• Title/Summary/Keyword: Diamines

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Intercalation of Primary Diamines in the Layered Perovskite Oxides, $HSr_2Nb_3o_{10}$

  • 홍영식;김시중
    • Bulletin of the Korean Chemical Society
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    • v.17 no.8
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    • pp.730-735
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    • 1996
  • The layered perovskite oxide, KSr2Nb3O10, was synthesized. The interlayer potassium cations were readily exchanged by protons in hydrochloric acid solution to give the protonation compound, HSr2Nb3O10·0.5H2O. The intercalation compounds, [NH3(CH2)nNH3]xSr2Nb3O10, were also obtained by acid-base reactions between the protonation compound and organic bases, 1,n-alkyldiamines. The interlayer distances in the intercalation compounds were linearly increased with the increase of the number of carbon (Δc/Δn=1.05 Å) in 1,n-alkyldiamines. The intercalated alkyldiammonium ions formed a paraffin-like monolayer with average tilting angle (θ) of ca. 56°. The intercalation reactions occurred stoichiometrically. The thermal decomposition process of the intercalation compounds showed distinct three steps due to the desorption of hydrated water, the decomposition of organic moiety, and the decomposition of Sr-related compounds.

Synthesis and Properties of Noel Platinum(IV) Complexes Involving Asymmetric Chiral Diamines as Carrier Ligands

  • 이은주;전무진;손윤수
    • Bulletin of the Korean Chemical Society
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    • v.20 no.11
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    • pp.1295-1298
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    • 1999
  • Novel platinum(IV) complexes with asymmetric chiral diamine ligands cis,cis,trans-A2PtCl2(X)2 (X = OH, OCOCH3, OCOC2H5, A2 =NH2CH(CH3)CH2NH(c-C6H11)(apcha), NH2CH(CH3)CH2NH(c-C5H9)(apcpa)) have been prepared. One of the platinum(IV) complexes, (apcpa)PtCl2(OCOC2H5)2(6), was subjected to X-ray crystallographic analysis. The crystal structure of (apcpa)PtCl2(OCOC2H5)2 (monoclinic, P21 (No. 4), a = 9.1391(1), b = 22.2517(1), c = 10.0687(1)Å, β= 109.105(1)。 , V = 1934.80(3)Å3 , Z = 4, R1 = 0.0532) exhibits that the platinum atom achieves a typical octahedral arrangement with two nitrogen atoms in cis positions and two carboxylato group in trans positions. The spectroscopic data disclose that these platinum(IV) complexes are stable and their molecular structures are retained in aqueous solution. The title complexes are highly cytotoxic in vitro but do not exhibit oral anticancer activity in vivo.

Rapid Formation of Optically Active and Organosoluble Polyamides Containing L-Alaninephthalimide Side Chain via Microwave Irradiation

  • Mallakpour, Shadpour;Rafiee, Zahra
    • Macromolecular Research
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    • v.17 no.11
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    • pp.901-906
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    • 2009
  • Several aromatic optically active polyamides (PA)s were synthesized from 5-(2-phthalimidiylpropanoylamino)isophthalic acid with various aromatic diamines via direct polycondensation with triphenyl phosphite and pyridine in the presence of calcium chloride and N-methyl-2-pyrrolidone under microwave irradiation and conventional heating conditions. Under the optimized conditions, the reaction mixture was irradiated for 2 min. with a 100% irradiation power (900 W). The resulting polymers were obtained in high yield and moderate inherent viscosity ranging from 0.35 to 0.60 dL/g. All synthesized polymers showed excellent solubility in amide-type solvents. Thermogravimetric analysis revealed a 10% weight loss temperature and char yield at $600^{\circ}C$ in a nitrogen atmosphere of > $350^{\circ}C$ and > 58%, respectively, which suggests that the resulting PAs have good thermal stability.

Preparation and Thermal Properties of Enaminonitriles-Terminated Reactive Polymer Precursors

  • 박원순;길덕수;공명선
    • Bulletin of the Korean Chemical Society
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    • v.19 no.3
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    • pp.291-295
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    • 1998
  • Various enaminonitriles-terminated reactive polymer precursors containing rigid aromatic and flexible alkyl units were prepared from the corresponding diamines and 1-chloro-1-phenyl-2,2-dicyanoethene (1). All the enaminonitriles-terminated precursors were characterized by spectroscopies and elemental analysis. They were highly soluble in DMF and NMP, and partially soluble in common organic solvents such as THF and acetone. They showed a large exotherm around 350 ℃ attributable to the thermal polymerization by crosslinking of the dicyanovinyl group. Upon heating the precursors, heat-resistant and insoluble network polymers were obtained. Thermogravimetric analyses of the precursors containing rigid aromatic moiety exhibited thermal stability with a 10% weight loss around 420-480 ℃ and 75-88% residual weight at 500 ℃ under nitrogen.

