• Title/Summary/Keyword: NMR titration

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Host-Guest Interactions Between Macrocycles and Methylsubstituted Anilinium Ions

  • Lee, Shim-Sung;Jung, Jong-Hwa;Chang, Duk-Jin;Lee, Bu-Yong;Kim, Si-Joong
    • Bulletin of the Korean Chemical Society
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    • v.11 no.6
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    • pp.521-527
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    • 1990
  • The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials, indicating the complex formation. The values of formation constants, log Κ for 10 species of methylsubstituted anilinium ion complexes with 18-crown-6 varies from 2.7 to 4.8 in methanol at $25^{\circ}C$. The stability order of complexes for 18-crown-6 is anilinilum > 4-methyl > 3,4-dimethyl > 3-methyl > 3,5-dimethyl > 2,4-dimethyl > 2,5-dimethyl > 2,3-dimethyl > 2-methyl > 2,6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques, the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential, ${\Delta}E_{1/2}$. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.

The Synthesis of Artery Wall Targeted Gene Carrier Using Low Molecular Water-Soluble Chitosan (저분자량 수용성 키토산을 이용한 동맥 벽 표적성 유전자 전달체의 합성)

  • Choi Chang-Yong;Jang Mi-Kyeong;Nah Jae-Woon
    • Polymer(Korea)
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    • v.30 no.4
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    • pp.279-285
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    • 2006
  • Non-viral gene carriers continue to attract a great deal of interest due to advantageous safety profile. Among the non-viral gene carriers, cationic liposomes or synthetic gene carriers are efficient DNA carriers in vitro. but their in vivo applications are greatly hampered because of low biocompatibility. On the other hand, chitosan, a natural cationic polysaccharide, is a candidate non-viral vector for gene delivery because of its low cytotoxicity and high positive charges. In this work, targeted gene carrier was synthesized to target artery wall cells using low molecular water-soluble chitosan (LMWSC). The molecular weight $(M_W)$ and degree of de acetylation (DDA) of LMWSC were measured by relative viscometer and Kina titration. respectively. The structure of LMWSC was analyzed by measuring FTIR, $^1H-NMR,\;and\;^{13}C-NMR$. AWBP-PEG-g-LMWSC was synthesized by conjugation of the artery wall binding peptide (AWBP), a specific targeting peptide, to the end of pegylated LMWSC as a gene carrier to target artery wall cells. The synthesized AWBP-PEG-g-LMWSC were analyzed by measuring FTIR, $^1H-NMR$, zeta -potentiometer, and atomic force microscopy (AFM).

The Study of Nitrogen Doner Atoms Chelating Compounds for Removing Heavy Metals (Cd2+,Pb2+,Zn2+,Cu2+) (중금속이몬(Cd2+,Pb2+,Zn2+,Cu2+)제거를 위한 질소를 주개원자로 하는 리간드들의 착화합물 형성에 관한 연구)

  • 김선덕;김준광;김정성
    • Journal of Environmental Science International
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    • v.12 no.4
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    • pp.497-501
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    • 2003
  • The new tridentate ligands of nitrogen donor atoms N,N-Bis(2-amino-ethyI)-benzyl-amine 2HCI(BABEA. 2HCI) and 2,6-Bis(amino-methyl)-pyridien. 2HCI(BAMP. 2HCI) were synthesized as their dihydrochloride salts and characterized by TA, IR. Mass and NMR spectroscopy. The protonation constants of the ligands and stability constants for Cd$^{2+}$, Pb$^{2+}$, Zn$^{2+}$and Cu$^{2+}$ ions were determined by potentiometric titration in aqueous solutions and compared with those of analogous ligands. The effect stability constants of ligands and metal ions for removal of heavy metals in aqueous solution were described.

Dihydrogen Phosphate Selective Anion Receptor Based on Acylhydrazone

  • Pandian, T. Senthil;Kang, Jongmin
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.2025-2028
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    • 2014
  • Anion receptor 1 based on acylhydrazone has been designed and synthesized. UV-vis and $^1H$ NMR titration showed that receptor 1 is selective receptor for dihydrogen phosphate ($H_2PO_4{^-}$). Dihydrogen phosphate was complexed by the receptor 1 via at least 4 hydrogen bonding interactions, contributing from two amide N-Hs and two imine C-Hs. In addition, nitrogen in the aromatic ring could make 2 additional hydrogen bondings with OH groups in the dihydrogen phosphate. However, the receptor 1 could make only 4 hydrogen bonds with halides. Therefore, receptor 1 could bind anions through hydrogen bonds with a selectivity in the order of $H_2PO_4{^-}$ > $Br^-$ > $Cl^-$ in highly polar solvent such as DMSO.

