ॐਬࢥ৘‫ٸ‬๺֞"ฤ֞ȊǟȑȥǾȄ܎ౖ֞঴ȅȉȂȋǟǴƶ਴ৄ
Creationof

Organic-Inorganic

HybridPhotofunctional

Nanodevices Based on Self-Assembly of Chlorophylls‫ףڽ‬નഒࡣ¸‫֣ؼ‬પԙ໊‫ܞ‬ԙ൉໊ԙҭҠԙǮÓǴ¸‫އ¸ࠆ݋‬ӏ¸ҥҀ¸¸Department of Chemistry, Faculty of Science and Engineering,¸¸Kinki University, Associate Professor, Yoshitaka SAGAཋ൫ǝȑǴȃȤǪȃ¸‫ܑݗ‬໓ƶ܎ǣȈȦǩÓ඄՘ǌ܎ऻඦ໊ࣕǚ݉Ǝౖ֞঴ȅȉ޳໬ƶ਴ৄƷ¹ӚஉƲ࠮੶ҧౖ‫ࡡٸ‬Ӕǚ‫ٺ‬঵ơǓƎƐƯƶ‫ݶ‬ফ֧ƶપƕƲӀભƯƊǓºƥƛƯ෭‫ףڽ‬ƯƷ¹ஔਘƳƒƙǓ๲ǔƧਬࠃƯƊǓ܎‫ݜ‬঵ǚࡹ෭ưƟƧ࠰ফન‫ٸ‬ƶ܎ౖ֞঴ȅȉȂȋǟǴƶ਴ৄǚ๋ࠉơºǪȨȨȐǞȦॐਬáຢ໻ਬâƶ࠺ۡਭॎҠƳǐƫƮ܎ౖ֞঴൉ϳǚܲૼƟ¹ฤ֞൝ࡐáǬǟਬǌǼǺȮâưൖ‫ݜ‬ҠơǓƛưƯ¹ȂȋǟǴưƟƮࡑພҧౖƲౖ֞঴ưϩ୩঴ǚದ‫۔‬ƝƣǓº෭‫ףڽ‬ƶ܎ౖ֞঴ȅȉȂȋǟǴƷ¹࠰ফન‫ٸ‬ƶ‫ܑݗ‬໓ॐਬ੢Օઃຨ஢૴ǌकǣȈȦǩÓ‫܎ٸ‬ऻඦ໊ࣕȅȉȂȋǟǴưƟƮ҃ພơǓºǆƧ‫ݗ‬ƌౖ֞঴ƳҦƐƮ¹ǪȨȨȐǞȦ࠺ۡࢥ‫ݜ‬ઑƶিൟӕ঴½ȥǰǟǪȦҧౖưƌƫƧ໅஝ǚিƓƟƧíգ؈ƳǌƝƟƌîưƌƎപҦҤ૮ǚ๺ơǓȂȋǟǴǚܲૼơǓºAbstract
Photofunctional nanomaterials such as high-performance light-energy conversion
devices and optical computers are important to construct comfortable and sustainable
society. In this study, I construct novel photofunctional nanodevices mimicking
photosynthetic systems that are excellent natural photoactive devices. In the present
nanodevices, photofunctional parts consist of self-assembly of chlorophylls andhybridization with inorganic compounds provides unique functions and stability, which
are appropriate for practical use. The present photofunctional nanodevices will bedeveloped to high-performance dye-sensitized solar cells and energy saving nanoscale
devices for optical computers. In addition to high-performance, the chlorophyll selfassembly will provide a value-added such as green sustainable devices due to theirbiodegradable and recycling properties.

