• Title/Summary/Keyword: 2-D NMR

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Successive Synthesis of Well-Defined Star-Branched Polymers by an Iterative Approach Based on Living Anionic Polymerization

  • Higashihara Tomoya;Inoue Kyoichi;Nagura Masato;Hirao Akira
    • Macromolecular Research
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    • v.14 no.3
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    • pp.287-299
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    • 2006
  • To successively synthesize star-branched polymers, we developed a new iterative methodology which involves only two sets of the reactions in each iterative process: (a) an addition reaction of DPE or DPE-functionalized polymer to a living anionic polymer, and (b) an in-situ reaction of 1-(4-(4-bromobutyl)phenyl)-1-phenylethylene with the generated 1,1-diphenylalkyl anion to introduce one DPE functionality. With this methodology, 3-, 4-, and 5-arm, regular star-branched polystyrenes, as well as 3-arm ABC, 4-arm ABCD, and a new 5-arm ABCDE, asymmetric star-branched polymers, were successively synthesized. The A, B, C, D, and E arm segments were poly(4-trimethylsilylstyrene), poly(4-methoxystyrene), poly(4-methylstyrene), polystyrene, and poly(4-tert-butyldimethylsilyloxystyrene), respectively. All of the resulting star-branched polymers were well-defined in architecture and precisely controlled in chain length, as confirmed by SEC, $^1H$ NMR, VPO, and SLS analyses. Furthermore, we extended the iterative methodology by the use of a new functionalized DPE derivative, 1-(3-chloromethylphenyl)-1-((3-(1-phonyletheny1)phenyl) ethylene, capable of introducing two DPE functionalities via one DPE anion reaction site in the reaction (b). The number of arm segments of the star-branched polymer synthesized by the methodology could be dramatically increased to 2, 6, and up to 14 by repeating the iterative process.

The Study on the Superconducting MRI Magnet of 68 cm in Room Temperature Bore (68 cm 상온 보아를 갖는 MRI용 초전도마그네트에 관한 연구)

  • Jin, H.B.;Oh, B.H.;Cho, J.W.;Oh, S.S.;Kwon, Y.K.;Ha, D.W.;Lee, E.Y.;Kim, H.J.;Kim, O.K.;Choi, B.J.;Ryu, K.S.
    • Proceedings of the KOSOMBE Conference
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    • v.1996 no.11
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    • pp.142-146
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    • 1996
  • In this paper, we present the main research results on the 2 Tesla class - superconducting MRI magnet which we have developed. Multi section type superconducting MRI main coil and various superconducting shims were designed and fabricated for obtaining the high field homogeneity, which is requested in the MR imaging. After assembling the magnet with room temperature bore cryostat field homogenity has been measured and analyzed by NMR field mapping system. According to this, field homogeneity of 22 ppm / 30 cm dsv was confirmed.

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CORRELATION BETWEEN BIS-GMA : TEGDMA RATIO AND DEGREE OF CONVERSION IN VARIOUS LAYERS OF COMPOSITE AFTER ADDITIONAL HEAT CURING (수종 복합레진 내의 bis-GMA와 TEGDMA의 구성비가 레진 인레이 법에 의한 부가적 열처리시 복합레진의 표면 및 내부의 중합률 변화에 미치는 영향)

  • Park, Seong-Ho;Chung, Chan-Moon
    • Restorative Dentistry and Endodontics
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    • v.21 no.2
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    • pp.642-651
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    • 1996
  • The purpose of this study was to evaluate the relationship between monomer compositions and the changes in the degree of conversion in the various layers of composites after additional heat curing. Four types of composites and 3 types of inlay ovens were used in this study. Composite was placed in a 4-mm thick teflon mold, and light cured from the top for 60 seconds. Ten samples were prepared for each composite ; 5 of these were additionally heat cured in an inlay oven as the manufacturer recommended. After light curing or light and heat curing, the samples were sectioned into four parts and assigned to groups A, B, C, or D according to their distance from the light source. These sections were then thinned to 50-$70{\mu}m$, and these wafers were analyzed with a Fourier Transform Infrared Spectrometer(FI-IR) to determine the degree of conversion. A standard baseline technique was used to calculate the degree of conversion. $^{13}C$ NMR spectra of bis-GMA, TEGDMA and bis-EMA, were acquired using a Varian Gemini spectrometer operated at 200 MHz. $CDCl_3$ solvent was used for qualitative analysis. The degree of conversion was affected by bis-GMA : TEGDMA ratio but it seemed to be also affected by other factors. When the composites were heat cured, significant increases in the degree of conversion were noted throughout the samples, but the amount of increase differed between materials. Thus, clinical performance of a heat-treated composite inlay may be different depending on materials.