Synthesis and Fluorescence Properties of New Rhodamine 6G Derivarives Containing Hydroxy Coumarin Moiety (새로운 로다민 6G 하이드록시 쿠마린 유도체의 합성과 형광특성)

  • Park, Seong Ho;Chang, Seung Hyun
    • Journal of Environmental Science International
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    • v.25 no.9
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    • pp.1283-1288
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    • 2016
  • In this study, we synthesized fluorescent sensors from rhodamine 6G derivatives and hydroxy coumarin. The synthetic routes to the rhodamine 6G derivatives containing hydroxy coumarin are shown in Fig. 1. Two derivatives were synthesized through Schiff base reactions. The structures of the new compounds were confirmed by melting point, $^1H$-NMR, and GC-MS analyses. The compounds were found to selectively bind to tin ($Sn^{2+}$) ion by fluorescence titration using various metal cations. Longer carbon chains gave more sensitivity. $Sn^{2+}$ ions exhibited the strongest fluorescence among the nime ions. The binding analysis using Job plots suggested that compounds form 1:1 complexes with the $Sn^{2+}$ ions.

Phosgen-free Synthesis of Oligoureas Having Amino End-groups: Their Application to the Synthesis of Poly(urea-imide)

  • Chang, Ji-Young;Kim, Beom-Jin
    • Fibers and Polymers
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    • v.3 no.2
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    • pp.55-59
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    • 2002
  • The thermal reaction of acetoacetanilide in the presence of aniline or phenol yielded carbanilide in quantitative yields. This reaction was applied to the synthesis of polyurea. Bisacetoacetamides were prepared from diamines and diketene in DMF. They were thermally polymerized in the presence of phenol or a diamine (6FDA) to yield polyureas of low molecular weights. The polymers were soluble in DMSO and NMP. $^1{H-NMR}$ analysis showed that they had amino group terminated structures. Poly(urea-imide) was synthesized by the reaction of an oligourea diamine with pyromellitic dianhydride in NMP. The concentration of terminal amino groups was determined by an acid-base titration. The thermal property of poly(urea-imide) was evaluated by thermogravimetric analysis (TGA). Initial decompisition took place at 332-$350^{\circ}C$.

Characterizations of Novel Poly(aspartic acid) Derivatives Conjugated with γ-Amino Butyric Acid (GABA) as the Bioactive Molecule

  • Kim, Seung-Il;Son, Chang-Mo;Jeon, Young-Sil;Kim, Ji-Heung
    • Bulletin of the Korean Chemical Society
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    • v.30 no.12
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    • pp.3025-3030
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    • 2009
  • Novel poly(aspartic acid) derivatives conjugated with $\gamma$-amino butyric acid, GABA, moieties, and their amphiphilic analogs were synthesized and characterized. The chemical structures of these polymers were confirmed by FT-IR and $^1H$ NMR spectroscopy. Their physicochemical properties in aqueous media were characterized by electrophonetic light scattering spectrophotometry (ELS), acid-base titration, and UV-spectroscopy. In addition, the in vitro cell activity of the GABA-conjugated polymer was examined. These results indicated that GABA-conjugated poly(aspartic acid) derivatives showed cell-growth activity and nanoparticle formation of a suitable size within aqueous media. These polymers have potential application in the cosmetic and pharmaceutical fields.

Synthesis and Biological Activity of Poly[(tri-O-acetyl-D-glucal)-alt-(maleic anhydride)] Derivatives

  • Han, Man-Jung;Lee, Choong-Whan;Kim, Ki-Ho;Lee, Won-Young
    • Bulletin of the Korean Chemical Society
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    • v.12 no.1
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    • pp.85-87
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    • 1991
  • Poly[(tri-O-acetyl-D-glucal)-alt-(maleic anhydride)] was synthesized by free radical copolymerizations of the relevant comonomers. The alternating sequence of the copolymer was confirmed by $^1$H-NMR, elemental analysis, and titration of anhydride groups incorporated into the copolymer. Hydrolysis of the copolymer under different conditions resulted in poly[(2-acetoxymethyl-3,4-diacetoxytetrahydropyran-5,6-diyl) (1,2-dicarboxyethylene)] and poly[(2-hydroxymethyl-3,4-dihydroxytetrahydropyran-5,6-diyl) (1,2-dicarboxyethylene)]. The cytotoxicities of these polymers measured against normal and tumor cells (3LL, B16) in vitro were found to be higher than that of DIVEMA, a prototype polymer having a high antitumor activity.

