2003 Fiscal Year Annual Research Report

様々な配向を有する金属含有非天然型ペプチドの合成

Research Project

Project/Area Number	14740363
Research Institution	Osaka University
Principal Investigator	岡村高明大阪大学, 大学院・理学研究科, 助手 (90252569)
Keywords	非天然型アミノ酸 / 非天然型ペプチド / アミド / コバルトセニウム / ビピリジン / アミノ安息香酸 / L-アミノ酸
Research Abstract	コバルトセニウム骨格を有するアミノ酸[(NH_2C_5H_4)Co(C_5H_4COOH)](PF_6)の単独重合を試みたところアミドが互いに結合した環状2量体が生成することが明らかとなった。ESI-MSの結果から、わずかに3量体の生成を確認したに止まり高分子化は困難であることが明らかとなった。コバルトセニウム型アミノ酸誘導体の溶液中、固体中での分子内、分子間水素結合形成、アニオンとの相互作用についても昨年に引き続きさらに検討した。類似化合物である[Co(C_5H_4NHCOCH_3)_2]Cl-H_2Oの結晶構造では2つのアミド平面は本来安定であるはずの逆平行ではなく、2つのNHが同じ方向を向き分子内でNH…Cl…H_2O…HN水素結合を形成していることが明らかとなった。一方、金属を配位できるビピリジン骨格を有する非天然型アミノ酸や、その類似体パラアミノ安息香酸と天然のL-アミノ酸を逐次交互共重合し2次構造の形成について検討した。パラアミノ安息香酸とL-ロイシンを縮合反応させ、Boc-Leu-NHC_6H_4COOEt (Boc=t-butoxycarbonyl)を得た。これを通常のペプチド合成の手法により脱保護と逐次縮合重合しBoc-(Leu-NHC_6H_4CO)_n-OEt (n=1,2,4,6)を得た。TFE(2,2,2-trifluoroethanol)とDMSO中で可視紫外吸収スペクトルを測定したところ、270-280nm付近にπ-π^*またはCT遷移と考えられる強い吸収が観測され、鎖長の伸長に伴いわずかに長波長側にシフトして観測された。強度はモノマーユニット当たりに換算するとほぼ同一であった。同様の条件でCDスペクトルを測定すると、この領域に強いコットン効果が観測され、モノマーユニット当たりの強度はnが1,2,4と増加するに伴い大きくなった。n=6ではn=4と同等または小さくなった。以上の結果は光学活性なL-ロイシンのα-炭素の不斉が分子全体の2次構造に不斉をもたらしたことを意味する。また、n=4で極大となったことから、4量体を基本単位とするようなヘリックス構造を形成していることを示している。

Research Products

(23 results)

All Other

All Publications (23 results)