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Sesquiterpenoids from the Stem Bark of Aglaia grandis

  • Harneti, Desi;Permatasari, Atika Ayu;Anisshabira, Amallya;Naini, Al Arofatus;Nurlelasari, Nurlelasari;Mayanti, Tri;Maharani, Rani;Safari, Agus;Hidayat, Ace Tatang;Farabi, Kindi;Supratman, Unang;Azmi, Mohamad Nurul;Shiono, Yoshihito
    • Natural Product Sciences
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    • v.28 no.1
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    • pp.6-12
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    • 2022
  • Five sesquiterpenoids, 7-epi-eudesm-4(15)-ene,1β,6α-diol (1), 7-epi-eudesm-4(15)-ene,1β,6α-diol (2), saniculamoid D (3), aphanamol I (4), and 4β,10α-dihydroxyaromadendrane (5), were isolated from the stem bark of Aglaia grandis. The compounds' (1-5) chemical structures were identified by spectroscopic data including, IR, NMR (1H, 13C, DEPT 135°, HMQC, HMBC, 1H-1H COSY), and HRTOFMS, as well as by comparing with the previously reported spectral data. Therefore, this study described the structural elucidation of compounds 1-5 and evaluated their cytotoxic effects against Hela cervical and B16F10 melanoma cells for the first time, but no significant result was discovered.

Development of Biologically Active Compounds from Edible Plant Sources XXII. Triterpenoids from the Aerial Parts of Sajabalssuk (Artemisia princeps PAMPANINI) (식용식물자원으로부터 활성물질의 탐색-XXII. 사자발쑥(Artemisia princeps PAMPANINI)의 지상부로부터 Triterpenoid의 분리)

  • Bang, Myun-Ho;Cho, Jin-Gyeong;Song, Myoung-Chong;Lee, Dae-Young;Han, Min-Woo;Chung, Hae-Gon;Jeong, Tae-Sook;Lee, Kyung-Tae;Choi, Myung-Sook;Baek, Nam-In
    • Applied Biological Chemistry
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    • v.51 no.3
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    • pp.223-227
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    • 2008
  • The aerial parts of Sajabalssuk (Artemisia princeps PAMPANINI, Sajabalssuk) was extracted with 80% aqueous MeOH, and the concentrated extract was partitioned with EtOAc, n-BuOH and $H_2O$, successively. From the EtOAc fraction, three cycloartane-type triterpnoids and one ursane-type triterpenoid were isolated through the repeated silica gel, ODS and Sephadex LH-20 column chromatographies. From the results of physico-chemical data including NMR, MS and IR, the chemical structures of the triterpenoids were determined as wrightial (1), wrightial acetate (2), 27-norcycloart-20(21)-ene-25-al-3${\beta}$-ol acetate (3) and ursolic acid (4). No report has been found for isolation of compound 3 in the literature so far, and compounds 1, 2 and 3 were the first to be isolated from Sajabalssuk (Artemisia princeps PAMPANINI, Sajabalssuk). Also, compound 1 showed Acyl-CoA:Cholesterol acyltransferase (hACAT-1) and hACAT-2 inhibitory activity with the $IC_{50}$ values of 33.0 and 45.0 ${\mu}g/ml$, respectively. Compounds 2 and 3 inhibited hACAT-1 activity with the $IC_{50}$ values of 12.0 and 16.0 ${\mu}g/ml$, respectively.

New hydroperoxylated and 20,24-epoxylated dammarane triterpenes from the rot roots of Panax notoginseng

  • Shang, Jia-Huan;Sun, Wen-Jie;Zhu, Hong-Tao;Wang, Dong;Yang, Chong-Ren;Zhang, Ying-Jun
    • Journal of Ginseng Research
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    • v.44 no.3
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    • pp.405-412
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    • 2020
  • Background: Root rot is a serious destructive disease of Panax notoginseng, a famous cultivated araliaceous herb called Sanqi or Tianqi in Southwest China. Methods: The chemical substances of Sanqi rot roots were explored by chromatographic techniques. MS, 1D/2D-NMR, and single crystal X-ray diffraction were applied to determine the structures. Murine macrophage RAW264.7 and five human cancer cell lines were used separately for evaluating the antiinflammatory and cytotoxic activities. Results and Conclusion: Thirty dammarane-type triterpenes and saponins were isolated from the rot roots of P. notoginseng. Among them, seven triterpenes, namely, 20(S)-dammar-25-ene-24(S)-hydroperoxyl-3β,6α,12β,20-tetrol (1), 20(S)-dammar-3-oxo-23-ene-25-hydroperoxyl-6α,12β,20-triol (2), 20(S)-dammar-12-oxo-23-ene-25-hydroperoxyl-3β,6α,20-triol (3), 20(S)-dammar-3-oxo-23-ene-25-hydroperoxyl-12β,20-diol (4), 20(S),24(R)-epoxy-3,4-seco-dammar-25-hydroxy-12-one-3-oic acid (5), 20(S),24(R)-epoxy-3,4-seco-dammar-25-hydroxy-12-one-3-oic acid methyl ester (6), and 6α-hydroxy-22,23,24,25,26,27-hexanordammar-3,12,20-trione (7), are new compounds. In addition, 12 known ones (12-16 and 19-25) were reported in Sanqi for the first time. The new Compound 1 showed comparable antiinflammatory activity on inhibition of NO production to the positive control, whereas the known compounds 9, 12, 13, and 16 displayed moderate cytotoxicities against five human cancer cell lines. The results will provide scientific basis for understanding the chemical constituents of Sanqi rot roots and new candidates for searching antiinflammatory and antitumor agents.

