RESUMO
We synthesized methoxy poly(ethylene glycol)-b-poly(alpha,L-glutamic acid) (mPEGGA) diblock copolymer by ring-opening polymerization of N-carboxy anhydride of gamma-benzyl-L-glutamate (NCA) using amino-terminated methoxy polyethylene glycol (mPEG) as macroinitiator. Polyelectrolyte complexation between mPEGGA as neutral-block-polyanion and chitosan (CS) as polycation has been scrutinized in aqueous solution as well as in the solid state. Water-soluble polyelectrolyte complexes (PEC) can be formed only under nonstoichiometric condition while phase separation is observed when approaching 1:1 molar mixing ratio in spite of the existence of hydrophilic mPEG block. This is likely due to mismatch in chain length between polyanion block of the copolymer and the polycation or hydrogen bonding between the components. Hydrodynamic size of primary or soluble PEC is determined to be about 200 nm, which is larger than those reported in some literatures. The increase in polyion chain length of the copolymer leads to the increase in the hydrodynamic size of the water-soluble PEC. Formation of spherical micelles by the mPEGGA/CS complex at nonstoichiometirc condition has been confirmed by the scanning electron microscopy observation and transmission electron microscopy observations. The homopolymer CS experiences attractive interaction with both mPEGA and PGA blocks within the copolymer. Competition of hydrogen bonding and electrostatic force in the system or hydrophilic mPEG segments weakens the electrostatic interaction between the oppositely charged polyions. The existence of hydrogen bonding restrains the mobility of mPEG chains of the copolymer and completely prohibits crystallization of mPEG segments. In vitro culture of human fibroblasts indicates that mPEGGA/CS-based materials have potential in biomedical application, especially in tissue engineering.
Assuntos
Materiais Biocompatíveis/química , Quitosana/química , Eletrólitos/química , Polietilenoglicóis/química , Ácido Poliglutâmico/análogos & derivados , Ânions , Fibroblastos/metabolismo , Humanos , Concentração de Íons de Hidrogênio , Espectroscopia de Ressonância Magnética , Teste de Materiais , Micelas , Modelos Químicos , Ácido Poliglutâmico/química , Polímeros/química , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
A methoxypoly(ethylene glycol)-block-poly(α,L-glutamic acid) (mPEGGA) diblock copolymer is synthesized. Using QCM measurements, it is shown that (CS/mPEGGA)(n) film construction takes place over two build-up stages (exponential-to-linear). UV-vis spectra reveal the regular increase of the multilayer film growth at different molecular weights of mPEGGA. Contact angle and surface morphology investigation prove that the hydrophilicity of CS/mPEGGA multilayer film-modified substrate becomes better and the surface becomes rough. Significantly reduced cell adhesion is observed on the CS/mPEGGA multilayer film coated surface.
Assuntos
Adesão Celular , Quitosana/química , Materiais Revestidos Biocompatíveis/síntese química , Ácido Glutâmico/química , Polietilenoglicóis/química , Polímeros/síntese química , Células Cultivadas , Materiais Revestidos Biocompatíveis/química , Teste de Materiais , Peso Molecular , Polímeros/química , Células-Tronco/citologia , Propriedades de SuperfícieRESUMO
A novel PAA-b-PLGA diblock copolymer is synthesized and characterized that has excellent cell adhesion and biocompatibility. Fluorescent DiO labeling is used to monitor the attachment and growth of hASCs on the film surface, and cell proliferation over time is studied. Results show that PLLA modified by a CS/PAA-b-PLGA multilayer film can promote the attachment of human hASCs and provide an advantageous environment for their proliferation. The multilayer film presents excellent biocompatibility and cell adhesive properties, which will provide a new choice for improving the cell attachment in surface modification for tissue engineering. Hydroxyl, carboxyl and amine groups in the CS/PAA-b-PLGA multilayer film may be combined with drugs and growth factors for therapy and differentiation.
Assuntos
Resinas Acrílicas/síntese química , Ácido Glutâmico/síntese química , Resinas Acrílicas/química , Materiais Biocompatíveis/química , Adesão Celular , Proliferação de Células , Células Cultivadas , Portadores de Fármacos , Ácido Glutâmico/química , Humanos , Interações Hidrofóbicas e Hidrofílicas , Células-Tronco/metabolismo , Propriedades de Superfície , Alicerces TeciduaisRESUMO
A new biocompatible film based on chitosan and poly(L-glutamic acid) (CS/PGA), created by alternate deposition of CS and PGA, was investigated. FT-IR spectroscopy, UV-vis spectroscopy and QCM were used to analyze the build-up process. The growth of CS and PGA deposition are both exponential to the deposition steps at first. After about 9 (CS/PGA) depositions, the exponential to linear transition takes place. QCM measurements combined with UV-vis spectra revealed the increase in the multilayer film growth at different pH (4.4, 5.0 and 5.5). The build-up of the multilayer stops after a few depositions at pH = 6.5. A muscle myoblast cell (C2C12) assay showed that (CS/PGA)(n) multilayer films obviously promote C2C12 attachment and growth.