt_3)_2-C_4H_2S-C_4H_2S$-CHO], a thienyl Ni(II) complex containing a terminal aldehyde group, with phosphonium ylide was examined.

A Study on the Optimal Preparation Condition of Fungicide Propineb (살균제 Propineb의 제조 공정 최적화 연구)

  • Shin, Hee-Kwan;Woo, Je-Wan
    • The Korean Journal of Pesticide Science
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    • v.8 no.4
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    • pp.272-279
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    • 2004
  • The process for the preparation of fungicide propineb starting with 1,2-diaminopropane was studied on the optimal condition base. Side reaction producing toxic material 1,2-propylenethiourea could be ieduced effectively by using phase transfer catalyst and the product was noticed to show a great improvement in yield and purity. Especially when the phase transfer catalyst tetraphenylphosphonium bromide is used, the yield and the purity of the product were found to be best with up to 95 and 96% respectively and the byproduct content was shown within 1.7%. Also, the contents of wetting agent AES and dispersing agent APS were optimally chosen $3.1\sim4.0%$ and $4.0%\sim5.0%$ respectively for the improvement of suspensibility and wettability of Propineb WP.

Comparison of Properties of Two Kinds of Anion Exchange Membranes with Different Functional Group for Alkaline Fuel Cells (알칼라인 연료전지용 다른 작용기들을 갖는 두 종류의 음이온 교환 막들의 특성 비교)

  • LEE, SEUNGYEON;YOO, DONG JIN
    • Transactions of the Korean hydrogen and new energy society
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    • v.29 no.5
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    • pp.458-465
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    • 2018
  • This study reports the fabrication of anion exchange membranes (AEMs) containing two kinds of functional groups: i) trimethylphosphite (TMP) and ii) trimethylamine (TMA). We carried out the synthesis of polymers to enhance thermal stability and ion conductivity. The alternative polymer was prepared using 2,2-bis(4-hydroxy-3-methylphenyl)propane and decafluorobiphenyl. The membrane was fabricated by solution casting method. The thermal stability of membranes was examined by TGA. The physiochemical properties of membranes were also investigated in terms of water uptake, swelling ratio, ion exchange capacity, and ion conductivity. The hydroxide ion conductivity of the membranes reached about 20.2 mS/cm for quaternary ammonium poly(arylene ether) (QA-PAE) containing TMA moiety and 5.1 mS/cm for quaternary phosphonium PAE (QP-PAE) containing TMP moiety at $90^{\circ}C$.

Effect of Benzalkonium Chloride on Percutaneous Absoption of Antisense Phosphorothioate Oligonucleotides

  • Lee, Young-Mi;Lee, Sung-Hee;Ko, Geon-Il;Kim, Jae-Baek;Sohn, Dong-Hwan
    • Archives of Pharmacal Research
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    • v.19 no.6
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    • pp.435-440
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    • 1996
  • The effect of benzalkonium chloride on skin permeability of partially modified antisense phosphorothioate oligonucleotides (PS-ODN), which are designed as scar formation inhibitor, was investigated using Franz Diffusion Cell. When the concentration ratio of PS-ODN-quarternary ammonium salt complex is more than 1:100, the apparent partition coefficient (APC) of each complex was increased in the following order; tetraphenyl phosphonium chloride (TPP) < cetyltrimethyl ammonium bromide(CTAB) < benzalkonium chloride (BZ). The permeability of PS-ODN through the rat skin increased in the presence of BZ. The fluxs of PS-ODN with BZ were increased by addition of Pluronic F 68 or Triton X-100 to phosphate buffered saline (PBS), respectively. When the mole ratio of PS-ODN to BZ is 1:10, the fluxs penetrated of PS-ODN with BZ was greatest. The increase of the permeability in the presence of BZ might be due to the formation of lipophilic ion-pair complex between PS-ODN and BZ. By regulation of mole ratio of PS-ODN to BZ, the development of topical dosage forms using PS-ODN as scar formation inhibitor will be possible with minimal systemic exposure.

