Asymmetric Polymerization of (S)-N-Maleoyl-L-Leucine Allyl Ester and Chiral Recognition Ability of Its Polymer as Chiral Stationary Phase for HPLC

Gao, Huajing; Isobe, Yukio; Onimura, Kenjiro; Oishi, Tsutomu

doi:10.1295/polymj.pj2006231

Cited by 17 publications

(15 citation statements)

References 39 publications

(29 reference statements)

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“…[1][2][3] There are many achiral molecules reported to show chirality induced by certain chiral templates, [4][5][6][7] in which the chirality of achiral molecules can be induced through the interactions of achiral molecules with the chiral templates and the chirality of achiral molecules usually follows the chirality of the templates.…”

mentioning

confidence: 99%

Induced Circular Dichroism of Anionic Porphyrin TPPS Aggregates in DNA Solutions

Liao

Liu

et al. 2009

Polym. J.

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Induced circular dichroism (CD) of achiral anionic tetrakis (4-sulfonatophenyl) porphine (TPPS) in polyanionic DNA solutions was investigated. Induced CD signals of the anionic TPPS aggregates in both cholesteric liquid crystal DNA solutions and isotropic DNA solutions are all observed within an appropriate pH range. When the pH value is less than 5, the induced CD signals of TPPS are split in the isotropic DNA solutions, which should result from the helical arrangement of TPPS molecules within the TPPS aggregates with L-or D-type helix. The induced CD signals without splitting of TPPS aggregates in the cholesteric liquid crystal DNA solutions should result from the helical arrangement of the aggregates like molecule screwing along the cholesteric helix axis. When the pH value is higher than 5.2, no induced CD can be observed in the isotropic solutions and the cholesteric liquid crystal DNA solutions, because the electrostatic repulsion force between the non-protonated TPPS molecules and the bases on DNA chains prevents the chiral induction. The mechanism of the different induced CD signals of TPPS aggregates in the DNA solutions is discussed.KEY WORDS: Porphyrin / DNA / Chirality / Induced chirality from achiral components is an attractive field in recent years.1-3 There are many achiral molecules reported to show chirality induced by certain chiral templates, [4][5][6][7] in which the chirality of achiral molecules can be induced through the interactions of achiral molecules with the chiral templates and the chirality of achiral molecules usually follows the chirality of the templates.In cholesteric liquid crystals, the local orientation direction of the molecules is perpendicular to the helix axis and is regularly rotated with a constant twist angle. Therefore, the cholesteric liquid crystal structure is believed to be a good chiral template, which can precisely control the molecular orientation through intermolecular interactions. Many achiral dye molecules can be arranged helically in the cholesteric liquid crystals and show induced CD signals, [8][9][10][11][12][13][14] that is liquid crystal induced CD.DNA is a chiral molecule, which is used as a chiral template to induce many achiral dyes to show induced CD signals. [15][16][17][18][19][20][21] DNA aqueous solution can form cholesteric liquid crystal structure when the concentration is higher than the critical value 22 and can induce the chirality of achiral dye molecules, such as Ethidium bromide, Bisbenzimide, etc. 23Tetrakis(4-sulfonatophenyl) porphine (TPPS) is a achiral dye. It can form stable J-aggregate or H-aggregate, which depends on the pH value and ionic strength in the system. TPPS aggregates can be easily induced to show chirality by many cationic chiral and achiral templates, such as L-(or D-) Trp film, 24 gemini-Type Amphiphiles, 25 polylutamic acid 26 and polylysine, 27 chitosan, 28 etc. Usually, these templates are just cationic, which can be directly interacted with the anionic TPPS. However, there are few reports about induced chiralit...

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confidence: 99%

Induced Circular Dichroism of Anionic Porphyrin TPPS Aggregates in DNA Solutions

Liao

Liu

et al. 2009

Polym. J.

