Summary

Realizzazione superidrofobiche Materiali Polimerici per applicazioni biomediche

Published: August 28, 2015
doi:

Summary

Two- and three-dimensional superhydrophobic polymeric materials are prepared by electrospinning or electrospraying biodegradable polymers blended with a lower surface energy polymer of similar composition.

Abstract

Materiali superhydrophobic, con superfici possiedono stati non a contatto col permanenti o metastabili, sono di interesse per un numero di applicazioni biomediche e industriali. Qui si descrive come electrospinning o electrospraying una miscela polimerica contenente un biodegradabile, biocompatibile poliestere alifatico (ad esempio, policaprolattone e poli (-glycolide co lactide-)), come componente principale, drogato con un copolimero composto idrofobico del poliestere e un stearate- poli modificato (carbonato di glicerolo) offre un biomateriale superhydrophobic. Le tecniche di fabbricazione di electrospinning o electrospraying forniscono la rugosità superficiale e porosità maggiore su e all'interno delle fibre o particelle, rispettivamente. L'uso di un copolimero a bassa energia superficiale drogante che si fonde con il poliestere e può essere stabilmente elettrofilate o electrosprayed offre questi materiali superhydrophobic. Parametri importanti quali la dimensione delle fibre, composizione del copolimero drogante e / o concentration, ei loro effetti sulla bagnabilità sono discussi. Questa combinazione di chimica dei polimeri e di processo offre un approccio versatile per sviluppare materiali specifici dell'applicazione utilizzando tecniche scalabili, che possono generalizzabile ad una classe più ampia di polimeri per una varietà di applicazioni.

Introduction

Superfici superidrofobiche sono generalmente classificati come espositrici contatto con l'acqua apparente angoli superiori a 150 ° con un basso angolo di contatto isteresi. Queste superfici sono fabbricati introducendo elevata rugosità superficiale su materiali a bassa energia superficiale di stabilire un conseguente interfaccia aria-liquido-solido che resiste bagnare 1-6. A seconda del metodo di fabbricazione, superfici sottili o multistrato superhydrophobic, multistrato rivestimenti substrato superhydrophobic, o strutture superhydrophobic anche sfusi può essere preparato. Questo idrorepellenza permanente o semi-permanente è una proprietà utile che viene impiegato per la preparazione delle superfici autopulenti 7, dispositivi microfluidici 8, antivegetativa superfici cellule / proteine ​​9,10, superfici-trascinare la riduzione di 11, e dispositivi di somministrazione dei farmaci 12- 15. Recentemente, stimoli-responsive materiali superhydrophobic sono descritti in cui la non bagnato allo stato bagnato è attivata da chimici, fisici, O stimoli ambientali (ad esempio, la luce, pH, temperatura, ultrasuoni, e applicato il potenziale elettrico / corrente) 14,16-20, e questi materiali trovano impiego per applicazioni aggiuntive 21-25.

Le prime superfici superhydrophobic sintetici sono stati preparati trattando le superfici di materiali con methyldihalogenosilanes 26, ed erano di valore limitato per applicazioni biomediche, come i materiali utilizzati non erano adatti per l'uso in vivo. Qui si descrive la preparazione di superfici e materiali superhydrophobic rinfusa da polimeri biocompatibili. Il nostro approccio comporta electrospinning o electrospraying una miscela polimerica contenente un biodegradabile, biocompatibile poliestere alifatico come componente principale, drogato con un copolimero composto idrofobico del poliestere e un poli (carbonato di glicerolo) stearato modificato 27-30. Le tecniche di fabbricazione forniscono la rugosità superficiale maggiore e porosità acceso e all'interno della FIBErs o particelle, rispettivamente, mentre l'uso di un drogante copolimero fornisce un polimero a bassa energia superficiale che si fonde con il poliestere e può essere stabilmente elettrofilate o electrosprayed 27,31,32.

