Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials

A straight forward strategy of heparin surface grafting employs a terminal reactive-aldehyde group introduced through nitrous acid depolymerization. An advanced method that allows simultaneously monitoring of both heparin molar mass and monomer/aldehyde ratio by size exclusion chromatography, multi-...

Full description

Bibliographic Details
Main Authors: Irvine, Scott Alexander, Steele, Terry W. J., Bhuthalingam, Ramya, Li, Min, Boujday, Souhir, Prawirasatya, Melissa, Neoh, Koon Gee, Boey, Freddy Yin Chiang, Venkatraman, Subbu S.
Other Authors: School of Materials Science & Engineering
Format: Journal Article
Language:English
Published: 2017
Subjects:
Online Access:https://hdl.handle.net/10356/80595
http://hdl.handle.net/10220/42175
_version_ 1826126331179433984
author Irvine, Scott Alexander
Steele, Terry W. J.
Bhuthalingam, Ramya
Li, Min
Boujday, Souhir
Prawirasatya, Melissa
Neoh, Koon Gee
Boey, Freddy Yin Chiang
Venkatraman, Subbu S.
author2 School of Materials Science & Engineering
author_facet School of Materials Science & Engineering
Irvine, Scott Alexander
Steele, Terry W. J.
Bhuthalingam, Ramya
Li, Min
Boujday, Souhir
Prawirasatya, Melissa
Neoh, Koon Gee
Boey, Freddy Yin Chiang
Venkatraman, Subbu S.
author_sort Irvine, Scott Alexander
collection NTU
description A straight forward strategy of heparin surface grafting employs a terminal reactive-aldehyde group introduced through nitrous acid depolymerization. An advanced method that allows simultaneously monitoring of both heparin molar mass and monomer/aldehyde ratio by size exclusion chromatography, multi-angle laser light scattering and UV-absorbance (SEC-MALLS–UV) has been developed to improve upon heparin surface grafting. Advancements over older methods allow quantitative characterization by direct (aldehyde absorbance) and indirect (Schiff-based absorbance) evaluation of terminal functional aldehydes. The indirect quantitation of functional aldehydes through labeling with aniline (and the formation of a Schiff-base) allows independent quantitation of both polymer mass and terminal functional groups with the applicable UV mass extinction coefficients determined. The protocol was subsequently used to synthesize an optimized heparin-aldehyde that had minimal polydispersity (PDI < 2) and high reaction yields (yield >60% by mass). The 8 kDa weight averaged molar mass heparin-aldehyde was then grafted on polycaprolactone (PCL), a common implant material. This optimized heparin-aldehyde retained its antithrombin activity, assessed in freshly drawn blood or surface immobilized on PCL films. Anticoagulant activity was equal to or better than the 24 kDa unmodified heparin it was fragmented from.
first_indexed 2024-10-01T06:50:57Z
format Journal Article
id ntu-10356/80595
institution Nanyang Technological University
language English
last_indexed 2024-10-01T06:50:57Z
publishDate 2017
record_format dspace
spelling ntu-10356/805952023-07-14T15:49:43Z Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials Irvine, Scott Alexander Steele, Terry W. J. Bhuthalingam, Ramya Li, Min Boujday, Souhir Prawirasatya, Melissa Neoh, Koon Gee Boey, Freddy Yin Chiang Venkatraman, Subbu S. School of Materials Science & Engineering Heparin Aniline A straight forward strategy of heparin surface grafting employs a terminal reactive-aldehyde group introduced through nitrous acid depolymerization. An advanced method that allows simultaneously monitoring of both heparin molar mass and monomer/aldehyde ratio by size exclusion chromatography, multi-angle laser light scattering and UV-absorbance (SEC-MALLS–UV) has been developed to improve upon heparin surface grafting. Advancements over older methods allow quantitative characterization by direct (aldehyde absorbance) and indirect (Schiff-based absorbance) evaluation of terminal functional aldehydes. The indirect quantitation of functional aldehydes through labeling with aniline (and the formation of a Schiff-base) allows independent quantitation of both polymer mass and terminal functional groups with the applicable UV mass extinction coefficients determined. The protocol was subsequently used to synthesize an optimized heparin-aldehyde that had minimal polydispersity (PDI < 2) and high reaction yields (yield >60% by mass). The 8 kDa weight averaged molar mass heparin-aldehyde was then grafted on polycaprolactone (PCL), a common implant material. This optimized heparin-aldehyde retained its antithrombin activity, assessed in freshly drawn blood or surface immobilized on PCL films. Anticoagulant activity was equal to or better than the 24 kDa unmodified heparin it was fragmented from. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore) Accepted version 2017-03-16T04:54:55Z 2019-12-06T13:52:54Z 2017-03-16T04:54:55Z 2019-12-06T13:52:54Z 2015 Journal Article Irvine, S. A., Steele, T. W. J., Bhuthalingam, R., Li, M., Boujday, S., Prawirasatya, M., et al. (2015). Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials. Colloids and Surfaces B: Biointerfaces, 132, 253-263. 0927-7765 https://hdl.handle.net/10356/80595 http://hdl.handle.net/10220/42175 10.1016/j.colsurfb.2015.05.023 en Colloids and Surfaces B: Biointerfaces © 2015 Elsevier. This is the author created version of a work that has been peer reviewed and accepted for publication by Colloids and Surfaces B: Biointerfaces, Elsevier. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [http://dx.doi.org/10.1016/j.colsurfb.2015.05.023]. 32 p. application/pdf
spellingShingle Heparin
Aniline
Irvine, Scott Alexander
Steele, Terry W. J.
Bhuthalingam, Ramya
Li, Min
Boujday, Souhir
Prawirasatya, Melissa
Neoh, Koon Gee
Boey, Freddy Yin Chiang
Venkatraman, Subbu S.
Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials
title Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials
title_full Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials
title_fullStr Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials
title_full_unstemmed Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials
title_short Quantification of aldehyde terminated heparin by SEC-MALLS-UV for the surface functionalization of polycaprolactone biomaterials
title_sort quantification of aldehyde terminated heparin by sec malls uv for the surface functionalization of polycaprolactone biomaterials
topic Heparin
Aniline
url https://hdl.handle.net/10356/80595
http://hdl.handle.net/10220/42175
work_keys_str_mv AT irvinescottalexander quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials
AT steeleterrywj quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials
AT bhuthalingamramya quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials
AT limin quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials
AT boujdaysouhir quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials
AT prawirasatyamelissa quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials
AT neohkoongee quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials
AT boeyfreddyyinchiang quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials
AT venkatramansubbus quantificationofaldehydeterminatedheparinbysecmallsuvforthesurfacefunctionalizationofpolycaprolactonebiomaterials