• Title/Summary/Keyword: Dendron

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Synthesis and Magnetic Properties of Dendron Capped Fe2O3 Nanoparticles

  • George, Sheby M.;Hong, In-Seok;Kim, Jin-Kwon
    • Bulletin of the Korean Chemical Society
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    • v.29 no.8
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    • pp.1545-1553
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    • 2008
  • Using a one-pot reaction technique, monodisperse $\gamma-Fe_2O_3$ nanoparticles were prepared by thermal decomposition of Fe$(CO)_5$ in the presence of a long alkyl chain terminated dendron surfactant. The size of the particles is controlled by adjusting the concentration of the dendron ligands in the reaction solution. Spherical, 2 nm sized nanoparticles were obtained with a 3:1 ratio of dendrons to Fe$(CO)_5$, while 4.6 nm sized particles were formed with a 1:3 ratio. Superparamagetic properties of 2 nm, 4 nm, and 4.6 nm sized particles were measured using a SQUID magnetometer.

Precise Synthesis of Dendron-Like Hyperbranched Polymers and Block Copolymers by an Iterative Approach Involving Living Anionic Polymerization, Coupling Reaction, and Transformation Reaction

  • Hirao Akira;Tsunoda Yuji;Matsuo Akira;Sugiyama Kenji;Watanabe Takumi
    • Macromolecular Research
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    • v.14 no.3
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    • pp.272-286
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    • 2006
  • Dendritic hyperbranched poly(methyl methacrylate)s (PMMA)s, whose branched architectures resemble the 'dendron' part(s) of dendrimer, were synthesized by an iterative methodology consisting of two reactions in each iteration process: (a) a coupling reaction of u-functionalized, living, anionic PMMA having two tert-butyldimethylsilyloxymethylphenyl(SMP) groups with benzyl bromide(BnBr)-chain-end-functionalized PMMA, and (b) a transformation reaction of the introduced SMP groups into BnBr functionalities. These two reactions, (a) and (b), were repeated three times to afford a series of dendron-like, hyperbranched (PMMA)s up to third generation. Three dendron-like, hyperbranched (PMMA)s different in branched architecture were also synthesized by the same iterative methodology using a low molecular weight, functionalized 1,1-diphenylalkyl anion prepared from sec-BuLi and 1,1-bis(3-tert-butyldime-thylsilyloxymethylphenyl)ethylene in the reaction step (b) in each iterative process. Furthermore, structurally similar, dendron-like, hyperbranched block copolymers could be successfully synthesized by the iterative methodology using $\alpha$-functionalized, living, anionic poly(2-(perfluorobutyl) ethyl methacrylate) (PRfMA) in addition to $\alpha$-functionalized, living PMMA. Accordingly, the resulting block copolymers were comprised of both PMMA and PRfMA segments with different sequential orders. After the block copolymers were cast into films and annealed, their surface structures were characterized by angle-dependent XPS and contact angle measurements. All three samples showed significant segregation and enrichment of PRfMA segments at the surfaces.

Photoresponsive Azobenzene-cored Dendrons with Terminal Vinyl Groups

  • Choi, Dae-Ock;Lee, Ji-Hye;Shin, Kyong-Ha;Shin, Eun-Ju
    • Bulletin of the Korean Chemical Society
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    • v.28 no.6
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    • pp.983-989
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    • 2007
  • Azobenzene-cored dendrons having the photoisomerizable azobenzene core and terminal vinyl groups have been prepared. Absorption bands of azobenzene-cored dendrons are similar except more intense 280 nm band in higher generation azobenzene dendron. All three azobenzene-cored dendrons show reversible photoisomerization similar to simple azobenzene, irrespective of the generation of dendron. On 350 nm irradiation, absorption band around 344 nm decreases and 436 nm band increases. Photoisomerization reactions are very fast for all three azobenzene-cored dendron and the reaction efficiency is dependent of its generation and solvent. In the dark, slow thermal reversion to original absorption spectrum is observed.

