• Title/Summary/Keyword: Supramolecular aggregates

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Effect of Carotenoides on the in vitro Aggregation of Bacteriochlorophyll e

  • Hirabayashi, Hiroki;Ohmura, Satoshi;Ishii, Takasada;Uehara, Kaku
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.370-372
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    • 2002
  • In order to investigate effect of the carotenoids (Car) on aggregation of Bacterochlorophyll (BChl) in chlorosome, we studied the spectral difference in aggregates of BChl e formed in the absence and presence of a few kinds of Car in dimethyl sulfoxide (DMSO) -water solution. The absorption spectra of aggregates made of only BChl e and those made of a mixture of BChl e and Car were almost the same. However, the kinetics and circular dichroism (CD) spectra of aggregate of these were markedly different by kind of Car. Specifically, the rate of aggregation for a mixture of BChl e and isorenietene that contains phenyl as end groupe was faster than that for only BChl e. CD spectra of aggregates made of a mixture of BChl e and isorenietene dramatically changed compared to that made of only BChl e. We propose that BChl might form several kinds of rod-like supramolecular structures to in the presence of some kind of Car in chlorosome.

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Synthesis, Self-assembly, and Catalytic Activity of 1H-Imidazole Amphiphiles

  • Park, Jun-Ha;Kim, Min-Soo;Seo, Sang-Hyuk;Chang, Ji-Young
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2193-2198
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    • 2011
  • We prepared polycatenar 1H-imidazole amphiphiles having a structure in which a 1H-imidazole head was connected through a benzene ring to a pheny group having two or three oligo(ethylene glycol) chains and studied their supramolecular assembly by fluorescence spectroscopy, transmission electron microscopy (TEM) and atomic force microscopy (AFM). When the aqueous solutions of the amphiphiles ($5{\times}10^{-5}M{\sim}10^{-3}M$) were deposited onto a carbon-coated copper grid and dried, twisted structures with diameters of ~200-300 nm were imaged by TEM and AFM. We presume that the structures comprised a chain of the amphiphile dimers formed via successive hydrogen bonding between the 1H of the imidazole group and 3N of the neighboring one. In a solution of pH 4, entangled fibers with diameters of several nanometers were observed by TEM. In a pH 10 solution, film-like aggregates formed exclusively. The 1H-imidazole amphiphiles hydrolyzed tetraethoxysilane to induce gelation to form fibrous and spherical silica structures at neutral pH in aqueous solutions. No silica was formed when imidazole was used instead of the amphiphiles, suggesting that the selfassembled aggregates of the amphiphiles were responsible for the gelation.

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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수정진동자를 이용한 Au 표면에서 avidin-biotin 결합 리포좀 막의 구조 분석

  • Park, Jong-Won;Han, Seong-Ung;Gwon, Jeong-Hun;Park, Jin-Yeong;Jo, Hong-Sik;Lee, Haeng-Ja;Jang, Sang-Mok
    • 한국생물공학회:학술대회논문집
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    • 2000.04a
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    • pp.546-549
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    • 2000
  • Liposomes and proteoliposomes, artificial membranes, can interact with many solutes, such as drugs, peptides and proteins. Immobilization of (proteo)liposomes as supramolecular aggregates on gold surfaces have potential applications in nanotechnology and biosensors. We demonstrate a quartz crystal analyzer (QCA) method to monitor the construction of multi layers of unilamellar liposomes based on avidin-biotin binding on gold surface using quartz crystal microbalance(QCM). Thus, QCA provides an on line and efficient method to detect the protein membranes construction and have applications to biosensing system.