Poliesteri alifatici biodegradabili come il poli (acido lattico) (PLA), poli (acido glicolico) (PGA), poli (lattico co acido acido -glycolic) (PLGA) e policaprolattone (PCL) sono polimeri utilizzati in dispositivi clinicamente approvati e prominente in materiali Ricerca Biomedica a causa della loro non-tossicità, biodegradabilità, e la facilità di sintesi 33. PGA e PLGA debuttato nella clinica come suture riassorbibili nel 1960 e 1970, rispettivamente primi anni 34-37. Da allora, questi poli (idrossiacidi) sono stati trasformati in una serie di altri fattori di forma per applicazioni specifiche, come ad esempio micro- e nanoparticelle 40,41 38,39, wafer / dischi 42, maglie 27,43, schiume 44, e 45 film </sup>.

Poliesteri alifatici, nonché altri polimeri di interesse biomedico, possono essere elettrofilate per produrre nano o maglie microfibra strutture che possiedono elevata area superficiale e porosità e resistenza alla trazione. Tabella 1 elenca i polimeri sintetici elettrofilate per varie applicazioni biomediche e loro corrispondenti riferimenti. Electrospinning e electrospraying sono tecniche rapide e commercialmente scalabili. Queste due tecniche simili si basano sull'applicazione di alta tensione (repulsione elettrostatica) per superare la tensione superficiale di una soluzione polimerica / fondere in una configurazione pompa a siringa è diretto verso un bersaglio a terra 46,47. Quando questa tecnica viene utilizzata in combinazione con polimeri a bassa energia superficiale (polimeri idrofobi come poli (monostearato co caprolactone- -glycerol)), il conseguente superhydrophobicity materiali per mostre.

Per illustrare questo approccio generale sintetico e trattamento dei materialialla costruzione di materiali superhydrophobic da polimeri biomedici, si descrive la sintesi di polycaprolactone- superhydrophobic e poli (lactide- co -glycolide) materiali basati su come esempi rappresentativi. Il rispettivo poli droganti copolimero (Monostearato co caprolactone- -glycerol) e poli (Monostearato co lactide- -glycerol) vengono prima sintetizzate, poi mescolato con policaprolattone e poli (lactide- co -glycolide), rispettivamente, e infine elettrofilate o electrosprayed. I materiali risultanti sono caratterizzati da SEM imaging e angolo di contatto goniometry, e testati de vitro e in vivo biocompatibilità. Infine, bagnatura massa attraverso tridimensionali maglie superhydrophobic viene esaminato con mdc tomografia microcomputed.

Protocol

1. Synthesizing Functionalizable poli (1,3-glicerolo carbonate- co caprolattone) 29 e poli (1,3-glicerolo carbonate- co -lactide) 27,28. Sintesi monomero. Sciogliere cis -2-fenil-1,3-diossano-5-olo (50 g, 0,28 moli, 1 eq.) In 500 ml di tetraidrofurano anidro (THF) e mescolate in ghiaccio sotto azoto. Aggiungere idrossido di potassio (33,5 g, 0,84 mol, 3 eq.), Finemente tritato con un mortaio e pestello. Mettere pallone in bagno di ghiaccio. A…

Representative Results

Attraverso una serie di trasformazioni chimiche, il monomero funzionale carbonato di 5-benzilossi-1,3-diossan-2-one è sintetizzato come solido bianco cristallino (Figura 1A). 1 H NMR conferma la struttura (Figura 1B) e spettrometria di massa e analisi elementare confermare la composizione. Questo solido viene poi copolimerizzato sia con D, L o -lactide ε-caprolattone con una apertura di anello di reazione tin-catalizzata a 140 ° C. Dopo purificazione mediante prec…

Discussion

Il nostro approccio alla costruzione di materiali superhydrophobic da polimeri biomedici combina chimica dei polimeri sintetici con le tecniche di lavorazione di polimeri di electrospinning e electrospraying. Queste tecniche forniscono sia fibre o particelle, rispettivamente. In particolare, policaprolattone e poli (lactide- co -glycolide) materiali a base superhydrophobic vengono preparati usando questa strategia. Variando la composizione del copolimero idrofobo, copolimero cento nella miscela polimerica final…

Declarações

The authors have nothing to disclose.

Acknowledgements

Funding was provided in part by BU and the NIH R01CA149561. The authors wish to thank the electrospinning/electrospraying team including Stefan Yohe, Eric Falde, Joseph Hersey, and Julia Wang for their helpful discussions and contributions to the preparation and characterization of superhydrophobic biomaterials.

