Selectivity differences of coordination compound stationary phases for polyaromatic hydrocarbons and polar analytes in gas and liquid phases

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Abstract

A precursor solution to the metal–organic framework (MOF), Cd(1,4,7,10-tetrakis(4-carboxybenzyl)-1,4,7,10-tetraazacyclododecane), was aged in a surface-functionalised 250 m-diameter capillary, togenerate a film containing the constituents of the bulk phase crystalline material. EDX analysis revealed ahigher ratio of ligand elements (C, N and O) to Cd in the capillary coated phase compared to that achievedfrom bulk synthesis in a vial. Separation performance of the coated capillary for gas chromatography (GC)was compared to the performance of the original MOF crystals packed in tips for liquid elution chromatography(LEC) towards the separation of polycyclic aromatic hydrocarbons (PAHs) and small probe analytes with different properties. This study showed that different retention mechanisms were observed for the same set of analytes in gas and liquid phases. Independently of the trend of vapour pressure difference, the GC result showed less specific size selective retention, but with stronger retention towards larger PAHs .A linear solvation energy relationship correlation further revealed enhanced retention contributions(positive stationary phase descriptor values) by cavity formation/dispersion interactions and H-bonding with acid functionality of the probe analytes in both GC and LEC (though stronger in LEC), whilst H bonding with basic functional groups slightly increased retention in GC; retention was strengthened bydipole–dipole/dipole–induced dipole interactions only in LEC.
Original languageEnglish
Pages (from-to)167–171
Number of pages5
JournalJournal of Chromatography A
Volume1500
DOIs
Publication statusPublished - 2017

Keywords

  • Capillary coating
  • Crystallisation dimension
  • Interpenetrated metal-organic material
  • Linear solvation energy relationship
  • Liquid chromatography
  • Separation-in-tip

Cite this

@article{98f3de57a0d8489592ce0b83495ff0b4,
title = "Selectivity differences of coordination compound stationary phases for polyaromatic hydrocarbons and polar analytes in gas and liquid phases",
abstract = "A precursor solution to the metal–organic framework (MOF), Cd(1,4,7,10-tetrakis(4-carboxybenzyl)-1,4,7,10-tetraazacyclododecane), was aged in a surface-functionalised 250 m-diameter capillary, togenerate a film containing the constituents of the bulk phase crystalline material. EDX analysis revealed ahigher ratio of ligand elements (C, N and O) to Cd in the capillary coated phase compared to that achievedfrom bulk synthesis in a vial. Separation performance of the coated capillary for gas chromatography (GC)was compared to the performance of the original MOF crystals packed in tips for liquid elution chromatography(LEC) towards the separation of polycyclic aromatic hydrocarbons (PAHs) and small probe analytes with different properties. This study showed that different retention mechanisms were observed for the same set of analytes in gas and liquid phases. Independently of the trend of vapour pressure difference, the GC result showed less specific size selective retention, but with stronger retention towards larger PAHs .A linear solvation energy relationship correlation further revealed enhanced retention contributions(positive stationary phase descriptor values) by cavity formation/dispersion interactions and H-bonding with acid functionality of the probe analytes in both GC and LEC (though stronger in LEC), whilst H bonding with basic functional groups slightly increased retention in GC; retention was strengthened bydipole–dipole/dipole–induced dipole interactions only in LEC.",
keywords = "Capillary coating, Crystallisation dimension, Interpenetrated metal-organic material, Linear solvation energy relationship, Liquid chromatography, Separation-in-tip",
author = "Yada Nolvachai and Chadin Kulsing and Hawes, {Chris S} and Batten, {Stuart R} and Turner, {David R} and Marriott, {Philip J}",
year = "2017",
doi = "10.1016/j.chroma.2017.04.037",
language = "English",
volume = "1500",
pages = "167–171",
journal = "Journal of Chromatography A",
issn = "0021-9673",
publisher = "Elsevier",

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TY - JOUR

T1 - Selectivity differences of coordination compound stationary phases for polyaromatic hydrocarbons and polar analytes in gas and liquid phases

AU - Nolvachai, Yada

AU - Kulsing, Chadin

AU - Hawes, Chris S

AU - Batten, Stuart R

AU - Turner, David R

AU - Marriott, Philip J

PY - 2017

Y1 - 2017

N2 - A precursor solution to the metal–organic framework (MOF), Cd(1,4,7,10-tetrakis(4-carboxybenzyl)-1,4,7,10-tetraazacyclododecane), was aged in a surface-functionalised 250 m-diameter capillary, togenerate a film containing the constituents of the bulk phase crystalline material. EDX analysis revealed ahigher ratio of ligand elements (C, N and O) to Cd in the capillary coated phase compared to that achievedfrom bulk synthesis in a vial. Separation performance of the coated capillary for gas chromatography (GC)was compared to the performance of the original MOF crystals packed in tips for liquid elution chromatography(LEC) towards the separation of polycyclic aromatic hydrocarbons (PAHs) and small probe analytes with different properties. This study showed that different retention mechanisms were observed for the same set of analytes in gas and liquid phases. Independently of the trend of vapour pressure difference, the GC result showed less specific size selective retention, but with stronger retention towards larger PAHs .A linear solvation energy relationship correlation further revealed enhanced retention contributions(positive stationary phase descriptor values) by cavity formation/dispersion interactions and H-bonding with acid functionality of the probe analytes in both GC and LEC (though stronger in LEC), whilst H bonding with basic functional groups slightly increased retention in GC; retention was strengthened bydipole–dipole/dipole–induced dipole interactions only in LEC.

AB - A precursor solution to the metal–organic framework (MOF), Cd(1,4,7,10-tetrakis(4-carboxybenzyl)-1,4,7,10-tetraazacyclododecane), was aged in a surface-functionalised 250 m-diameter capillary, togenerate a film containing the constituents of the bulk phase crystalline material. EDX analysis revealed ahigher ratio of ligand elements (C, N and O) to Cd in the capillary coated phase compared to that achievedfrom bulk synthesis in a vial. Separation performance of the coated capillary for gas chromatography (GC)was compared to the performance of the original MOF crystals packed in tips for liquid elution chromatography(LEC) towards the separation of polycyclic aromatic hydrocarbons (PAHs) and small probe analytes with different properties. This study showed that different retention mechanisms were observed for the same set of analytes in gas and liquid phases. Independently of the trend of vapour pressure difference, the GC result showed less specific size selective retention, but with stronger retention towards larger PAHs .A linear solvation energy relationship correlation further revealed enhanced retention contributions(positive stationary phase descriptor values) by cavity formation/dispersion interactions and H-bonding with acid functionality of the probe analytes in both GC and LEC (though stronger in LEC), whilst H bonding with basic functional groups slightly increased retention in GC; retention was strengthened bydipole–dipole/dipole–induced dipole interactions only in LEC.

KW - Capillary coating

KW - Crystallisation dimension

KW - Interpenetrated metal-organic material

KW - Linear solvation energy relationship

KW - Liquid chromatography

KW - Separation-in-tip

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DO - 10.1016/j.chroma.2017.04.037

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VL - 1500

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JO - Journal of Chromatography A

JF - Journal of Chromatography A

SN - 0021-9673

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