Surface modification of chromatography adsorbents by low temperature low pressure plasma

A. Arpanaei, Bjorn Winther Jensen, E. Theodosiou, P. Kingshott, T. J. Hobley, O. R T Thomas

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

In this study we show how low temperature glow discharge plasma can be used to prepare bi-layered chromatography adsorbents with non-adsorptive exteriors. The commercial strong anion exchange expanded bed chromatography matrix, Q HyperZ, was treated with plasmas in one of two general ways. Using a purpose-designed rotating reactor, plasmas were employed to either: (i) remove anion exchange ligands at or close to the exterior surface of Q HyperZ, and replace them with polar oxygen containing functions ('plasma etching and oxidation'); or (ii) bury the same surface exposed ligands beneath thin polymer coatings ('plasma polymerization coating') using appropriate monomers (vinyl acetate, vinyl pyrrolidone, safrole) and argon as the carrier gas. X-ray photoelectron spectroscopy analysis (first ~10nm depth) of Q HyperZ before and after the various plasma treatments confirmed that substantial changes to the elemental composition of Q HyperZ's exterior had been inflicted in all cases. The atomic percent changes in carbon, nitrogen, oxygen, yttrium and zirconium observed after being exposed to air plasma etching were entirely consistent with: the removal of pendant Q (trimethylammonium) functions; increased exposure of the underlying yttrium-stabilised zirconia shell; and introduction of hydroxyl and carbonyl functions. Following plasma polymerization treatments (with all three monomers tested), the increased atomic percent levels of carbon and parallel drops in nitrogen, yttrium and zirconium provided clear evidence that thin polymer coats had been created at the exteriors of Q HyperZ adsorbent particles. No changes in adsorbent size and surface morphology, nor any evidence of plasma-induced damage could be discerned from scanning electron micrographs, light micrographs and measurements of particle size distributions following 3h exposure to air (220V; 35.8WL-1) or 'vinyl acetate/argon' (170V; 16.5WL-1) plasmas. Losses in bulk chloride exchange capacity before and after exposure to plasmas enabled effective modification depths within hydrated Q HyperZ adsorbent particles to be calculated as 0.2-1.2μm, depending on the conditions applied. The depth of plasma induced alteration was strongly influenced by the power input and size of the treated batch, i.e. dropping the power or increasing the batch size resulted in reduced plasma penetration and therefore shallower modification. The selectivity of 'surface vs. core' modification imparted to Q HyperZ by the various plasma treatments was evaluated in static and dynamic binding studies employing appropriate probes, i.e. plasmid DNA, sonicated calf thymus DNA and bovine serum albumin. In static binding studies performed with adsorbents that had been exposed to plasmas at the 5g scale (25gL-1 of plasma reactor), the highest 'surface/core' modification selectivity was observed for Q HyperZ that had been subjected to 3h of air plasma etching at 220V (35.8WL-1). This treatment removed ~53% of 'surface' DNA binding at the expense of a 9.3% loss in 'core' protein binding. Even more impressive results were obtained in dynamic expanded bed adsorption studies conducted with Q HyperZ adsorbents that had been treated with air (220V, 3h) and 'vinyl acetate/argon' (170V, 3h) plasmas at 10.5g scale (52.5gL-1 of plasma reactor). Following both plasma treatments: the 10% breakthrough capacities of the modified Q HyperZ adsorbents towards 'surface' binding DNA probes dropped very significantly (30-85%); the DNA induced inter-particle cross-linking and contraction of expanded beds observed during application of sonicated DNA on native Q HyperZ was completely eradicated; but the 'core' protein binding performance remained unchanged cf. that of the native Q HyperZ starting material.

