• Journal of Photoscience
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• 제9권2호
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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

• Macromolecular Research
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• 제15권1호
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• pp.59-64
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• 2007

Star-shaped, nonlinear optical (NLO) material was synthesized and its optical, thermal, and electro-optic properties were investigated. Three NLO-active dipolar chromophores containing a phenylene ring substituted with a bulky alkyl chain as a conjugation bridge were chemically bonded to the core of 1,1,1-tris(4-hydroxyphenyl)ethane to form a dendritic architecture. The chemical structure and purity of the chromophore were verified by NMR spectroscopy. The chromophore exhibited a broad absorption band centered at around 608 nm tailing up to 760 nm in toluene solution and also showed a discernible solvatochromic shift in more polar solvent. The chloroform solution of the dendrimer produced an absorption band with a red-shifted maximum as large as 28 nm when compared to that of the toluene solution. It was thermally stable up to $275^{\circ}C$ in a nitrogen atmosphere and had a glass transition temperature of $76^{\circ}C$. In a preliminary result, the polymer film containing the dendritic compound exhibited a shift of 19 pm/V taken at $1.55{\mu}$.

• 한국응용과학기술학회지
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• 제21권1호
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• pp.24-30
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• 2004

New electroluminescent materials based on anthracene chromophore with naphthylethenyl substituent, 9,10-bis($\alpha$-naphthylethenyl)anthracene (a-BNA), as well as four kinds of its derivatives were synthesized, and luminescent properties of these materials were investigated. Electrolumineecent(EL) emission band was discussed based on their substituent structure differences. It was found that the emission band strongly depends on the molecular structure of introduced substituent. It can be tuned from 557 nm to 591 nm by changing the substituent structures. On the other hand, the anthracene chromophore with bulky substituent possessed high melting point and they gave stable films through vacuum-sublimation. The double layer EL device of ITO/TPD/emission layer/Mg:Ag was employed, and exhibited efficient orange light originating from emitting materials. EL emission with a maximum luminance was observed in the b-BNA emitting material, : maximum luminance was about 8,060 cd $m^{-2}$ at an applied voltage of 10 V and current density of 680 $mA/cm^2$. In conclusion, the electroluminescent properties also showed good difference with their substituent structure.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.11-12
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• 2006

Incorporation of chromophores into multi-chromophore-containing dendrimers is shown to lead to a significant enhancement in electro-optic activity. These results are reasonably well simulated by pseudo-atomistic Monte Carlo calculations that permit dendrimers to interpenetrate (entangle). Calculations also lead to the correct prediction of material densities. An even greater enhancement in electro-optic activity is observed when such dendrimer materials are doped with a second chromophore. This latter effect may reflect an Ising-lattice-type phenomenon where one chromophore impacts the ordering of the other and vice versa.

• Macromolecular Research
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• 제14권6호
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• pp.603-609
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• 2006

Tricyanopyrrolidene chromophores were prepared in order to compare their macroscopic nonlinear optical (NLO) properties with a conjugated structure through the long molecular axis. A thiophene or phenyl ring was tethered to an ethylenic bond; it may act as a lateral moiety to disrupt the planarity of a chromophore and lessen the electrostatic interaction. Thin film composites of these chromophores dissolved in amorphous polycarbonate (APC) were fabricated. Real time pole and probe method was employed to investigate the change of electro-optic (EO) signal during poling. The EO properties and their relaxation behaviors of the guest-host systems containing newly synthesized chromophores were investigated in detail.

• 대한화학회지
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• 제48권1호
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• pp.107-110
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• 2004

• Journal of Photoscience
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• 제9권2호
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• pp.126-129
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• 2002

The chromophore/protein interactions in the photocycle intermediates of photoactive yel- low protein (PYP) were probed by site-directed mutagenesis. The absorption spectra of L- intermediates produced from E46Q, T50V, and R52Q mutants were calculated using the absorption spectra of dark states and difference absorption spectra between L-intermediates and dark states, and compared with that of PYP$\_$L/. The absorption spectrum of R52Q$\_$L/ agreed with that of PYP$\_$L/, but those of E46Q$\_$L/ and T50V$\_$L/ were red-shifted. The effect of these mutations on the absorption spectrum for L-intermediate was comparable to that for the dark state, suggesting that the interaction around the phe-nolic oxygen of the chromophore is conserved in PYP$\_$L/ unlike the crystal structure. On the other hand, we have reported that the absorption spectra of Y 42F$\_$M/, T50V $\_$M/, and R52Q$\_$M/ agreed with that of PYP$\_$M/, but that of E46Q$\_$M/ was red-shifted, suggesting that the hydrogen bond of the chromophore with Glu46 is conserved but that with Tyr42 is broken in PYP$\_$M/. These results suggest that the chromophore inter-acts with Glu46 throughout the photocycle, but never directly interacts with Arg52. This model con- flicts with some of the structural model of PYP intermediates proposed based on the high-resolution X -ray crystallography.

• Journal of Photoscience
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• 제9권2호
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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.

• 폴리머
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• 제36권6호
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• pp.795-802
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• 2012

소수성 고분자 표면을 화학적 처리를 통해 활성화시키고 화학반응을 통해 발색단을 도입하는 연구를 진행하였다. 2-Triphenylstannylthioethyl acrylate를 자외선 조사시켜 고분자 필름을 만들었다. 필름 표면에 노출된 주석치환체를 불소이온으로 처리하여 SH를 형성함으로써 필름표면에 많은 SH를 생성시켰고 적외석 흡수스펙트럼으로 이를 확인하였다. 아크릴 유도체로 만든 발색단 물질을 노출된 SH와 반응시켜 필름 표면에 여러 발색단을 도입할 수 있었고 이를 자외선-가시광선 흡수스펙트럼으로 관찰할 수 있었다. 2-Triphenylstannylthioethyl acrylate와 tris(hydroxymethyl) ethane에서 유도된 triacrylate를 혼합하여 얻은 광경화 필름에서 단분자 함량 변화에 따른 SH의 표면 노출량을 변화시킬 수 있음을 흡수스펙트럼을 통해 관찰하였다. 유사하게, 2-tributylstannylthioethyl acrylate를 이용한 광경화 필름을 만들어 표면반응 연구를 진행하였다. 이 경우, 불소이온 처리를 통한 표면 활성화는 약 5분 이내로 빠르게 진행되었다. 이소시안 작용기를 갖는 발색단을 합성하여 필름과 반응시켜 표면에 발색단 도입하는 비교연구를 진행하였다. 아크릴 유도체가 표면 SH와 반응이 24시간 이상을 요구하는 반면 이소시안 유도체는 10분 이내에 결합반응이 완료되었다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2010년도 춘계학술대회 초록집
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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.