• Title/Summary/Keyword: $^{31}P$ solid-state NMR

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Radical Addition Reaction of Phosphorous based Flame Retardant with End Groups of PET (2) - Reaction of Resorcinol bis(diphenyl phosphate) - (PET 말단에 대한 인계난연제의 라디칼계 부가반응 (2) - 리소시놀비스다이페닐포스페이트의 반응 -)

  • Kim, Min-Kwan;Sohn, Kwang-Ho;Ghim, Han-Do
    • Textile Coloration and Finishing
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    • v.24 no.1
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    • pp.39-44
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    • 2012
  • To improve flame retardation of poly(ethylene terephthalate) (PET) against burning, resorcinol bis(diphenyl phosphate) (RDP), phosphorous containing flame retardant, was incorporated into PET backbone by radical reaction pathway. Radical endcapping of PET with RDP was confirmed by spectroscopic and thermal analysis. From 400 MHz $^{31}P$ solid state FT-NMR spectrum of PET with RDP (PET-RDP), phosphorus spectra peak in RDP was found at ca. -10 ppm. Furthermore, P-C bond stretching vibration peaks were found ca. $530cm^{-1}$ in FT-IR spectrums of PET-RDP. These results indicated that RDP can be chemically bound at the ends of PET by radical addition method. Thermal characteristics of pure PET (pPET) and PET-RDP were measured and evaluated by TGA thermal analysis. There was not significant changes in thermal characteristics of PET-RDP compared to that of pPET.

Modulation of the Specific Interaction of Cardiolipin with Cytochrome c by Zwitterionic Phospholipids in Binary Mixed Bilayers: A $^2H$-and $^{31}P$-NMR Study

  • Kim, Andre;Jeong, In-Chul;Shim, Yoon-Bo;Kang, Shin-Won;Park, Jang-Su
    • BMB Reports
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    • v.34 no.5
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    • pp.446-451
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    • 2001
  • The interaction of cytochrome c with binary phospholipid mixtures was investigated by solid-state $^2H$- and $^{31}P$-NMR. To examine the effect of the interaction on the glycerol backbones, the glycerol moieties of phosphatidylcholine (PC), and cardioliph (CL) were specifically deuterated. On the binding of cytochrome c to the binary mixed bilayers, no changes in the quadrupole splittings of each of the components were observed for the PC/PG, PE/CL and PE/PG liposomes. In contrast, the splittings of CL decreased on binging of protein to the PC/CL liposomes, although those of PC did not change at all. This showed that cytochrome c specifically interacts with CL in PC/CL bilayers, and penetrates into the lipid bilayer to some extent so as to perturb the dynamic structure of the glycerol backbone. This is distinctly different from the mode of interaction of cytochrome c with other binary mixed bilayers. In the $^{31}P$-NMR spectra, line broadening and a decrease of the chemical shift anisotropy were observed on the binding of cytochrome c for all binary mixed bilayers that were examined. These changes were more significant for the PC/CL bilayers. Furthermore, the line broadening is more significant for PC than for CL in PC/CL bilayers. Therefore, it can be concluded that with the polar head groups, not only CL but also PC are involved in the interaction with cytochrome c.

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Effects of Residual Solvents in the Phase Transition, Transition Enthalpy, and Transition Temperature of Phospholipid Membranes (잔류 유기 용매가 모델 세포 지질막의 상전이, 상전이 엔탈피 및 상전이 온도에 미치는 영향)

  • An, Eun Seol;Choi, Jae Sun;Lee, Dong Kuk
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.40 no.2
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    • pp.163-170
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    • 2014
  • Lipid membranes composed of phosphatidylcholine (PC) are used in biophysical study to mimic cellular membranes and interactions between the membrane and chemicals, where organics solvents are used in dissolving lipids or chemicals. Later, solvents are removed from the solution under nitrogen gas at room temperature, followed by the further removal of the solvent at vacuum condition for several hours. In this process, some solvents are easily removed under described conditions above and others are required more severe conditions. In this study, $^{31}P$ solid-state nuclear magnetic resonance (SSNMR) techniques and differential scanning calorimetry (DSC) were used to see any changes in the line shapes of $^{31}P$ NMR spectra of multilamellar vesicles (MLVs) samples of POPC and in the phase change temperature of multilamellar vesicles (MLVs) of DPPC in DSC thermogram with or without any residual solvents. The thermodynamic parameters associated with the solvents did exhibit noticeable changes depending on solvent types. Thus, it is concluded that solvents should be carefully chosen and removed completely and experimental results should also be interpreted with caution particularly for the experiments investigating lipid phase changes and related topics.

