• Journal of Photoscience
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• 제8권2호
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• pp.75-77
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• 2001

The Grignard reaction of methyl pyropheophorbide-a (MPP-a) was performed to introduce lengthy alkyl chain for improving lipophilicity. After the introduction of alkyl chain to the both of carbonyls, peripheral aldehyde and cyclopentanone, the obtained diol 3 was subjected to dehydration to give monodehydrate product 4 selectively. The Qy band of prepared compounds were affected by the substituents on the Qy axis (N$\sub$21/-N$\sub$23/).

• Journal of Photoscience
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• 제8권1호
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• pp.23-25
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• 2001

The methyl pheophorbide-a (MP-a) and methyl pyropheophorbide-a (MPP-a) were modified by reaction of exocyclic ketone in E-ring with nucleophilic reagent and several chlorin derivatives were synthesized. The change of the structure in E-ring served an expanding conjugation region and introduction of electron-withdrawing group, which strongly influenced the visible spectra. The Qy bands of synthesized compounds were affected by the substituents on the Qy axis(N$\sub$21/-N$\sub$23/).

• Bulletin of the Korean Chemical Society
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• 제34권2호
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• pp.453-459
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• 2013

In phtosynthetic light harvesting complexes, the electronic transition energies of chlorophylls are influenced by the Coulombic interaction with nearby molecules. Variation of the interactions caused by structural inhomogeneity in biological environment results in a distribution of disordered electronic transition energies of chlorophylls. In order to provide a practical guide to predict qualitative tendency of such distribution, we model four porphyrin derivatives including chlorophyll a molecule interacting with an external positive charge and calculate their transition energies using the time dependent density functional method. It is found that ${\pi}-{\pi}^*$ transition energies of the molecules are generally blue-shifted by the charge because this stabilizes occupied molecular orbitals to a greater extent than unoccupied ones. Furthermore, new transitions in the visible region emerge as a result of the red-shift in energy of an unoccupied Mg orbital and it is suggested that light-induced electron transfer may occur from the tetrapyrrole ring to the central magnesium when the molecules are interacting with a positive charge.

• Bulletin of the Korean Chemical Society
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• 제27권7호
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• pp.1083-1085
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• 2006

• 한국광과학회:학술대회논문집
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• 한국광과학회 2001년도 학술대회지
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• pp.25-25
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• 2001

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2465-2468
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• 2011

• Bulletin of the Korean Chemical Society
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• 제32권9호
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• pp.3473-3476
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• 2011

• Journal of Photoscience
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• 제9권2호
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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.

• Bulletin of the Korean Chemical Society
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• 제30권1호
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• pp.205-213
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• 2009

This study reports on the geometry optimizations and electronic structure calculations for methyl pyropheophorbide (MPPa), tropolonyl methyl pyropheophorbides (TMPPa, ITMPPa), and cationic tropolonyl methyl pyropheophorbides ($TMPPa^+{{\cdot}BF_4}^-,\;ITMPPa^+{{\cdot}BF_4}^-,\;TMPPa^+,\;and\;ITMPPa^+$) using Local Spin Density Approximation (LSDA/ 6-31G*) and the Restricted Hatree-Fock (RHF/6-31G*) level theory. From the calculated results, we found that substituted cationic tropolonyl groups have larger structural effects than those of substituted neutral tropolonyl groups. The order of structural change effects is $ITMPPa^+ > ITMPPa^+{{\cdot}BF_4}^-$ > ITMPPa, as a result of the isopropyl group. Because it is an electron-releasing group, the substituted isopropyl group electronic effect on a 3-position tropolone increases the Highest Occupied Molecular Orbital and Lowest Unoccupied Molecular Orbital (HOMO-LUMO) energy gap. It was constituted that the larger the cationic characters of these photosensitizers, the smaller the HOMOLUMO band gaps are. The orbital energies of the cationic systems and the ions are stronger than those of a neutral system because of a strong electrostatic interaction. However, this stabilization of orbital energies are counteracted by the distortion of chlorin macrocycle, which results in a large destabilization of chlorin-based compound HOMOs and smaller destabilization of LUMOs as shown in TMPPa (ITMPPa), $TMPPa^+{{\cdot}BF_4}^- (ITMPPa^+{{\cdot}BF_4}^-),\;and\;TMPPa^+\;(ITMPPa^+)$ of Figure 6 and Table 6-7. These results are in reasonable agreement with normal-coordinate structural decomposition (NSD) results. The HOMO-LUMO gap is an important factor to consider in the development of photodynamic therapy (PDT).

• Journal of Photoscience
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• 제9권2호
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• pp.362-363
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• 2002

Since chlorophyll a and bacteriochlorophyll a are asymmetric molecules, an external ligand can coordinate to the central Mg atom either from the chiorin macrocycle side where the C13$^2$-methoxycarbonyl moiety protrudes (denoting as the 'back' side) or frome the other side (the 'face' side). We investigated which side of the macrocycle is favored for the ligand coordination, by survey of the highly resolved crystal structures of various photosynthetic proteins and theoretical model calculations. It is found that chlorophyll a as well as bacteriochlorophyll a and b in the photosynthetic proteins mostly bind their ligands on the 'back' sides. This finding was confirmed by the theoretical calculations for methyl chlorophyllide a and methyl bacteriochlorophyllide a as models: the 'back' type ligand-(bacterio )chlorophyll complex was more stable than the 'face' type one. The calculations predicted influence of the Cl3$^2$-stereochemistry on the choice of the side of the ligand coordination, which is discussed in relation to the presence of the Cl3$^2$-epimer of chlorophyll a in photosystem I reaction center [I].