• Textile Coloration and Finishing
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• v.24 no.4
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• pp.281-287
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• 2012

Poly(phenylene sulfide) films containing acetophenone as a photoinitiator were photocrosslinked under UV irradiation using a continuous UV irradiator. The gel fraction of the irradiated PPS in 1-Chloro naphthalene reached 94.7% with increasing UV energy and the photoinitiator concentration in the film upto $200J/cm^2$ and 12wt% respectively. Solid state $^1C$ NMR analysis suggested that the crosslinking occurred between the phenylene chains in PPS, indicating that the acetophenone may the phenylene hydrogens and subsequently adjacent polymer radicals could be recombined to form the crosslinked structure. The crosslinking improved the thermal behavior of PPS such as loss of $T_g$ and $T_c$, higher melting point and lower melting enthalphy as well as significantly higher peak pyrolysis temperature as much as $63.5^{\circ}C$. Surprisingly the tensile toughness of the most crosslinked PPS increased by 842%, resulting from the substantial enhancements in tensile modulus, strength and strain as much as 76%, 236% and 240% respectively. Also dynamic mechanical measurement indicated that the distance between crosslinks in the crosslinked PPS reached 85.3 g/mol corresponing to a crosslink density of 0.012 mol/g.

• Bulletin of the Korean Chemical Society
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• v.20 no.3
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• pp.291-296
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• 1999

The immobilization of APTMS(3-(2-aminoethylamino)propyltrimethoxysilane) and AAPTMS(3-(2-(2-aminoethyl)aminoethylanino)propyltrimethoxysilane) on the surface of high quality mesoporous molecular sieves MCM-41 and MCM-48 have been confirmed by F.T.-IR spectroscopy, Raman spectroscopy, 29Si solid state NMR, and a surface polarity measurement using Reichardt's dye. The formation of metal (Co(Ⅱ), Ni(Ⅱ), and Cu(Ⅱ)) complexes by immobilized aminosilanes have been investigated by photoacoustic spectroscopy(PAS). The assignment of UV-Vis. PAS bands makes it possible to identify the structure of metal complexes within mesoporous molecular sieves. Co(Ⅱ) ion may be coordinated mainly in a tetrahedral symmetry by two APTMS onto MCM-41, and in an octahedral one by two AAPTMS. Both Ni(Ⅱ) and Cu(Ⅱ) coordinated by aminosilanes within MCM-41 form possibly the octahedral complexes such as [Ni(APTMS)2(H20)2]2+, [Ni(AAPTMS)2]2+, [Cu(APTMS)2(H2O)2]2+, and [Cu(AAPTMS)(H2O)3]2+, respectively. The PAS band shapes of complexes onto MCM-48 are similar to those of corresponding MCM-41 with the variation of PAS intensity. Most of metal ion(Ⅱ) within MCM-41 and MCM-48 are coordinated by aminosilanes without the impregnation on the surface.

• Journal of the Korean Wood Science and Technology
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• v.32 no.3
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• pp.15-24
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• 2004

The present work was undertaken to investigate the anatomical and chemical characteristics of transgenic poplar down-regulated with antisense OMT gene. Also the distribution of lignin in transgenic poplar trees was investigated at cellular level. No visible abnormal phenotype was observed in the fibers and vessel elements of transgenic poplar. Any marked differences in the staining intensities of Wiesner and Mäule color reaction were not identified in the transgenic poplar. TEM micrographs did not show any staining intensities in the cell walls stained with KMnO₄. Interestingly, the UV spectroscopy of semi-thin sections exhibited a distinct decrease of lignin absorption at 280 nm in the vessel walls, indicating transgenic poplar wood with lower amount of guaiacyl lignin in vessel elements. Chemical composition of antisense OMT poplar was almost identical to that of wild-type poplar. Klason lignin content of transgenic poplar did not show any significant difference from that of the controls. The solid state NMR spectra revealed the transgenic poplar with only slightly more syringyl lignin than the control. The present work showed that antisense OMT gene constructed in the poplar was not enough to reduce the overall content of Klason lignin, and suggested that the expression of transformation was confined to vessel walls.

• Journal of Energy Engineering
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• v.20 no.1
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• pp.36-43
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• 2011

Plant biomass has been proposed as an alternative source of petroleum-based chemical compounds. Especially, aromatic chemical compounds can be obtained from lignin by depolymerization processes because the lignin consist of complex aromatic materials. In this study, kraft lignin, the largest emitted substance among several kinds of lignin in Korea, was used as a starting material and was characterized by solid-state $^{13}C$-Muclear Magnetic Resonance($^{13}C$-NMR), Fourier Transform Infrared Spectroscopy(FT-IR), Elemental Analysis(EA). The depolymerization of kraft lignin was studied at water-phenol mixture solvent in near critical region and the experiments were conducted using a batch type reactor. The effects of water-to-phenol ratio and reaction temperature($300-400^{\circ}C$) were investigated to determine the optimum operating conditions. Additionally, the effects of formic acid as a hydrogen-donor solvent instead of $H_2$ gas were examined. The chemical species and quantities in the liquid products were analyzed using gas chromatography-mass spectroscopy(GC-MS), and solid residues(char) were analyzed using FT-IR. GC-MS analysis confirmed that the aromatic chemicals such as anisole, o-cresol(2-methylphenol), p-cresol(4-methylphenol), 2-ethylphenol, 4-ethylphenol, dibenzofuran, 3-methyl cabazole and xanthene were produced when phenol was added in the water as a co-solvent.

