• Rapid Communication in Photoscience
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• v.4 no.3
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• pp.59-62
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• 2015

We investigated photo-induced electron transfer (PET) in a dye-labeled peptide, fluorophore-Ala-Gly-Gln-Tyr, employing time-resolved fluorescence. As an effort to develop new functional dyes, we studied an acriflavine derivative for the electron-acceptor in the excited state from tyrosine, an electrondonor in the ground-state. The pH dependence of the fluorescence lifetime of the model peptide indicates that electron transfer between the excited dye and tyrosine occurs when the tyrosine is deprotonated. The proton-coupled electron transfer appears to be sequential rather than concerted. We also report direct time measurements on the end-to-end loop formation processes of the peptide in water.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.25 no.9
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• pp.711-716
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• 2012

Based on both organic synthesis and theoretical calculations on the effects of molecular orbital energy levels of amines on the fluorescence properties of the fluorophore, fluorescent "turn-on" chemosensors detecting hazardous substances, including aldehyde chemicals and $Hg^{2+}$ ion, were developed.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.937-940
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• 2004

• Proceedings of the Korean Vacuum Society Conference
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• 2002.06a
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• pp.38-39
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• 2002

• Rapid Communication in Photoscience
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• v.4 no.2
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• pp.41-44
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• 2015

Biomolecular photo-damaging activity of a water-soluble cationic porphyrin was examined using human serum albumin (HSA), a water-soluble protein as a target biomolecule model by a fluorometry. Dichlorophosphorus(V) tetraphenylporphyrin ($Cl_2P(V)TPP$), was synthesized and used as a photosensitizer. This porphyrin could bind to HSA and cause the photosensitized oxidation of HSA through the singlet oxygen generation and the oxidative photo-induced electron transfer (ET). Near infrared emission spectroscopy demonstrated the photosensitized singlet oxygen generation by this porphyrin. Decrement of the fluorescence lifetime of $Cl_2P(V)TPP$ by HSA supported the ET mechanism. Furthermore, the estimated Gibb's energy indicated that the ET mechanism is possible in the terms of energy. Because oxygen concentration in cancer cell is relatively low, ET mechanism is considered to be advantageous for photosensitizer of photodynamic therapy.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.587-596
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• 2014

A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.272-272
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• 2013

The attractive features of photosynthetic reaction center proteins for energy application make them useful in solar energy conversion to hydrogen fuel or electrical energy. Almost unity charge separation quantum yield and its rapid speed of ~1ns, absorbance region in visible light (480~740 nm) and high proportion of photosynthetically active solar energy of 48.5% allowed photosystem1 to exploited as a bio-material for photo-energy devices. Directionality of photosystem1 in electron transfer can solve main problem in two-step water splitting process where back reaction deteriorates the overall efficiency. In the study, photosystem1 was extracted from spinach and the photo-induced excited electron in the reaction center was utilized in various field of light energy application. First, hydrogen evolving system realized by photodeposition of platinum at the end of the electron transfer chain, with combining specific semiconductor to oxidize water in the first step of Z-scheme. The evaluation by gas-chromatography demonstrated hydrogen evolution through the system. For the further application of photoelectrical material on electrode, photosystem1 have been controlled by copper ion, which is expected to assemble photosystem in specific orientation followed by maximized photoelectrical ability of film. The research proposed concrete methods for combining natural protein and artificial materials in one system and suggested possibility of designing interface between biological and inorganic materials.

• Rapid Communication in Photoscience
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• v.4 no.2
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• pp.37-40
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• 2015

To examine the photosensitized biomolecules damaging activity, dimethoxyP(V)tetrakis(2-naphthyl)porphyrin (NP) and dimethoxyP(V)tetraphenylporphyrin (PP) were synthesized. The naphthyl moiety of NP hardly deactivated the photoexcited P(V)porphyrin ring in ethanol. In aqueous solution, the naphthyl moiety showed the quenching effect on the photoexcited porphyrin ring, possibly through electron transfer and self-quenching by a molecular association. Binding interaction between human serum albumin (HSA), a water soluble protein, and these porphyrins could be confirmed by the absorption spectral change. The apparent association constant of NP was larger than that of PP. It is explained by that more hydrophobic NP can easily bind into the hydrophobic pockets of HSA. The photoexcited PP effectively induced damage of the tryptophan residue of HSA, through electron transfer-mediated oxidation and singlet oxygen generation. NP also induced HSA damage during photo-irradiation and the contributions of the electron transfer and singlet oxygen mechanisms were speculated. The electron transfer-mediated mechanism to the photosensitized protein damage should be advantageous for photodynamic therapy in hypoxic condition. The quantum yield of the HSA photodamage by PP was significantly larger than that of NP. The quenching effect of the naphthyl moiety is considered to suppress the photosensitized protein damage. In conclusion, the naphthalene substitution to the P(V)porphyrins can enhance the binding interaction with hydrophobic biomacromolecules such as protein, however, this substitution may reduce the photodynamic effect of P(V)porphyrin ring in aqueous media.

• Applied Chemistry for Engineering
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• v.20 no.3
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• pp.351-353
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• 2009

Pyrylium fluoroborates undergo a wide range of synthetically useful reactions because of the positive charge. And the electron accepting nature has resulted in their widespread use as sensitizers for photo-induced electron transfer (PET) reactions. In this experiment, 2,6-disubstituted pyrylium fluoroborates are synthesized from the reaction between $3^{\prime}$-chloroacetophenone and excess orthoformate in an acidic medium (acetic anhydride/acid). Synthesized products are confirmed by $^1H-NMR$, FT-IR and TOF Mass spectroscopies. Also, photo-properties are analyzed with an UV-Vis spectrophotometer.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1995.11a
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• pp.281-284
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• 1995

A molecular photodiode was fabricated with hetero-Langmuir-Blodgett (LB) film consisting of an electron accepter(A) and sensitizer. N-Allyl-N-[3-propylamido-N\",N\"-야(n-octadecyl)]-4,4-bipyridum Dibromide and 7,8-dimethyl-10-dodecyl isoalloxan-zine were used as A and S units, respectively. By aligning hefter-LB film of A/S units on ITO glass with an aluminium thin film, a molecular photodiode with the structure of Metal/Insulator/Metal(MIM) was constructed. Due to excitation by irradiation with a 460nm monochromatic light source, the photo-induced unidirectional flow of electrons in the MIM device could be achieved and was detected as photocurrents. The direction of energy flow was in accordance with the energy level profile across the LB films. The photo switching function was achieved and the rectifying characteristics was obserbed in the molecular devise.