–1–঵֎ՐưƷЂƲǒ¹ǪȨȨǹÓțƳƒ
ƙǓ BChl ƶ࠺ۡਭॎҠƳƷǺȮȌǪࡐƔշຌƣƢ¹ॐਬƶǇƶ੏۶߁ພƯȅȉܲ੧ઑǚ‫ٺ‬঵ƟƮƌǓºƟƧƔƫƮ¹ƥƶܲૼ‫໊ۍ‬ƷೝԔஇ૒࣐ƯƊǒ¹ॶ‫ܞ‬இƳ฾ජƟǌơƌ‫ڈ‬ƯƊǓưƌƐǓºƥƛƯ෭‫ףڽ‬ƯƷ¹ǪȨȨǹÓțǚ฾ජƟƧ BChl ȝȂȦॐਬƶ࠺ۡࢥ৘ઑǚ܎ౖ֞૒ϳưƟ¹ƥƶࢍǒǚǹȦ-ǭȦ඲ƳǐƫƮฤ֞޳໬áǲȨǨǰȮȈǾ
ȃȪÓǪ¾-Si-O-Si-âƯ೦ൗƟƧॠ֩ƲȅȉǦȒǶȦǚଳৄơǓáই 2âºƛǔǆƯǪȨȨǹÓțǚ฾ජƟƧȝȂȦưƟƮ BChl ǌƥƶȝȂȦॐਬǚࠚࡐǌӧ฻ԩ঴‫ޱ‬ƯඤǛƨȚǶȦƔଳৄƝǔƮƕƧƔ¹ƛǔǑƶȚǶȦໞࠃƷഩϩ୩ƯƊǒຜњƓǑࡷǒࢽơƛưƔ‫ݷ‬బƲƧǉ¹ౖ֞঴޳໬ưƟƮƶகӬƷഩҧౖƨƫƧº෭‫ףڽ‬ƶ๺֞-ฤ֞ȊǟȑȥǾȄ‫ٸ‬ȅȉǦȒǶȦƷ¹ƛǔǑƶ๓ભ஝ǚ‫ݣ‬൓ơǓưưǊƳ¹܎‫ݜ‬঵ଵൟࠃǲǴȁțƳ໔‫א‬ƟƧ๺֞-ฤ֞ൖ‫ݜ‬ȅȉ޳໬ưƲǒƐǓºǆƧ¹‫ܑݗ‬໓܎ǣȈȦǩÓ඄՘ȂȋǟǴǌ܎ऻඦ໊ࣕȅȉ

1.¸‫๋ףڽ‬இ܎‫ݜ‬঵Ʒઃຨ܎ǣȈȦǩÓǚܑ໓໴ƗҠԙǣȈȦǩÓƳ඄՘ơǓ๲ǔƧǲǴȁțƯƊǓºƛƶ¹܎ౖ֞঴ൟࠃƔȅȉȜÓȃȦǥÓǻÓƯুธƳ౴૷ƝǔƮƌǓ܎‫ݜ‬঵ଵൟࠃǲǴȁțƶܲૼ‫ۍ‬໊Ʒ¹‫ݗ‬ஶ܎ౖ֞঴ȂȋǟǴǚܲૼơǓƎƐƯ¹໴ƌ০‫ॴࠉڐ‬ǚຌƐƎǓư݂ƐǑǔǓºƥƛƯ෭‫ףڽ‬ƯƷ¹໻ॐ܎‫ݜ‬঵ެ‫ظ‬ƶࢥ܎ǝȮȁȅਭॎƯƊǓíǪȨȨǹÓțîƶॐਬࢥ৘ઑƶଵൟࠃܲ੧ǚ֏೎ưƟƧ¹ॠ֩Ʋ๺֞-ฤ֞ȊǟȑȥǾȄ‫ౖ֞܎ٸ‬঴ȅȉȂȋǟǴǚ਴ৄơǓƛưǚ๋இưƟƧºíǪȨȨǹÓțîƳƒƌƮƷ¹ࢥ܎ॐਬƯƊǓȋǪȁȥǥǪȨȨȐǞȦáBChlâƶ࠺ۡӔ‫ݜ‬ઑƔࠚࡐГൟࠃ෽Ư϶ǆǔƧ¹ȅȉȜÓȃȦǥÓǻÓƶ܎ౖ֞঴ໞࠃƯƊǓáই 1âºઁƶ܎‫ݜ‬‫ޑݛ‬͔ಠ݄ാOߦُBChl‫ߦآݻ‬ङ৒(ɭɃɉࢁɊɎ‫ٳ‬ন)HO CH3R20HOR7N

