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Volumn 131, Issue 13, 2009, Pages 4710-4719

Double helix formation of oligoresorcinols in water: Thermodynamic and kinetic aspects

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC INTERACTIONS; CHAIN EXCHANGE; DOUBLE HELIX; DOUBLE HELIX FORMATION; DOUBLE-STRANDED HELICES; FREE ENERGY CHANGE; H NMR SPECTRA; HYPOCHROMICITY; KINETIC ANALYSIS; KINETIC ASPECTS; NEUTRAL WATER; NEW SERIES; OPTICALLY ACTIVE; VAN'T HOFF ANALYSIS;

EID: 67749143943     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja808585y     Document Type: Article
Times cited : (80)

References (131)
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    • In our previous study (ref 9a, 11merR2 was synthesized via the Suzuki coupling of 1merRBP and 9merBr2. However, the crude product contained side products including the 10mer of which the polarity and the molecular size are quite similar to those of 11merHR2, thus making the purification of 11merR2 using chromatography extremely difficult. The new synthetic route employed in the present study adopts the Suzuki coupling of 7merRI and 4merRBP, in which the purification was attained without much of a problem see the Supporting Information
    • In our previous study (ref 9a), 11merR2 was synthesized via the Suzuki coupling of 1merRBP and 9merBr2. However, the crude product contained side products including the 10mer of which the polarity and the molecular size are quite similar to those of 11merHR2, thus making the purification of 11merR2 using chromatography extremely difficult. The new synthetic route employed in the present study adopts the Suzuki coupling of 7merRI and 4merRBP, in which the purification was attained without much of a problem (see the Supporting Information).
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    • The observed shifts (δobs) were fit to the equation δobs ) δdimer + (δmonomer- δdimer)[{-1 + (1 + 8KaC)1/2}/(4KaC)], where C corresponds to the total concentration of the oligoresorcinol and δmonomer and δdimer are the chemical shifts of the monomer and the dimer, respectively.
    • The observed shifts (δobs) were fit to the equation δobs ) δdimer + (δmonomer- δdimer)[{-1 + (1 + 8KaC)1/2}/(4KaC)], where C corresponds to the total concentration of the oligoresorcinol and δmonomer and δdimer are the chemical shifts of the monomer and the dimer, respectively.
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    • The observed molar absorptivities (εobs) were fit to the equation εobs ) εdimer/2 + (εmonomer- εdimer/2)[{-1 + (1 + 8KaC)1/2}/(4KaC)], where C corresponds to the total concentration of the oligoresorcinol and εmonomer and εdimer are the molar absorptivities of the monomer and dimer, respectively.
    • The observed molar absorptivities (εobs) were fit to the equation εobs ) εdimer/2 + (εmonomer- εdimer/2)[{-1 + (1 + 8KaC)1/2}/(4KaC)], where C corresponds to the total concentration of the oligoresorcinol and εmonomer and εdimer are the molar absorptivities of the monomer and dimer, respectively.
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    • In general, the quantitative performance of MALDI-TOF-MS is not sufficient because of variability in the ionization potentials for different compounds. However, some groups recently used MALDI-TOF-MS for quantitative analyses of noncovalent assemblies of proteins and saccharides. In our case, it is reasonable to assume that the ionization potentials for the homo- and heterodouble helices with the same chain lengths are almost the same, because their chemical structures are quite similar to each other except for the chiral oligomers that possess chiral alkyl groups at both ends of the strands. (a) Jespersen, S.; Niessen, W. M. A.; Tjaden, U. R.; van der Greef, J. J. Mass Spectrom. 1995, 30, 357-64.
    • In general, the quantitative performance of MALDI-TOF-MS is not sufficient because of variability in the ionization potentials for different compounds. However, some groups recently used MALDI-TOF-MS for quantitative analyses of noncovalent assemblies of proteins and saccharides. In our case, it is reasonable to assume that the ionization potentials for the homo- and heterodouble helices with the same chain lengths are almost the same, because their chemical structures are quite similar to each other except for the chiral oligomers that possess chiral alkyl groups at both ends of the strands. (a) Jespersen, S.; Niessen, W. M. A.; Tjaden, U. R.; van der Greef, J. J. Mass Spectrom. 1995, 30, 357-64.


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