• 제목/요약/키워드: $PH_3$

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Syntheses and Structures of 1,2,3-Substituted Cyclopentadienyl Titanium(IV) Complexes

  • Joe, Dae-June;Lee, Bun-Yeoul;Shin, Dong-Mok
    • Bulletin of the Korean Chemical Society
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    • 제26권2호
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    • pp.233-237
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    • 2005
  • Cyclopentadiene compounds, 2-[CR'R(OMe)]-1,3-Me$_2C_5H_3$ (R, R' = 2,2'-biphenyl, 2) and 2-[CR'R(OSiMe$_3$)]-1,3-Me$_2C_5H_3$ (R, R' = 2,2'-biphenyl, 3; R = ph, R' = ph, 4; R = 2-naphthyl, R' = H, 5) are readily synthesized from 2-bromo-3-methoxy-1,3-dimethylcyclopentene (1). Reaction of the cyclopentadienes with Ti(NMe$_2$)$_4$ in toluene results in clean formation of the cyclopentadienyl tris(dimethylamido)titanium complexes, which are transformed to the trichloride complexes, 2-[CR'R(OMe)]-1,3-Me$_2C_5H_2$}TiCl$_3$ (R, R' = 2,2'-biphenyl, 6) and {2-[CR'R(OSiMe$_3$)]-1,3-Me$_2C_5H_2$}TiCl$_3$ (R, R' = 2,2'-biphenyl, 7; R = ph, R' = ph, 8; R = 2-naphthyl, R' = H, 9). Attempts to form C1-bridged Cp/oxido complexes by elimination of MeCl or Me$_3$SiCl were not successful. X-ray structures of 6, 7 and an intermediate complex {2-[Ph$_2$C(OSiMe$_3$)]-1,3-Me$_2C_5H_2$}TiCl$_2$(NMe$_2$) (10) were determined.

大氣中의 酸性降下物의 增加에 따른 Ctenidium molluscum 등 4 종 蘇類의 窒酸還元酵素 活性 (Natrate reductase activity of 4 mosses including ctenidium molluscum in relation to increasing acidic deposition from atmosphere)

  • Ihm, Byung-Sun;Lee, Jeom-Sook
    • The Korean Journal of Ecology
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    • 제15권4호
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    • pp.355-363
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    • 1992
  • Nitrate reductase activity(NRA) and induced NRA were compared in 4 species of moss ctenidium molluscum, homalothecium, tortella tortusa and neckera crispa collected from limestone in england. the NRA and dry weight of the c. molluscum were also measured after spraying with acidic deposition adjusted to ph 5.6, 4.6, 3.6 and 2.8 with one of two molar ratios of nitric to sulfuric acid, i.e. 1:0(N alone) and 1:2(1N+2S) for 20 days. All 4 species showed high NR leavels in the upper part of cut shoots and occurred maximum inducation of NRA within 6h. c. molluscum had the highest NRA levels among 4 species. after daily spraying of acidic deposition, NRA of c. molluscum was increased much more largely at ph 6 and ph 3.6 derived from N alone than from 1N+2S. However that was decreased at ph 2.8 derived both from N alone and 1N+2S . Decline of dry weight had occurred at ph 3.6 and 2.8 derived both from N alone and 1N+2S. Whereas substantial fertilization effect was observed at ph 4.6 derived from N alone. the data suggest that c. molluscum are able to utilize nitrate more effectivery than any other species, and NRA induction are more sensitive than growth response to nitrogen content of acidicdeposition in a short- term. however toxic effects was detected at high $NO_3$ supply and low phacidic deposition.