R20N NMgN N

HO R3R8N
R20R12O
COO-farnesyl

R8N

R7OOOOSiSiRRN

R8M
Nn

R7N

R12COOR17 OnMg
N૕ख़ǻȯɭɭȾĘɠĦ‫ޑݛ‬ാǸȯɭɭɕȣɫЕ‫ڝ‬৒Ǚ೥ȋșǳǑȘħ

NR12മ‫׾‬ԤǴ‫ٳ‬਽ǦȘරӟ+൥ӟಗ‫ֹُڝ‬ӟ஗ࣵɊɎȫɗȻɫ

OOOlong chainnই 2¸෭‫ףڽ‬ƯܲૼơǓॐਬࢥ৘‫ٸ‬

ই 1¸໻ॐ܎‫ݜ‬঵ެ‫ظ‬ƶࢥ܎ǝȮȁ๺֞-ฤ֞ȊǟȑȥǾȄ܎ౖ֞঴ȅȉȅ½ǪȨȨǹÓțƶ฾࠿ই.

ǦȒǶȦƶ฾࠿ই

–2–ȂȋǟǴǀƶகӬǚ๋ࠉƟƧ¹ॐਬࢥ৘‫ٸ‬ȅȉǦȒǶȦƶ֏಻रǀƶࢥ৘Ҡǌ۞୩ҠƳշơǓ‫ףڽ‬ǚ݉ƫƧº2.¸‫ډףڽ‬ӄ¸ǆƢ܎ౖ֞঴൉ϳƶܲ঵঵ൟưƲǓԇࡾǪȨȨȐǞȦ຃௮ઑǚӬದơǓƧ
ǉ¹ൖঝƶ܎‫ݜ‬঵ি൝ƓǑଋࢽƟഁ຤Ƴ҃ƠƮ๺֞ҠԙஇƳӡ඄ơǓƛưƯ੩‫ޒ‬ǌଇढ़‫ؽ‬ੳƔЂƲǓ࠺ۡӔ‫ݜ‬঴ǪȨȨȐǞȦ຃௮ઑǚଳৄƟƧáই 3âºƛǔǑƶଳৄƟƧǪȨȨȐǞȦൟࠃǚǥǪǺȂǲȦȃȥǣȃǨǲǲȤȮ¹ȁȃȤǣȃǨǲǲȤȮư‫੻؁‬Ɲƣ¹ଳৄऽ‫ڨ‬ǚ‫ޚ‬உҠơǓƛưƯ¹๺֞-ฤ֞ൖ‫ٸݜ‬ƶǪȨȨȐǞȦॐਬ࠺ۡӔ‫ݜ‬ઑǚܲૼơǓƛưƳ঵‫ܐ‬ƟƧºҧࠜ‫ࢌט‬¹Ѥమॐ঴¹௫இ܎ߧຽƲƱƶ੯୩‫ڤ‬үƓǑ¹ஔਘƶǪȨȨǹÓțƳ་ࠨƟƧॐਬࢥ৘‫ٸ‬ଵൟࠃƔ‫ٺ‬঵ƟƮƌǓƛư
ƔǗƓƫƧºǆƧ¹ܲૼƟƧॐਬࢥ৘‫ٸ‬ଵൟࠃƷેӔ‫ݜ‬ǚ੨ॳơǓӧ฻ԩ঴‫ޱ‬ǌǪȨȨȐǞȦൟࠃƶଇढ़‫ؽ‬ੳƶે
R3OH

R7R8NR 20

NM

NN
R12O
COO–R17ই 3¸࠺ۡӔ‫ݜ‬঴ǪȨȨȐǞȦ຃௮ઑƶൟࠃܲ੧.¸M=Mg or Zn, R3=H or
CH3, R7=CH3 or CHO, R17=CH3 or
farnesyl, R20=H or CH3.

