• Title/Summary/Keyword: Silyl functional group

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Photoaddition Reactions of N-Methylthiophthalimide with $\alpha$-Silyl-n-electron Donors via Single Electron Transfer-Desilylation and Hydrogen Atom Abstraction Pathways

  • Yoon, Ung-Chan;Oh, Sun-Wha;Moon, Seong-Chul;Hyung, Tae-Gyung
    • Journal of Photoscience
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    • v.9 no.1
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    • pp.17-22
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    • 2002
  • Studies have been conducted to explore photoaddition reactions of N-methylthiophthalimide with $\alpha$-silyl-n-electron donors Et$_2$NCH$_2$SiMe$_3$, n-PrSCH$_2$SiMe$_3$ and EtOCH$_2$SiMe$_3$. Photoaddition of $\alpha$-silyl amine Et$_2$NCH$_2$SiMe$_3$ to N-methylthiophthalimide occurs in $CH_3$CN and benzene to produce non-silicon containing adduct in which thiophthalimide thione carbon is bonded to $\alpha$-carbon of $\alpha$-silyl amine in place of the trimethylsilyl group. In contrast, photoaddition of EtOCH$_2$SiMe$_3$ to N-methylthiophthalimide generates two diastereomeric adducts in which thiophthalimide thione carbon is connected to $\alpha$-carbon of $\alpha$-silyl ether in place of u-hydrogen. Based on a consideration of the oxidation potentials of u-silyl-n-electron donors and the nature of photoadducts, mechanism for these photoadditions involving single electron transfer(SET) -desilylation and H atom abstraction pathways are proposed.

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Silyl-group functionalized organic additive for high voltage Ni-rich cathode material

  • Jang, Seol Heui;Jung, Kwangeun;Yim, Taeeun
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1345-1351
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    • 2018
  • To allow stable cycling of layered nickel-rich cathode material at high voltage, silyl-functionalized dimethoxydimethylsilane is proposed as a multi-functional additive. In contrast to typical functional additive, dimethoxydimethylsilane does not make artificial cathode-electrolyte interfaces by electrochemical oxidation because it is quite stable under anodic polarization. We find that dimethoxydimethylsilane mainly focuses on scavenging nucleophilic fluoride species that can be produced by electrolyte decomposition during cycling, leading to improving interfacial stability of both nickel-rich cathode and graphite anode. As a result, the cell cycled with dimethoxydimethylsilane-controlled electrolyte exhibits 65.7% of retention after 100 cycle, which is identified by systematic spectroscopic analyses for the cycled cell.

Dipole-Forming Photochemical Group Transfer Reactions of Phthalimides and ${\alpha}-Ketoamides$

  • Yoon, Ung-Chan;Mariano Patrick S.
    • Journal of Photoscience
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    • v.12 no.3
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    • pp.155-162
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    • 2005
  • Results of studies of SET-promoted dipole-forming photochemical group transfer reactions of phthalimide and ${\alpha}-ketoamide$ derivatives are discussed. Azomethine ylide forming photochemical reactions, which are initiated by intramolecular SET from tethered silylmethyl-, carboxymethyl-, and ${\beta}-hydroxyethyl$ containing electron donors to excited states of phthalimides, related maleimides, and conjugated imides, are presented first. Following this, investigations of regioselective 1,4-dipole forming photochemical reactions of N-trialkylsilylmethyl- and N-trialkylstannyl-${\alpha}$-ketoamides are described.

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Effects of the Variation of Silyl Hydride-to-Vinyl Ratios in Dental Polyvinylsiloxane Impression Materials (실리콘 폴리머의 비닐그룹에 대한 가교제의 Si-H 비율이 폴리비닐실록산 치과용 인상재의 물성에 미치는 영향)

  • Ju, Dong-Hyun;Jeong, Young-Hwa;Song, Ho-Jun;Choi, Chang-Nam;Park, Yeong-Joon
    • Elastomers and Composites
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    • v.44 no.2
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    • pp.150-155
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    • 2009
  • This study examined the effects of the concentration variation of the silyl hydride (Si-H) functional group in polymethylhydrogen siloxane cross-linker and the vinyl-functional group in silicone prepolymer on the physical properties of the dental polyvinylsiloxane impression materials (PVS). When the SiH/Vinyl ratio was 1.6 (Group $\underline{C6}$ containing ${\underline{C}}ross$-linker $\underline{6}$ parts), the setting rate was too slow even though their tensile strength was the highest within the tested groups. When the SiH/Vinyl ratio was 3.2 (Group C12), the setting rate was too fast to allow appropriate working time even though their mechanical properties were good. The C14 group showed rather lower tensile strength compared to the groups having lower cross-linker contents. Notably, too much incorporation of cross-linker, like C16 group, induced delay of the setting, by which the mechanical and manipulation properties were detrimentally affected.