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Grignard Coupling Reaction of Bis(chloromethyl)diorganosilanes with Dichloro(diorgano)silanes: Syntheses of 1,3-Disilacyclobutanes

  • 조연석;유복렬;안삼영;정일남
    • Bulletin of the Korean Chemical Society
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    • 제20권4호
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    • pp.427-430
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    • 1999
  • The Grignard coupling reaction of bis(chloromethyl)diorganosilanes [(ClCH2)2SiR1R2: R1 = R2 = Me, la; R1 = Me, R2 = Ph, lb; R1 = R2 = Ph, lc] with diorganodichlorosilanes [(Cl2SiR3R4: R3 = R4 = Me, 2a; R3 = Me, R4 = Ph, 2b; R3 = R4 = Ph, 2c] at THE reflux temperature gave the intermolecular C-Si coupling product of 1,1,3,3-tetraorgano-1,3-disilacyclobutanes 3a-f in poor to moderate yields ranging from 7% to 50% along with polydiorganosilapropanes. The cyclization reaction of la-c with methyl-substituted dichlorosilanes 2a, b gave 1,3-disilacyclobutanes 3a-c, e, d in moderate yields (42-50%), while the same reaction with dichlorodiphenylsilane (2c) to 1,3-disilacyclobutanes 3d, f resulted in low yield (7-18%) probably due to the steric hindrance of two-phenyl groups on the silicon of 2c.

순수 알루미나와 탄소나노튜브 강화 알루미나 복합체의 극초단 펄스레이저 가공특성 비교 (Comparison of Ablation Characteristics of Carbon Nanotube reinforced Hybrid Al2O3 by using Ultrashort Pulse Laser)

  • 이준영;윤지욱;강명창;조성학
    • 한국기계가공학회지
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    • 제12권6호
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    • pp.23-29
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    • 2013
  • In this paper, pure $I_{ph}$ and hybrid carbon nanotube reinforced $I_{ph}$ were sintered using the SPS(spark plasma sintering) method for high densification. A nanosecond laser (${\lambda}=1063nm$, ${\tau}P=10ns$) and a femtosecond laser (${\lambda}=1027nm$, ${\tau}P=380fs$) were installed on an optical system for the micromachining test. The ablation characteristics of the pure $I_{ph}$ and CNT/$I_{ph}$ composites, such as thermal effect and ablation depth, were investigated using FE-SEM and a confocal microscope device. Laser machining results for the two mating materials showed improved performances: CNT/$I_{ph}$ composites showed good surface morphology of hole drilling without a melting zone due to the composites' high thermal properties; also, the ablated depth of CNT/$I_{ph}$ was higher than that of pure $I_{ph}$.

(펜타메틸시클로펜타디에닐) 비스(포스핀)루테늄의 염화물과 수소화물 유도체 (Chloro- and Hydrido Complexes of (Pentamethylcyclopentadienyl) bis(phosphine)ruthenium)

  • 이동환
    • 대한화학회지
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    • 제36권2호
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    • pp.248-254
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    • 1992
  • 에탄올 용매 중에서, 착물 $[({\eta}^5-C_5Me_5)RuCl_2]_2$ (1)에 대하여 과량의 포스핀을 반응시켜 비스(포스핀)루테늄 유도체$({\eta}^5-C_5Me_5)Ru(PR_3)_2Cl(PR_3=PMe_3,\; PMe_2Ph,\;PEt_3,\;PMePh_2$, 1/2DPPE, 1/2DPPB) (2a${\sim}$2f)를 합성하였다. 이 유도체들은 에탄올 용매 중에서 $NaBH_4$와 반응하여 상응하는 황색의 착수소화물 $({\eta}^5-C_5Me_5)Ru(PR_3)_2Hl(PR_3=PMe_3,\;PEt_3,\;PMePh_2$, 1/2 DPPE, 1/2DPPB) (3a${\sim}$3e)을 생성한다. 착염화물 (2a${\sim}$2f)와 착수소화물 (3a∼3e)는 모두 결정으로 얻어졌으며, IR, $^1H-NMR$ 그리고 원소분석으로 동정되었다.