Original languageEnglish
Pages (from-to)6905-6916
Number of pages12
JournalJournal of Chromatography A
Volume1217
Issue number44
DOIs
Publication statusPublished - 2010 Oct 29
Externally publishedYes

Fingerprint

Chromatography
Adsorbents
Surface treatment
Plasmas
Pressure
Temperature
Yttrium
Plasma etching
Argon
Plasma polymerization
Air
Anions
DNA
Polymers
Nitrogen
Safrole
Carbon
Monomers
Protein Binding
Polymerization

Keywords

  • Anti-fouling
  • Expanded bed adsorption
  • Ion exchange
  • Non-adsorptive surfaces
  • Plasma etching/polymerization
  • Protein and plasmid DNA separation
  • Size exclusion
  • Support cross-linking

ASJC Scopus subject areas

  • Analytical Chemistry
  • Organic Chemistry
  • Biochemistry

Cite this

Arpanaei, A., Winther Jensen, B., Theodosiou, E., Kingshott, P., Hobley, T. J., & Thomas, O. R. T. (2010). Surface modification of chromatography adsorbents by low temperature low pressure plasma. Journal of Chromatography A, 1217(44), 6905-6916. https://doi.org/10.1016/j.chroma.2010.08.069

Surface modification of chromatography adsorbents by low temperature low pressure plasma. / Arpanaei, A.; Winther Jensen, Bjorn; Theodosiou, E.; Kingshott, P.; Hobley, T. J.; Thomas, O. R T.

In: Journal of Chromatography A, Vol. 1217, No. 44, 29.10.2010, p. 6905-6916.

