• Bulletin of the Korean Chemical Society
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• 제28권6호
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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.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1835-1836
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• 2010

• Macromolecular Research
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• 제16권2호
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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.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3899-3903
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• 2011

General, fast, and efficient fusion methods for the synthesis of dendrimers with 1,3-diynes at a core were developed. The synthetic strategy was employed the oxidative homo-coupling of terminal alkyne. The oxidative homo-coupling reaction of the alkyne-functionalized Frechet-type dendrons 1-Dm was allowed to provide first through fourth generation dendrimers 2-Gm with 1,3-diynes at core. The fusion of the propargylfunctionalized PAMAM dendrons 3-Dm by homo-coupling of terminal alkyne lead to the formation of symmetric PAMAM dendrimers 4-Gm. Their structure of dendrimers was confirmed by $^1H$ and $^{13}C$ NMR spectroscopy, IR spectroscopy, mass spectrometry, and GPC analysis.

• Bulletin of the Korean Chemical Society
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• 제28권10호
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• pp.1771-1776
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• 2007

The synthesis of well-defined dendrons based on aliphatic polyether dendritic cores and glassy polystyrene peripheries is described. The synthetic route involves a combination of living anionic polymerization and a stepwise convergent method consisting of iterative Williamson etherification and hydroboration/oxidation reactions. On the basis of molecular weight, as characterized by gel permeation chromatography (GPC), the first generation dendron (Generation-1) shows a random coil conformation like a linear polystyrene, while higher generations (Generation-2 and 3) reveal globular forms in solution.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.91-92
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• 2006

The fine-tuned dendrons provide unique supramolecular self-assemblies in various environments such as in water, organic media, and solid-liquid interfaces. They form nanotubes, vesicles, thin films, columns, lamellar nanoribbons depending on the condition of self-assembly process. Unique characteristics of self-assembly of the amide dendrons are described. In addition, elucidation of the structural correlation between the building blocks and the assemblies, stabilization of assembled structure, and transformation of supramolecular assemblies by using external stimuli. Particular emphasis is placed on the formation of cyclodextrin-covered organic nanotubes derived from self-assembly of amide dendrons and their supramolecular transformation. Finally, unique biosensory characteristics of the self-assembled nanotubes will be discussed.

• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2703-2706
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• 2012

New C60 fullerenes derivatives [G1]-C60 (1) and [G2]-C60 (2) comprising of phenylenevinylene bridges and phenylquinoline peripheral surface groups were synthesized by 1,3-dipolar cycloaddition reaction of fullerene C60 with azomethine ylide in situ generated from [Gx]-CHO dendrons (x = 1 and 2) and sarcosine.

• Bulletin of the Korean Chemical Society
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• 제29권6호
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• pp.1167-1172
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• 2008

We investigated the glass transition temperatures ($T_g$) of dendrons consisting of conformationally mobile aliphatic polyether dendritic cores plus glassy peripheral polystyrenes (PSs), and linear PSs in the molecular weight range of 1000-8500 g/mol. We compared their $T_g$ behavior depending on their polymeric architecture. The linear PSs show a typical growth of $T_g$ up to 92.5 ${^{\circ}C}$ as the molecular weight increases to 8300 g/mol, while the dendrons display nearly constant $T_g$ values of 58-61 ${^{\circ}C}$, despite the increase of molecular weight with each generation. The striking contrast of Tg behavior would be mainly attributed to the fact that the dendrons keep the ratio of $N_e$/M ($N_e$: number of peripheral chain ends, M: molecular weight) over all the generations. Additionally, for the influence of dendritic spacers on glass transition temperature we prepared dimeric PSs with different linkage groups such as aliphatic ether, ester and amide bonds. We found that the dimer with the ether spacer exhibited the lowest glass transition at 55.4 ${^{\circ}C}$, while the amide linked dimer showed the highest glass transition temperature at 74.2 ${^{\circ}C}$. This indicates that the peripheral PS chains are effectively decoupled by the conformationally flexible ether spacer. The results from this study demonstrated that polymeric architecture and dendritic core structures play a crucial role in the determination of glass transition behavior, providing a strategy for the systematic engineering of polymer chain mobility.

• Macromolecular Research
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• 제12권5호
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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.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3933-3940
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• 2011

General, fast, and efficient stitching methods for the synthesis of dendrimers with linear PEG units at a core, as dendritic-linear-dendritic materials, were developed. The synthetic strategy involved the click reaction between an alkyne and an azide. The linear core building blocks, three dialkyne-PEG units, were chosen to serve as the alkyne functionalities for dendrimer growth via click reactions with the azide-dendrons. These three building blocks were employed together with the azide-functionalized Fr$\acute{e}$chet-type dendrons in a convergent strategy to synthesize the Fr$\acute{e}$chet-type dendrimers with different linear core units. Their structure of dendrimers was confirmed by $^1H$ and $^{13}C$ NMR spectroscopy, IR spectroscopy, mass spectrometry, and GPC analysis.