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Chiral [Iminophosphoranyl]ferrocenes: Synthesis, Coordination Chemistry, and Catalytic Application

  • Co, Thanh Thien;Shim, Sang-Chul;Cho, Chan-Sik;Kim, Dong-Uk;Kim, Tae-Jeong
    • Bulletin of the Korean Chemical Society
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    • 제26권9호
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    • pp.1359-1365
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    • 2005
  • A series of new chiral [iminophosphoranyl]ferrocenes, {${\eta}^5-C_5H_4-(PPh_2=N-2,6-R_2-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-PPh^2-2-CH(Me)NMe_2$} (1: R = Me, $^iPr$), {${\eta}^5{-C_5H_4-(PPh_2=N-2,6-R_2}^1-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-(PPh_2=N-2,6-R_2-C_6H_3)-2-CH(Me)R_2$} (2: $R^1\;=\;Me,\;^iPr;\;R^2\;=\;NMe_2$, OMe), and $({\eta}^5-C_5H_5)Fe${${\eta}^5-C_5H_4-1-PR_2-2-CH(Me)N=PPh_3$} (3:R = Ph, $C_6H_{11}$) have been prepared from the reaction of [1,1'-diphenylphosphino-2-(N,N-dimethylamino) ethyl]ferrocene with arylazides (1 & 2) and the reaction of phosphine dichlorides ($R_3PCl_{2}$) with [1,1'-diphenylphosphino-2-aminoethyl]ferrocene (3), respectively. They form palladium complexes of the type $[Pd(C_3H_5)(L)]BF_4$ (4-6: L = 1-3), where the ligand (L) adopts an ${\eta}^2-N,N\;(2)\;or\;{\eta}^2$-P,N (3) as expected. In the case of 1, a potential terdentate, an ${\eta}^2$-P,N mode is realized with the exclusion of the –=NAr group from the coordination sphere. Complexes 4-6 were employed as catalysts for allylic alkylation of 1,3-diphenylallyl acetate leading to an almost stoichiometric product yield with modest enantiomeric excess (up to 74% ee). Rh(I)-complexes incorporating 1-3 were also prepared in situ for allylic alkylation of cinnamyl acetate as a probe for both regio- and enantioselectivities of the reaction. The reaction exhibited high regiocontrol in favor of a linear achiral isomer regardless of the ligand employed.

PROPERTIES OF INDUCED INVERSE POLYNOMIAL MODULES OVER A SUBMONOID

  • Cho, Eunha;Jeong, Jinsun
    • Korean Journal of Mathematics
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    • 제20권3호
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    • pp.307-314
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    • 2012
  • Let M be a left R-module and R be a ring with unity, and $S=\{0,2,3,4,{\ldots}\}$ be a submonoid. Then $M[x^{-s}]=\{a_0+a_2x^{-2}+a_3x^{-3}+{\cdots}+a_nx^{-n}{\mid}a_i{\in}M\}$ is an $R[x^s]$-module. In this paper we show some properties of $M[x^{-s}]$ as an $R[x^s]$-module. Let $f:M{\rightarrow}N$ be an R-linear map and $\overline{M}[x^{-s}]=\{a_2x^{-2}+a_3x^{-3}+{\cdots}+a_nx^{-n}{\mid}a_i{\in}M\}$ and define $N+\overline{M}[x^{-s}]=\{b_0+a_2x^{-2}+a_3x^{-3}+{\cdots}+a_nx^{-n}{\mid}b_0{\in}N,\;a_i{\in}M}$. Then $N+\overline{M}[x^{-s}]$ is an $R[x^s]$-module. We show that given a short exact sequence $0{\rightarrow}L{\rightarrow}M{\rightarrow}N{\rightarrow}0$ of R-modules, $0{\rightarrow}L{\rightarrow}M[x^{-s}]{\rightarrow}N+\overline{M}[x^{-s}]{\rightarrow}0$ is a short exact sequence of $R[x^s]$-module. Then we show $E_1+\overline{E_0}[x^{-s}]$ is not an injective left $R[x^s]$-module, in general.

노인의 견관절 가동범위에 관한 연구 (A Study on Shoulder Joint ROM of the Elderly)

