• 제목/요약/키워드: Radical transfer

검색결과 236건 처리시간 0.028초

Triphenylphosphine Phenylimide의 전기화학적인 환원 (Electrochemical Reduction of Triphenylphosphine Phenylimide)

  • 박종민
    • 대한화학회지
    • /
    • 제18권5호
    • /
    • pp.341-353
    • /
    • 1974
  • Triphenylphosphine phenylimide의 비수용액에서의 전기화학적인 환원반응을 polarography, cyclic voltammetry, controlled-potential coulometry 및 electron spin resonance 법을 써서 고찰하였다. 이 유기인화합물은 one-electon transfer에 따라서 anion radical이 형성되나 순간일 뿐이고 protonation과 재차 one-electon reduction 결과 인과 질소사이의 이중결합이 끊어진다. 그 결과 아닐린이 주요 반응생성물로서 발견되었다. 또 한편 동반하는 화학반응결과 생긴 주산물의 하나인 triphenylposphine oxide의 환원결과 인과 페닐 사이의 단일결합이 끊어지는 것도 관찰할 수 있었다.

  • PDF

Mono-dehalogenation of gem-Dihalocyclopropanes Using Tetracarbonylhydridoferrate

  • Shim, Sang-Chul;Lee, Seung-Yub;Lee, Dong-Yub;Choi, Heung-Jin
    • Bulletin of the Korean Chemical Society
    • /
    • 제15권10호
    • /
    • pp.845-849
    • /
    • 1994
  • Tetracarbonylhydridoferrate, $HFe(CO)^-_4$, generated by the reaction of $Fe(CO)_5$ with alkaline solution, is a good reducing agent for mono-dehalogenation of gem-dihalocyclopropanes. It also acts as a good reducing catalyst under phase transfer reaction conditions. 1,1-Dibromo-2-phenylcyclopropane and 1,1-dichloro-2-phenylcyclopropane were reduced to the corresponding mono-dehalogenated products in excellent yields. Thermodynamically stable trans-l-bromo-2-phenyl cyclopropane was formed as the major product over the cis-isomer, trans/cis=3/2. The 1-bromo-2-phenyl cyclopropane radical intermediate was formed by single electron transfer from $HFe(CO)^-_4$. Dissociation of bromide anion, followed abstraction of hydrogen radical from alcoholic solvent would lead to the formation of the stable trans-isomer. The further mechanistic aspects were discussed.

Preparation of Branched Polystyrene Using Atom Transfer Radical Polymerization Techniques and Protection-Deprotection Chemistry

  • Kwark, Young-Je
    • Macromolecular Research
    • /
    • 제16권3호
    • /
    • pp.238-246
    • /
    • 2008
  • A new strategy using protection-deprotection chemistry was used to prepare branched polymers using the ATRP method only. Among the several monomers with different protecting groups, vinyl benzyl t-butyloxy carbonate (VBt-BOC) and 4-methyl styrene (4-MeSt) could be polymerized successfully to form backbones using the ATRP method in a controlled fashion. The protected groups in the backbones were converted to alkyl bromides and used as initiating sites for branch formation. The benzyl t-butyloxy carbonate groups in the backbones containing VBt-BOC units were first deprotected to benzyl alcohol by trifluoroacetic acid, then converted to benzyl bromide by reacting them with triphenylphosphine/carbon tetrabromide. The benzyl bromide groups in the backbones containing 4-MeSt units could be generated by bromination of the methyl groups using N-bromosuccinimide/benzoyl peroxide. The structures of the prepared polymers were well-controlled, as evidenced by the controlled molecular weight as well as the narrow and unimodal molecular weight distribution.

전해산화에 의한 백금전극상 전도성 폴리아닐린 피막의 생장 거동(II) (Growth Behavial Couctive PolyanilineFilm on a Platinum Electrode by Electrochemical Oxidation (II))

  • 신성호;이주성
    • 한국표면공학회지
    • /
    • 제21권3호
    • /
    • pp.95-102
    • /
    • 1988
  • The anodic oxidation of aniline in aqueous sulfuric acid solution on a platinum was studied. To examine of mechanism of this reaction, the date were obtained during controlled potential electrolysis, aided by computer system. The reaction mechanism was assumed the electrochemical-chemical-electrochemical(ECE) mechanism. We obtained the result that the intial charge transfer step proceeds through a radical cation, and this radical cation were bound cation led to may type of dimer in which p-aminodiphenylamine was de-electronated again to give the polymer.

