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2021-06-18T13:39:04+09:00
2021-06-18T13:39:04+09:00
2021-06-18T13:39:04+09:00
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Ritsumeikan Univ.KO-361
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1 g
10 36 574.5 780 re
f
BT
0 g
/TT0 1 Tf
14.25 0 0 14.25 42.907 788.25 Tm
(Synthesis of Bacteriochlorins by Modifying Natural Chlorophylls and Thei\
r Optical)Tj
7.643 -1.211 Td
(Properties in Monomeric and Oligomeric States)Tj
/TT1 1 Tf
12 0 0 12 483.6836 742.5 Tm
(Michio Kunieda)Tj
-36.599 -2.313 Td
(Bacteriochlorin, one of cyclic tetrapyrrole derivatives, is utilized in \
natural photosynthesis as photoactive)Tj
-1 -1.5 Td
(pigments. Since a bacteriochlorin )Tj
/C2_0 1 Tf
13.635 0 Td
<028C>Tj
/TT1 1 Tf
(-conjugate system is a double reduced porphyrin derivative, it is sensit\
ive)Tj
-13.635 -1.5 Td
(to be oxidized and decomposed even under ambient conditions.)Tj
1 -2.5 Td
(In chapter 2, I synthesized stable bacteriochlorin derivatives by use of\
Diels-Alder reactions of 8-vinyl-)Tj
-1 -1.5 Td
(chlorins with tetracyanoethylene. Such synthetic bacteriochlorins posses\
sing the 8-alkylidene group)Tj
0 -1.5 TD
(resembled with natural bacteriochlorophyll\(BChl\))Tj
/TT2 1 Tf
20.022 0 Td
(s-b/g )Tj
/TT1 1 Tf
(possessing the 8-ethylidene group and were)Tj
-20.022 -1.5 Td
(chemically more stable than the natural pigments due to no hydrogen atom\
s at the 7,8-positions. Furthermore)Tj
T*
(a series of 3-substituted bacteriochlorins were available. The electroni\
c absorption properties of 3-substituted)Tj
T*
(bacteriochlorins showed that their Qy maxima were controlled by the 3-su\
bstituents to be red-shifted in the)Tj
T*
(order of ethyl, hydroxyethyl, vinyl, acetyl and formyl group, which was \
consistent with that in 3-substituted)Tj
T*
(chlorins.)Tj
1 -2.5 Td
(In chapters 3 and 4, I investigated oligomeric properties of synthetic b\
acteriochlorin molecules.)Tj
-1 -1.5 Td
(Bacteriochlorins are generally utilized in purple bacterial light-harves\
ting antenna system \(LH1\) by assistance)Tj
T*
(of protein scaffold to make exciton coupling among the molecules, wherea\
s chlorins in green bacterial)Tj
T*
(antenna make exciton coupling only by their self-aggregation. In chapter\
3, I synthesized self-aggregative)Tj
0 -1.562 TD
(magnesium 3-\(1-hydroxyethyl\)-bacteriochlorin and separated its 3)Tj
8.25 0 0 8.25 351.3965 421.5 Tm
(1)Tj
12 0 0 12 355.5215 420 Tm
(-epimers. Their self-aggregation was)Tj
-26.918 -1.562 Td
(strongly dependent on the 3)Tj
8.25 0 0 8.25 165.8066 402.75 Tm
(1)Tj
12 0 0 12 169.9316 401.25 Tm
(-stereochemistry; red-shift value by self-aggregation of the 3)Tj
8.25 0 0 8.25 461.4941 402.75 Tm
(1)Tj
/TT2 1 Tf
12 0 0 12 465.6191 401.25 Tm
(R)Tj
/TT1 1 Tf
( -epimer was 2170)Tj
-36.093 -1.562 Td
(cm)Tj
8.25 0 0 8.25 47.1602 384 Tm
(-1)Tj
12 0 0 12 54.0325 382.5 Tm
( while that of 3)Tj
8.25 0 0 8.25 126.6829 384 Tm
(1)Tj
/TT2 1 Tf
12 0 0 12 130.8079 382.5 Tm
(S)Tj
/TT1 1 Tf
( -epimer was 1280 cm)Tj
8.25 0 0 8.25 243.4426 384 Tm
(-1)Tj
12 0 0 12 250.3149 382.5 Tm
(. Especially, self-aggregation of the 3)Tj
8.25 0 0 8.25 429.9165 384 Tm
(1)Tj
/TT2 1 Tf
12 0 0 12 434.0415 382.5 Tm
(R)Tj
/TT1 1 Tf
( -epimer showed similar)Tj
-33.462 -1.5 Td
(electronic absorption property with LH1.)Tj
1 -2.5 Td
(In chapter 4, I synthesized chemically stable self-aggregative 7- or 8-o\
xo-bacteriochlorins. As compared)Tj
-1 -1.5 Td
(with the above self-aggregative bacteriochlorins modified from natural B\
Chl-)Tj
/TT2 1 Tf
31.045 0 Td
(a)Tj
/TT1 1 Tf
(, the present oxo-)Tj
-31.045 -1.5 Td
(bacteriochlorins were chemically stable because they had no hydrogen ato\
ms at the 7,8-positions. The self-)Tj
0 -1.5 TD
(aggregation behaviors of 7- or 8-oxo-bacteriochlorins were controlled by\
the situation of 8- or 7-dialkyl)Tj
T*
(groups. Molecular modelings of their dodecamers showed that 7-oxo-8-dial\
kyl-bacteriochlorin self-)Tj
T*
(aggregated with less hindered motif than 8-oxo-7-dialkyl-bacteriochlorin\
did.)Tj
ET
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H\j >wI&B`ٰCд$cylOtFk;