Research output: Contribution to journalArticle

Arpanaei, A, Winther Jensen, B, Theodosiou, E, Kingshott, P, Hobley, TJ & Thomas, ORT 2010, 'Surface modification of chromatography adsorbents by low temperature low pressure plasma', Journal of Chromatography A, vol. 1217, no. 44, pp. 6905-6916. https://doi.org/10.1016/j.chroma.2010.08.069
Arpanaei A, Winther Jensen B, Theodosiou E, Kingshott P, Hobley TJ, Thomas ORT. Surface modification of chromatography adsorbents by low temperature low pressure plasma. Journal of Chromatography A. 2010 Oct 29;1217(44):6905-6916. https://doi.org/10.1016/j.chroma.2010.08.069
Arpanaei, A. ; Winther Jensen, Bjorn ; Theodosiou, E. ; Kingshott, P. ; Hobley, T. J. ; Thomas, O. R T. / Surface modification of chromatography adsorbents by low temperature low pressure plasma. In: Journal of Chromatography A. 2010 ; Vol. 1217, No. 44. pp. 6905-6916.
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abstract = "In this study we show how low temperature glow discharge plasma can be used to prepare bi-layered chromatography adsorbents with non-adsorptive exteriors. The commercial strong anion exchange expanded bed chromatography matrix, Q HyperZ, was treated with plasmas in one of two general ways. Using a purpose-designed rotating reactor, plasmas were employed to either: (i) remove anion exchange ligands at or close to the exterior surface of Q HyperZ, and replace them with polar oxygen containing functions ('plasma etching and oxidation'); or (ii) bury the same surface exposed ligands beneath thin polymer coatings ('plasma polymerization coating') using appropriate monomers (vinyl acetate, vinyl pyrrolidone, safrole) and argon as the carrier gas. X-ray photoelectron spectroscopy analysis (first ~10nm depth) of Q HyperZ before and after the various plasma treatments confirmed that substantial changes to the elemental composition of Q HyperZ's exterior had been inflicted in all cases. The atomic percent changes in carbon, nitrogen, oxygen, yttrium and zirconium observed after being exposed to air plasma etching were entirely consistent with: the removal of pendant Q (trimethylammonium) functions; increased exposure of the underlying yttrium-stabilised zirconia shell; and introduction of hydroxyl and carbonyl functions. Following plasma polymerization treatments (with all three monomers tested), the increased atomic percent levels of carbon and parallel drops in nitrogen, yttrium and zirconium provided clear evidence that thin polymer coats had been created at the exteriors of Q HyperZ adsorbent particles. No changes in adsorbent size and surface morphology, nor any evidence of plasma-induced damage could be discerned from scanning electron micrographs, light micrographs and measurements of particle size distributions following 3h exposure to air (220V; 35.8WL-1) or 'vinyl acetate/argon' (170V; 16.5WL-1) plasmas. Losses in bulk chloride exchange capacity before and after exposure to plasmas enabled effective modification depths within hydrated Q HyperZ adsorbent particles to be calculated as 0.2-1.2μm, depending on the conditions applied. The depth of plasma induced alteration was strongly influenced by the power input and size of the treated batch, i.e. dropping the power or increasing the batch size resulted in reduced plasma penetration and therefore shallower modification. The selectivity of 'surface vs. core' modification imparted to Q HyperZ by the various plasma treatments was evaluated in static and dynamic binding studies employing appropriate probes, i.e. plasmid DNA, sonicated calf thymus DNA and bovine serum albumin. In static binding studies performed with adsorbents that had been exposed to plasmas at the 5g scale (25gL-1 of plasma reactor), the highest 'surface/core' modification selectivity was observed for Q HyperZ that had been subjected to 3h of air plasma etching at 220V (35.8WL-1). This treatment removed ~53{\%} of 'surface' DNA binding at the expense of a 9.3{\%} loss in 'core' protein binding. Even more impressive results were obtained in dynamic expanded bed adsorption studies conducted with Q HyperZ adsorbents that had been treated with air (220V, 3h) and 'vinyl acetate/argon' (170V, 3h) plasmas at 10.5g scale (52.5gL-1 of plasma reactor). Following both plasma treatments: the 10{\%} breakthrough capacities of the modified Q HyperZ adsorbents towards 'surface' binding DNA probes dropped very significantly (30-85{\%}); the DNA induced inter-particle cross-linking and contraction of expanded beds observed during application of sonicated DNA on native Q HyperZ was completely eradicated; but the 'core' protein binding performance remained unchanged cf. that of the native Q HyperZ starting material.",
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N2 - In this study we show how low temperature glow discharge plasma can be used to prepare bi-layered chromatography adsorbents with non-adsorptive exteriors. The commercial strong anion exchange expanded bed chromatography matrix, Q HyperZ, was treated with plasmas in one of two general ways. Using a purpose-designed rotating reactor, plasmas were employed to either: (i) remove anion exchange ligands at or close to the exterior surface of Q HyperZ, and replace them with polar oxygen containing functions ('plasma etching and oxidation'); or (ii) bury the same surface exposed ligands beneath thin polymer coatings ('plasma polymerization coating') using appropriate monomers (vinyl acetate, vinyl pyrrolidone, safrole) and argon as the carrier gas. X-ray photoelectron spectroscopy analysis (first ~10nm depth) of Q HyperZ before and after the various plasma treatments confirmed that substantial changes to the elemental composition of Q HyperZ's exterior had been inflicted in all cases. The atomic percent changes in carbon, nitrogen, oxygen, yttrium and zirconium observed after being exposed to air plasma etching were entirely consistent with: the removal of pendant Q (trimethylammonium) functions; increased exposure of the underlying yttrium-stabilised zirconia shell; and introduction of hydroxyl and carbonyl functions. Following plasma polymerization treatments (with all three monomers tested), the increased atomic percent levels of carbon and parallel drops in nitrogen, yttrium and zirconium provided clear evidence that thin polymer coats had been created at the exteriors of Q HyperZ adsorbent particles. No changes in adsorbent size and surface morphology, nor any evidence of plasma-induced damage could be discerned from scanning electron micrographs, light micrographs and measurements of particle size distributions following 3h exposure to air (220V; 35.8WL-1) or 'vinyl acetate/argon' (170V; 16.5WL-1) plasmas. Losses in bulk chloride exchange capacity before and after exposure to plasmas enabled effective modification depths within hydrated Q HyperZ adsorbent particles to be calculated as 0.2-1.2μm, depending on the conditions applied. The depth of plasma induced alteration was strongly influenced by the power input and size of the treated batch, i.e. dropping the power or increasing the batch size resulted in reduced plasma penetration and therefore shallower modification. The selectivity of 'surface vs. core' modification imparted to Q HyperZ by the various plasma treatments was evaluated in static and dynamic binding studies employing appropriate probes, i.e. plasmid DNA, sonicated calf thymus DNA and bovine serum albumin. In static binding studies performed with adsorbents that had been exposed to plasmas at the 5g scale (25gL-1 of plasma reactor), the highest 'surface/core' modification selectivity was observed for Q HyperZ that had been subjected to 3h of air plasma etching at 220V (35.8WL-1). This treatment removed ~53% of 'surface' DNA binding at the expense of a 9.3% loss in 'core' protein binding. Even more impressive results were obtained in dynamic expanded bed adsorption studies conducted with Q HyperZ adsorbents that had been treated with air (220V, 3h) and 'vinyl acetate/argon' (170V, 3h) plasmas at 10.5g scale (52.5gL-1 of plasma reactor). Following both plasma treatments: the 10% breakthrough capacities of the modified Q HyperZ adsorbents towards 'surface' binding DNA probes dropped very significantly (30-85%); the DNA induced inter-particle cross-linking and contraction of expanded beds observed during application of sonicated DNA on native Q HyperZ was completely eradicated; but the 'core' protein binding performance remained unchanged cf. that of the native Q HyperZ starting material.