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“…Very recently, we have published the asymmetric polymerizations of (S)-N-maleoyl-L-leucine propargyl ester 37,38 and (S)-N-maleoyl-L-leucine allyl ester, 39 both of which having an unsaturated reactive group in the side ester group of RMI. The optical resolutions of the chemically bonded-type chiral stationary phases (CSPs) using their polymers were also discussed.…”

Section: Chiral (S)-n-maleoyl-l-valine Methyl Ester ((S)-mvmi)mentioning

confidence: 99%

Asymmetric Polymerizations of N-Substituted Maleimides Bearing L-Leucine Ester Derivatives and Chiral Recognition Abilities of Their Polymers

Oishi

Gao

Nakamura

et al. 2007

Polym J

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ABSTRACT:Two kinds of N-substituted maleimides bearing L-leucine ester derivatives ((S)-RLMI), i.e. (S)-Nmaleoyl-L-leucine methyl ester ((S)-MLMI) and (S)-N-maleoyl-L-leucine benzyl ester ((S)-BnLMI), were synthesized from maleic anhydride, L-leucine, and corresponding alcohols. Asymmetric polymerizations were carried out to obtain optically active polymers. Specific rotations of the poly (RLMI)s were influenced by N-substituents, initiators, solvents and temperature. Chiroptical properties and structures of the poly((S)-RLMI)s obtained were investigated by GPC, CD, and NMR measurements. Optical activities of the poly((S)-RLMI)s obtained with anionic polymerization were attributed to excessive chiral centers of the main chain induced through the polymerizations in addition to the chirality of the N-substituents. The chiral stationary phases (CSPs) for high performance liquid chromatography (HPLC) were prepared and the chiral recognition abilities of the optically active poly((S)-RLMI)s were also discussed.

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“…5 Synthetic helical polymers are used in a variety of applications, including the separation of racemic compounds, the production of chemical and biological sensors and the catalysis of asymmetric syntheses. [6][7][8][9] In recent years, a variety of synthetic helical polymers have been synthesized, including poly(acetylene)s, 10 poly(m-phenylene)s, 11 poly(isocyanide)s 12 and poly(N-propargylalkylamide)s. 13 These polymers stabilize their conformations by steric repulsion and intramolecular hydrogen bonding among side-chain groups. In particular, poly(phenylene-ethynylene)s (PPEs) have attracted attention because of their easy synthesis via the Sonogashira-Hagihara coupling reaction.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of optically active poly(phenylene-ethynylene)s containing chiral oxazoline derivatives

Rattanatraicharoen

Yamabuki

Oishi

et al. 2011

Polym J

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Novel optically active (S)-2-(3,5-diiodophenyl)oxazoline derivatives ((S)-DIPhROx)) (R¼4-benzyl (1a), 4-phenyl (1b)) were synthesized and polymerized using the Sonogashira-Hagihara coupling reaction to obtain the poly(phenylene-ethynylene)s bearing oxazoline derivatives in the weight range from 1060 to 17 300 in 40-72% yields. The polymers were thermally stable up to 220 1C. All the polymers exhibited higher specific rotation values than the model compound did. Moreover, these polymers also showed intense circular dichroism (CD) signals in the transition region of the conjugated main chain, whereas almost no induced Cotton effect was observed for the model compound. The results of the specific rotation and CD and ultraviolet analyses indicate that the optical activities of the polymers arise not only from the configurational chirality of the optically active oxazoline pendant groups but also from elements of higher-order structure such as the helical conformation.

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Asymmetric Polymerization of (S)-N-Maleoyl-L-Leucine Allyl Ester and Chiral Recognition Ability of Its Polymer as Chiral Stationary Phase for HPLC

Cited by 17 publications

References 39 publications

Induced Circular Dichroism of Anionic Porphyrin TPPS Aggregates in DNA Solutions

Induced Circular Dichroism of Anionic Porphyrin TPPS Aggregates in DNA Solutions

Asymmetric Polymerizations of N-Substituted Maleimides Bearing L-Leucine Ester Derivatives and Chiral Recognition Abilities of Their Polymers

Synthesis and characterization of optically active poly(phenylene-ethynylene)s containing chiral oxazoline derivatives

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