• 제목/요약/키워드: $^3H$

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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.

Is Autophagy a Prerequisite for Steroidogenesis in Leydig Cells?

  • Ji-Eun Park;Yoon-Jae Kim;Jong-Min Kim
    • 한국발생생물학회지:발생과생식
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    • 제27권3호
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    • pp.149-157
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    • 2023
  • We investigated the involvement of autophagy with steroidogenesis in testicular Leydig cells. Human chorionic gonadotropin (hCG)-stimulated T production in Leydig cells was not remarkably altered in the presence of an autophagy inhibitor 3-methyladenine (3-MA). Although pretreatment with 3-MA demonstrated a tendency to decrease hCG-induced T production, the differences were significant only at a higher time point of 24 h following hCG. Microtubule associated protein light chain 3 (LC3)-II was detectable in the control cells in all the experiments. The hCG-induced increase in steroidogenic acute regulatory protein (StAR) and cytochrome P450 side chain cleave (P450scc) protein levels were not significantly altered by 3-MA. Leydig cells isolated from immature rat testes 12 h following hCG treatment showed relatively increased levels of LC3-II protein compared to the control group. Furthermore, LC3-II levels shown in these cells reached almost the identical to those from normal adult testes. However, LC3-II protein levels were almost comparable or even slightly lower than the controls at 48 h following hCG. Expression of StAR and P450scc was upregulated at both 12 and 48 h after hCG. We also used MA-10 cells, the mouse Leydig cell line, in this experiment. When dibutyryl cyclic-AMP was treated with MA-10 cells, P4 levels were significantly increased in the cell culture medium. However, P4 levels tended to decrease in the presence of 3-MA, but the difference was not statistically significant. This was consistent with the results of the rat Leydig cell experiments. Together, we believe that although autophagy participates in steroidogenesis and enhances steroidogenic efficacy of Leydig cells, it may not be a decisive cellular process for steroidogenesis, specifically in the mature Leydig cells.

히스톤 메틸화 변형을 통한 배아줄기세포의 후성 유전학적 조절 (Epigenetic Regulation by Modification of Histone Methylation in Embryonic Stem Cells)

  • 하양화;김영은;박정아;박상규;이영희
    • 한국발생생물학회지:발생과생식
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    • 제15권4호
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    • pp.273-279
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    • 2011
  • 후성유전학적 조절은 DNA 서열상의 변화 없이도 유전자의 기능을 변화시킬 수 있는 현상을 뜻한다. 염색체의 후성유전학적 상태는 히스톤 변형, DNA 변형 그리고 RNAi에 의한 유전자 침묵 등에 의해 조절된다. 본 총설에서는 배아줄기세포에서의 후성 유전학적 조절에 영향을 주는 요인으로서 히스톤(histone)의 메틸화에 초점을 맞추었다. 배아줄기세포에서 발현되는 유전자의 조절에는 두 가지 단백질 복합체가 관여한다. Polycomb repressive complex 2(PRC2)는 EED, EZH2, SUZ1를 주요인자로 포함하며, H3K27의 trimethylation(H3K27me3)을 증가시킴으로써 유전자의 발현을 억제한다. 이와는 대조적으로 Trithorax group(TrxG) 복합체는 주요인자로 MLL family를 포함하며, H3K4의 trimethylation(H3K4me3) 시킴으로써 유전자의 발현을 활성화한다. PRC2 및 TrxG는 다양한 보조 단백질을 포함한다. 배아줄기세포에서 후성유전학적 조절의 두드러진 특징은 H3K27me3과 H3K4me3이 동시에 나타나는 이가 상태(bivalent state)이다. PRC2와 TrxG 복합체 그리고 H3K4나 K3K27의 메틸화에 특이적으로 작용하는 탈메틸효소(demethylase)가 한데 어우러져 배아줄기세포에서 만능성 관련 유전자와 발달 관련 유전자의 발현을 조절함으로써 줄기세포의 유지 및 분화에 기여한다. 따라서 후성유전학적 조절인자들에 대한 보다 자세한 연구는 배아줄기세포를 보다 잘 이해하고 활용하는데 도움을 줄 것이다.

