Chemoselective cross-linking and functionalization of alginate via Staudinger ligation

Kerim M. Gattás-Asfura, Cherie L. Stabler

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

In this study, we demonstrate the applicability of functionalized alginate to serve as a platform for the covalent cross-linking or immobilization of complementary phosphine functionalized groups via the chemoselective Staudinger ligation scheme. Azide groups were covalently linked to alginate through a heterobifunctional polyethylene glycol (PEG) linker and carbodiimide. Degree of azide functionalization was varied as a function of carbodiimide concentration and determined by proton nuclear magnetic resonance ( 1H NMR) and infrared spectroscopy. Spontaneous and covalently cross-linked alginate-PEG gels were generated via the Staudinger ligation scheme upon incubation of the azide functionalized alginate with PEG chains having 1-methyl-2- diphenylphosphinoterephthalate (MDT) as end groups. Modulation of the MDT to N 3 ratio resulted in variability of gel characteristics. In addition, azide functionalized alginate retained its capacity to instantaneously form hydrogels via electrostatic interaction with multivalent cations such as Ca 2+ and Ba 2+. Subsequently, covalent linkage of phosphine functionalized agents postgelation of the alginate was feasible, as illustrated via linkage of MDT-PEG-carboxyfluorescein. Capitalization of the chemoselective and cell compatible Staudinger ligation scheme for covalent cross-linking of alginate hydrogels may enhance the utility of this polymer for the stable encapsulation of various cell types, in addition to their use in the immobilization of labeling agents, proteins, and other bioactive molecules.

Original languageEnglish
Pages (from-to)3122-3129
Number of pages8
JournalBiomacromolecules
Volume10
Issue number11
DOIs
StatePublished - Nov 9 2009

Fingerprint

Alginate
phosphine
Azides
Polyethylene glycols
Carbodiimides
Hydrogels
Gels
Nuclear magnetic resonance
Coulomb interactions
alginic acid
Encapsulation
Labeling
Nuclear magnetic resonance spectroscopy
Cations
Infrared spectroscopy
Polymers
Positive ions
Modulation
Proteins
Molecules

ASJC Scopus subject areas

  • Bioengineering
  • Materials Chemistry
  • Polymers and Plastics
  • Biomaterials

Cite this

Chemoselective cross-linking and functionalization of alginate via Staudinger ligation. / Gattás-Asfura, Kerim M.; Stabler, Cherie L.

In: Biomacromolecules, Vol. 10, No. 11, 09.11.2009, p. 3122-3129.

Research output: Contribution to journalArticle

Gattás-Asfura, Kerim M. ; Stabler, Cherie L. / Chemoselective cross-linking and functionalization of alginate via Staudinger ligation. In: Biomacromolecules. 2009 ; Vol. 10, No. 11. pp. 3122-3129.
@article{deb8c4e4453848b3b298a2246ccdbd36,
title = "Chemoselective cross-linking and functionalization of alginate via Staudinger ligation",
abstract = "In this study, we demonstrate the applicability of functionalized alginate to serve as a platform for the covalent cross-linking or immobilization of complementary phosphine functionalized groups via the chemoselective Staudinger ligation scheme. Azide groups were covalently linked to alginate through a heterobifunctional polyethylene glycol (PEG) linker and carbodiimide. Degree of azide functionalization was varied as a function of carbodiimide concentration and determined by proton nuclear magnetic resonance ( 1H NMR) and infrared spectroscopy. Spontaneous and covalently cross-linked alginate-PEG gels were generated via the Staudinger ligation scheme upon incubation of the azide functionalized alginate with PEG chains having 1-methyl-2- diphenylphosphinoterephthalate (MDT) as end groups. Modulation of the MDT to N 3 ratio resulted in variability of gel characteristics. In addition, azide functionalized alginate retained its capacity to instantaneously form hydrogels via electrostatic interaction with multivalent cations such as Ca 2+ and Ba 2+. Subsequently, covalent linkage of phosphine functionalized agents postgelation of the alginate was feasible, as illustrated via linkage of MDT-PEG-carboxyfluorescein. Capitalization of the chemoselective and cell compatible Staudinger ligation scheme for covalent cross-linking of alginate hydrogels may enhance the utility of this polymer for the stable encapsulation of various cell types, in addition to their use in the immobilization of labeling agents, proteins, and other bioactive molecules.",
author = "Gatt{\'a}s-Asfura, {Kerim M.} and Stabler, {Cherie L.}",
year = "2009",
month = "11",
day = "9",
doi = "10.1021/bm900789a",
language = "English",
volume = "10",
pages = "3122--3129",
journal = "Biomacromolecules",
issn = "1525-7797",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - Chemoselective cross-linking and functionalization of alginate via Staudinger ligation