Inhibition of Low Density Lipoprotein-oxidation, ACAT-1, and ACAT-2 by Lignans from the Bark of Machilus thunbergii

  • Shrestha, Sabina;Park, Ji-Hae;Lee, Dae-Young;Cho, Jin-Gyeong;Lee, Do-Gyeong;Cho, Moon-Hee;Jeong, Tae-Sook;Kang, Hee-Cheol;Baek, Nam-In
    • Journal of Applied Biological Chemistry
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    • v.54 no.1
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    • pp.63-66
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    • 2011
  • The bark of Machilus thunbergii was extracted with 80% aqueous methanol (MeOH), and the concentrated extract was partitioned using ethyl acetate (EtOAc), butanol (n-BuOH), and $H_2O$, successively. From the EtOAc fraction, five lignans were isolated through the repeated silica gel, octadecyl silica gel (ODS) and, Sephadex LH-20 column chromatography. Based on nuclear magnetic resonance (NMR), mass spectroscopy (MS), and infrared spectroscopy (IR) spectroscopic data, the chemical structures of the compounds were determined to be machilin A (1), machilin F (2), licarin A (3), nectandrin A (4), and nectandrin B, (5). This study presents comparative account of five lignans from M. thunbergii bark contributing inhibition of low density lipoprotein (LDL), ACAT-1, and ACAT-2. Compounds 2-5 showed varied degree of antioxidant activity on LDL with $IC_{50}$ values of 2.1, 11.8, 15.3, and $4.1{\mu}M$. Compounds 1, 2, and 3 showed inhibition activity on ACAT-1 with values $63.4{\pm}6.9%$ ($IC_{50}=66.8{\mu}M$), $53.7{\pm}0.9%$ ($IC_{50}=109.2{\mu}M$), and $78.7{\pm}0.2%$ ($IC_{50}=40.6{\mu}M$), respectively, at a concentration of 50 mg/mL, and on ACAT-2 with values $47.3{\pm}1.5%$ ($IC_{50}=149.7{\mu}M$), $39.2{\pm}0.2%$ ($IC_{50}=165.2{\mu}M$), and $52.1{\pm}1.0%$ ($IC_{50}=131.0{\mu}M$, respectively, at a concentration of 50 mg/mL.

Effects of Microbacterium laevaniformans Levans Molecular Weight on Cytotoxicity

  • Oh, Im-Kyung;Yoo, Sang-Ho;Bae, In-Young;Cha, Jae-Ho;Lee, Hyeon-Gyu
    • Journal of Microbiology and Biotechnology
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    • v.14 no.5
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    • pp.985-990
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    • 2004
  • Levans produced from Microbacterium laevaniformans were isolated, characterized, and fractionated by molecular weight. TLC, HPLC, and GC-MS analyses of the exopolysaccharide showed that it was a fructan-type polymer and was composed of (2,6)- and (2,1)-glycosidic linkages. $^{13}C$-NMR analysis proved that the polysaccharide was mainly a $\beta$-(2,6)-linked levan-type polysaccharide. To investigate the cytotoxicity of the acetone-precipitated levan fractions such as M1, M2, and M3, HepG2, P388D1, U937, SNU-1, and SNUC2A cell lines were screened. Among the cell lines tested, the cytotoxicity of M1- M3 fractions were detected from only SNU-1 and HepG2 cells at the dosage level of $100-800\mu\textrm{g}ml$. The M2 fraction M_r$, 80,000) at 400 $mu{g/ml}$ had the greatest cell growth inhibition (84.6%) on SNU-1, while the M1 $(M_r$, 50,000) at $800\mu\textrm{g}ml$ showed the greatest (46.32%) on HepG2. To obtain more uniform M_r$ fractions of levan, the levan was further fractionated from S1 $(M_r$ 1,000,000) to S5 $(M_r$ 10,000) using gel permeation chromatography. Again, the S1-S5 fractions had strong cytotoxicity on SNU-1 and HepG2 cell lines. The greatest inhibition effects of S4 $(M_r$ 80,000) on SNU-1 and S5 $(M_r$ 10,000) on HepG2 were shown to be 49.5% and 73.0%, respectively. The cytotoxicity of the levan fractions was more effective on SNU-1 than on HepG2. Although the relationship between the Mw and the cytotoxicity was not clear, smaller $M_r$, fractions of levan showed greater growth inhibition effect on the cancer cell lines in general. Therefore, it was indicated that a specific Mw class of levan is responsible for the effective cytotoxicity.