Patterned Surfaces in Self-Organized Block Copolymer Films with Hexagonally Ordered Microporous Structures

  • Hayakawa Teruaki;Kouketsu Takayuki;Kakimoto Masa-alki;Yokoyama Hideaki;Horiuchi Shin
    • Macromolecular Research
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    • v.14 no.1
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    • pp.52-58
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    • 2006
  • A novel fabrication of the patterned surfaces in the polymer films was demonstrated by using the self-organizing character of the block copolymers of polystyrene-b-oligothiophenes and polystyrene-b-aromatic amide dendron. Hexagonally arranged open pores with a micrometer-size were spontaneously formed by casting the polymer solutions under a moist air flow. The amphiphilic character of the block copolymers played the crucial role as a surfactant to stabilize the inverse emulsion of water in the organic solvent, and subsequently the aggregated structure of the hydrophilic oligothiophene or aromatic amide dendron segments remained on the interiors of the micropores. The chemical composition on the top of the surface of the microporous films was characterized by energy-filtering transmission electron microscopy (EFTEM) or a time-of-flight secondary ion mass spectrometer (ToF-SIMS). The characterizations clearly indicated that the patterned surfaces in the self-organized block copolymer films with the hexagonally ordered microporous structures were fabricated in a single step.

Thermal and Solid State Assembly Behavior of Amphiphilic Aliphatic Polyether Dendrons with Octadecyl Peripheries

  • Chung, Yeon-Wook;Lee, Byung-Ill;Cho, Byoung-Ki
    • Macromolecular Research
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    • v.16 no.2
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    • pp.113-119
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    • 2008
  • A series of amphiphilic dendrons n-18 (n: generation number, 18: octadecyl chain) based on an aliphatic polyether denderitic core and octadecyl peripheries were synthesized using a convergent dendron synthesis consisting of a Williamson etherification and hydroboration/oxidation reactions. This study investigated their thermal and self-assembling behavior in the solid state using differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) absorption spectroscopy, and small angle X-ray scattering (SAXS). DSC indicated that the melting transition and the corresponding heat of the fusion of the octadecyl chain decreased with each generation. FT-IR showed that the hydroxyl focal groups were hydrogen-bonded with one another in the solid state. DSC and FT-IR indicated microphase-separation between the hydrophilic dendritic cores and hydrophobic octadecyl peripheries. SAXS data analysis in the solid state suggested that the lower-generation dendrons 1-18 and 2-18 self-assemble into lamellar structures based upon a bilayered packing of octadecyl peripheries. In contrast, the analyzed data of higher-generation dendron 3-18 is consistent with 2-D oblique columnar structures, which presumably consist of elliptical cross sections. The data obtained could be rationalized by microphase-separation between the hydrophilic dendritic core and hydrophobic octadecyl peripheries, and the degree of interfacial curvature associated with dendron generation.

Synthesis of Diblock Codendrimer by Double Click Chemistry

  • Lee, Jae Wook;Han, Seung Choul;Ji, Won Ho;Jin, Sung-Ho;Kim, Ji Hyeon
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4103-4108
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    • 2012
  • Efficient double click methods for the synthesis of diblock codendrimers were developed. The synthetic strategy involved the sequential click reactions between an alkyne and an azide. The short core building block, 1,4-diazidobutane, was chosen to serve as the azide functionalities for dendrimer growth via click reactions with the alkyne-functionalized PAMAM dendrons as hydrophilic dendron and alkyne-functionalized Fr$\acute{e}$chet-type dendrons as hydrophobic dendron. The structure of diblock codendrimers was confirmed by $^1H$ and $^{13}C$ NMR spectroscopy, IR spectroscopy, mass spectrometry, and GPC analysis.

Self-Organization of Dendron-Poly(ethylene glycol) Conjugates in an Aqueous Phase

  • Kim, Kyoung-Taek;Lee, Im-Hae;Park, Chiyoung;Song, Yu-Mi;Kim, Chul-Hee
    • Macromolecular Research
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    • v.12 no.5
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    • pp.528-533
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    • 2004
  • We have prepared amide dendrons having alkyl peripheral units and various focal moieties through a convergent synthetic approach. The amphiphilic properties, due to hydrophilic amide branches and the hydrophobic peripheral units, provide an opportunity for the amide dendrons to self-organize in water. The dendritic architecture itself is also one of the critical factors in the self-organization of the amide dendrons in water. In particular, function-alization was performed at the focal point to elucidate the relationship between the focal functionality and the self-organized structures of the dendritic building blocks in the aqueous phase. The dendron having a short poly(ethylene glycol) monomethyl ether (MeO-PEG) unit (M$\_$n/ =750) as the focal moiety formed a vesicular organization in water. As the size of the hydrophilic focal MeO-PEG increased to M$\_$n/ =2,000 and 5,000, the self-organized structures became rod-type and spherical micelles, respectively. Our observation of multiple morphologies for amide dendrons is in good agreement with previous reports that indicated that the micellar structures changed from vesicles to rod-types and then to spheres upon increasing the size of the hydrophilic moiety of the amphiphiles.