About: Premicellar interaction of PEO-PPO-PEO triblock copolymers with partially hydrophobic alcohols: NMR study     Goto   Sponge   NotDistinct   Permalink

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  • The interactions of three alcohols, namely, 2-butanol (BuOH), 3-methyl-2-butanol (MeBuOH), and 3,3-dimethyl-2-butanol (Me2BuOH) with propylene oxide octamer (PO8) and the copolymers (EO)8(PO)13(EO)8 (L35) and (EO)13(PO)30(EO)13 (L64) in D2O were studied using 13C NMR spectra and relaxations and 1H PFG NMR diffusion measurements. For L64, it was shown that the temperature at which the PO chain starts to change its conformation under dehydration decreases by 6 K for each additional methyl group in the alcohol molecule (i.e. with increasing its hydrophobicity), and the analogous conformation states are attained at temperatures approximately 10 K lower compared using ketonic analogs of the alcohols under the same conditions. Also, the first signs of L64 aggregation, according to the normalized diffusion coefficients, are at temperatures 7, 10, and 13 K lower for BuOH, MeBuOH, and Me2BuOH, respectively. These effects are much weaker for (PO)13 in L35 or nonexistent for (PO)8 in PO8, thus showing the role of cooperativity in dehydration and aggregation processes. According to diffusion measurements, the molar fraction of the alcohol hydrogen bonded to L64 increases with its hydrophobicity and, in an apparent conflict with thermodynamics, with increasing temperature at which also higher NOE can be observed. Strong hydrogen bond interaction, which is in cooperation with hydrophobic interaction, does not preclude the exchange between bound and free states of the alcohol, however. Using 13C transverse relaxation, its correlation time is shown to be of the order of 10 ms.
  • The interactions of three alcohols, namely, 2-butanol (BuOH), 3-methyl-2-butanol (MeBuOH), and 3,3-dimethyl-2-butanol (Me2BuOH) with propylene oxide octamer (PO8) and the copolymers (EO)8(PO)13(EO)8 (L35) and (EO)13(PO)30(EO)13 (L64) in D2O were studied using 13C NMR spectra and relaxations and 1H PFG NMR diffusion measurements. For L64, it was shown that the temperature at which the PO chain starts to change its conformation under dehydration decreases by 6 K for each additional methyl group in the alcohol molecule (i.e. with increasing its hydrophobicity), and the analogous conformation states are attained at temperatures approximately 10 K lower compared using ketonic analogs of the alcohols under the same conditions. Also, the first signs of L64 aggregation, according to the normalized diffusion coefficients, are at temperatures 7, 10, and 13 K lower for BuOH, MeBuOH, and Me2BuOH, respectively. These effects are much weaker for (PO)13 in L35 or nonexistent for (PO)8 in PO8, thus showing the role of cooperativity in dehydration and aggregation processes. According to diffusion measurements, the molar fraction of the alcohol hydrogen bonded to L64 increases with its hydrophobicity and, in an apparent conflict with thermodynamics, with increasing temperature at which also higher NOE can be observed. Strong hydrogen bond interaction, which is in cooperation with hydrophobic interaction, does not preclude the exchange between bound and free states of the alcohol, however. Using 13C transverse relaxation, its correlation time is shown to be of the order of 10 ms. (en)
Title
  • Premicellar interaction of PEO-PPO-PEO triblock copolymers with partially hydrophobic alcohols: NMR study
  • Premicellar interaction of PEO-PPO-PEO triblock copolymers with partially hydrophobic alcohols: NMR study (en)
skos:prefLabel
  • Premicellar interaction of PEO-PPO-PEO triblock copolymers with partially hydrophobic alcohols: NMR study
  • Premicellar interaction of PEO-PPO-PEO triblock copolymers with partially hydrophobic alcohols: NMR study (en)
skos:notation
  • RIV/61389013:_____/13:00391711!RIV14-GA0-61389013
http://linked.open...avai/predkladatel
http://linked.open...avai/riv/aktivita
http://linked.open...avai/riv/aktivity
  • I, P(GA203/09/1478), P(GAP205/11/1657)
http://linked.open...iv/cisloPeriodika
  • 5
http://linked.open...vai/riv/dodaniDat
http://linked.open...aciTvurceVysledku
http://linked.open.../riv/druhVysledku
http://linked.open...iv/duvernostUdaju
http://linked.open...titaPredkladatele
http://linked.open...dnocenehoVysledku
  • 98913
http://linked.open...ai/riv/idVysledku
  • RIV/61389013:_____/13:00391711
http://linked.open...riv/jazykVysledku
http://linked.open.../riv/klicovaSlova
  • pluronics; hydrophobic interaction; hydrophobic alcohols (en)
http://linked.open.../riv/klicoveSlovo
http://linked.open...odStatuVydavatele
  • GB - Spojené království Velké Británie a Severního Irska
http://linked.open...ontrolniKodProRIV
  • [37F0558D0577]
http://linked.open...i/riv/nazevZdroje
  • Magnetic Resonance in Chemistry
http://linked.open...in/vavai/riv/obor
http://linked.open...ichTvurcuVysledku
http://linked.open...cetTvurcuVysledku
http://linked.open...vavai/riv/projekt
http://linked.open...UplatneniVysledku
http://linked.open...v/svazekPeriodika
  • 51
http://linked.open...iv/tvurceVysledku
  • Dybal, Jiří
  • Kříž, Jaroslav
http://linked.open...ain/vavai/riv/wos
  • 000319968500003
issn
  • 0749-1581
number of pages
http://bibframe.org/vocab/doi
  • 10.1002/mrc.3942
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