Amine and Olefin Complexes of Pt(II) Having a PCP-Pincer Ligand

  • Park, Soon-Heum
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.132-136
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    • 2002
  • $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)\;(OTf=CF_3SO_3^-)$ readily reacts with various amines to afford cationic amine complexes $[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(amine)](OTf)\;(amine=NH_3,\;NHMe_2,\;NHC_4H_8,\;NH_2Ph,\;NH_2(Tol-p))$ in high yields. These complexes have been fully characterized by IR, $^1H-,\;^{19}F{^1H}-,\;and\;^{31}P{^1H}-NMR$ spectroscopy, and elemental analyses. Reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with acrylonitrile quantitatively produced the ${\pi}$-olefinic complex $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)](OTf)$ which is only stable in solution in the presence of acrylonitrile. Attempt at isolating this complex in the pure solid state was failed due to partial decomposition into $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ The equilibrium constants $(K_{eq}=[Pt(PCP)-(NH_2R)^+][CH_2=CHCN]/[Pt(PCP)(CH_2=CHCN)^+][NH_2R]:\;[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)]^++NH_2R{\rightleftarrows}[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(NH_2R)]^++CH_2=CHCN=Ph,\;p-tolyl)$ were calculated to be 0.28 (for R = Ph) and 3.1 (R = p-tolyl) at $21^{\circ}C$. The relative stability of the ${\sigma}$-donor amine versus the ${\pi}$-olefinic acrylonitrile complex has been found largely dependent upon the amine-basicity $(pK_b)$, implicating that acrylonitrile practically competes with amine in the platinum coordination sphere. On the contrary to the formation of the acrylonitrile complex, no reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with other olefins such as ethylene, styrene and methyl acrylate was observed.

A Study on the Preparation of Powder Coatings Containing Halogen-Free Flame Retardant and Fire Safety (Halogen-Free 난연제를 포함하는 파우더 코팅소재 제조 및 화재안전성 연구)

  • Lee, Soon-Hong;Chung, Hwa-Young;Kim, Dae-In;Noh, Tae-Joon
    • Journal of the Korean Society of Safety
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    • v.26 no.4
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    • pp.47-58
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    • 2011
  • Halogen free intumescent flame retardants(IFRS), such as the mixture of melamine phosphate(MP) and char forming agents(pentaerythritol(PER), di-pentaerythritol(DiPER), tris(2-hydroxyethyl) isocyanurate(THEIC)), were prepared and characterized. Polypropylene(PP)/$IFR_S$ composites were also prepared in the presence of ethylene diamine phosphate(EDAP) as a synergist and used into flame retardant PP powder coatings. Thermoplastic PP powder coatings at 20 wt% flame retardant loading were manufactured by extruded and then mechanical cryogenic crushed to bring them in fine powder form. These intumescent flame retardant powder coatings($IFRPC_S$) were applied on mild steel surface for the purpose of protection and decorative. It is a process in which a $IFRPC_S$ particles coming in contact with the preheated mild steel surface melt and form a thin coating layer. The obtained MP flame retardant was analyzed by utilizing FTIR, solid-state $^{31}P$ NMR, ICP, EA and PSA. The mechanical properties as tensile strength, melt flow index(MFI) and the thermal property as TGA/DTA and the fire safety characteristics as limiting oxygen index(LOI), UL94 test, SEM were used to investigate the effect of $IFRPC_S$. The experimental results show that the presence of $IFR_S$ considerably enhanced the fire retardant performances as evidenced by the increase of LOI values 17.3 vol% and 32.6 vol% for original PP and $IFRPC_S$-3(PP/MP-DiPER/EDAP), respectively, and a reduction in total flaming combustion time(under 15 sec) in UL94 test of $IFRPC_S$. The prepared $IFRPC_S$-3 have good comprehensive properties with fire retardancy 3.2 mm UL94 V-0 level, LOI value 32.6%, tensile strength $247.3kg/cm^2$, surface roughness Ra $0.78{\mu}m$, showing a better application prospect. Through $IFRPC_S$-2(PP/MP-PER/EDAP) and $IFRPC_S$-3 a better flame retardancy than that of the $IFRPC_S$-1(PP/MP/EDAP) was investigated which was responsible for the formed more dense and compact char layer, improved synergy effect of MP and PER/DiPER.