• Title/Summary/Keyword: Phosphine oxide

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Asymmetric Intramolecular Diels-Alder Cycloadditions of 2-Pyrone-3-Carboxylates and Synthesis of Vitamin $D_3$ A Ring Phosphine Oxide

  • 조천규;Gary H. Posner
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.957-961
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    • 1998
  • Intramolecular Diels-Alder cycloadditions of 2-pyrone-3-carboxylates with trans-vinyl silaketal groups tethered via a chiral, non-racemic 1,3-butanediol auxiliary proceeded in unexpected stepwise cycloadditions through ionic intermediates to provide cis-disubstituted bicylolactones. The ratio of two isomers, exo and endo, was 5 to 1, and each isomer was found to be diastereomerically pure (>99% de). Their relative and absolute stereochemistries were determined by $^1H$ NMR spectroscopy and confirmed by X-ray crystallography of minor, endo-adduct 9. The major exo-adduct was successfully transformed to (-)-2-butyl substituted A-ring phophine oxide 16, a key element for the synthesis of 2-butyl vitamin D3.

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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Nonmonotonic Ordering of Lanthanon Nitrates in the Phosphine Oxide Extraction Systems (稀土類元素의 溶媒抽出의 不均一性)

  • C. T. Rhee
    • Journal of the Korean Chemical Society
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    • v.7 no.4
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    • pp.271-276
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    • 1963
  • The distribution ratio of lanthanon nitrates in the TBPO- and TOPO-toluene systems were studied radiometrically as a function of solvent, nitrate and atomic number(Z). The plots of log Kd vs. Z shows two straight lines which are crossing at Z = 63∼64. The solvent dependency was same for lighter and heavier lanthanons but nitrate dependency was different between the two parts.

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Carbon monoxide activation of delayed rectifier potassium currents of human cardiac fibroblasts through diverse pathways

  • Bae, Hyemi;Kim, Taeho;Lim, Inja
    • The Korean Journal of Physiology and Pharmacology
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    • v.26 no.1
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    • pp.25-36
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    • 2022
  • To identify the effect and mechanism of carbon monoxide (CO) on delayed rectifier K+ currents (IK) of human cardiac fibroblasts (HCFs), we used the wholecell mode patch-clamp technique. Application of CO delivered by carbon monoxidereleasing molecule-3 (CORM3) increased the amplitude of outward K+ currents, and diphenyl phosphine oxide-1 (a specific IK blocker) inhibited the currents. CORM3-induced augmentation was blocked by pretreatment with nitric oxide synthase blockers (L-NG-monomethyl arginine citrate and L-NG-nitro arginine methyl ester). Pretreatment with KT5823 (a protein kinas G blocker), 1H-[1,-2,-4] oxadiazolo-[4,-3-a] quinoxalin-1-on (ODQ, a soluble guanylate cyclase blocker), KT5720 (a protein kinase A blocker), and SQ22536 (an adenylate cyclase blocker) blocked the CORM3 stimulating effect on IK. In addition, pretreatment with SB239063 (a p38 mitogen-activated protein kinase [MAPK] blocker) and PD98059 (a p44/42 MAPK blocker) also blocked the CORM3's effect on the currents. When testing the involvement of S-nitrosylation, pretreatment of N-ethylmaleimide (a thiol-alkylating reagent) blocked CO-induced IK activation and DL-dithiothreitol (a reducing agent) reversed this effect. Pretreatment with 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)-21H,23H porphyrin manganese (III) pentachloride and manganese (III) tetrakis (4-benzoic acid) porphyrin chloride (superoxide dismutase mimetics), diphenyleneiodonium chloride (an NADPH oxidase blocker), or allopurinol (a xanthine oxidase blocker) also inhibited CO-induced IK activation. These results suggest that CO enhances IK in HCFs through the nitric oxide, phosphorylation by protein kinase G, protein kinase A, and MAPK, S-nitrosylation and reduction/oxidation (redox) signaling pathways.

