• Title/Summary/Keyword: Chain initiation

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Photopolymerization of Methyl Methacrylate with 1,4-$C_6H_4(SiH_{3-x}Me_x)_2$

  • U, Hui Gwon;O, Eun Mi;Park, Jong Hak;Kim, Bo Hye;Kim, Yong Nam;Yun, Chan Ho;Ham, Hui Suk
    • Bulletin of the Korean Chemical Society
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    • v.21 no.3
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    • pp.291-294
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    • 2000
  • The bulk photopolymerization of methyl methacrylate(MMA) with bis(silane)s such as 1,4-$C_6H_4(SiH_3)_2$ (1) and 1,4-$C_6H_4(SiH_2Me)_2$ (2) was performed to produce poly(MMA)s possessing the corresponding bis(silyl) moiety as an end group. For the bis(silane)s, while the polymerizaiton yields and the polymer molecular weights decreased, the TGA residue yields and the relative intensities of Si-H IR stretching bands increased as the relative bis(silane) concentration over MMA increased. The polymerizaion yield, polymer molecular weight, and TGA residue yield of MMA with 1 were found to be higher than those with 2. The bis(silane)s appears to influence significantly upon the photopolymerization of MMA as both chain initiation and chain transfer agents.

Thermo-Degradation Kinetics of Polyethylene (폴리에틸렌의 열분해 Kinetics)

  • Cha, Wang Seog
    • Applied Chemistry for Engineering
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    • v.10 no.3
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    • pp.432-437
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    • 1999
  • Pyrolysis of polyethylene was carried out in the stainless steel reactor of internal volume of $10cm^3$. Pyrolysis reactions were performed at temperature $390{\sim}450^{\circ}C$ and the pyrolysis products were collected separately as reaction products and gas products. The molecular weight distributions(MWDs) of each product were determined by HPLC-GPC and GC analysis. Distribution balance equation for MWDs of random and specific products were proposed to account for initiation-termination and propagation-depropagation, such as hydrogen abstraction, chain cleavage, coupling of polymer and radical. A separate chain-end scission process produces low molecular weight noncondensable gases(C1 through C5) of average molecular weight 38. Activation energies of the random-chain scission and chain-end scission rate parameters, respectively, were determined to be 35, 17 kcal/mole.

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The Inhibitory Effect of Chlorophyllin is Influenced by Different Promotion Stages in DMBA-TPA-induced Mouse Skin Carcinogenesis

  • Kim, Jin;Yook, Jong-In;Park, Kwang-Kyun;Lee, Eun-Ha;Jung, So-Young;Joon, Yin-Liu;Kyung, Chul-Hong;Kim, Ju;Chung, Won-Yoon
    • Environmental Mutagens and Carcinogens
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    • v.19 no.1
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    • pp.46-55
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    • 1999
  • To develop a chemopreventive strategy based on the different stages of premalignant lesions, we hypothesized that the inhibitory effect of chemopreventive agents is influenced by different promotion stages during carcinogenesis. DMBA-TPA-induced skin carcinogenesis was used with ICR mice and chlorophyllin (CHL) was applied as a chemopreventive agent. In vitro assay was performed with Salmonella typhi. TA100 to observe any anti-mutagenic activity of CHL against DMBA. Pre-initiation and pre-promotion effects of CHL were observed by CHL treatment before initiation and before promotion. To evaluate the inhibitory effect at different promotion stages, each group was divided into three subgroups after TPA promotion for 6, 18 and 24 weeks, respectively ; the first subgroup was immediately sacrificed after termination of TPA, the second subgroup was treated with CHL, and the third subgroup was sacrificed 8 weeks after termination of TPA without CHL treatment. The degrees of epithelial dysplasia, papilloma formation, and invasive carcinoma were observed histologically, and GST-Pi expression was observed immunohistochemically. ODC mRNA level was analyzed by reverse transcriptase-polymerase chain reaction. Results showed : CHL dose-dependently inhibited the mutation of Salmonella typhi. TA100; the incidence of epithelial dysplasia and papilloma formation was lower in pre-initiation and pre-promotion CHL-treated mice than DMBA-TPA-treated mice; no invasive carcinoma developed in pre-initiation CHL-treated groups, while 67% of DMBA-TPA treated mice had carcinomas; GST-Pi expression decreased when CHL was treated before initiation and before promotion; and when CHL was treated after termination of TPA application at 18 and 24- week-TPA promotion stages, respectively, the incidence of epithelial dysplasia and papilloma was markedly reduced compared to non-treated groups. When comparing the incidence of epithelial dysplasia and papilloma between the immediately-sacrificed subgroup and the non-treated group with a waiting period, we speculated that the 18-week-TPA promotion stage might belong to the promoter-independent progression stage. At the 18-week-TPA promotion stage, the level of ODC mRNA in the CHL-treated group was clearly reduced to the level of normal tissue. Taking these results together, CHL showed both anti-initiation and anti-promotion effects, while the inhibitory effect of CHL was prominent in the 18-week-TPA promotion stage. However, CHL seems to be incapable of completely blocking the progression in the 24-week-TPA promotion stage.