• Korean Chemical Engineering Research
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• v.49 no.2
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• pp.181-186
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• 2011

In this study, we used 3-(trimethoxysilyl)propylmethacrylate(MPS) silane coupling agent for surface modification of silica nanoparticles. We studied effects of reaction conditions such as solvent pH, MPS hydrolysis time, reaction time, and molar ratio of MPS to Si-OH groups on silica nanoparticle surfaces, on the surface modification reactions of silica nanoparticles. Fourier Transform Infrared Spectroscopy(FTIR), Elemental Analysis(EA) and solid state crosspolarization magic angle spinning(CP/MAS) Nuclear Magnetic Resonance Spectroscopy(NMR) techniques were used to determine the type and the degree of surface modification. We found MPS reacts preferentially with Si-OH groups of the silica nanoparticles as monomeric form at solvent pH = 4.5. But increasing hydrolysis time of MPS from 30 mins to 90 mins, and molar ratio of MPS to Si-OH groups on silica nanoparticle surfaces, we found that MPS reacts preferentially with Si-OH groups of the silica nanoparticles as oligomeric form.

• Polymer(Korea)
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• v.36 no.5
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• pp.668-676
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• 2012

In this study, we modified silica nanoparticles with bis[3-(trimethoxysilyl)propyl]amine (BTMA) silane coupling agent to introduce secondary amino groups on the silica surface. After modification of silica, we investigated effects of different types of (meth)acrylate group containing monomers on the Michael addition reaction to introduce reactive (meth)acrylate groups on the BTMA modified silica surface. We used two kinds of (meth)acrylate monomers, trimethylolpropane ethoxylate triacrylate (TMPET) which has three identical acrylate groups, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) which has one acrylate and one methacrylate group. We used fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and solid state cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR) to understand reactions between NH groups on the silica surface with (meth)acrylate groups of TMPET and AHM monomers. We found almost complete Michael addition reaction between all three acrylate groups of TMPET with NH groups on the BTMA modified silica. But, for the AHM treatment of BTMA modified silica, we found Michael addition reaction occurred only between acrylate groups of AHM and NH groups of silica surface, not between methacrylate groups of AHM and NH groups of BTMA modified silica surface.

• 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.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1283-1288
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• 2010

A novel polyaminopolycarboxylate ligand with many coordination sites, N,N,$N^1,N^1,N^2,N^2$-[( 2,4,6-tri(aminomethyl)-pyridine]hexakis(acetic acid) (TPHA), was designed and synthesized and its lanthanide complexes $Na_6Tb_2$(TPHA)$Cl_6{\cdot}14H_2O$, $Na_6Eu_2$(TPHA)$Cl_6{\cdot}8H_2O$, $Na_6Gd_2$(TPHA)$Cl_6{\cdot}11H_2O$ and $Na_6Sm_2$(TPHA)$Cl_6{\cdot}9H_2O$ were successfully prepared. The ligand and the complexes were characterized by elemental analysis, IR, mass, NMR and TG-DTA. The TG-DTA studies indicated that the complexes had a high thermal stability, whose initial decomposition temperature was over $270^{\circ}C$. The luminescence properties of the complexes in solid state were investigated and the results suggested that $Tb^{3+}$ and $Eu^{3+}$ ions could be sensitized efficiently by the ligand, especially the Tb(III) complex displayed a very strong luminescence intensity (> 10000) and only displayed characteristic metal-centered luminescence. Also, the correlative comparison between the structure of ligand and luminescence properties showed how the number of the coordination atoms of ligand can be a prominent factor in the effectiveness of ligand-to-metal energy transfer.

• 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.

• Tribology and Lubricants
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• v.32 no.5
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• pp.141-146
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• 2016

The diketopyrrolopyrrole (DPP) pigment is a bicyclic 8-π-electron system containing two lactam units. Typical DPP derivative pigments have melting points of over 350°C and very low solubility in most solvents, and show absorption in the visible region with a molar extinction coefficient of 33,000 dm²mol⁻¹ and strong photoluminescence with maxima in the range 500–600 nm. X-ray structure analyses of DPP show that the whole molecule is almost in one plane. The phenyl rings are twisted out of the heterocyclic plane and the intermolecular hydrogen bonding between neighboring lactam NH and carbonyl units influences the structure of the DPP pigment in the solid state. In this study, mono-N-alkylation and mono-N-arylation were undertaken for Pigment Red 264 or Pigment Orange 73 with alkyl halide and aryl halide, respectively, in the presence of sodium tert-butoxide as a base catalyst to improve the solubility of DPP pigments and their application as CO₂ indicators. The synthetic yield was in the range 11–88%. The indicator dyes are highly soluble in organic solvents and shows pH-dependent absorption (λ_max 501 and 572 nm for the protonated and deprotonated forms, respectively) and emission (λ_max 524 and 605 nm for the protonated and deprotonated forms, respectively) spectra. The mono-N-alkylated and mono-N-arylated DPP pigment was identified by ¹H-NMR (¹H-Nuclear Magnetic Resonance Spectrometer), FT-IR (Fourier Transform Infrared Spectroscopy), and MS (Mass Spectrometry). According to the results of color and hue properties obtained by a color matching analyzer, the synthesized DPP pigment material can be used as a CO₂ indicator.