[Publications] K.Takahashi, M.Doi, A.Kobayashi, T.Taguchi, A.Onoda, T.Okamura, H.Yamamoto, N.Ueyama: "Formation of 6-,7- or 8-membered ring intra-side-chain NHO hydrogen bond toward Ca-binding oxyanion in Poly(allylaminocarboxylate) ligands stabilizes CaCO_3vaterite crystals"J.Cryst.Growth. 263・1-4. 552-563 (2004)
[Publications] K.Takahashi, M.Doi, A.Kobayashi, T.Taguchi, A.Onoda, T.Okamura, H.Yamamoto, N.Ueyama: "Direct Observation of Polymer-Binding Site on Calcite Crystal by FE/SEM : Regulation of Binding Abilities by a Rotation of Amide Group in Poly(carboxylate) to CaCO_3 Crystals"Chem.Lett.. 33・2. 192-193 (2004)
[Publications] K.Takahashi, T.Okamura, H.Yamamoto, N.Ueyama: "5-(tert-Butylamino)-5-oxopentanoic acid"Acta Cryst.. E60. o19-o21 (2004)
[Publications] X.-M.Ouyang, Z.-W.Li, T.-a.Okamura, Y.-Z.Li, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Construction of metal-organic frameworks through coordination and hydrogen bonding interactions : Syntheses, structures and photoluminescent properties of metal complexes with macrocyclic ligand"J.Solid State Chem.. 177・1. 350-360 (2004)
[Publications] H.-F.Zhu, L.Li, T.Okamura, W.Zhao, W.-Y.Sun, N.Ueyama: "Syntheses, Structures and Photoluminescence Properties of Ag(I),Cu(II),Zn(II) and Mn(II) Complexes with N,N'Bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine"Bull.Chem.Soc.Jpn. 76・4. 761-767 (2003)
[Publications] H.-F.Zhu, W.-Y.Sun, T.Okamura, N.Ueyama: "Hydrothermal synthesis and structural characterization of one-dimensional coordination polymers of cobalt(II) and nickel(II) with 1,3,5-benzenetriacetic acid"Inorg.Chem.Commun.. 6・2. 168-173 (2003)
[Publications] W.Zhao, H.F.Zhu, T.A.Okamura, W.Y.Sun, N.Ueyama: "Synthesis and crystal structure of blue luminescent cadmium(II) coordination networks with 4,4 '-bis(imidazol-1-ylmethyl)biphenyl from different solvent systems"Supramol.Chem.. 15・5. 345-352 (2003)
[Publications] Y.Wang, X.-M.Ouyang, T.-a.Okamura, W.-Y.Sun, N.Ueyama: "Syntheses and structures of two photofluorescent infinite one-dimensional chains from assembly of tetradentate dipyridyl ligand with cadmium(II) and silver(I) salts"Inorg.Chim.Acta. 353. 68-74 (2003)
[Publications] S.-Y.Wan, Y.-Z.Li, T.Okamura, J.Fan, W.-Y.Sun, N.Ueyama: "Syntheses, Structures, and Properties of Two-Dimensional Honeycomb Networks from the Assembly of the Tripodal Ligand 2,4,6-Tris[4-(imidazol-1-ylmethyl)phenyl]-1,3,5-triazine with Metal Salts"Eur.J.Inorg.Chem.. 20. 3783-3789 (2003)
[Publications] N.Ueyama, K.Takahashi, A.Onoda, T.Okamura, H.Yamamoto: "Conformational switching between carboxylic acid and carboxylate anion states by NH center dot center dot center dot O hydrogen bonding"Macromol.Symp.. 204. 287-294 (2003)
[Publications] S.Takamizawa, E.-i.Nakata, T.Saito, T.-a.Okamura, N.Ueyama: "Microporous solid based solely upon an intermolecular NH … O and NH … Cl hydrogen bond network"Inorg.Chem.Commun.. 6・9. 1239-1242 (2003)
[Publications] K.Takahashi, T.Okamura, H.Yamamoto, N.Ueyama: "A 1:1 diastereoisomeric complex of trans-2-{[(R)-(+)-1-phenylethylamino]-carbonyl}-cyclohexanecarboxylic acid"Acta Cryst.. E59. o1953-o1955 (2003)
[Publications] X.-M.Ouyang, D.-J.Liu, T.Okamura, H.-W.Bu, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Syntheses, structures and photoluminescent properties of cadmium(II),silver(I)and copper(I) complexes with novel long chain tetradentate ligands"Dalton Trans.. 9. 1836-1845 (2003)
[Publications] X.-M.Ouyang, B.-L.Fei, T.Okamura, H.-W.Bu, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Synthesis, Crystal Structures, and Properties of Four Two-Dimensional Network Complexes with Multidentate Bis(Schiff Base) Ligands"Eur.J.Inorg.Chem.. 4. 618-627 (2003)
[Publications] A.Onoda, T.Okamura, H.Yamamoto, N.Ueyama: "2,6-Bis(triphenylacetylamino)phenol"Acta Cryst.. E59. o1202-o1204 (2003)
[Publications] A.Onoda, K.Kawakita, T.Okamura, H.Yamamoto, N.Ueyama: "A distorted square-planar Pd^<II> complex with a shortened Pd-Cl bond induced by the bulky terpyridyl ligand 6,6"-dimesityl-2,2':6',2"-terpyridine"Acta Cryst.. E59. m291-m293 (2003)
[Publications] A.Onoda, K.Kawakita, T.Okamura, H.Yamamoto, N.Ueyama: "(Acetonitrile)(6,6"-dimesityl-2,2':6'2"-terpyridine)copper(I) hexafluorophosphate"Acta Cryst.. E59. m266-m267 (2003)
[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Three-dimensional photoluminescent pillared metal-organic framework with 4.82 topological channels obtained from the assembly of cadmium(II) acetate and trimellitic salts"New J.Chem.. 27・10. 1409-1411 (2003)
[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Discrete and Infinite Cage-Like Frameworks with Inclusion of Anionic and Neutral Dpecies and with Interpenetration Phenomena"Chem.Eur.J. 9・19. 4724-4731 (2003)
[Publications] J.Fan, M.-H.Shu, T.Okamura, Y.-Z.Li, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Solvent effect on the structure and topology of metal-orgainc frameworks with the rigid tripodal star ligand 1,3,5-tris(1-imidazoyl)banzene and lead(II) nitrate"New J.Chem.. 27・9. 1307-1309 (2003)
[Publications] J.Fan, W.Y.Sun, T.Okamura, W.X.Tang, N.Ueyama: "Novel metal-organic frameworks with specific topology from new tripodal ligands:1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzen"Inorg.Chem.. 42・10. 3168-3175 (2003)
[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Novel One-Dimensional Tubelike and Two-Dimensional Polycatenated Metal-Organic Frameworks"Inorg.Chem.. 42・1. 158-162 (2003)
[Publications] T.Okamura, N.Ueyama: "Comprehensive Coordination Chemistry II (全10巻の中、第4巻4.8 Tungstenの章を執筆)(Ed.by J.A.McCleverty and T.J.Meyer)"Elsevier Ltd.. 866(529-573) (2004)