Miscibility and Specific Intermolecular Interaction Strength of PBl/Pl Blends Depending on Polyimide Structures (폴리이미드의 구조에 따른 방향족 PBI/PI 블렌드의 상용성 및 상호작용의 세기)

  • Ahn, Tae-Kwang
    • Applied Chemistry for Engineering
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    • v.9 no.2
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    • pp.185-192
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    • 1998
  • Four kinds of polyamicacids(PAAs) were prepared by the condensation reaction of four diamines with different linkages, 3,3'-diaminodiphenyl sulfone(3,3'-$DDSO_2$), 4,4'-diaminodiphenyl sulfone(4,4'-$DDSO_2$), 4,4'-methylene dianiline(4,4'-MDA) and 4,4'-oxydianiline(4,4'-ODA), and dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) using the solvent, dimethylacetamide(DMAc). These four PAAs were blended with poly[2,2-(m-phenylene)-5,5'-bibenzimidazole](PBI) from the solution blending. Then called as Blend-I, II, III, and IV, respectively. Cast films or precipitated powders of the PBI/PAA blends were cured at a higher temperature than expected Tg to transform into PBI/PIs blends. Miscibility, specific intermolecular interaction for miscibility and their relative strength as a function of polyimide chemical structure with different four diamines in the PBI/PI systems were investigated. Four blends used in this study were all miscible, and the specific intermolecular interactions existing in these blends was thought to be the hydrogen bonding between the N-H of PBI and the C=O of PIs. The hydrogen bonding in the blends were shown to be stronger in the Blend-III and Blend-IV than Blend-I and II. It is speculated that the differences of hydrogen bonding strength of PBI/PI blends are dependent upon chemical structures of PIs, that is, PIs consisting of $SO_2$ group have a weaker hydrogen bonding strength than those of O or $CH_2$ group because the former has a larger spacer than the latter.

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Synthesis of Polyimides with Layered Structure from Diamines Containing Flexible Side Chains (유연한 곁가지를 가진 디아민으로부터 층상 구조의 폴리이미드 합성)

  • Han Seung San;Yi Mi Hye;Choi Kil-Yeong;Im Seung Soon;Kim Yong Seok
    • Polymer(Korea)
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    • v.30 no.1
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    • pp.56-63
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    • 2006
  • We have synthesized two types of diamine monomers containing various chain length to prepare polyimides with layered structure. By using these diamines, homo-polyimides and co-polyimides having hydrophobic and hydrophilic segment of flexible side chain were synthesized. The segregated layered structures were formed by repulsive force with main chain as the side chains reach a critical length because the rigid main chains are packed into layered structure with the flexible side chains occupying the space between layers. As a result, the gallery space of each homo-polyimide was increased at spacing of $32.7\~48{\AA}\;or\;7\~10.5{\AA}$ as the increased hydrophobic or hydrophilic side chain length through X-ray diffraction. The gallery space of co-polyimides was also showed similar phenomenon by repulsive force of side chains with different properties. We have also confirmed that gallery space and molar volume were significantly depended on length of flexible side chain via molecular modeling.

Biological Monitoring of Workers Exposed to Diisocyanates using Urinary Diamines (소변 중 디아민을 이용한 디이소시아네이트 노출 근로자의 생물학적 모니터링)

  • Lee, Jong Seong;Kim, Boowook;Shin, Jungah;Baek, JinEe;Shin, Jae Hoon;Kim, Ji-hye
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.26 no.2
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    • pp.178-187
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    • 2016
  • Objectives: Diisocyanates are a potent inducer of diseases of the airways, especially asthma. In this study, toluenediamine(TDA) and methylenedianiline(MDA) in urine were evaluated as biomarkers of exposure to tolunenediisocyanate(TDI) and methylenediphenyl diisocyanate(MDI), respectively. Methods: Workers exposed to TDI and MDI, as well as non-occupationally exposed subjects, were studied and pre- and post-shift urine samples were collected from 8 control subjects and 8 workers from a factory which manufactures polyurethane products for reducing noise and vibration in automobiles. Airborne TDI and MDI(n=8) were sampled on solvent-free glass filters impregnated with n-butylamine and detected by liquid chromatography atmospheric pressure ionization tandem mass spectrometry. Urinary TDA and MDA were detected as pentafluoropropionic acid anhydride(PFPA) derivatives by liquid chromatography electrospray ionization tandem mass spectrometry. Results: The median levels of urinary 2,6-TDA(p<0.001), 2,4-TDA(p=0.001), and MDA(p<0.001) of workers in post-shift samples were significantly higher than those of controls. The median levels of urinary 2,6-0TDA($0.63{\mu}g/g$ creatinine vs $0.34{\mu}g/g$ creatinine, p=0.017) and MDA($4.21{\mu}g/g$ creatinine vs $3.18{\mu}g/g$ creatinine, p=0.017) of workers in post-shift samples were significantly higher than those of the pre-shift samples. There were significant correlations between the urinary 2,6-TDA, 2,4-TDA, and MDA of workers in post-shift samples and the airborne 2,6-TDI(rho=0.952, p<0.001), 2,4-TDI(rho=0.833, p=0.001), and MDI(rho=0.952, p<0.001). Conclusions: These urinary diamines, metabolites of diisocyanates, in post-shift samples were useful biomarkers to assess occupational exposure to diisocyanates.