  • 엄기매;양윤권
    • 대한물리치료과학회지
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    • 제8권2호
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    • pp.997-1003
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    • 2001
  • The purpose of this study is to know the average of pint range of motion and difference according to the aging for the elderly, This study consisted of elder male(n=75) and elder female(n=l09), The result of assessment and analysis in shoulder pint range of motion are as follows: 1) The average shoulder flexion pint range of motion in 60-69(from sixty to sixty-nine)years old are 163.04(Left-Male), 162.91(Right-Male), 158.74 (Left-Female), 158.74 (Right-Female). 70-79years old are 149.40(L-M), 152.38(R-M), 153,37(L-F), 153.37(R-F). 80-89 years old are 149.57(L-M), 147.93(R-M), 151.17(L-F), 150.33(R-F). There was no significant difference among group, 2) The average shoulder extension pint range of motion in 60-69years old are 48.15(L-M), 47.20(R-M), 45.16(L-F), 44.23(R-F), 70-79years old are 37.l1(L-M), 38.70(R-M), 35.17(L-F), 36.71(R-F), 80-89 years old are 34.46(L-M). 36.71(R-M), 33.90(L-F), 33.09(R-F). There was significant difference among group(p<.05). 3) The average shoulder abduction pint range of motion in 60-69years old are 164.22(L-M), 165.96(R-M), 159.34(L-F), 159.97(R-F), 70-79years old are 152.27(L-M), 155.05(R-M), 152.32(L-F), 53.66(R-F), 80-89 years old are 152.17(L-M), 153.76(R-M), 147.53(L-F), 147.37(R-F). There was significant difference in right shoulder abduction among group(p<05). 4) The average shoulder internal rotation pint range of motion in 60-69years old are 63.52(L-M), 65.70(R-M), 64.16(L-F), 64.61(R-F), 70-79years old are 64.50(L-M), 65.81(R-M) 61.10(L-F), 61.83(R-F). 80-89 years old are 61.60(L-M), 61.66(R-M), 57.53(L-F), 57.53(R-F). There was no significant difference among group. 5) The average shoulder external rotation pint range of motion in 60-69years old are 50.87(L-M), 50.22(R-M), 51.03(L-F), 50.42(R-F), 70-79years old are 50.91(L-M), 50.20(R-M) 48.37(L-F), 50.20(R-F). 80-89 years old are 46.83(L-M), 47.93(R-M), 43.43(L-F), 43.72(R-F).There was significant difference in left shoulder external rotation among group(p<.05).

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A CONDITION FOR THE COMMUTATIVITY OF RINGS

  • Quadri, Murtaza A.;Ashraf, Mohd.
    • Kyungpook Mathematical Journal
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    • 제27권2호
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    • pp.187-189
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    • 1987
  • In the present paper a result [10] of the authors has been generalized as follows: Let l, m, n be fixed positive integers and R be a semi prime ring in which $[(xy)^l,(xy)^m-(yx)^n]=0$ for all $x,y{\in}R$, then R is commutative.

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Synthesis and Characterization of Molybdenum(V)-Oxo Complexes with ONO-Donors

  • 김정숙;김희정;구본권
    • Bulletin of the Korean Chemical Society
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    • 제16권1호
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    • pp.26-29
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    • 1995
  • Six-coordinate molybdenum(Ⅴ)-oxo complexes (PyH)[MoOCl2L] and (R4N)-[MoOCl2L] (R=CH3 and C2H5) with N-salicylidene-2-aminophenol(L1) and its derivatives(L2=5-CH3, L3=3-CH3O, L4=5,6-C4H4 and L5=5-NO2) as ONO-donor ligands have been synthesized and the spectral and electrochemical properties of the complexes by elemental analysis, molar conductivity, UV-vis, IR, 1H NMR and CV have been studied.

N-Linked Glycosylation 저해에 의한 닭의장풀 추출물의 미백효능 (Whitening Effect of Dayflower (Commelina communis L.) Extract by Inhibition of N-Linked Glycosylation Process and Melanogenesis)

  • 박선희;이방용;이승현;한창성;김진국;김경태;김기호;김영희
    • 대한화장품학회지
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    • 제35권1호
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    • pp.73-78
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    • 2009
  • 닭의장풀(Commelina communis L. Dayflower) 추출물의 미백효능을 확인하기 위하여 B16 melanoma 세포를 이용하여 melanin 생성에 관련된 다양한 실험을 실시하였다. 닭의장풀 추출물은 버섯 tyrosinase 활성 실험에서 저해 효과를 보이지 않았으나, melanin 생성 저해효과를 나타내었다. B16-F10 멜라노마 세포를 이용한 활성시험 결과에서, 닭의장풀 추출물은 1,000 ${\mu}g/mL$의 농도에서 약 32%의 멜라닌 생성을 억제하였으며, 세포내 티로시나제 활성 억제 능도 우수하여 닭의장풀 추출물 250 ${\mu}/mL$ 이상의 농도에서 50% 이상의 저해 효과를 보였다. 추출물의 생성 기작에 대한 영향을 조사한 결과, melanin 합성의 key protein 인 tyrosinase 발현의 우수한 저해 능력을 보였고, tyrosinase related protein-1 (TRP-1)의 발현 억제와 tyrosinase related protein-2 (TRP-2)의 N-glycosylatin 억제를 통해 melanin 합성이 억제되는 것으로 분석되었다. 따라서 닭의장풀 추출물은 melanin 합성에 필수적인 효소(tyrosinase, TRP-1)의 발현 저해 및 TRP-2의 N-glycosylation 억제를 통해 미백 효과를 나타내는 것으로 확인되었으며, 이에 따라 본 추출물은 melanin 합성의 효소 경로를 저해하는 미백 소재로 활용할 수 있을 것으로 사료된다.