2003 Fiscal Year Annual Research Report

様々な配向を有する金属含有非天然型ペプチドの合成

Principal Investigator

岡村 高明 大阪大学, 大学院・理学研究科, 助手 (90252569)

Research Products

[Publications] K.Takahashi, T.Okamura, H.Yamamoto, N.Ueyama: "5-(tert-Butylamino)-5-oxopentanoic acid"Acta Cryst.. E60. o19-o21 (2004)

[Publications] H.-F.Zhu, L.Li, T.Okamura, W.Zhao, W.-Y.Sun, N.Ueyama: "Syntheses, Structures and Photoluminescence Properties of Ag(I),Cu(II),Zn(II) and Mn(II) Complexes with N,N'Bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine"Bull.Chem.Soc.Jpn. 76・4. 761-767 (2003)

[Publications] H.-F.Zhu, W.-Y.Sun, T.Okamura, N.Ueyama: "Hydrothermal synthesis and structural characterization of one-dimensional coordination polymers of cobalt(II) and nickel(II) with 1,3,5-benzenetriacetic acid"Inorg.Chem.Commun.. 6・2. 168-173 (2003)

[Publications] W.Zhao, H.F.Zhu, T.A.Okamura, W.Y.Sun, N.Ueyama: "Synthesis and crystal structure of blue luminescent cadmium(II) coordination networks with 4,4 '-bis(imidazol-1-ylmethyl)biphenyl from different solvent systems"Supramol.Chem.. 15・5. 345-352 (2003)

[Publications] Y.Wang, X.-M.Ouyang, T.-a.Okamura, W.-Y.Sun, N.Ueyama: "Syntheses and structures of two photofluorescent infinite one-dimensional chains from assembly of tetradentate dipyridyl ligand with cadmium(II) and silver(I) salts"Inorg.Chim.Acta. 353. 68-74 (2003)