Extraction Behavior of Am(III) and Eu(III) From Nitric Acid Using Room Temperature Ionic Liquid (질산용액으로부터 이온성 액체를 이용한 Am(III)과 Eu(III)의 추출 거동)

  • Kim, Ik-Soo;Chung, Dong-Yong;Lee, Keun-Young;Lee, Eil-Hee
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.16 no.3
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    • pp.347-357
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    • 2018
  • The applicability of room temperature ionic liquids (RTILs), 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([$C_nmim$] [$Tf_2N$]), was investigated for the extraction of Am(III) and Eu(III) from nitric acid using n-octyl(phenyl)-N,N-diisobutyl carbamoylmethyl phosphine oxide (CMPO) and tri-n-butylphosphate (TBP) as extractants. The distribution ratios of Am(III) and Eu(III) in CMPO-TBP/[$C_nmim$][$Tf_2N$] were measured as a function of various parameters such as the concentrations of nitric acid, CMPO, and TBP. The results were compared with those obtained in CMPO-TBP/n-dodecane (n-DD). With comparable concentrations of the extractants, the distribution ratios obtained with RTILs were much higher than those obtained with n-DD. It was observed that the extraction efficiency was less for Eu(III) than for Am(III). The extraction of Am(III) and Eu(III) decreased with increases in the feed acidity for all three RTILs. The results suggest that the extraction of Am(III) and Eu(III) by CMPO in RTILs from nitric acid proceeds through the cation-exchange mechanism. The distribution ratios of Am(III) and Eu(III) increased with increases in the concentration of CMPO for all three RTILs. A linear regression analysis of the extraction data resulted in a straight line with a slope of about 3, suggesting the involvement of 3 molecules of CMPO during the extraction process.

Orange Phosphorescent Organic Light-emitting Diodes Using a Spirobenzofluorene-type Phospine Oxides as Host Materials

  • Jeon, Young-Min;Lee, In-Ho;Lee, Chil-Won;Lee, Jun-Yeob;Gong, Myoung-Seon
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2955-2960
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    • 2010
  • Spiro-type orange phosphorescent host materials, 9-diphenylphosphine oxide-spiro[fluorene-7,9'-benzofluorene] (OPH-1P) and 5-diphenylphosphine oxide-spiro[fluorene-7,9'-benzofluorene] (OPH-2P) were successfully prepared by a lithiation reaction followed by a phosphination reaction with diphenylphosphinic chloride. The EL characteristics of OPH-1P and OPH-2P as orange host materials doped with iridium(III) bis(2-phenylquinoline)acetylacetonate ($Ir(pq)_2acac$) were evaluated. The electroluminescence spectra of the ITO (150 nm)/DNTPD (60 nm)/NPB (30 nm)/OPH-1P or OPH-2P: $Ir(pq)_2acac$ (30 nm)/BCP (5 nm)/$Alq_3$ (20 nm)/LiF (1 nm)/Al (200 nm) devices show a narrow emission band with a full width at half maximum of 75 nm and $\lambda_{max}$ = 596 nm. The device obtained from OPH-1P doped with 3% $Ir(pq)_2acac$ showed an orange color purity of (0.580, 0.385) and an efficiency of (14 cd/A at 7.0 V). The ability of the OPH-P series to combine a high triple energy with a low operating voltage is attributed to the inductive effect of the P=O moieties and subsequent energy lowering of the LUMO, resulting in the enhancement of both the electron injection and transport in the device. The overall result is a device with an EQE > 8% at high brightness, but operating voltage of less than 6.4 V, as compared to the literature voltages of ~10 V.

