• Title/Summary/Keyword: H-chromophore

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ANION INDUCED BLUE TO PURPLE TRANSITION IN BACTERIORHODOPSIN

  • Singh, Anil K.;Kapil, Mrunalini M.
    • Journal of Photoscience
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    • v.3 no.2
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    • pp.71-76
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    • 1996
  • Anil K. Singh, Mrunalini M. Kapil, Department of Chemistry, Indian Institute of Technology Bombay - 400076, INDIA Purple membrane (PM, $\lambda$$_{max}$ 570 nm) of H. halobium on treatment with sulphuric acid changes its colour to blue ($\lambda$$_{max}$ 608 nm). The purple chromophore can be regenerated from the blue chromophore by exogeneous addition of anions such as CI$^-$ and HPO$_4^{2-}$. Chloride ion is found to be more effective than the dibasic phosphate ion in regenerating the purple chromophore. Nevertheless, one thing common to the anion regeneration is that both CI$^-$ and HPO$_4^{2-}$ show marked pH effect. At pH 1.0 the efficiency of regeneration of the purple chromophore is greater than at pH 2.0, for the same anion concentration. Fluorescence and circular dichroic studies indicate that the proteins do not undergo drastic changes at the secondary' or tertiary structure level and the native structure is preserved during this transition. However, chromophoric-site interactions between retinal and the apoprotein are affected during this colour transition. A molecular mechanism is advanced for this transition.

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The Synthesis of Indigoid-Type Dyes Based on Isatin $\alpha-Chloride$ (Isatin $\alpha-chloride$에 의한 인디고계 염료의 합성)

  • Park, Soo-Youl;Shin, Seung-Rim;Shin, Joung-Il;Jun, Kun
    • Textile Coloration and Finishing
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    • v.19 no.3
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    • pp.6-11
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    • 2007
  • The indigoid-type dyes based on isatin $\alpha-chloride$ were synthesized and the dyes were discussed with relevance to the "H-chromophore" or "cross-conjugated chromophore". The color-changed properties of the dyes were also investigated by means of visible absorption spectra. The novel dyes from isatin $\alpha-chloride$ are of theoretical interest and such dyes can be used as continuous pH indicators in acid/base titrimetric analyses.

Photochromism of Phytochromes and Cph1 Requires Critical Amino Acids and Secondary Structure in the N-Terminal Domain

  • Seo Hak-Soo;Bhoo Seong-Hee
    • Journal of Microbiology and Biotechnology
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    • v.16 no.9
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    • pp.1441-1447
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    • 2006
  • The light perception and phototransformation of phytochromes are the first process of the phytochrome-mediated light signal transduction. The chromophore ligation and its photochromism of various site-specific and deletion mutants of pea phytochrome A and bacterial phytochrome-like protein (Cph1) were analyzed in vitro. Serial truncation mutants from the N-terminus and C-terminus indicated that the minimal N-terminal domain for the chromophore ligation spans from the residue 78 to 399 of pea phytochrome A. Site-specific mutants indicated that several residues are critical for the chromophore ligation and/or photochromism. Histidine-324 appears to serve as an anchimeric residue for photochromism through its H-bonding function. Isoleucine-80 and arginine-383 playa critical role for the chromophore ligation and photochromism. Arginine-383 is presumably involved in the stabilization of the Pfr form of pea phytochrome A. Apparently, the amphiphilic ${\alpha}$-helix centered around the residue-391 is in the chromophore pocket and critical for the chromophore ligation.

The rate-determining step in the dark state recovery process in the photocycle of PYP

  • Sasaki, Jun;Kumauchi, Masato;Hamada, Norio;Tokunaga, Fumio
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.130-133
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    • 2002
  • The last step in the photocycle of photoactive yellow protein (PYP) is a spontaneous recovery of the dark state from the active state in which the p-coumaric acid chromophore is thermally isomerized, concomitantly with the deprotona- tion of the chtomophore and the refolding of the protein moicty. For the purpose of understanding the mechanism of the thermal back-isomerization, we have investigated the rate-determining step by analyzing mutant PYPs of Met100, which was previously shown to play a major role in facilitating the reaction (1). The mutation to Lys, Leu, Ala, or Glu decelerated the dark state recovery by 1 to 3 three orders of magnitude. By evaluating temperature-dependence and pH-dependence of the kinetics of the dark state recovery, it was found that the retardation by mutations resulted from elevation of the activation enthalpy ( H$\^$┿/) and that the pKa of the chromophore, which was affected by the mutation, is in a linier correlation with the amplitude of the rate constants. It was, therefore, deduced from the correlation that the free energy for crossing the activated state in the dark recovery process is proportional to the free energy for the deprotonation of the chromophore, identifying the rate-determining step as the deprotonation of the chromophore. (1) Devanathan, S. Genick, U. K. Canestrelli, I. L. Meyer, T. E. Cusanovich, M. A. Getzoff, E. D. Tollin, G., Biochemistry 1998, 37, 11563 - 11568

