• Title/Summary/Keyword: Supramolecular assembly

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Self-assembly and Mechanism of L-Alanine-based Dihydrazide Derivative as Excellent Gelator of Organic Solvents

  • Wang, Chuan-Sheng;Wang, Xiao-Hong;Li, Zhi-Yuan;Wei, Wei;Shi, Zhong-Liang;Sui, Zhi-Tong
    • Bulletin of the Korean Chemical Society
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    • v.32 no.4
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    • pp.1258-1262
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    • 2011
  • A new organogelator, L-Alanine dihydrazide derivative can self-assemble in various organic solvents and turned them into thermally reversible physical supramolecular organogels at extremely low concentrations (< 2 wt %). The gel-sol phase transition temperatures ($T_{GS}$) were determined as a function of gelator concentration and the corresponding enthalpies (${\Delta}H_g$) were extracted. Scanning electron microscopy (SEM) measurements revealed that the interspaces of fiber-like network structures were diminished with the increasing of the LMOG concentration. FT-IR spectroscopy studies revealed that hydrogen-bonding and hydrophobic interaction were the driving forces for the formation of the gels. Based on the data of XRD and molecular modeling, the possible packing modes for the formation of organogelator aggregates were proposed.

Conjugated Oligomers Combining Fluorene and Thiophene Units : Towards Supramolecular Electronics

  • Leclere, Ph.;Surin, M.;Sonar, P.;Grimsdale, A.C.;Mllen, K.;Cavallini, M.;Biscarini, F.;Lazzaroni, R.
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.228-228
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    • 2006
  • Conjugated oligomers, used as models for fluorene-thiophene copolymers, are compared in terms of the microscopic morphology of thin deposits and the optical properties. The AFM images and the solid-state absorption and emission spectra are interpreted in line with the structural data, in terms of the assembly of the conjugated molecules. The compound with a terthiophene central unit and fluorene end-groups shows well-defined monolayer-by-monolayer assembly into micrometer-long strip-like structures, with a crystalline herringbone-type organization within the monolayers. Polarized confocal microscopy indicates a strong orientation of the crystalline domains within the stripes. In contrast, the compound with a terfluorene central unit and thiophene end groups forms no textured aggregates. The difference in behavior between the two compounds most probably originates from their different capability of forming densely-packed assemblies of ${\pi-pi}$ interacting molecules. These assemblies are used as active elements in organic field effect transistors designed by using soft lithography technique.

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Electron-transfer Properties of Viologen Self-assembled MonoLayers in Different Electrolyte Solutions (전해질 변화에 따른 Viologen 자기조립박막의 전하이동 특성 연구)

  • Lee, D.Y.;Park, S.H.;Shin, H.K.;Park, J.C.;Chang, J.S.;Kwon, Y.S.
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.17 no.12
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    • pp.1337-1340
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    • 2004
  • The self-assembled monolayers of alkane derivatives with sulfur containing head groups on gold substrates have been widely examined recently, since the binding between S atoms and Au surface is strong. The viologen has been widely investigated their well-behaved electrochemistry including electron transfer mediation, the surface-enhanced of the adsorption and the behavior of supramolecular assemblies at electrode surfaces in theses and various studies. Yiologen monolayers are formed onto QCM by self-assembly method. We studied the relationship of electron transfer from changing the anions in 0.1 M NaCl and NaClO$_4$ electrolyte solution. The EQCM measurements revealed the anions transfer during reduction and oxidation, respectively From the EQCM data, the well-defined shape peaks were nearly equal charges by cyclic voltammetry.

Self-Aggregation of Synthetic Magnesium Bacteriochlorins as a Photosynthetic Antenna Model

  • Kunieda, Michio;Mizoguchi, Tadashi;Tamiaki, Hitoshi
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.353-355
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    • 2002
  • We prepared 3-(1-hydroxyethyl)-bacteriopyrochlorophy11-a (3) possessing magnesium atom and phytyl ester from modification of natural bacteriochlorophyll(BChl)-a. A dichloromethane solution of (3$^1$R) and (3$^1$S)-3 was diluted with 100~1000 fold volume of cyclohexane to give new species absorbing near-infrared lights. The resulting Q, maximum of (3$^1$R)-3 was 860 nm and red-shifted by 2150 $cm^{-1}$ / from the monomeric. In the nonpolar organic solvent, epimeric (3$^1$S)-3 showed a 1ess red-shifted peak at 798 nm as well as a residual monomeric band. Such visible spectra indicated that 3 diastereose1ectively aggregated in cyclohexane to afford oligomers possessing a simi1ar supramolecular structure with chlorosomal aggregates of natural BChl-d, 7,8-dehydro-form of 3.