Biodegradation of Kraft Lignins by White-Rot Fungi(I) -Lignin from Pitch Pine- (백색부후균에 의한 크라프트 리그닌의 분해(I) -리기다소나무 리그닌-)

  • 김명길;안원영
    • Journal of Korea Foresty Energy
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    • v.17 no.1
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    • pp.56-70
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    • 1998
  • This study was carried out to investigate the structural characteristics of kraft lignin and the wood degrading characteristics, the productivity of ligninolytic enzymes and the enzymatic degradation of kraft lignin by white-rot fungi. To purify kraft lignin, precipitation of kraft pulping black liquors of pitch pine meal was done by titration with lN $H_{2}SO_{4}$ reaching to pH 2, and isolation of the precipitates done by centrifugation. The isolated precipitates from pitch pine were redissloved in lN NaOH, reprecipitated by titration with lN $H_{2}SO_{4}$, washed with deionized water, and kept ofr analysis after freeze drying. Fractionation of the precipitates in solution by successive extraction with $CH_{2}Cl_{2}$ and MeOH, and the fractionates were named SwKL, SwKL I, SwKL II, and SwKL III for pitch pine kraft lignin. The more molecular weights of kraft lignin increased, the less phenolic hydroxyl groups and the more aliphatic hydroxyl groups. Because as the molecular weights increased, the ratio of etherified guaiayl/syringyl(G/S ratio) and the percentage were increased. The spectra obtained by 13C NMR and FTIR assigned by comparing the chemical shifts of various signals with shifts of signals from autherized ones reported. The optimal growth temperature and pH of white-rot fungi in medium were $28^{\circ}C$ and 4.5-5.0, respectively. Especially, in temperature and pH range, and mycelial growth, the best white-rot fungus selected was Phanerochaete chrysosporium for biodegradation. For the degradation pathways, the ligninolytic fungus jcultivated with stationary culture using medium of 1% kraft lignin as a substrate for 3 weeks at $28^{\circ}C$. The weight loss of pitch pine kraft lignin was 15.8%. The degraded products extracted successively methoanol, 90% dioxane and diethyl ether. The ether solubles were analyzed by HPLC. Kraft lignin degradation was initiated in $\beta$-O-4 bonds of lignin by the laccase from Phanerochaete chrysosporium and the degraded compounds were produced from the cleavage of $C\alpha$-$C\beta$ linkages at the side chains by oxidation process. After $C\alpha$-$C\beta$ cleavage, $C\alpha$-Carbon was oxidized and changed into aldehyde and acidic compounds such as syringic acid, syringic aldehyde and vanilline. And the other compound as quinonemethide, coumarin, was analyzed. The structural characteristics of kraft lignin were composed of guaiacyl group substituted functional OHs, methoxyl, and carbonyl at C-3, -4, and -5 and these groups were combinated with $\alpha$ aryl ether, $\beta$ aryl ether and biphenyl. Kraft lignin degradation pathways by Phanerochaete chrysosporium were initially accomplished cleavage of $C\alpha$-$C\beta$ linkages and $C\alpha$ oxidation at the propyl side chains and finally cleavage of aromatic ring and oxidation of OHs.

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Preparation of Poly(vinyl butyral) by Precipitation Method and Its Characterization (침전법에 의한 폴리비닐부티랄의 제조 및 특성분석)

  • 서광원;김덕준
    • Polymer(Korea)
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    • v.26 no.2
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    • pp.168-173
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    • 2002
  • Poly (vinyl butyral) (PVB) was synthesized by acetalization of poly (vinyl alcohol) (PVA) PVB was prepared in particulate forms in water, and chemical and physical properties of the products were characterized using various techniques. The prepared PVB had size distribution from 100 to 700 $\mu\textrm{m}$ with mean diameter of about 380 $\mu\textrm{m}$. The chemical structure of PVB was characterized using FT/IR and NMR, and the average degree of acetalization was determined to be 77% from the titration measurement. DSC data showed that the crystalline structure of PVA vanished as acetalization reaction proceeded to produce PVB, and the glass transition temperature emerged at about $70^{\circ}C$. TGA data showed that PVB was much more thermally stable than PVA, and showed no degradation up to $300^{\circ}C$. Solubility test showed that PVB was soluble in alcohols but Insoluble in water, being totally different from PVA.