Expression of Replication-Independent Chicken H3.3 Histone Gene without Introns

  • Son, Seung-Yeol;Hong, Bum-Shik
    • BMB Reports
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    • 제30권3호
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    • pp.200-204
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    • 1997
  • We eliminated introns from replication independent chicken H3.3 histone gene using a H3.3 cDNA clone and a genomic H3.3 clone. After introduction into Rat 3 cells, we observed its pattern of expression by analyzing mRNA from different phases of the cell cycle. Even without introns, the H3.3 gene was expressed constitutively at a low level throughout the cell cycle. This indicates that the introns in the H3.3 gene are not responsible for the cell cycle-independent expression of the gene. This result contradicts previous reports that suggested their importance in cell cycle regulated expression. We believe that other regions of the gene, promoter, coding region, and/or 3'-end of the gene, are involved in its expression pattern.

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고분자와의 블랜딩에 의한 헤테로폴리산의 촉매 특성 제어 (Control of Catalytic Properties of Heteropoly Acid by Blending it with a Polymer)

  • 송인규;이종국;이화영
    • 공업화학
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    • 제5권5호
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    • pp.819-824
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    • 1994
  • Dimethylformamide를 공통용매로 하여 $H_3PMo_{12}O_{40}$와 polysulfone를 동시에 녹여 분리막 형태의 $H_3PMo_{12}O_{40}$-polysulfone 필름을 제조하였다. SEM 및 EDX 분석 결과 필름 촉매상에서 $H_3PMo_{12}O_{40}$는 매우 고른 상태로 잘 분산되어 있음을 확인되었다. ESCA 분석결과에 의하면 Mo의 산화상태에는 변화가 없었다. 에탄을 전환반응에서 $H_3PMo_{12}O_{40}$-polysulfone 필름 촉매는 $H_3PMo_{12}O_{40}$보다 낮은 산반응특성과 높은 산화반응 특성을 보였으며, 산화반응의 활성은 약 10배 정도 크게 나타났다. 산 특성의 감소는 $H_3PMo_{12}O_{40}$의 산점과 강하게 결합된 dimethylformamide에 기인하여, 산화특성의 증가는 촉매의 고른 분산에 기인하였다. 흡착실험 결과 블랜딩 후 $H_3PMo_{12}O_{40}$의 표면 특성은 크게 증가하였으나 내부 특성은 큰 변화가 없는 것으로 나타났다. 따라서 헤테로폴리산을 고분자와 블랜딩시킬 경우 헤테로폴리산이 지니는 산 및 산화환원 특성의 제어는 물론 촉매의 표면 및 내부 특성 제어가 가능할 것으로 여겨진다.

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Crystal Structures and Luminescence Properties of [Ln(NTA)2·H2O]3- Complexes (Ln = Sm3+, Eu+3, Gd3+, Tb3+, Ho3+, and NTA = Nitrilotriacetate)

  • Kang, Jun-Gill;Kang, Hee-Jung;Jung, Jae-Sun;Yun, Sock-Sung;Kim, Chong-Hyeak
    • Bulletin of the Korean Chemical Society
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    • 제25권6호
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    • pp.852-858
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    • 2004
  • Crystal structures of lanthanide complexes with NTA (NTA = nitrilotriacetate) are reported. The complexes of $[Ln(NTA)_2{\cdot}H_2O]^{3-}$ (Ln = Sm, Eu, Gd, Tb and Ho) crystallize in the orthorhombic space group Pccn. In the structures, the trivalent lanthanide ions are completely encapsulated via coordination to the two nitrogen atoms and the six carboxylate oxygen atoms of the two NTA ligands, and one water oxygen atoms. The complexes form a slightly distorted capped-square-antiprism polyhedron. Of the complexes, $[Eu(NTA)_2{\codt}H_2O]^{3-}$,\;[Tb(NTA)_2{\cdot}H_2O]^{3-}\;and\;[Dy(NTA)_2{\cdot}H_2O]^{3-}$ excited at the 325 He-Cd line produce very characteristic luminescence features, arising mostly from the f ${\to}$ f transitions. The absolute quantum yields of these complexes are determined at room temperature. Surprisingly, the $[Dy(NTA)_2{\cdot}H_2O]^{3-}$ complex is more luminescent than the $[Eu(NTA)_2{\cdot}H_2O]^{3-}\;and\;[Tb(NTA)_2{\cdot}H_2O]^{3-}$ complexes.

Molecular Cloning and Characterization of a Flavanone-3-hydroxylase Gene from Rubus occidentalis L.