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Raman Spectroscopy of Irradiated Normoxic Polymethacrylic Acid Gel Dosimeter

  • Bong, Ji-Hye;Choi, Kyu-Seok;Yu, Soo-Chang;Kwon, Soo-Il;Cho, Yu-Ra;Park, Chae-Hee;Park, Hyung-Wook
    • Bulletin of the Korean Chemical Society
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    • v.32 no.2
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    • pp.625-629
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    • 2011
  • A quantitative analysis of the decreasing rate of the monomer and increasing rate of the polymerization was made by monitoring radiation level increments using Raman spectroscopy within the therapeutic radiation range for a normoxic polymethacrylic acid gel dosimeter. The gel dosimeter was synthesized by stirring materials such as gelatin, distilled water, methacrylic acid, hydroquinone and tetrakis phosphonium chloride at $50^{\circ}C$, and the synthesized gel was contained in a 10- mm diameter and 32-mm high vial to conduct measurement. 24 hours after gel synthesis, it was irradiated from 0 Gy to 20 Gy by 2 Gy using a Co-60 radiotherapy unit. With use of the Cryo FE-SEM, structural changes in the 0 Gy and 10 Gy gel dosimeters were investigated. The Raman spectra were acquired using 532-nm laser as the excitation source. In accordance with fitting the changes in C-COOH stretching (801 $cm^{-1}$), C=C stretching (1639 $cm^{-1}$) and vinyl $CH_2$ stretching (3114 $cm^{-1}$) vibrational modes for monomer and $CH_2$ bending vibrational mode (1451 $cm^{-1}$) for polymer, sensitive parameter S for each mode was calculated. The values of S for monomer bands and polymer band were ranged in $6.0{\pm}2.6$ Gy and $7.2{\pm}2.3$ Gy, respectively, which shows a relatively good conformity of the decreasing rate of monomer and the increasing rate of polymerization within the range of error.

Atom-efficient Preparation of 9, 9'-Bis[4-(2'-hydroxy-3'-acryloyloxypropoxy)phenyl]fluorene (9, 9'-비스[4-(2'-하이드록시-3'-아크릴로일옥시프로폭시) 페닐]플루오렌의 원자효율적 합성)

  • Jung, Hyeok-Jin;Hong, Seong-Jae;Seo, Kwang-Beom;Shim, Jae-Jin;Ra, Choon-Sup
    • Clean Technology
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    • v.17 no.4
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    • pp.325-328
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    • 2011
  • Atom-efficient preparation of 9, 9'-bis[4-(2'-hydroxy-3'-acryloyloxypropoxy) phenyl]fluorene (3), the extensively used building block for fluorene-containing acrylic epoxy polymers has been described. The epoxide ring opening esterification of 9, 9-bis[4-(glycidyloxy)phenyl]fluorene (1) with acrylic acid was catalyzed by some onium salts such as quaternary ammonium and phosphonium salts. While the coupling reactions depend greatly on the kind of the onium salts, the reaction of 9, 9-bis[4-(glycidyloxy)phenyl]fluorene (1) with acrylic acid proceed most efficiently in the presence of a catalytic amount of tetrabutylphosphonium bromide at $110^{\circ}C$ with 90% yield. This reaction is a cleaner reaction that minimizes the use of reactants and the production of chemical wastes.