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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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Analysis of Avidin-biotinylated Liposome Layers on Au Electrode by Quartz Crystal Analyzer (수정진동자를 이용한 Au 표면에서 avidin-biotin 결합 리포좀 막의 형성구조 분석)

  • Song, Seong-Hun;Cho, Hong-Sig;Park, Jong-Won;Kim, Kwang;Nakamura, Chikashi;Yang, Qing;Miyake, Jun;Chang, Sang-Mok
    • KSBB Journal
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    • v.15 no.5
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    • pp.497-500
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    • 2000
  • Liposomes and proteoliposomes, artificial membranes, can interact with many solutes, such as drugs, peptides and proteins. The immobilization of (prot대)liposomes as supramolecular aggregates on gold surfaces have potential applications in nano and biosensor technology. We demonstrated a quartz crystal analyzer (QCA) based method to monitor the construction of multi-layers of unilamellar liposomes based on avidin-biotin binding on gold surfaces using a quartz crystal microbalance (QCM). Thus, the QCA provides an on line and efficient method of detecting the construction of protein membranes, which has applications in biosensing systems.

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Preparation of Polymeric Self-Assembly and Its Application to Biomaterials

  • Cho, Chong-Su;Park, In-Kyu;Nah, Jae-Woon;Toshihiro Akaike
    • Macromolecular Research
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    • v.11 no.1
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    • pp.2-8
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    • 2003
  • The self-assembly of polymers can lead to supramolecular systems and is related to the their functions of material and life sciences. In this article, self-assembly of Langmuir-Blodgett (LB) films, polymer micelles, and polymeric nanoparticles, and their biomedical applications are described. LB surfaces with a well-ordered and layered structure adhered more cells including platelet, hepatocyte, and fibroblast than the cast surfaces with microphase-separated domains. Extensive morphologic changes were observed in LB surface-adhered cells compared to the cast films. Amphiphilic block copolymers, consisting of poly(${\gamma}$-benzyl L-glutamate) (PBLG) as the hydrophobic part and poly(ethylene oxide) (PEO) [or poly(N-isopropylacrylamide) (PNIPAAm)] as the hydrophilic one, can self-assemble in water to form nanoparticles presumed to be composed of the hydrophilic shell and hydrophobic core. The release characteristics of hydrophobic drugs from these polymeric nanoparticles were dependent on the drug loading contents and chain length of the hydrophobic part of the copolymers. Achiral hydrophobic merocyanine dyes (MDs) were self-assembled in copolymeric nanoparticles, which provided a chiral microenvironment as red-shifted aggregates, and the circular dichroism (CD) of MD was induced in the self-assembled copolymeric nanoparticles.

Design of the Artificial Antenna System in Photosynthesis

  • Tamiaki, Hitoshi;Yagai, Shiki
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.66-69
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    • 2002
  • Zinc chlorin 1 possessing tertiary 3$^1$_hydroxy and 13$^1$-oxo groups was synthesized as a model for the antenna chlorophylls of photosynthetic green bacteria. Self-aggregation of 1 in nonpolar organic solvents was examined and compared to 2 and 3 possessing a secondary and primary 3$^1$_hydroxy group, respectively. Zinc chlorin 1 self-aggregated in I%(v/v) CH$_2$Cl$_2$-hexane to form oligomers and showed a red-shifted Qy maximum at 704 nm compared to the monomer (648 nm in CH$_2$CI2$_2$). This red-shift is larger than that of 3$^1$S-2 (648 to 697 nm) and comparable to that of3$^1$R-2 (648 to 705 nm), but smaller than that of 1 (648 to 740 nm), indicating that while a single 3$^1$-methyl group (primary to secondary OH) suppressed tight and/or extended aggregation, the additional 3$^1$-methyl group (secondary to tertiary OH) did not further suppress aggregation. The relative stability of the aggregates was in the order 3> 3$^1$R-2∼ 1 > 3$^1$S-2 as determined by visible spectral analyses. Molecular modeling calculations on oligomers of zinc chlorins 1, 3$^1$ R-2 and 3 gave similar well-ordered energy-minimized structures, while 3 stacked more tightly than 3$^1$ R- 2 and 1. In contrast, 3$^1$S-2 gave a relatively disordered (twisted) structure. The calculated oligomeric structures could explain the visible spectral data of 1-3 in nonpolar organic solvents. Moreover, self- aggregation of synthetic zinc 13$^1$_oxo-hlorins 4-6 possessing a 2-hydroxyethyl, 3-hydroxypropyl and 3- hydroxy-I-propenyl group at the 3-position in nonpolar organic solvents was discussed.

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