Chiral Pool Synthesis of N-Cbz-cis-(3R,4R)-3-methylamino-4-methylpiperidine from L-Malic acid

  • Hao, Bao-Yu;Liu, Jin-Qiang;Zhang, Wei-Han;Chen, Xin-Zhi
    • Bulletin of the Korean Chemical Society
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    • 제34권5호
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    • pp.1371-1377
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    • 2013
  • A new synthetic route to N-Cbz-cis-(3R,4R)-3-methylamino-4-methylpiperidine, key intermediate for CP-690,550, was disclosed with L-malic acid as the chiral pool starting material. The title compound was obtained in 16 steps with a total yield of 26% and more than 98% ee.

Convergence Properties of a Spectral Density Estimator

  • Gyeong Hye Shin;Hae Kyung Kim
    • Communications for Statistical Applications and Methods
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    • 제3권3호
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    • pp.271-282
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    • 1996
  • this paper deal with the estimation of the power spectral density function of time series. A kernel estimator which is based on local average is defined and the rates of convergence of the pointwise, $$L_2$-norm; and; $L{\infty}$-norm associated with the estimator are investigated by restricting as to kernels with suitable assumptions. Under appropriate regularity conditions, it is shown that the optimal rate of convergence for 0$N^{-r}$ both in the pointwiseand $$L_2$-norm, while; $N^{r-1}(logN)^{-r}$is the optimal rate in the $L{\infty}-norm$. Some examples are given to illustrate the application of main results.

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항암제 내성 L1210세포의 Glutathione 대사 관련효소 유전자의 발현 양상 (Gene Expression of Enzymes Related to Glutathione Metabolism in Anticancer Drug-resistant L1210 Sublines)

  • 김성용;김재룡;김정희
    • Journal of Yeungnam Medical Science
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    • 제12권1호
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    • pp.32-47
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    • 1995
  • 생쥐의 백혈병세포 L1210과 항암제에 대하여 내성이 유도된 L1210AdR, L1210VcR과 L1210Cis에서 glutathione의 농도와 glutathione의 합성 조절에 관여하는 ${\gamma}$-glutamylcysteine synthetase(GCS)와 ${\gamma}$-glutamyl transpeptidase (GGT), 세포 이물질을 축합하는데 촉매하는 glutathione S-transferase(GST)의 효소 활성도와 유전자의 발현 여부를 관찰하였다. 세포내 glutathione농도(${\mu}M/mg$ protein)는 L1210이 $0.41{\pm}0.003$, L1210AdR가 $0.73{\pm}0.006$, L1210VcR은 $1.16{\pm}0.060$, L1210Cis가 $2.19{\pm}0.282$으로 모세포에 비하여 내성세포에서 통계적으로 유의한 증가를 관찰하였다. Buthionine sulfoxamine(BSO)를 1 ${\mu}M$농도로 첨가하여 12시간 배양한 세포들에서의 glutathione농도는 L1210이 88%, L1210AdR가 85%, L1210VcR이 89%, 그리고 L1210Cis는 79%의 감소를 보였다. GCS의 활성도(nM/mg protein/min)는 L1210이 104인데 비하여 L1210AdR가 128, L1210VcR는 227, 및 L1210Cis는 212로 증가하였다. GGT의 활성도(nM/mg protein/min)는 L1210이 $2.15{\pm}0.531$이었고, L1210AdR은 $2.80{\pm}0.498$, L1210VcR은 $2.42{\pm}0.389$, 그리고 L1210Cis는 $2.98{\pm}0.623$으로 내성인 세포들에서 증가하였으며 L1210AdR과 L1210Cis에서 유의하였다. GST활성도(nM/mg protein/min)는 L1210이 $16.70{\pm}4.798$이었고, L1210AdR은 $14.51{\pm}3.402$, L1210VcR은 $19.52{\pm}4.255$, L1210Cis $17.77{\pm}4.495$로 L1210VcR과 L1210Cis가 약간의 증가를 보였으며, L1210AdR은 오히려 감소를 보였다. DNA의 slot blot에서 GCS, GGT, GST 유전자의 모세포와 내성세포간에 별다른 차이를 보이지 않았다. Northern hybridization에서 GCS는 약 4.5kb 크기의 band, GST-${\pi}$는 약 1.05kb 크기의 band를 보였으며 내성세포 모두에서 발현 증가가 관찰되었다. GGT의 경우 크기가 다른 6개의 band가 보였으며 특히 11.5 kb크기의 band에서 L1210AdR과 L1 210VcR의 발현이 증가하였으며, L1210VcR에서는 L1210과 다른 내성세포에서 보이는 1.95kb크기의 band가 보이지 않고 2.2kb 크기의 다른 band가 관찰되었다. 이상에서 L1210AdR과 L1210VcR의 내성에는 mdr1 유전자가 관여하고, L1210Cis의 내성에는 특히 glutathione이 중요하다. GCS, GGT 및 GST등의 활성도 및 유전자의 발현도 내성세포들에서 증가하였으며 이중 GCS는 내성세포내의 glutathione 합성에 가장 중요한 조절인자라 할 수 있다.

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