AU - Gattás-Asfura, Kerim M.

AU - Stabler, Cherie L.

PY - 2009/11/9

Y1 - 2009/11/9

N2 - In this study, we demonstrate the applicability of functionalized alginate to serve as a platform for the covalent cross-linking or immobilization of complementary phosphine functionalized groups via the chemoselective Staudinger ligation scheme. Azide groups were covalently linked to alginate through a heterobifunctional polyethylene glycol (PEG) linker and carbodiimide. Degree of azide functionalization was varied as a function of carbodiimide concentration and determined by proton nuclear magnetic resonance ( 1H NMR) and infrared spectroscopy. Spontaneous and covalently cross-linked alginate-PEG gels were generated via the Staudinger ligation scheme upon incubation of the azide functionalized alginate with PEG chains having 1-methyl-2- diphenylphosphinoterephthalate (MDT) as end groups. Modulation of the MDT to N 3 ratio resulted in variability of gel characteristics. In addition, azide functionalized alginate retained its capacity to instantaneously form hydrogels via electrostatic interaction with multivalent cations such as Ca 2+ and Ba 2+. Subsequently, covalent linkage of phosphine functionalized agents postgelation of the alginate was feasible, as illustrated via linkage of MDT-PEG-carboxyfluorescein. Capitalization of the chemoselective and cell compatible Staudinger ligation scheme for covalent cross-linking of alginate hydrogels may enhance the utility of this polymer for the stable encapsulation of various cell types, in addition to their use in the immobilization of labeling agents, proteins, and other bioactive molecules.

AB - In this study, we demonstrate the applicability of functionalized alginate to serve as a platform for the covalent cross-linking or immobilization of complementary phosphine functionalized groups via the chemoselective Staudinger ligation scheme. Azide groups were covalently linked to alginate through a heterobifunctional polyethylene glycol (PEG) linker and carbodiimide. Degree of azide functionalization was varied as a function of carbodiimide concentration and determined by proton nuclear magnetic resonance ( 1H NMR) and infrared spectroscopy. Spontaneous and covalently cross-linked alginate-PEG gels were generated via the Staudinger ligation scheme upon incubation of the azide functionalized alginate with PEG chains having 1-methyl-2- diphenylphosphinoterephthalate (MDT) as end groups. Modulation of the MDT to N 3 ratio resulted in variability of gel characteristics. In addition, azide functionalized alginate retained its capacity to instantaneously form hydrogels via electrostatic interaction with multivalent cations such as Ca 2+ and Ba 2+. Subsequently, covalent linkage of phosphine functionalized agents postgelation of the alginate was feasible, as illustrated via linkage of MDT-PEG-carboxyfluorescein. Capitalization of the chemoselective and cell compatible Staudinger ligation scheme for covalent cross-linking of alginate hydrogels may enhance the utility of this polymer for the stable encapsulation of various cell types, in addition to their use in the immobilization of labeling agents, proteins, and other bioactive molecules.

UR - http://www.scopus.com/inward/record.url?scp=70449475340&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=70449475340&partnerID=8YFLogxK

U2 - 10.1021/bm900789a

DO - 10.1021/bm900789a

M3 - Article

VL - 10

SP - 3122

EP - 3129

JO - Biomacromolecules

JF - Biomacromolecules

SN - 1525-7797

IS - 11

ER -