Effects of Silicone Polymer Blends on Physical Properties of Dental Polyvinylsiloxane Impression Materials (실리콘폴리머의 혼합사용이 폴리비닐실록산 치과용 인상재의 물성에 미치는 영향)

  • Lim, Chang-Ha;Kim, Min-Kang;Kim, Young-Chul;Park, Nam-Cook;Song, Ho-Jun;Park, Yeong-Joon
    • Elastomers and Composites
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    • v.44 no.1
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    • pp.76-83
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    • 2009
  • The purpose of this study was to investigate the effects of combined use of several types of silicone polymers on the physical properties of the dental polyvinylsiloxane impression materials (PVS). Four types of silicone prepolymers having different molecular weight and vinyl group position, and two types of cross-linkers having differently located silyl hydride functional groups were used in various combinations for the formulation. The samples containing bimodal or trimodal prepolymers showed higher tensile strength, elongation at break, and elastic deformation than those containing only one type of prepolymer. The samples using CR210 cross-linker which has side- and terminal-silyl hydride groups showed higher elastic deformation and elongation at break than those using CR101 cross-liker which has side-only silyl hydride group. High vinyl content prepolymer having side vinyl group delayed setting even though it enhanced tensile strength. Further studies are needed to clarify the specific role of this component on setting time and to find appropriate controlling methods for making improved PVS with optimum workability.

Primary study of sterols composition of Rhodiola sachalinensis by using GC/MS (GC/MS를 이용한 고산 홍경천의 스테롤 구성에 대한 초기연구)

  • Jin, Yinzhe;Li, Xifeng;Li, Donghao;Row, Kyung Ho
    • Analytical Science and Technology
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    • v.22 no.3
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    • pp.219-227
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    • 2009
  • The steroid compounds in Rhodiola sachalinensis were determined with adsorption column chromatographic purification and GC/MS. Sterols were extracted by sonication and Soxhlet with ethanol and dichloromethane, respectively. The extract was partitioned with chloroform and water using liquid-liquid extraction, and purified with a silica column after the sterols had been converted to the corresponding silyl derivatives with BSTFA. Eighteen free sterols, including $\beta$-sitosterol, stigmasterol and cycloartenol, and nine sterol conjugates were found from Rhodiola sachalinensis by GC/MS. Among them, cholest-5-ene-3-ol, cholesterol, stigmasterol, $\beta$-sitosterol were confirmed and quantified with sterol standards. Most sterols were presented in the chloroform part, with $C_{29}$ being the most abundant group in this sterol group. $\beta$-sitosterol was the most abundant compound with a relative content of 45.94% followed by ergost-7-ene-3-ol (11.33%), 4,14-dimethyl-ergosta-8,24(28)-diene-3-ol (7.07%), stigmasterol (6.09%), cycloartenol (5.43%) and 4-methyl-cholest-5-ene-3-ol (5.39%).

Simultaneous GC/MS Analyses of Organic acids and Amino acids in Urine using TMS-TFA derivative (TMS-TFA 유도체화를 이용한 소변여지 중 유기산과 아미노산의 GC/MS 동시분석)

  • Yoon, Hye-Ran
    • Analytical Science and Technology
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    • v.19 no.1
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    • pp.107-114
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    • 2006
  • Early diagnosis and medical intervention are critical for the treatment of patients with metabolic disorders. A rapid analytical method was developed for simultaneous quantification of organic acids and amino acids in urine without labor-intensive pre-extraction procedure showing high sensitivity and specificity. A new method consisted of simple two-step trimethylsilyl (TMS)-trifluoroacetyl (TFA) derivatization using GC/MS-selective ion monitoring (SIM). Filter paper urine specimens were dried under nitrogen after being fortified with internal standard (tropate) in a mixture of distilled water and methanol. Methyl orange was added to the residue as indicator reagent. Silyl derivative of carboxylic functional group was followed by trifluoroacetyl derivative for amino functional group. N-methyl-N-(trimethylsilyl-trifluoroacetamide) and N-methyl-bistrifluoroacetamide were consecutively added and heated for 15-20 min at $65^{\circ}C-70^{\circ}C$, for TMS-TFA derivative, respectively. This reactant was analyzed by GC/MS-SIM. Linear dynamic range showed 0.001-50 mg with the detection limit of (S/N=3) 10-200 ng, and the quantification limit of 80-900 ng in urine. Correlation coefficient of regression line was 0.994-0.998. When the method was applied to the patients 'urine, it clearly differentiated the normal from the patient with metabolic disorder. The study showed that the developed method could be the method of choices in rapid and sensitive screening for organic aciduria and amino acidopathy.