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Title: The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands

Environmental remediation requires ion-selective polymers that operate under a wide range of solution conditions. In one example, removal of trivalent and divalent metal ions from waste streams resulting from mining operations before they enter the environment requires treatment at acidic pH. The monoethyl ester phosphate ligands developed in this report operate from acidic solutions. They have been prepared on polystyrene-bound ethylene glycol, glycerol, and pentaerythritol, and it is found that intra-ligand hydrogen bonding affects their metal ion affinities. The affinity for a set of trivalent (Fe(III), Al(III), La(III), and Lu(III)) and divalent (Pb(II), Cd(II), Cu(II), and Zn(II)) ions is greater than that of corresponding neutral diethyl esters and phosphonic acid. In an earlier study, hydrogen bonding was found important in determining the metal ion affinities of immobilized phosphorylated polyol diethyl ester coordinating ligands; their Fourier transform infrared (FTIR) band shifts indicated that the basicity of the phosphoryl oxygen increased by hydrogen bonding to auxiliary –OH groups on the neighboring polyol. The same mechanism is operative with the monoprotic resins along with hydrogen bonding to the P–OH acid site. This is reflected in the FTIR spectra: the neutral phosphate diethyl ester resins have the P=O band at 1265 cm -1 whilemore » the monoethyl ester resins have the band shifted to 1230 cm -1; hydrogen bonding is further indicated by the broadness of this region down to 900 cm -1. Of the polymers studied, monoprotic pentaerythritol has the highest metal ion affinities.« less
Authors:
 [1] ;  [2]
  1. City Univ. of New York, New York City, NY (United States). Graduate Center, Hunter College and Dept. of Chemistry
  2. City Univ. of New York, New York City, NY (United States). Hunter College and Dept. of Chemistry
Publication Date:
Grant/Contract Number:
FG02-02ER15287
Type:
Accepted Manuscript
Journal Name:
Materials
Additional Journal Information:
Journal Volume: 10; Journal Issue: 8; Journal ID: ISSN 1996-1944
Publisher:
MDPI
Research Org:
City Univ. of New York, New York City, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymer; ligand; metal ions; separations
OSTI Identifier:
1429097

Alexandratos, Spiro D., and Zhu, Xiaoping. The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands. United States: N. p., Web. doi:10.3390/ma10080968.
Alexandratos, Spiro D., & Zhu, Xiaoping. The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands. United States. doi:10.3390/ma10080968.
Alexandratos, Spiro D., and Zhu, Xiaoping. 2017. "The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands". United States. doi:10.3390/ma10080968. https://www.osti.gov/servlets/purl/1429097.
@article{osti_1429097,
title = {The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands},
author = {Alexandratos, Spiro D. and Zhu, Xiaoping},
abstractNote = {Environmental remediation requires ion-selective polymers that operate under a wide range of solution conditions. In one example, removal of trivalent and divalent metal ions from waste streams resulting from mining operations before they enter the environment requires treatment at acidic pH. The monoethyl ester phosphate ligands developed in this report operate from acidic solutions. They have been prepared on polystyrene-bound ethylene glycol, glycerol, and pentaerythritol, and it is found that intra-ligand hydrogen bonding affects their metal ion affinities. The affinity for a set of trivalent (Fe(III), Al(III), La(III), and Lu(III)) and divalent (Pb(II), Cd(II), Cu(II), and Zn(II)) ions is greater than that of corresponding neutral diethyl esters and phosphonic acid. In an earlier study, hydrogen bonding was found important in determining the metal ion affinities of immobilized phosphorylated polyol diethyl ester coordinating ligands; their Fourier transform infrared (FTIR) band shifts indicated that the basicity of the phosphoryl oxygen increased by hydrogen bonding to auxiliary –OH groups on the neighboring polyol. The same mechanism is operative with the monoprotic resins along with hydrogen bonding to the P–OH acid site. This is reflected in the FTIR spectra: the neutral phosphate diethyl ester resins have the P=O band at 1265 cm-1 while the monoethyl ester resins have the band shifted to 1230 cm-1; hydrogen bonding is further indicated by the broadness of this region down to 900 cm-1. Of the polymers studied, monoprotic pentaerythritol has the highest metal ion affinities.},
doi = {10.3390/ma10080968},
journal = {Materials},
number = 8,
volume = 10,
place = {United States},
year = {2017},
month = {8}
}