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Discovery and Characterization of a Thermostable NADH Oxidase from Pyrococcus horikoshii OT3

  • Koh, Jong-Uk;Chung, Hyun-Jung;Chang, Woo-Young;Tanokura, Masaru;Kong, Kwang-Hoon
    • Bulletin of the Korean Chemical Society
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    • 제30권12호
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    • pp.2984-2988
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    • 2009
  • A gene (PH0311) encoding a hypothetical protein from the genome sequence data of the hyperthermophilic archaeon Pyrococcus horikoshii OT3 was cloned and over-expressed in Escherichia coli. The purified recombinant protein was found to possess FAD-dependent NADH oxidase activity, although it lacked sequence homology to any other known general NADH oxidase family. The product of the PH0311 gene was thus designated PhNOX (NADH oxidase from Pyrococcus horikoshii), with an estimated molecular weight of 84 kDa by gel filtration and 22 kDa by SDS-PAGE, indicating it to be a homotetramer of 22 kDa subunits. PhNOX catalyzed the oxidation of reduced ${\beta}$-NADH with subsequent formation of $H_2O_2$ in the presence of FAD as a cofactor, but not ${\alpha}$-NADH, ${\alpha}$-NADPH, or ${\beta}$-NADPH. PhNOX showed high affinity for ${\beta}$-NADH with a Km value of 3.70 ${\mu}$M and exhibited optimum activity at pH 8.0 and 95$^{\circ}C$ as it is highly stable against high temperature.

Phytosphingosine과 Phytosphingosine-1-phosphate의 화장품 소재 특성 연구 (Study on phytosphingosine and Phytosphingosine-1-phosphate as a cosmetic ingredient)

  • 문지선;김영은;표영희
    • 한국응용과학기술학회지
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    • 제34권2호
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    • pp.382-393
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    • 2017
  • 본 연구에서는 Phytosphingosine(PhS)과 Phytosphingosine-1-phosphate(PhS1P)를 피부 미용 측면에서 생리활성을 연구하여 화장품 소재로서 가능성 여부를 규명하고자 B16F10 멜라닌 세포, RAW264.7 대식 세포, HDF 섬유아세포를 이용하여 3가지 세포에 대한 독성을 파악하고 항염증, 항 멜라닌, MMP-1 발현 억제, Western blot analysis 실험을 통해 효과를 확인 하고자한다. 본 실험 결과 B16F10, RAW264.7, HDF 세포에 대한 독성이 낮은 것으로 확인하였으며, 항염증 NO 저해능 실험에서 PhS1P이 PhS보다 더 강력한 저해활성을 나타냈다. MMP-1 발현 또한 마찬가지로 PhS1P이 더 우수했고, 그 기작은 ERK 활성 감소에 의한 것임을 확인하였다. 한편, 멜라닌 생성 저해능은 알부틴 보다 우수하였으며, 그 작용은 Tyrosinase 발현을 억제하는 것임을 확인하였다. 이상의 결과를 종합하면, 생리활성물질인 PhS과 PhS1P는 주름개선 및 미백화장품의 피부 개선을 위한 기능성화장품으로 활용 가능성을 확인할 수 있었다.

Geometrical Characteristics and Reactivities of Tetracoordinated Pd Complexes: Mono- and Bidentate Ligands and Charged and Uncharged Ligands

  • Yoo, Jin-Seon;Ha, Dong-Su;Kim, Jae-Sang;Kim, Bong-Gon;Park, Jong-Keun
    • Bulletin of the Korean Chemical Society
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    • 제29권3호
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    • pp.627-640
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    • 2008
  • The geometrical structures, atomic charges, and relative energies of tetracoordinated Pd complexes [PdCl3Z (Z = Cl-, Br-, OH?-, H2O, NH3, PH3), PdCl2Z2 (Z = Br-, OH?-, H2O, NH3, PH3), PdZ?2X (Z = Cl-, OH?-, H2O, NH3, PH3; X = oxalate, O2-?CCO2-), and PdZ2Y (Z = Cl?-, OH?-, H2O, NH3, PH3; Y = succinate, CO2-?CHCHCO2-?)] and the ligand exchange reactions of the Pd complexes were investigated using the ab initio second order Mller-Plesset perturbation (MP2) and Density Functional Theory (DFT) methods. The geometrical characteristics of the tetracoordinated Pd(II) complexes with mono- and bidentate ligands, the effects of the atomic charges for the charged and uncharged ligands, the (dz2-p ) interactions between the dz2-orbital of Pd(II) and the p -orbital of bidentates, and the relative stabilities between the isomers of PdCl2Z2 and PdZ2Y were investigated in detail. The potential energy surfaces for the ligand exchange reactions used for the conversions of {[PdCl2(NH3)2] + H2O} to {[PdCl(NH3)2(H2O)]+ + Cl?-?} and {[PdCl2(PH3)2] + H2O} to {[PdCl(PH3)2(H2O)]+ + Cl?-?]} were investigated. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes were also examined quantitatively.