Site-Specific Mutagenesis of the gshI Gene for Increasing the Activity of ${\gamma}$-Glutamylcysteine Synthetase in Escherichia coli K-12

  • Kwak, Joon-Hyeok;Nam, Yong-Suk;Lee, Se-Yong
    • BMB Reports
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    • v.31 no.3
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    • pp.254-257
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    • 1998
  • The gshI gene from the Escherichia coli K-12 strain codes for ${\gamma}-glutamylcysteine$ synthetase which mediates the rate-limiting step of glutathione biosynthesis. The isolated gshI gene from E. coli K-12 has an unusual translation initiation codon, UUG. The 494th amino acid is Ala rather than Gly which was found in a mutant strain E. coli B. In order to improve the translational rate of the gshI gene of E. coli K-12, the initiation codon, UUG, was changed to the usual AUG codon by the site-specific mutagenesis. This change has resulted in a 53% increase of ${\gamma}-glutamylcysteine$ synthetase activity. The enzyme activity was also improved by replacing $Ala^{494}$ with Val (A494V) or Leu (A494L). The replacement of $Ser^{495}$ with Thr (S495T) also resulted in a 62% increase of the enzyme activity. Therefore, the specific activity of ${\gamma}-glutamylcysteine$ synthetase was increased with the increasing chain length of the aliphathic amino acid at the site of the 494th amino acid (Ala<$Val{\leq}Leu$).

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Changes in Diagnostic Methods for Pulmonary Tuberculosis between 2005 and 2013

  • Ahn, Bin;Kim, Joohae;Yoo, Chul-Gyu;Kim, Young Whan;Han, Sung Koo;Yim, Jae-Joon
    • Tuberculosis and Respiratory Diseases
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    • v.78 no.3
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    • pp.227-231
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    • 2015
  • Background: Diagnostic methods for pulmonary tuberculosis (TB) have recently advanced. The aim of this study was to evaluate the changes in TB diagnostic tests that prompted the initiation of anti-TB treatment over time in South Korea, an industrialized country with an intermediate TB burden. Methods: Patients diagnosed with pulmonary TB in the first halves of 2005 and 2013 at a tertiary referral hospital were included. Diagnostic methods that prompted the initiation of anti-TB treatment were compared between the 2 groups of patients. Results: A greater proportion of patients were diagnosed with pulmonary TB using bronchoscopy in 2013 than in 2005 (26.7% vs. 6.6%, respectively; p<0.001), while the proportion of patients clinically diagnosed with pulmonary TB was lower in 2013 than in 2005 (24.7% vs. 49.0%, respectively; p<0.001). Additionally, more patients started anti-TB treatment based on positive polymerase chain reaction (PCR) results for Mycobacterium tuberculosis DNA in 2013 than in 2005 (47.3% vs. 7.9%, respectively; p<0.001). Conclusion: The initiation of treatment for pulmonary TB in South Korea has become more frequently based on PCR and the use of bronchoscopic specimens.