‫ؽ‬ੳҠǚ੨ॳơǓ߱ƳઓƟƮଙƟƗϩ୩ҠƟƮƌǓƛưƔฯǑƓưƲǒ»ǲȨǨǰȮȈǾȃȪÓǪƶ‫ٺ‬঵Ɣ܎ౖ֞঴൉ϳưƲǓǪȨȨǹÓț‫ٸ‬ॐਬࢥ৘ઑƶϩ୩ҠƳપƕƗ֒ຌơǓƛưƔ࠷ƝǔƧº¸ƊǗƣƮ¹ǪȨȨȐǞȦൟࠃఝƳǲȨǨǰȮȈǾȃȪÓǪǚ‫ٺ‬঵ƟƎǓȃȥǣȃǨǲǲȥȦ֏ǚ๺ơǓ࠺ۡӔ‫ݜ‬঴ψѹǪȨȨȐǞȦ຃௮ઑǚॠ֩Ƴ‫ݜ‬঵Ɵ¹ƥƶ࠺ۡӔ‫װݜ‬௫ǚଳǁƧº¸੶ƌƮ¹ǪȨȨǹÓț‫ٸ‬ॐਬࢥ৘ઑƯඔࢥƟƧ܎ǣȈȦǩÓǚஞૄơǓǲǴȁțǚܲૼơǓƧǉƳ¹ǪȨȨǹÓț‫ٸ‬ॐਬࢥ৘ઑƓǑƶ༐֬ǣȈȦǩÓƶࢄຓઑưƲǒƐǓȋǪȁȥǥǪȨȨȐǞȦ຃௮ઑǚଳৄƟƧºƛǔǚψѹǪȨȨȐǞȦॐਬࢥ৘ઑưưǊƳພƌƧưƛǕ¹ȅȉǦȒǶȦƯƶ༐֬ǣȈȦǩÓЃ௫ǚհ੯ơǓƛưƳ঵‫ܐ‬ƟƧºƥƶǣȈȦǩÓЃ௫ܑ໓Ʒ 33%ư‫ۂ‬৘ǊǑǔ¹ஔਘǪȨȨǹÓțƳೝǁƮୢƌ૮ưƲƫƧº¸ǆƧ¹ଳৄƟƧॐਬࢥ৘‫ౖ֞܎ٸ‬঴ȅȉǦȒǶȦƶ֏಻ǀƶ۞୩Ҡǚ݉ƌ»ԇࡾ‫ۉ‬೰‫؛‬ƯհߒƟƧºǦǼǥȮ঴ȘȥșÓƯƊǓȘȥǝȥȦǝȚȮǚພƌ
Ʈ¹ഒ฻ƔǝȆǥȮ঴ƶॐਬࢥ৘‫ٸ‬ȅȉǦȒǶȦǚ‫ݗ‬ธஶƯ۞୩ҠơǓƛưƳǊ঵‫ܐ‬Ɵ¹ƥƶीઙǌഒ฻ธஶǚ‫ۍ‬ࠃյ໺‫ۉ‬೰‫؛‬ǌ‫؁‬ऒ஝ȧÓǱÓ‫ۉ܎ڏ‬೰‫؛‬Ưհ੯ơǓƛưƳ঵‫ܐ‬ƟƧºǦǼǥȮ঴ȘȥșÓưƟƮȘȥȥǳȮǚພƌƧưƕƷȅȉǦȒǶȦƶ۞୩Ҡ໷ƔࣺƲƗƲǒ¹ǦǼǥȮ঴ȘȥșÓƶਏવƳǐǓȅȉǦȒǶȦƶ֏಻रƯƶഒ฻ธஶƶর‫۽‬ƔҧౖƯƊǓƛưƔ࠷‫މ‬ƝǔƧºǆƧ¹‫܉‬۶৘਽඲ƳǐǓॐਬ–3–ࢥ৘‫ٸ‬ȅȉǦȒǶȦƶ֏಻ǀƶં਽ࢥ৘ҠƳǊ঵‫ܐ‬ƟƧºƝǑƳ¹۞୩Ҡऽ‫ڨ‬ǚ‫ڸ‬௟ơǓƛưƯȅȉǦȒǶȦǚൟߧƝƣƮ۞୩ҠƟ¹‫؁‬ऒ஝ȧÓǱÓ‫ڏ‬܎‫ۉ‬೰‫؛‬ǚພƌƧ૒ГȅȉǦȒǶȦƶҧࠜҠư‫܎ڏ‬ǴȕǪȃȦ੯୩Ƴ঵‫ܐ‬Ɵ
Ƨº3.¸‫ףڽ‬঵ү¸໻ॐ܎‫ݜ‬঵ެ‫ظ‬ƶࢥ܎ǝȮȁȅଵൟࠃ½ǪȨȨǹÓțǚ฾ජƟƧॐਬࢥ৘‫ٸ‬๺֞-ฤ֞ȊǟȑȥǾȄȅȉǦȒǶȦǚܲૼơǓධ඲ཉǚԏ໔Ɵ¹ൟࠃܲ੧ƶЂƲǓǪȨȨȐǞȦॐਬൟࠃǚພƌǓƛưƯൟ܎௾঴ƶЂƲǓȅȉǦȒǶȦǚܲૼƟƧºǆƧ¹ȅȉǦȒǶȦƳƒƙǓǪȨȨǹÓț‫ٸ‬ॐਬࢥ৘ଵൟࠃƯඔࢥƟƧ܎ǣȈȦǩÓƶஞૄǲǴȁțǚܲૼƟƧºƝǑƳ¹ॐਬࢥ৘‫ٸ‬ȅȉǦȒǶȦƶ֏಻रǀƶ۞୩Ҡ½ࢥ৘ҠưҧࠜҠǚ݉ƎƛưƔƯƕƧº4.¸‫ۼݶ‬ƶӀભưದக¸֏ਨஇƲ฻ưƟƮƷ¹෭‫ףڽ‬Ư߁ৄƟƧॐਬӔ‫ݜ‬ઑఝඤȅȉǦȒǶȦǚພƌƧ໻ॐ܎‫ݜ‬঵ެ‫ظ‬ǝȮȁȅƶଵൟࠃܲ੧ưౖ֞ӕฯǚ݉ƎºٌઑஇƳƷ¹ࢫີƶȝȂȦଵൟࠃƳƷஉພƔ‫ݷ‬బƨƫƧ੯୩඲ƳǐǓܲ੧½ౖ֞ӕ৖Ɣ‫װ‬ƚǑǔǓº҃ພஇƲ฻ưƟƮƷ¹‫ܑݗ‬໓܎ǣȈȦǩÓ඄՘ȂȋǟǴܲૼǌȅȉȁǪȉȨǳÓǀƶகӬǚƷƓǓºٌઑஇƳƷ»෭‫ףڽ‬Ư߁ৄƟƧॐਬӔ‫ݜ‬ઑఝඤȅȉǦȒǶȦƶƝǑƲǓ‫ݗ‬ธஶࢥ৘Ҡǌ໷ࠃȄǾȃஇ۞୩ҠǚƝǑƳॳǉƥƶ൝঴ǚӕ৖ơǓƛưƯ¹܎ౖ֞঴ȂȋǟǴǀƶ҃ພǚ๋ࠉơº5.¸ದഒཉ൫ȥǴȃ