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Molecular Wire World Having Metal Complexes

  • Choi, Chang-Shik
    • Rapid Communication in Photoscience
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    • v.3 no.3
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    • pp.42-47
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    • 2014
  • Development of molecular and supramolecular systems showing efficient photoinduced energy or electron transfer are of current research interest due to their applications in various chemical and biological processes. Various polypyridine metal complexes including Ru(II), Ru(III), Os(II), Pt(II), Fe(II), Re(I), Ir(III) and so on as a metal center introduce for expanding some more understanding of molecular-scale photoelectronics. Their complexes are concisely classified by the types of relay ligands as follows; (a) metal-direct ligand-metal system; dinuclear or trinuclear systems, (b) metal-nonconjugated ligand-metal system and metal-nonconjugated ligand system having flexible/rigid ligand, (c) metal-conjugated ligand-metal system, and (d) conjugated ligand-metal-conjugated ligand system and metal-self assembly ligand-metal system. It is pointed out that the role played by the relay ligands is important in constructing the metal complexes.

Supramolecular Nanodevice Based on Helical Encapsulation of Photo-/Electroactive Oligomers

  • Kim, Oh-Kil
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.167-167
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    • 2006
  • Photo-/electroactive donor-acceptor (D-A) chromophores were synthesized and investigated for energy- and electron-transfer (ET/eT) properties, for which the chromophores are supramolecularly integrated by encapsulation with helical amylose, rendering the chromophores aggregation-free and rigidified along the helical axis and thus, a remarkably enhanced fluorescence intensity. Fluorescence quenching studies indicated that the helical encapsulation gives the ET/eT a clear D-A distance dependence unlike with the encapsulation-free counterparts, being reflected in their florescence decay profile. Another notable difference is that the helical supramolecule of the chromophores forms a perpendicularly oriented self-assembly. Transport behavior in the solid state will be also discussed.

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Ordered Fragmentation of pDNA induced by PEG-PLL block copolymer -Correlation between Condensation degree and Biological Activity by Cell-Free System-

  • Osada, Kensuke;Doi, Motoyoshi;Shiotani, Tomonori;Yamasaki, Yuichi;Kataoka, Kazunori
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.254-254
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    • 2006
  • The sensitivity of plasmid DNA (pDNA) to S1 nuclease, an enzyme to cleave a single-strand DNA, was dramatically modulated through a supramolecular assembly (polyion complex micelle) with a synthetic block copolymer, poly(ethylene glycol)-b-poly(L-lysine) (PEG-PLL). The pDNA condensed in stoichiometric charge ratio was cleaved into 7 fragments each being 10/12, 9/12, 8/12, 6/12, 4/12, 3/12, and 2/12 of the original DNA length, on the other hand, the pDNA condensed in higher charge ratios (>4), were digested into non-specific manner. Condensation of the pDNA was investigated from two viewpoints that how does the rigid DNA molecules fold and condense and how does the condensation influence their biological activity.

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Synthesis and Characterization of Methyltriethoxysilyl-Mediated Mesoporous Silicalites

  • Rabbani, Mohammad Mahbub;Oh, Weon-Tae;Nam, Dae-Geun
    • Transactions on Electrical and Electronic Materials
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    • v.12 no.3
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    • pp.119-122
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    • 2011
  • A series of mesoporous silicalites was synthesized using different compositions of tetraethylorthosilicate and methyltriethoxysilane (MTES) as the silica source. Cetyltrimethylammonium bromide was used as the organic template. Their detailed pore structures were investigated by transmission electron microscopy, X-ray diffraction, and N2 adsorption method. The thermal properties of these silicalites were studied by thermogravimetric analysis. The increased amount of MTES destroyed mesoporous channels and reduced pore sizes from 3.4 nm to 2.8 nm in calcined silicalites. The calcined silicalite transformed completely into an amorphous state at 30% MTES loading. Methyl pending groups of MTES hindered the structural ordering of ≡Si-O- frameworks, resulting in an amorphous structure. This was caused by the insufficient formation of supramolecular assembly with the organic template. No capillary condensation step was found in MS 7/3 silicalite. The other capillary condensation steps shifted toward the lower relative pressure with increasing MTES content, indicating the reduction of pore sizes.