  • PDF

A Route for Sulfuranyl Radical by an Electron Transfer from Sodium Naphthalenide to a Triarylsulfonium Salt$^1$

  • Kim, Kyong-Tae;Bae, Hye-Kyung
    • Bulletin of the Korean Chemical Society
    • /
    • 제8권3호
    • /
    • pp.165-167
    • /
    • 1987
  • Reaction of 5-(2-thianthreniumyl)thianthrene perchlorate with sodium naphthalenide in the presence of benzenethiol in tetrahydrofuran at -$78^{\circ}C$ proceeded via a formation of a sulfuranyl radical to give thianthrene (66%), 2-phenylthiothianthrene (33%), phenyl 2-(2-thianthrenylthio)phenyl sulfide (traceable amount), and some unknowns, along with naphthalene and very small amount of 1,4-dihydronaphthalene.

Generation of Reactive Oxygen Species in Bovine Somatic Cell Nuclear Transfer Embryos during Micromanipulation Procedures

  • Hwang, In-Sun;Bae, Hyo-Kyung;Park, Choon-Keun;Yang, Boo-Keun;Cheong, Hee-Tae
    • Reproductive and Developmental Biology
    • /
    • 제36권1호
    • /
    • pp.49-53
    • /
    • 2012
  • The present study was conducted to examine the generation of reactive oxygen species (ROS) during micromanipulation procedures in bovine somatic cell nuclear transfer (SCNT) embryos. Bovine enucleated oocytes were electrofused with donor cells, activated by a combination of Ca-ionophore and 6-dimethylaminopurine culture. Oocytes and embryos were stained in dichlorodihydrofluorescein diacetate or 3'-(p-hydroxyphenyl) fluorescein dye and the $H_2O_2$ or $^.OH$ radical levels were measured. $In$ $vitro$ fertilization (IVF) was performed for controls. The samples were examined with a fluorescent microscope, and fluorescence intensity was analyzed in each oocyte and embryo. The $H_2O_2$ and $^.OH$ radical levels of reconstituted oocytes were increased during manipulation (37.2~49.7 and 51.0~55.2 pixels, respectively) as compared to those of mature oocytes ($p$<0.05). During early $In$ $vitro$ culture, the ROS levels of SCNT embryos were significantly higher than those of IVF embryos ($p$<0.05). These results suggest that the cellular stress during micromanipulation procedures can generate the ROS in bovine SCNT embryos.

Synthesis and Characterization of Tetrathiafulvalene Charge Transfer Compounds with Iron and Antimony Halides

  • Kim Young In;Choi Sung Nak;Jung Woo Sung
    • Bulletin of the Korean Chemical Society
    • /
    • 제15권6호
    • /
    • pp.465-468
    • /
    • 1994
  • The charge transfer compounds $(TTF)_4FeCl_3{\cdot}CH_3OH,\;(TTF)_4SbCl_4\;and\;(TTF)_5(SbBr_4)_2{\cdot}CH_3COCH_3$ were prepared from reactions of the TTF (tetrathiafulvalene) and metal halides. The compounds were characterized by spectroscopic (UV,IR, EPR and XPS) methods, magnetic susceptibility and electrical conductivity measurements. The d.c electrical conductivities of the pressed pellets are in the order of $10^{-1}-10^{-3} Scm^{-1}$, which lies in the range of semiconductor region at room temperature. It means that the partially ionized TTF has stacked in low-dimensional chain in each compound. Spectroscopic properties also indicate that TTF molecules are partially ionized and charge transfer has occurred from (TTF)n to Fe(III) center in $(TTF)_4FeCl_3{\cdot}CH_3OH$ whereas to the $-SbX_4^-$ entity in $(TTF)_4SbCl_4\;and\;(TTF)_5(SbBr_4)_2{\cdot}CH_3COCH_3$. The EPR g values are consistent with TTF radical formation and EPR linewidths suggest the delocalization of unpaired electrons along TTF stacks. A signal arised from metal (Fe and Sb) ions were not detected in EPR spectra, indicating that metal ion is in the diamagnetic state in each compound. The diamagnetic state was also examined by the magnetic susceptibility measurement. The magnetic properties reveal the significant interaction between the $TTF^+$ radical cations in the stacks. The oxidation state of metal ions was also investigated by XPS spectra.