[Publications] N.Ueyama, K.Takahashi, A.Onoda, T.Okamura, H.Yamamoto: "Conformational switching between carboxylic acid and carboxylate anion states by NH center dot center dot center dot O hydrogen bonding"Macromol.Symp.. 204. 287-294 (2003)

[Publications] S.Takamizawa, E.-i.Nakata, T.Saito, T.-a.Okamura, N.Ueyama: "Microporous solid based solely upon an intermolecular NH … O and NH … Cl hydrogen bond network"Inorg.Chem.Commun.. 6・9. 1239-1242 (2003)

[Publications] K.Takahashi, T.Okamura, H.Yamamoto, N.Ueyama: "A 1:1 diastereoisomeric complex of trans-2-{[(R)-(+)-1-phenylethylamino]-carbonyl}-cyclohexanecarboxylic acid"Acta Cryst.. E59. o1953-o1955 (2003)

[Publications] X.-M.Ouyang, D.-J.Liu, T.Okamura, H.-W.Bu, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Syntheses, structures and photoluminescent properties of cadmium(II),silver(I)and copper(I) complexes with novel long chain tetradentate ligands"Dalton Trans.. 9. 1836-1845 (2003)

[Publications] X.-M.Ouyang, B.-L.Fei, T.Okamura, H.-W.Bu, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Synthesis, Crystal Structures, and Properties of Four Two-Dimensional Network Complexes with Multidentate Bis(Schiff Base) Ligands"Eur.J.Inorg.Chem.. 4. 618-627 (2003)

[Publications] A.Onoda, T.Okamura, H.Yamamoto, N.Ueyama: "2,6-Bis(triphenylacetylamino)phenol"Acta Cryst.. E59. o1202-o1204 (2003)

[Publications] A.Onoda, K.Kawakita, T.Okamura, H.Yamamoto, N.Ueyama: "A distorted square-planar Pd^<II> complex with a shortened Pd-Cl bond induced by the bulky terpyridyl ligand 6,6"-dimesityl-2,2':6',2"-terpyridine"Acta Cryst.. E59. m291-m293 (2003)

[Publications] A.Onoda, K.Kawakita, T.Okamura, H.Yamamoto, N.Ueyama: "(Acetonitrile)(6,6"-dimesityl-2,2':6'2"-terpyridine)copper(I) hexafluorophosphate"Acta Cryst.. E59. m266-m267 (2003)

[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Three-dimensional photoluminescent pillared metal-organic framework with 4.82 topological channels obtained from the assembly of cadmium(II) acetate and trimellitic salts"New J.Chem.. 27・10. 1409-1411 (2003)

[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Discrete and Infinite Cage-Like Frameworks with Inclusion of Anionic and Neutral Dpecies and with Interpenetration Phenomena"Chem.Eur.J. 9・19. 4724-4731 (2003)

[Publications] J.Fan, M.-H.Shu, T.Okamura, Y.-Z.Li, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Solvent effect on the structure and topology of metal-orgainc frameworks with the rigid tripodal star ligand 1,3,5-tris(1-imidazoyl)banzene and lead(II) nitrate"New J.Chem.. 27・9. 1307-1309 (2003)

[Publications] J.Fan, W.Y.Sun, T.Okamura, W.X.Tang, N.Ueyama: "Novel metal-organic frameworks with specific topology from new tripodal ligands:1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzen"Inorg.Chem.. 42・10. 3168-3175 (2003)

[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Novel One-Dimensional Tubelike and Two-Dimensional Polycatenated Metal-Organic Frameworks"Inorg.Chem.. 42・1. 158-162 (2003)

[Publications] T.Okamura, N.Ueyama: "Comprehensive Coordination Chemistry II (全10巻の中、第4巻4.8 Tungstenの章を執筆)(Ed.by J.A.McCleverty and T.J.Meyer)"Elsevier Ltd.. 866(529-573) (2004)

岡村高明大阪大学, 大学院・理学研究科, 助手 (90252569)