Synthesis, Potentiometric, Spectral Characterization and Microbial Studies of Transition Metal Complexes with Tridentate Ligand (세자리 리간드의 전이금속 착물에 대한 합성과 전위차 및 분광학적 확인 그리고 미생물학적 연구)

  • Jadhav, S.M.;Munde, A.S.;Shankarwar, S.G.;Patharkar, V.R.;Shelke, V.A.;Chondhekar, T.K.
    • Journal of the Korean Chemical Society
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    • v.54 no.5
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    • pp.515-522
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    • 2010
  • A relation between antimicrobial activities and the formation constants of solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with tridentate Schiff base ligand, 4-hydroxy-3(1-{2-(benzylideneamino)-phenylimino}-ethyl)-6-methyl-2Hpyran-2-one (HL) derived from o-phenylene diamines, dehydroacetic acid (DHA) and p-chloro benzaldehyde have been studied. The ligand and metal complexes were characterized by elemental analysis, conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, $^1H$-NMR, UV-vis and mass spectra. From the analytical data, the stiochiometry of the complexes was found to be 1:2 (metal:ligand) with octahedral geometry. The molar conductance values suggest the nonelectrolytic nature of metal complexes. The X-ray diffraction data suggests monoclinic crystal system for Ni(II) and orthorhombic crystal system for Cu(II) and Co(II) complexes. The IR spectral data suggest that the ligand behaves as tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behavior (TG/DTA) and kinetic parameters calculated by Coats-Redfern method suggests more ordered activated state in complex formation. The protonation constants of the complexes were determined potentiometrically in THF:water (60:40) medium at $25^{\circ}C$ and ionic strength ${\mu}=0.1\;M$ ($NaClO_4$). Antibacterial activities in vitro were performed against Staphylococcus aureu and Escherichia coli. Antifungal activities were studied against Aspergillus Niger and Trichoderma. The effect of the metal ions and stabilities of complexes on antimicrobial activities are discussed.

Synthesis of Newel Self-Developing Photosensitive Polyimide

  • Ahn, Byung-Hyun;Lee, Dae-Woo;Lee, Jin-Kook;Hong, Seong-Soo;Lee, Gun-Dae
    • Macromolecular Research
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    • v.8 no.1
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    • pp.19-25
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    • 2000
  • Aromatic diamine monomers containing allylic ester linkage, 1,5-bis(4-aminobenzoate)-1,2,3,4-tetrahydronaphthalene (4-DABTN) and 1,5-bis(3-amin obenzoate)-1,2,3,4-tetrahydronaphthalene (3-DABTN) were synthesized through the reaction of 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene and 4- or 3-nitrobenzoly chloride. By the reaction of these diamines with pyromellitic dianhydride (PMDA) or 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), poly(amic acid)s were obtained. The inherent viscosities of the poly(amic acid)s were between 0.55 and 1.31 dL/g. The poly(amic acid)s were converted to polyimides by chemical imidization. The thermogravimetric analysis (TGA) thermograms of these polyimides showed temperatures of 5% weight loss between 323 and 389$^{\circ}C$ in nitrogen atmosphere. The model compound ,1,5-bis (4-nitrobenzoate)-1,2,3,4-tetrahydronaphthalene (4-DNBTN), was decomposed to 4-nitrobenzoic acid and 5-(4-nitrobenzoate)-3,4-dihydronaphthalene upon addition of CF$_3$COOH.

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Characterization of Putrescine Uptake in Hamster Amelanocytic Melanoma AMEL-3 Cells

  • Garcia-Fernandez, Antonio J.;Rodriguez, Rosa A.;Perez-Pertejo, Yolanda;Balana-Fouce, Rafael
    • Molecules and Cells
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    • v.20 no.1
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    • pp.127-135
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    • 2005
  • The uptake of putrescine, spermidine and spermine by Fortner's hamster amelanocytic melanoma AMEL-3 cells was observed in this study to be time-dependent, temperature-sensitive, pH-dependent and saturable. Metabolic poisons nullified polyamine uptake, an indication that this is an energy-requiring mechanism. The presence of $Na^+$ ions was found to be requisite to full activity. Valinomycin, gramicidin, monensin and the calcium ionophore calcimycin were also observed to inhibit the process substantially. The transporter active site would seem to contain sulfhydryl groups. Other diamines and polyamine analogues, as well as cationic diamidines, suppressed putrescine uptake. The presence of the ornithine decarboxylase inhibitor DFMO in the culture medium induced putrescine inflows. Putrescine, in turn, induced the negative expression of the carrier, thus suggesting that this influx mechanism is governed by up/down regulation. The cationic diamidine CGP 40215A and its analogue CGP039937A competitively inhibited putrescine transport, with Ki values of 1.9 and $15{\mu}M$, respectively. The role of polyamine uptake in these cultures is discussed.