스티렌과 메틸아크릴레이트의 원자 이동 라디칼 공중합에서 중합조건에 따른 중합 특성 연구 (Effect of Polymerization Condition on Atom Transfer Radical Copolymerization Behaviors of Styrene with Methyl Acrylate)

  • 송선자;고영수
    • Korean Chemical Engineering Research
    • /
    • 제49권5호
    • /
    • pp.676-680
    • /
    • 2011
  • 스티렌과 메틸아크릴레이트(methyl acrylate, MA)를 원자라디칼이동 중합(atom radical transfer polymerization, ATRP)에서 주요한 중합공정 조건인 투입되는 MA 몰분율, 중합 온도, 중합 시간이 미치는 영향을 조사하였다. MA 몰분율이 증가할수록 분자량은 증가하고 중합시간이 3시간일 때 중합용액의 초기 모노머 몰 비와 생성되는 고분자의 조성비가 거의 선형 관계를 갖는다. 중합시간이 증가함에 따라 공중합체의 분자량은 증가하고, 공중합체의 MA 조성비가 감소함을 알 수 있다. 이를 통해 스티렌-MA 공중도 ATRP의 리빙 라디칼 중합 특징을 보이고 있음을 알 수 있다. 중합온도가 증가함에 따라 공중합체의 분자량은 크게 증가하고, 특히 $110^{\circ}C$의 고온에서 공중합체 내에 MA 조성비가 크게 증가함을 볼 수 있다.

Specific Binding of Streptavidin onto the Nonbiofouling Titanium/Titanium Oxide Surface through Surface-Initiated, Atom Transfer Radical Polymerization and Bioconjugation of Biotin

  • Kang, Sung-Min;Lee, Bong-Soo;Kim, Wan-Joong;Choi, In-Sung S.;Kil, Mun-Jae;Jung, Hyuk-Jun;Oh, Eu-Gene
    • Macromolecular Research
    • /
    • 제17권3호
    • /
    • pp.174-180
    • /
    • 2009
  • Chemical modification of titanium/titanium oxide (Ti/$TiO_2$) substrates has recently gained a great deal of attention because of the applications of Ti/$TiO_2$-based materials to biomedical areas. The reported modification methods generally involve passive coating of Ti/$TiO_2$ substrates with protein-resistant materials, and poly(ethylene glycol) (PEG) has proven advantageous for bestowing a nonbiofouling property on the surface of Ti/$TiO_2$. However, the wider applications of Ti/$TiO_2$ based materials to biomedical areas will require the introduction of biologically active moieties onto Ti/$TiO_2$, in addition to nonbiofouling property. In this work, we therefore utilized surface-initiated polymerization to coat the Ti/$TiO_2$ substrates with polymers presenting the nonbiofouling PEG moiety and subsequently conjugated biologically active compounds to the PEG-presenting, polymeric films. Specifically, a Ti/$TiO_2$ surface was chemically modified to present an initiator for atom transfer radical polymerization, and poly(ethylene glycol) methacrylate (pEGMA) was polymerized from the surface. After activation of hydroxyl groups of poly(pEGMA) (pPEGMA) with N,N'-disuccinimidyl carbonate, biotin, a model compound, was conjugated to the pPEGMA films. The reactions were confirmed by infrared spectroscopy, X-ray photoelectron spectroscopy, contact angle goniometry, and ellipsometry. The biospecific binding of target proteins was also utilized to generate micropatterns of proteins on the Ti/$TiO_2$ surface.