Y. Saga, S. Akai, T. Miyatake, H. Tamiaki
Excitation Energy Transfer from SelfAggregates of Zinc Chlorins to a
Bacteriochlorin in a Silicate Nanocapsule
Chemistry Letters 33, 544–545(2004).
Y. Saga, S. Akai, T. Miyatake, H. Tamiaki
Self-Assembly of Natural LightHarvesting Bacteriochlorophylls of Green
Sulfur Photosynthetic Bacteria in Silicate
Capsules as Stable Models ofChlorosomes
Bioconjugate Chemistry 17, 988–994(2006).
Y. Saga, H. Kida, Y. Nishikawa, H. Tamiaki
Chlorosomal Self-Aggregation of Zinc
Chlorophyll Derivatives in the Presenceof Cationic Surfactant Cetyltrimethylammonium Bromide and Organosilanesin Aqueous Phase
The Proceedings of the 14th International
Congress on Photosynthesis, in press.
Y. Saga, H. Tamiaki
Photofunctional Nanodevices Mimicking
Light-Harvesting Complexes of Green
Photosynthetic Bacteria
EncyclopediaofNanoscience
andNanotechnology, in press.
‫އ‬ӏҥҀ܎‫ݜ‬঵ǝȮȁȅƶ૒ГଵൟࠃȧȔȦƯƶӕ৖ –໻ॐ܎‫ݜ‬঵ެ‫ظ‬ƶ෽ӱǝȮȁȅưȝȂȦଵൟࠃҠԙư‫ أܞ‬58, 129–132 (2005).

–4–