AB - In this study we show how low temperature glow discharge plasma can be used to prepare bi-layered chromatography adsorbents with non-adsorptive exteriors. The commercial strong anion exchange expanded bed chromatography matrix, Q HyperZ, was treated with plasmas in one of two general ways. Using a purpose-designed rotating reactor, plasmas were employed to either: (i) remove anion exchange ligands at or close to the exterior surface of Q HyperZ, and replace them with polar oxygen containing functions ('plasma etching and oxidation'); or (ii) bury the same surface exposed ligands beneath thin polymer coatings ('plasma polymerization coating') using appropriate monomers (vinyl acetate, vinyl pyrrolidone, safrole) and argon as the carrier gas. X-ray photoelectron spectroscopy analysis (first ~10nm depth) of Q HyperZ before and after the various plasma treatments confirmed that substantial changes to the elemental composition of Q HyperZ's exterior had been inflicted in all cases. The atomic percent changes in carbon, nitrogen, oxygen, yttrium and zirconium observed after being exposed to air plasma etching were entirely consistent with: the removal of pendant Q (trimethylammonium) functions; increased exposure of the underlying yttrium-stabilised zirconia shell; and introduction of hydroxyl and carbonyl functions. Following plasma polymerization treatments (with all three monomers tested), the increased atomic percent levels of carbon and parallel drops in nitrogen, yttrium and zirconium provided clear evidence that thin polymer coats had been created at the exteriors of Q HyperZ adsorbent particles. No changes in adsorbent size and surface morphology, nor any evidence of plasma-induced damage could be discerned from scanning electron micrographs, light micrographs and measurements of particle size distributions following 3h exposure to air (220V; 35.8WL-1) or 'vinyl acetate/argon' (170V; 16.5WL-1) plasmas. Losses in bulk chloride exchange capacity before and after exposure to plasmas enabled effective modification depths within hydrated Q HyperZ adsorbent particles to be calculated as 0.2-1.2μm, depending on the conditions applied. The depth of plasma induced alteration was strongly influenced by the power input and size of the treated batch, i.e. dropping the power or increasing the batch size resulted in reduced plasma penetration and therefore shallower modification. The selectivity of 'surface vs. core' modification imparted to Q HyperZ by the various plasma treatments was evaluated in static and dynamic binding studies employing appropriate probes, i.e. plasmid DNA, sonicated calf thymus DNA and bovine serum albumin. In static binding studies performed with adsorbents that had been exposed to plasmas at the 5g scale (25gL-1 of plasma reactor), the highest 'surface/core' modification selectivity was observed for Q HyperZ that had been subjected to 3h of air plasma etching at 220V (35.8WL-1). This treatment removed ~53% of 'surface' DNA binding at the expense of a 9.3% loss in 'core' protein binding. Even more impressive results were obtained in dynamic expanded bed adsorption studies conducted with Q HyperZ adsorbents that had been treated with air (220V, 3h) and 'vinyl acetate/argon' (170V, 3h) plasmas at 10.5g scale (52.5gL-1 of plasma reactor). Following both plasma treatments: the 10% breakthrough capacities of the modified Q HyperZ adsorbents towards 'surface' binding DNA probes dropped very significantly (30-85%); the DNA induced inter-particle cross-linking and contraction of expanded beds observed during application of sonicated DNA on native Q HyperZ was completely eradicated; but the 'core' protein binding performance remained unchanged cf. that of the native Q HyperZ starting material.

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KW - Non-adsorptive surfaces

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KW - Protein and plasmid DNA separation

KW - Size exclusion

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