Synthesis and Dissociation Constants of Cationic Rhodium (I)-Triphenylarsine Complexes of Unsaturated Nitriles and Aldehyde

  • Chin, Chong-Shik;Park, Jeong-Han;Shin, Sang-Young;Kim, Choong-Il
    • Bulletin of the Korean Chemical Society
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    • 제8권3호
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    • pp.179-183
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    • 1987
  • Reactions of $Rh(ClO_4)(CO)(AsPh_3)_2$ with unsaturated nitriles and aldehyde, L, produce a series of new cationic rhodium (I) complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ (L = $CH_2$ = CHCN, $CH_2$ = C($CH_3$)CN, trans-$CH_3CH$ = CHCN, $CH_2$ = CH$CH_2$CN, trans-$C_6H_5CH$ = CHCN, and trans-$C_6H_5CH$ = CHCHD) where L are coordinated through the nitrogen and oxygen, respectively but not through the ${\pi}$-system of the olefinic group. Dissociation constants for the reaction, $[RhL(CO)(AsPh_3)_2]ClO_4$ $\rightleftharpoons$ $Rh(ClO_4)(CO)(AsPh_3)_2$ + L, have been measured to be $1.20{\times}10^{-4}$ M (L = $CH_2$ = CHCN), $1.05{\times}10^{-4}$ M (L = $CH_2$ = C($CH_3$)CN, $3.26{\times}10^{-5}$ M (L = trans-$CH_3$CH = CHCN) and $6.45{\times}10^{-5}$ M (L = $CH_2$ = CH$CH_2$CN) in chlorobenzene at $25^{\circ}C, and higher than those of triphenylphosphine complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ where L are the corresponding nitriles that are coordinated through the nitrogen atom. The differences in dissociation constants seem to be predominantly due to the differences in ${\Delta}H$ (not due to the differences in ${\Delta}S$). The weaker Rh-N (unsaturated nitriles) bonding in $AsPh_3$ complexes than in $PPh_3$ complexes (based on ${\Delta}H$ values) suggests that the unsaturated nitriles in 2∼5 are good ${\sigma}$-donor and poor ${\pi}$-acceptor.

패장(敗醬)의 급성 췌장염 억제 효과 (Inhibitory Effect of Aacute Pancreatitis by Patriniae Herba)

  • 박성주;정종길;서상완;황상욱;김영우;송달수;채영석;신민교;송호준
    • 대한본초학회지
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    • 제20권3호
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    • pp.93-100
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    • 2005
  • Objective : Patriniae Herba (PH) has long been used as a remedy for treating infectious diseases in Korea. In the present experiments, the author examined the effects of PH on the cholecystokinin-octapeptide (CCK)-induced acute pancreatitis (AP) in rats. Methods : Male Wistar rat weighing 200 to 250 g were divided into three groups. Normal untreated group, in treatment with PH group; PH (1g/kg) was administered orally, followed by $75\;{\mu}g/kg$ CCK subcutaneously three times, after 1, 3 and 5 h. This whole procedure was repeated for 5 days. In treatment with saline group, the protocol was the same as in treatment group with PH. The author determined the pancreatic weight/body weight ratio, the levels of pancreatic HSP60, HSP72 and the secretion of pro-inflammatory cytokines. Methods : Repeated CCK treatment resulted in the typical laboratory and morphological changes of experimentally induced pancreatitis. PH was significantly decreased the pancreatic weight/body weight ratio in CCK-induced AP. Futhermore, the author demonstrated that PH increased HSP60 and HSP72 compared with CCK-induced AP. Additionally, the secretion of $TNF-{\alpha},\;IL-1{\beta}$ and IL-6 the levels of amylase and lipase were lower than that saline. Conclusions : These results suggest that PH may has a inhibitory effect against CCK-induced AP.

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