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Synthesis of Sphene-pink Pigment under Various Firing Conditions

  • Lee, Hyun-Soo;Park, Joo-Seok;Lee, Byung-Ha
    • Journal of the Korean Ceramic Society
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    • v.46 no.6
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    • pp.615-620
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    • 2009
  • The present research was performed to determine the optimal firing condition and holding time for malayaite crystal, which is responsible for the stable pink-red coloration in glaze at high temperatures, using Cr$Cl_3$ as chromophore for the synthesis of $Cr_2O_3-SnO_2-CaO-SiO_2$ system pigments. The malayaite crystal was influenced by the raw materials used for synthesis, firing temperature, and holding time. Thus there are differences in the crystal phase and in the coloration according to the condition of synthesis. When Cr$Cl_3$ was used as chromophore, the pigment could be synthesized at lower temperatures, because Cr$Cl_3$ melts at $1500{^{\circ}C}$, which is much lower than the temperature at which $Cr_2O_3$ melts (higher than $2435{^{\circ}C}$). And the employed Cr ion showed a change in oxidation state. When a mineralizer was used to improve the employment of malayaite and the Cr ion, and the low temperature was maintained at which the malayaite crystal is produced, the production of malayaite crystal was promoted and the employment of chromophore was also promoted in the oxidation state of Cr (IV). The results of the experiment showed that the optimal firing condition was 18 h of holding time at $800{^{\circ}C}$, using Cr$Cl_3$ as chromophore, followed by 2 h at the raised temperature of $1150{^{\circ}C}$. The change in coloration of the Cr (IV) employed by malayaite showed a very rich color of red. Thus it was possible to effectively synthesize sphene-pink pigments with more red tint at a low temperature.

Purification and Chemical Characterization of Antibiotic MT-497 Produced by Streptomyces nigrifaciens GMT-497 (Streptomyces nigrifaciens GMT-4967이 생산하는 항생물질 MT-497의 분리와 화학적 특성)

  • 이영선;안순철;윤병대;민태익;이정형;이현선;안종석;민태익
    • Microbiology and Biotechnology Letters
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    • v.19 no.6
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    • pp.604-609
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    • 1991
  • Antibiotic MT-497 was purified from the culture broth of Streptomyces nigr$^1H-NMR$ and composition of amino acids, MT-497 was identified as one of the actinornycin antibiotics containing actinocin chromophore and the peptide with threonine, proline, methyl valine, sarcosine and aspartic acid.

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Synthesis of Dendrimer Containing Dialkylated-fluorene Unit as a Core Chromophore via Click Chemistry

  • Han, Seung-Choul;Jin, Sung-Ho;Lee, Jae-Wook
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.137-142
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    • 2012
  • The convergent synthetic strategy for the emissive dendrimers having the chromophore at core via the coppercatalyzed 1,3-dipolar cycloaddition reaction between alkyne and azide was described. 2,7-Diazido-9,9-dioctyl-9H-fluorene, designed to serve as the core in dendrimer, was stitched with the alkyne-functionalized Frechettype and PAMAM dendrons by the click chemistry leading to the formation of the corresponding fluorescent dendrimers in high yields. The preliminary photoluminescence studies indicated that 2,7-diazido-9,9-dioctyl-9H-fluorene showed no fluorescence due to the quenching effect from the electron-rich ${\alpha}$-nitrogen of the azido group but the dendrimers fluoresced due to the elimination of the quenching through the formation of the triazole ring.