Copolymerization of Ethylene and Norbornene via Polymethylene Bridged Dinuclear Constrained Geometry Catalysts

  • Zhu, Yin-Bang;Jeong, Eung-Yeong;Lee, Bae-Wook;Kim, Bong-Shik;Noh, Seok-Kyun;Lyoo, Won-Seok;Lee, Dong-Ho;Kim, Yong-Man
    • Macromolecular Research
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    • v.15 no.5
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    • pp.430-436
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    • 2007
  • The dinuclear half-sandwich CGCs (constrained geometry catalyst) with a polymethylene bridge, $[Ti({\eta}^5 : {\eta}^1-indenyl)SiMe_2NCMe_3]_2(CH_2)_n]$[n = 6 (1) and 12 (2)], have been employed in the copolymerization of ethylene and norbornene (NBE). To compare the mononuclear metallocene catalysts; $Ti({\eta}^5 : {\eta}^1-2-hexylindenyl)SiMe_2NCMe_3$ (3), $(Cp^* SiMe_2NCMe_3)$Ti (Dow CGC) (4) and ansa-$Et(Ind)_2ZrCI_2$ (5), were also studied for the copolymerization of ethylene and NBE. It was found that the activity increased in the order: 1 < 2 < 3 < 5 < 4, indicating that the presence of the bridge between two the CGC units contributed to depressing the polymerization activity of the CGCs. This result strongly suggests that the implication of steric disturbance due to the presence of the bridge may playa significant role in slowing the activity. Dinuclear CGCs have been found to be very efficient for the incorporation of NBE onto the polyethylene backbone. The NBE contents in the copolymers formed ranged from 10 to 42%, depending on the polymerization conditions. Strong chemical shifts were observed at ${\delta}$42.0 and 47.8 of the isotactic alternating NBE sequences, NENEN, in the copolymers with high NBE contents. In addition, a resonance at 47.1 ppm for the sequences of the isolated NBE, EENEE, was observed in the $^{13}C-NMR$ spectra of the copolymers with low NBE contents. The absence of signals for isotactic dyad at 48.1 and 49.1 ppm illustrated there were no isotactic or microblock (NBE-NBE) sequences in the copolymers. This result indicated that the dinuclear CGCs were effective for making randomly distributed ethylene-NBE copolymers.

Molecular Breeding of Tobacco Plants Resistant to TMV and PVY (분자생물학적 TMV 및 PVY 저항성 연초 육종)

  • E.K. Pank;Kim, Y.H.;Kim, S.S.;Park, S.W.;Lee, C.H.;K.H.Paik
    • Proceedings of the Korean Society of Tobacco Science Conference
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    • 1997.10a
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    • pp.134-152
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    • 1997
  • Plant viruses of tobacco including tobacco mosaic virus (TMV) and potato virus Y (PVY) cause severe economic losses in leaf-tobacco production. Cultural practices do not provide sufficient control against the viruses. Use of valuable resistant cultivars is most recommendable for the control of the viruses. However, conventional breeding programs are not always proper for the development of virus-resistant plants mostly owing to the frequent lack of genetic sources and introduction of their unwanted properties. Therefore, we tried to develop virus-resistant tobacco plants by transforming commercial tobacco cultivars, NC 82 and Burley 21, with coat protein (CP) or replicase (Nlb) genes of TMV and PVY necrosis strain (PVY-VN) with or without untranslated region (UTR) and with or without mutation. Each cDNA was cloned and inserted in plant expression vectors with 1 or 2 CaMV 35S promotors, and introduced into tobacco leaf tissues by Agrobacterium tumefaciens LBA 4404. Plants were regenerated in kanamycin-containing MS media. Regenerated plants were tested for resistance to TMV and PVY In these studies, we could obtain a TMV-resistant transgenic line transformed with TMV CP and 6 genetic lines with PVY-VN cDNAs out of 8 CP and replicase genes. In this presentation, resistance rates, verification of gene introduction in resistant plants, stability of resistance through generations, characteristics of viral multiplication and translocation in resistant plants, and resistance responses relative to inoculum potential and to various PVY strains will be shown. Yield and quality of leaf tobacco of a promising resistant tobacco line will be presented.

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