  • Lee, Seung Sik;Lee, Eun Mi;An, Byung Chull;Barampuram, Shyamkumar;Kim, Jae-Sung;Cho, Jae-Young;Lee, In-Chul;Chung, Byung Yeoup
    • 방사선산업학회지
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    • 제2권3호
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    • pp.121-128
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    • 2008
  • Flavanone-3-hydroxylase (F3H) is one of the key enzymes for the biosynthesis of flavonals, anthocyanins, catechins and proanthocyanins. F3H catalyzes the $3{\beta}$-hydroxylation of (2S)-flavonones to form (2R, 3R)-dihydroflavonols. In this report, we isolated a full-length cDNA of RocF3H from black raspberry (Rubus occidentalis L.) using a reverse transcriptase-PCR and rapid amplification of the cDNA ends (RACE)-PCR. The full-length cDNA of RocF3H contains a 1,098 bp open reading frame (ORF) encoding a 365 amino acid protein with a calculated molecular weight of about 41.1 kDa and isoelectric point (pI) of 5.45. The genomic DNA analysis revealed that the RocF3H gene had three exons and two introns. Comparison of the deduced amino acid sequence of the RocF3H with other F3Hs revealed that the protein is highly homologous with various plant species. The conserved amino acids ligating the ferrous iron and the residues participating in the 2-oxoglutarate binding (R-X-S) were found in RocF3H at the similar positions to other F3Hs. Southern blot analysis indicated that RocF3H exist a multi-gene family. The isolation of RocF3H gene will be helpful to further study the role of F3H gene in the biosynthesis of flavonoids in R. occidnetalis.

An ESR Study of Amino Acid and Protein Free Radicals in Solution Part VI. Enzymatic Inactivation of Lysozyme in Aqueous Solution Resulting from Exposure to $Ti-H_2O_2$ System and Gamma-Irradiation

  • Hong, Sun-Joo;Piette, L.H.
    • 대한화학회지
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    • 제16권2호
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    • pp.80-83
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    • 1972
  • The activity change of lysozyme resulted from its exposure to $Ti-H_2O_2$system in aqueous liquid at room temperature and to ${\gamma}$-irradiation in ice at $195^{\circ}K$ has been measured at room temperature with a Cary-14 spectrophotometer. The enzymatic activity of lysozyme which had been added to a previously flow-mixed solution of $TiCl_3$ and $H_2O_2$ (System I) was compared with the activity of a lysozyme-$H_2O_2$ solution after flow-mixing with $TiCl_3$ (System II), considering the differences between these two activity changes as the extent of the enzymatic inactivation by the involvement of OH radical reaction. The fraction of lysozyme inactivated by OH radical in the system containing 0.0025 M $TiCl_3-0.1M$ $H_2O_2$ (ph 3.5) was 13%, When the $TiCl_3$ concentration is double (pH 3.0), the fraction of enzyme inactivated increases to 36%. The activity of the system containing 0.025 M $TiCl_3-0.1$ M $H_2O_2$ (pH 1.5) was essentially zero. The results seem to support the previos view that the production of OH radical should be proportional to $TiCl_3$ concentration when $H_2O_2$ is present in excess. Increase in the extent of inactivation found in system I with increasing $TiCl_3$ concentration may be due to a pH effect. $H_2O_2$ seems to be less effective than $TiCl_3$ in the inactivation. 1% lysozyme solution, when ${\gamma}$-irradiated with a total dose of 3M rads, loses about 20% of its activity. Lowering of temperature also was found to yield a reduction in enzymatic activity.

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백금전극에서 크롬산염이온의 음극환원반응에 관한 연구 (A Study of Cathodic Reduction of Chromate Ion on Platinum)

  • 황김소
    • 대한화학회지
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    • 제18권2호
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    • pp.110-116
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    • 1974
  • 백금전극을 사용해서 $CrO_4^=$이온의 환원을 중성인 비완충용액과 pH 8∼10 범위의 완충용액 및 강한 알카리성용액에서 조사하였다. pH 8∼10 범위의 완충용액에서 $CrO_4^=$이온의 환원에 관여한 전하이전의 수는 pH가 증가하므로써 점점 증가되었다. $CrO_4^=$이온dl 0.2N NaOH 용액에서 환원되어 질때 반응기구가 다음과 같이 가정되었다. $CrO_4^=+H_2O+2e{\rightarrow}CrO_3^=+2OH^-,\;CrO_3^=3H_2O+e{\rightarrow}Cr(OH)_3+3OH^-$ pH 13.5이고 지지전해질인 $(CH_3)_4NOH$ 용액에서 $CrO_4^=$ 이온이 환원되어 질때 두째번 파에서 심한 흡착을 보여주었다. 0.1N KCl의 비완충용액에서 linear sweep voltammogram은 initial voltage와 voltage sweep rate에 따라 세개 혹은 네개의 분명한 파로 나타나지만 첫째번 파는 확산에 의해서만 된 파라고 설명하기에는 어려움이 있었다.

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