Synthesis of High Molecular Weight 3-Arm Star PMMA by ARGET ATRP

  • Jeon, Hyun-Jeong;Youk, Ji-Ho;Ahn, Sung-Hee;Choi, Jin-Hwan;Cho, Kwang-Soo
    • Macromolecular Research
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    • v.17 no.4
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    • pp.240-244
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    • 2009
  • High molecular weight(MW), 3-arm star poly(methyl methacrylate)(PMMA) with a narrow MW distribution($M_n$=570,000 g/mol, PDI=1.36) was successfully synthesized by activators regenerated by electron transfer(ARGET) atom transfer radical polymerization(ATRP). The polymerization was carried out with a trifunctional initiator/$CuBr_2$/N,N,N',N",N"-pentamethyldiethy lenetriamine(PMDETA) initiator/catalyst system in the presence of a tin(II) 2-ethylhexanoate [$Sn(EH)_2$] reducing agent at $90^{\circ}C$. The concentration of the copper catalyst was as low as 30 ppm, and a high initiation efficiency of the initiating sites was obtained. The chain-end functionality of the high MW, 3-arm star PMMA was confirmed by a chain extension experiment with styrene via ARGET ATRP, using the same catalyst system.

THERMAL POLYMERIZATION OF 2-HYDROXYETHYL METHACRYLATE WITH PHENYLSILANS (PHENYLSILANS와 2-HYDROXYETHYL METHACRYLATE의 열중합)

  • Sung, A Young
    • Journal of Korean Ophthalmic Optics Society
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    • v.5 no.2
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    • pp.87-90
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    • 2000
  • Poly(HEMA)s have been used as the optometric material for the preparation of soft contact lens. The bulk thermal polymerization of 2-hydroxyethyl methacrylate (HEMA) with various hydrosilanes such as $phSiH_3$, $phMeSiH_2$, and $ph2SiH_2$ were performed to produce poly(HEMA)s containing phenylsilyl end moeity. It was found for thermal polymerization that while the polymerization yield and polymer molcular weights decreased as the relative phenylsilane concentration increases, the TGA residue yields and the relative intensities of SiH IR stretching bands increased as the relative hydrosilane concentration increases over HEMA. The polymerization yield, molecular weight, and TGA residue for the thermal polymerization were higher than those for the photo polymerization. Thus, the hydrosilanes significantly influence on the polymerization as both chain-initiation and chain-transfer agents.

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Conformational Study of Cyclic Ac-Cys-Pro-Xaa-Cys-NHMe Peptides: a Model for Chain Reversal and Active Site of Disulfide Oxidoreductase

  • Park, Hae-Sook;Kim, Choon-mi;Kee, Kang-Young
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.330.2-330.2
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    • 2002
  • The conformational study on cyclic Ac-Cys-Pro-Xaa-Cys-NHMe (Ac-CPXC-NHMe: X = Ala, Val. Leu. Aib. Gly. His. Phe, Tyr. Asn. and Ser) peptides has been carried out using the ECEPP/3 force field and the hydration shell model in the unhydrated and hydrated states. This work has been undertaken to investigate structural implications of the CPXC sequence as the chain reversal for the initiation of protein folding and as the motif for active site of disulfide oxidoreductases. The backbone conformation DAAA is in common the most feasible for cyclic CPXC peptides in the hydrated state. which has a type 1${\beta}$-turn at the Pro-Xaa sequence. The proline residue and the hydrogen bond between backbones of two cystines appear to play a role in stabilizing this preferred conformation of cycilc CPXC peptides. However. the distributions of backbone conformations and ${\beta}$-turns may indicate that the cyclic CPXC peptide seems to exist as an ensemble of ${\beta}$-turns and coiled conformations. The intirnsic stability of the cyclic CPXC motif itself the active conformation appears to play a role in determining electrochemical properties of disulfide oxidoreductases.