Importance of The Location of The Negative-charged Counter-ion against The Protonated Schiff Base on The Chromophore Configuration of pharaonis Phoborhodopsin

  • Shimono, Kazumi;Ikeura, Yukako;Sudo, Yuki;Iwamoto, Masayuki;Kamo, Naoki
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.302-304
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    • 2002
  • pharaonis phoborhodopsin (ppR), a photophobic sensor of haloalkaliphilic bacteria, Natronobacterium phar-aonis, has retinal as a chromophore covalently bound to Lys in G-helix via a protonated Schiff base (PSB), as is the same as bacteriorhodopsin (bR). For ppR, the corresponding counter-ion is Asp residue (Asp75) located in C-helix. Here we investigated the influence of the protonated state of this counter-ion and its location on the chromophore configuration. Under alkaline condition, the chromophore configuration of D75E mutant was analyzed by HPLC. D75E had a much larger content of 13-cis isomer: the ratio of 13-cis to all-trans was 6:4 while the wild-type had this ratio of 1 :9. On the other hand, under acidic condition where Glu was associated, D75E had no 13-cis retinal isomer. Mutants whose Asp75 was replaced by neutral amino acids (D75N and D75Q) did not contain 13-cis retinal. Furthermore, retinal isomer compositions and the change in the visible ab- sorption spectra (indicating the dissociation state of Glu75) were measured under varying pH, and these were almost the same dependencies. These results indicate that an important factor determining the 13-cis isomer content is the presence of negative charge of the counter-ion against PSB, but not the size of this residue. Com- parison between the wild-type and D75E in alkaline solutions indicates the influence of the location of the counter-ion.

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Introduction of Chromophores on the Activated Surface of Poly(2-trialkylstannylthioethyl acrylate) Films (Poly(2-trialkylstannylthioethyl acrylate) 필름의 표면 활성화를 통한 발색단 도입)

  • Yun, Jong Chul;Do, Jung Yun
    • Polymer(Korea)
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    • v.36 no.6
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    • pp.795-802
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    • 2012
  • Surface modification of a hydrophobic acrylic polymer film has been performed through simple chemical treatment to give a reactive surface. 2-Triphenylstannylthioethyl acrylate was polymerized under UV-illumination with various contents of a comonomer. When the polymer film was treated with fluoride ion, thiol functional group (SH) was generated on the film surface, which was observed through infrared absorption spectroscopy. The surface was functionalized by thiol addition reaction to acrylic chromophores. The SH content on the surface was controlled with a comonomer, tris(hydroxymethyl)ethane triacrylate, and examined with UV-Vis absorbance of the chromophore attached film. Similarly, a polymer film from 2-tributylstannylthioethyl acrylate was prepared. Destannylation from the triphenylstannyl and tributylstannyl surface completed after 30 and 5 min, respectively. The SH-exposed surface was modified with an isocyanate attached chromophore within 10 min, while acrylic chromophore required 24 h.

Highly Efficient and Stable Organic Photo-Sensitizers based on Triphenylamine with Multi-anchoring Chromophore for Dye-sensitized Solar Cells (트리페닐아민을 이용한 염료감응형 태양전지 고효율 염료합성)

  • Yang, Hyunsik;Jung, Daeyoung;Jung, Miran;Kim, Jaehong
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.88.1-88.1
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    • 2010
  • Organic dyes, because of their many advantages, such as high molar extinction coefficients, convenience of customized molecular design for desired photophysical and photochemical properties, inexpensiveness with no transition metals contained, and environment-friendliness, are suitable as photosensitizers for the Dye-sensitized Solar Cell (DSSC). The efficiency of DSSC based on metal-free organic dyes is known to be much lower than that of Ru dyes generally, but a high solar energy-to-electricity conversion efficiency of up to 8% in full sunlight has been achieved by Ito et al. using an indoline dye. This result suggests that smartly designed and synthesized metal-free organic dyes are also highly competitive candidates for photosensitizers of DSSCs with their advantages mentioned above. Recently, the performance of DSSC based on metal-free organic dyes has been remarkably improved by several groups. We had reported the novel organic dye with double electron acceptor chromophore, which was a new strategy to design an efficient photosensitizer for DSSC. To verify the strategy, we synthesized organic dyes whose geometries, electronic structures and optical properties were derived from preceding density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. In this paper, we successfully synthesized the chromophore containing multi-acceptor push-pull system from triphenylamine with thiophene moieties as a bridge unit. Organic dyes with a single electron acceptor and double acceptor system were also synthesized for comparison purposes. The photovoltaic performances of these dyes were compared, and the recombination dark current curves and the incident photon-to-current (IPCE) efficiencies were also measured in order to characterize the effects of the multi-anchoring groups on the open-circuit voltage and the short-circuit current. In order to match specifications required for practical applications to be implemented outdoors, light soaking and thermal stability tests of these DSSCs, performed under $100mWcm^{-2}$ and $60^{\circ}C$ for 1000h.

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