Synthesis of a Fluorene Carbonate from Fluorenyl Epoxide Using Supercritical Carbon Dioxde (초임계이산화탄소를 이용한 플로레닐계 에폭사이드로부터 카보네이트 화합물의 합성)

  • Sim, Yun-Soo;Shim, Jae-Jin;Ra, Choon-Sup
    • Clean Technology
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    • v.16 no.4
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    • pp.239-244
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    • 2010
  • The carboxylation of the fluorenyl epoxide with a spiro framework, 9,9'-Bis(4-oxiranylmethoxyphenyl) fluorine (2) was catalyzed by some onium salts such as quaternary ammonium and phosphonium salts to produce the corresponding five-membered cyclic carbonate (3) in an efficient and environmentally benign fashion. The coupling reactions depend greatly on the kind of the halide anions and alkyl chain length of the onium salts. While the reaction was sensitive to the reaction temperature, the reaction trends suggest that the catalytic efficiency of the quaternary ammonium halides may correlate strongly with the melting points of the halides. The reactions using a catalytic amount (2 mol %) of quaternary ammonium bromide with an n-butyl chain at 75.9 bar of $CO_2$ and 393 K give the highest yield of the cyclic carbonate (92%).

Poly(ethylene terephthalate) Nanocomposite Fibers with Thermally Stable Organoclays (내열성 유기화 점토를 이용한 폴리(에틸렌 테레프탈레이트) 나노복합체 섬유)

  • Jung, Min-Hye;Chang, Jin-Hae
    • Polymer(Korea)
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    • v.31 no.6
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    • pp.518-525
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    • 2007
  • The thermomechanical properties and morphologies of nanocomposite fibers of poly(ethylene terephthalate)(PET) incorporating thermally stable organoclays are compared. Dodecyltriphenyl-phosphonium-mica($C_{12}PPh-Mica$) and 1-hexadecane benzimidazole-mica ($C_{16}BIMD-Mica$) were used as reinforcing fillers in the fabrication of PET hybrid fibers. Dispersions of organoclays with PET were studied by using the in-situ polymerization method at various organoclay contents to produce nano-scale composites. The thermo-mechanical properties and morphologies of the PET hybrid fibers were determined using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffraction (XRD), electron microscopy (SEM and TEM), and a universal tensile machine (UTM). Transmission electron microscopy (TEM) micrographs show that some of the clay layers are dispersed homogeneously within the polymer matrix on the nano-scale, although some clay particles are agglomerated. We also found that the addition of only a small amount of organoclay is enough to improve the thermal stabilities and mechanical properties of the PET nanocomposite fibers. Even polymers with low organoclay content (<5 wt%) were found to exhibit much higher thermo-mechanical values than pure PET fibers.

Phase-and Size-Controlled Synthesis of CdSe/ZnS Nanoparticles Using Ionic Liquid (이온성 액체에 의한 CdSe/ZnS 나노입자의 상과 크기제어 합성)

  • Song, Yun-Mi;Jang, Dong-Myung;Park, Kee-Young;Park, Jeung-Hee;Cha, Eun-Hee
    • Journal of the Korean Electrochemical Society
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    • v.14 no.1
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    • pp.1-8
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    • 2011
  • Ionic liquids are room-temperature molten salts, composed of organic mostly of organic ions that may undergo almost unlimited structural variation. We approach the new aspects of ionic liquids in applications where the semiconductor nanoparticles used as sensitizers of solar cells. We studied the effects of ionic liquids as capping ligand and/or solvent, on the morphology and phase of the CdSe/ZnS nanoparticles. Colloidal CdSe/ZnS nanoparticles were synthesized using a series of imidazolium ionic liquids; 1-R-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([RMIM][TFSI]), where R = ethyl ([EMIM]), butyl ([BMIM]), hexyl ([HMIM]), octyl ([OMIM]). The average size of nanoparticles was 8~9 nm, and both zinc-blende and wurtzite phase was produced. We also synthesized the nanoparticles using a mixture of trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([$P_{6,6,6,14}$][TFSI]) and octadecene (ODE). The CdSe/ZnS nanoparticles have a smaller size (5.5 nm) than that synthesized using imidazolium, and with a controlled phase from zinc-blende to wurtzite by increasing the volume ratio of [$P_{6,6,6,14}$][TFSI]. For the first time, the phase and size control of the CdSe/ZnS nanoparticles was successfully demonstrated using those ionic liquids.