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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Separation and Recovery of Ce, Nd and V from Spent FCC Catalyst (FCC 폐촉매로부터 Ce, Nd 및 V의 분리 회수 프로세스)

  • Jeon, Sung Kyun;Yang, Jong Gyu;Kim, Jong Hwa;Lee, Sung Sik
    • Applied Chemistry for Engineering
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    • v.8 no.4
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    • pp.679-684
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    • 1997
  • The major constituents in spent FCC catalysts are Si, Al, Fe, Ti, alkali metals and some others. The spent catalyst is also composed small amounts of rare metals such as Ce, Nd, Ni and V. The selective adsorption and concentration of Ce and Nd from the leaching solution of spent FCC catalysts with sulfuric acid($0.25mol/dm^3$) were carried out by the column method with a chelate resin having a functional group of aminophosphoric acid type. Ce and Nd were separated from eluate liquor containing Al, Nd and V by the precipitation process with oxalic acid. Vanadium is purified from chloride ion coexistance by solvent extraction, employing tri-n-octyl phosphine oxide as extractant with Al in the raffinate solution. Rare metals with the purity of 99 percent were obtained from the spent FCC catalyst.

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Types & Characteristics of Chemical Substances used in the LCD Panel Manufacturing Process (LCD 제조공정에서 사용되는 화학물질의 종류 및 특성)

  • Park, Seung-Hyun;Park, Hae Dong;Ro, Jiwon
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.29 no.3
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    • pp.310-321
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    • 2019
  • Objectives: The purpose of this study was to investigate types and characteristics of chemical substances used in LCD(Liquid crystal display) panel manufacturing process. Methods: The LCD panel manufacturing process is divided into the fabrication(fab) process and module process. The use of chemical substances by process was investigated at four fab processes and two module processes at two domestic TFT-LCD(Thin film transistor-Liquid crystal display) panel manufacturing sites. Results: LCD panels are manufactured through various unit processes such as sputtering, chemical vapor deposition(CVD), etching, and photolithography, and a range of chemicals are used in each process. Metal target materials including copper, aluminum, and indium tin oxide are used in the sputtering process, and gaseous materials such as phosphine, silane, and chlorine are used in CVD and dry etching processes. Inorganic acids such as hydrofluoric acid, nitric acid and sulfuric acid are used in wet etching process, and photoresist and developer are used in photolithography process. Chemical substances for the alignment of liquid crystal, such as polyimides, liquid crystals, and sealants are used in a liquid crystal process. Adhesives and hardeners for adhesion of driver IC and printed circuit board(PCB) to the LCD panel are used in the module process. Conclusions: LCD panels are produced through dozens of unit processes using various types of chemical substances in clean room facilities. Hazardous substances such as organic solvents, reactive gases, irritants, and toxic substances are used in the manufacturing processes, but periodic workplace monitoring applies only to certain chemical substances by law. Therefore, efforts should be made to minimize worker exposure to chemical substances used in LCD panel manufacturing process.

Effect of Photo Initiator Content and Light Exposure Time on the Fabrication of Al2O3 Ceramic by DLP-3D Printing Method (광개시제 함량과 노광 시간이 DLP기반 알루미나 3D 프린팅 공정에 미치는 영향)

  • Kim, Kyung Min;Jeong, Hyeondeok;Han, Yoon Soo;Baek, Su-Hyun;Kim, Young Do;Ryu, Sung-Soo
    • Journal of Powder Materials
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    • v.26 no.4
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    • pp.327-333
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    • 2019
  • In this study, a process is developed for 3D printing with alumina ($Al_2O_3$). First, a photocurable slurry made from nanoparticle $Al_2O_3$ powder is mixed with hexanediol diacrylate binder and phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide photoinitiator. The optimum solid content of $Al_2O_3$ is determined by measuring the rheological properties of the slurry. Then, green bodies of $Al_2O_3$ with different photoinitiator contents and UV exposure times are fabricated with a digital light processing (DLP) 3D printer. The dimensional accuracy of the printed $Al_2O_3$ green bodies and the number of defects are evaluated by carefully measuring the samples and imaging them with a scanning electron microscope. The optimum photoinitiator content and exposure time are 0.5 wt% and 0.8 s, respectively. These results show that $Al_2O_3$ products of various sizes and shapes can be fabricated by DLP 3D printing.