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Characterization of the Germinated Rices to Examine an Application Potentials as Functional Rice Processed Foods (기능성 쌀가공식품 원료료의 활용가능성 검토를 위한 발아미의 특성조사)

  • Kang, Mi-Young;Lee, Yeon-Ri;Nam, Seok-Hyun
    • Korean Journal of Food Science and Technology
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    • v.35 no.4
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    • pp.696-701
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    • 2003
  • Rice seeds of 4 cultivars including Whachung and Nampung, of the non-waxy rice cultivars, and Shinsunchalbyeo and Whachungchabyeo, of the waxy rice cultivars, were germinated at $27^{\circ}C$ for 3 days to compare the changes in some physico-chemical properties of the starch granules and the starch-hydrolysing enzyme activities during germination, respectively. With the starch granules, the amount of long glucose chains from amylose molecules were reduced in the non-waxy rices, while the chain length increased in the waxy rices. In the distribution profile of the glucose chain length from amylose molecules, we could observed that the chain length with DP (degree of polymerization) ranged 33 to 66 increased with the decreasing rate of the chain length with that above 130, regardless of the waxiness of rices. In addition, we observed that in contrast to a increase in chain length with DP ranged 14 to 33, the amount of short chains from A chain fraction decreased. Germination induced slight reduction in the polymerization rate of starch granules, and decrease in both initiation and termination temperatures for the gelatinization. ${\alpha}-Amylase$ activity of rices germinated for 3 days found to he higher than that of malt. Especially, the activity of Shinsunchalbyeo was revealed to be highest, about two fold higher than that of malt. In contrast, ${\beta}-amylase$ of the waxy rice found to be considerably less active than malt, although the waxy showed prevalent activity as compared to the non-waxy rices.

Proteomic Changes by Acupuncture Stimulation at HT7 in the Hippocampus of Rat Pups (신문혈 자침이 어린 백서 해마의 단백질 발현에 미치는 영향)

  • Bae, Chang-Hwan;Kim, Dong-Soo;Kim, Seung-Tae
    • Korean Journal of Acupuncture
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    • v.29 no.2
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    • pp.260-270
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    • 2012
  • Objectives : Hippocampus, a region of temporal lobe, plays an important role in the pathogenic mechanisms of brain diseases such as Alzheimer's disease, depression and temporal lobe epilepsy. This research is designed to investigate hippocampal changes after acupuncture stimulation at Shinmun(HT7) using 2-dimensional gel electrophoresis(2-DE). Methods : On postnatal-day 15, rat pups were randomly devided into Normal(NOR) or HT7 group. All of Pups kept with their mothers for 7 days, but pups in HT7 group received acupuncture stimulation at HT7 daily. On postnatal-day 21, hippocampus of each rat pup was dissceted 30 minutes after last acupuncture stimulation and the protein expressions were investigated using 2-DE. Results : After acupuncture stimulation at HT7, expression of 20 proteins were significantly increased. Succinate semialdehyde dehydrogenase, glyceraldehyde-3-phosphate dehydrogenase-like, transketolase, aconitate hydratase and phosphoglucomutase-1 were related to glucose methabolism. Eukaryotic initiation factor(eIF) 4A-II, eIF 4A-III, mitochondrial Tu translation elongation factor and chain A of crystal structure of the 70-Kda heat shock cognate protein involve in the protein synthesis in ribosome. Tubulin ${\beta}$-4 chain, tubulin T ${\beta}$-15 and tubulin ${\alpha}$-1B chain comprise cytoskeleton. Glutathione S-transferase(GST) ${\omega}$-1, GST P and GST Yb-3 can reduce oxidative stress. ${\beta}$-soluble N-ethylmaleimide-sensitive fusion protein attachment protein is required for vesicular transport between the endoplasmic reticulum and the Golgi apparatus, glycerol-3-phosphate dehydrogenase plays a major role in lipid biosynthesis, creatine kinase U-type catalyses the conversion of creatine and consumes adenosine triphosphate to create phosphocreatine and adenosine diphosphate. Platelet-activating factor acetylhydrolase IB subunit alpha and voltage depedent anion-selective channel protein 2 were also increased. Conclusions : The results suggest that acupuncture stimulation at HT7 may enhance glucose and lipid metabolism, protein synthesis, cytoskeletal substance and anti-oxidative stress in hippocampus.