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Structure of 81644-55-5

Chemical Structure| 81644-55-5

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O' ; Shea, KE ; Restrepo-Osorio, Rodrigo ;

Abstract: Poly- and perfluoroalkyl substances (PFAS) are pollutants of serious concern due to their adverse health effects, widespread use, and resistance to degradation. β-cyclodextrins (β-CDs) form strong β-CD:PFAS complexes with a wide variety of PFAS. We report herein the incorporation of ionizable functional groups on the primary rim of β-CD, to control the complexation of PFAS as a function of solution pH. The binding constants (KCD:PFAS) of short-chain and long-chain PFAS by amino-β-CDs and thiol-β-CDs decrease by 56 to 98 % with a change in solution pH from neutral to alkaline conditions. The observed reduction in binding constants (KCD:PFAS) with increased pH is assigned to the increased electrostatic repulsion between negatively charged functional group amended to the β-CD (host) and negatively charged PFAS polar head group (guest) under alkaline conditions. The inclusion of two pH-dependent ionizable functional groups to the host was achieved by employing 6-(3-hydroxybenzylamino)-6-deoxy-β- cyclodextrin [(3-OH)BnNHβ-CD]. The phenol functionality is converted from a neutral to an anionic species while the benzyl-amino group is cationic under neutral pH and converted to neutral charge under alkaline conditions, thus the β-CD host can be converted from a positive charge to a negative charge by varying solution pH. The (3-OH)BnNHβ-CD exhibits strong pH-modulated binding with long-chain perfluorocarboxylic acids (PFCAs), evidenced in an 88 % decrease in the association constant with PFOA under alkaline conditions. The association constant for (3-OH)BnNHβ-CD with hexafluoropropylene oxide dimer acid (HFPO-DA), a branched perfluoroether carboxylic acid (PFECA), however, decreases by nearly 50 % under alkaline conditions compared to an 81 % and 98 % decrease observed for mono-thiol and mono-amino β-CDs, respectively. A 95 % decrease in binding in PFOA is observed for mono-thiol-β-CD, while heptakis-(6-mercapto-6-deoxy)-β-cyclodextrin, with seven ionizable thiol groups leads to a modest 23 % decrease for complexation of PFOA with change from neutral to alkaline pH. Steric effects due to chain branching within PFAS in combination with size and number of substituents on the β-CD reduce the impact of pH effects on binding. This study demonstrates derivatization of β-CD with pH ionizable functional groups can be used to control the β-CD binding of PFAS as a possible strategy for the removal and recovery of PFAS from contaminated water streams.

Keywords: Host-guest complexation ; PFAS ; cyclodextrin ; remediation: pH

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Product Details of [ 81644-55-5 ]

CAS No. :81644-55-5
Formula : C42H70O34S
M.W : 1151.05
SMILES Code : OC[C@@H]1[C@]2([H])[C@@H]([C@@H](O)[C@](O[C@]3([H])[C@H](O[C@@](O[C@]4([H])[C@H](O[C@@](O[C@]5([H])[C@H](O[C@@](O[C@@]6([H])[C@H](O)[C@@H](O)[C@@](O[C@@H]6CO)([H])O[C@@]7([H])[C@H](O)[C@@H](O)[C@@](O[C@@H]7CO)([H])O[C@@]8([H])[C@H](O)[C@@H](O)[C@@](O[C@@H]8CO)([H])O2)([H])[C@H](O)[C@H]5O)CS)([H])[C@H](O)[C@H]4O)CO)([H])[C@H](O)[C@H]3O)CO)([H])O1)O
MDL No. :MFCD31537208
InChI Key :KBQFCFNGXZCYMC-FOUAGVGXSA-N
Pubchem ID :10931212

Safety of [ 81644-55-5 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 81644-55-5 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Upstream synthesis route of [ 81644-55-5 ]

[ 81644-55-5 ] Synthesis Path-Upstream   1~3

  • 1
  • [ 67217-55-4 ]
  • [ 81644-55-5 ]
YieldReaction ConditionsOperation in experiment
67%
Stage #1: With sodium hydroxide; thiourea In water at 80℃; for 9 h;
Stage #2: With hydrogenchloride In water at 20℃;
A 50 mL round bottom flask with a magnetic stirbar and a Schlenk adapter was charged with 1.00 g (0.776 mmol) of 19, 0.59 g (7.75 mmol) of thiourea (Aldrich) and 7.8 mL of 0.1N NaOH solution. The resulting mixture was heated at 80 °C for 6 hours under nitrogen. Next, 0.62g (15.5 mmol) of sodium hydroxide was added and the reaction mixture was heated at 80 °C under nitrogen for another hour. The reaction was allowed to cool to room temperature before it was brought to pH 4.0 with 10percent HCl. The total solution volume was brought to 20 mL and then was cooled in an ice bath before 0.8 mL of tetrachloroethylene was added. The reaction mixture was stirred vigorously at 0 °C for 0.5 h before the precipitated solid was collected in a fine glass frit. The solid was pumped down overnight to yield 0.60 g (67percent) of a white amorphous solid.
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[2] Patent: EP1133318, 2007, B1, . Location in patent: Page/Page column 32-33.
[3] Chinese Journal of Chemistry, 2017, vol. 35, # 7, p. 1125 - 1132.
[4] Chemical Communications, 2011, vol. 47, # 45, p. 12388 - 12390.
[5] Angewandte Chemie - International Edition, 2012, vol. 51, # 2, p. 450 - 454.
[6] Journal of the American Chemical Society, 1996, vol. 118, # 21, p. 5039 - 5046.
[7] Journal of the American Chemical Society, 2009, vol. 131, p. 1386 - 1387.
[8] Chemical Communications, 2010, vol. 46, # 23, p. 4094 - 4096.
[9] Journal of Materials Chemistry A, 2014, vol. 2, # 25, p. 9587 - 9593.
[10] New Journal of Chemistry, 2018, vol. 42, # 5, p. 3593 - 3601.
[11] ChemPhysChem, 2019, vol. 20, # 7, p. 984 - 990.
  • 2
  • [ 67217-55-4 ]
  • [ 17356-08-0 ]
  • [ 81644-55-5 ]
References: [1] Tetrahedron Letters, 2007, vol. 48, # 52, p. 9185 - 9189.
[2] Chemistry - A European Journal, 2013, vol. 19, # 32, p. 10526 - 10535.
[3] Chemical Communications, 2015, vol. 51, # 30, p. 6512 - 6514.
[4] Tetrahedron Letters, 1994, vol. 35, # 25, p. 4275 - 4278.
  • 3
  • [ 7585-39-9 ]
  • [ 81644-55-5 ]
References: [1] New Journal of Chemistry, 2015, vol. 39, # 1, p. 555 - 565.
 

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