Materials

Silicone oil Sigma-Aldrich 85409
Cis-2-Phenyl-1,3-dioxan-5-ol Sigma-Aldrich 13468
Benzyl bromide Sigma-Aldrich B17905 Toxic, lacrymator/eye irritant, use in chemical fume hood
Potassium hydroxide Sigma-Aldrich 221473 Corrosive
Rotary evaporator Buchi R-124
High-vacuum pump Welch 8907
Nitrogen, ultra high purity Airgas NI UHP300 Compressed gas
Tetrahydrofuran, stabilized with BHT Pharmaco-Aaper 346000 Flammable. Dried through column of XXX
Dichloromethane Pharmaco-Aaper 313000 Flammable, toxic.
Separatory funnel (1 L) Fisher Scientific 13-678-606
Sodium sulfate Sigma-Aldrich 239313
Ethanol, absolute Pharmaco-Aaper 111USP200 Flammable, toxic.
Buchner funnel Fisher Scientific FB-966-F
Methanol Pharmaco-Aaper 339000ACS Flammable, toxic.
Hydrochloric acid Sigma-Aldrich 320331 Corrosive. Diluted to 2N in distilled water.
Ethyl chloroformate, 97% Sigma-Aldrich 185892 Toxic, flammable, harmful to environment
Triethylamine (anhydrous) Sigma-Aldrich 471283 Toxic, flammable, harmful to environment
Diethyl ether Pharmaco-Aaper 373ANHACS Highly flammable. Purified through XXX column.
3,6-Dimethyl-1,4-dioxane-2,5-dione (D,L-lactide) Sigma-Aldrich 303143
Tin (II) ethylhexanoate Sigma-Aldrich S3252 Toxic.
ε-caprolactone (97%) Sigma-Aldrich 704067
Toluene, anhydrous Sigma-Aldrich 244511 Flammable, toxic.
Glass syringe Hamilton Company 1700-series
Deuterated chloroform Cambridge Isotopes Laboratories, Inc. DLM-29-10 Toxic
Nuclear magnetic resonance instrument Varian V400
Palladium on carbon catalyst Strem Chemicals, Inc. 46-1707
Hydrogenator unit Parr 3911
Hydrogenator shaker vessel Parr 66CA
Hydrogen Airgas HY HP300 Highly flammable.
Diatomaceous earth Sigma-Aldrich 22140
2H,2H,3H,3H-perflurononanoic acid Oakwood Products, Inc. 10519 Toxic.
Stearic acid Sigma-Aldrich S4751
N,N’-dicyclohexylcarbodiimide Sigma-Aldrich D80002 Toxic, irritant.
4-(dimethylamino) pyridine Sigma-Aldrich 107700 Toxic.
Hexanes Pharmaco-Aaper 359000ACS Toxic, flammable.
Gel permeation chromatography (GPC) system Rainin
GPC column Waters WAT044228
Differential scanning calorimeter TA Instruments Q100
Chloroform Pharmaco-Aaper 309000ACS Toxic.
N,N-dimethylformamide Sigma-Aldrich 227056 Toxic, flammable.
Polycaprolactone, MW 70-90 kg/mol Sigma-Aldrich 440744
Poly(lactide-co-glycolide), MW 136 kg/mol Evonik Industries LP-712
10-mL glass syringe Hamilton Company 81620
18 AWG blunt needle BRICO Medical Supplies BN1815
Electrospinner enclosure box Custom-built N/A Made of acrylic panels
High voltage DC supply Glassman High Voltage, Inc. PS/EL30R01.5 High voltages, electrocution hazard
Linear (translating) stage Servo Systems Co. LPS-12-20-0.2 Optional
Programmable motor & power supply Intelligent Motion Systems, Inc. MDrive23 Plus Optional
24V DC motor & power supply McMaster-Carr 6331K32 Optional
Aluminum collector drum Custom-built Optional
Syringe pump Fisher Scientific 78-0100I
Inverted optical microscope Olympus IX70
Scanning electron microscope Carl Zeiss Supra V55
Conductive copper tape 3M 16072
Aluminum SEM stubs Electron Microscopy Sciences 75200
Contact angle goniometer Kruss DSA100
Propylene glycol Sigma-Aldrich W294004 Toxic.
Ethylene glycol Sigma-Aldrich 324558 Toxic.
Ioxaglate Guerbet
Fetal bovine serum American Type Culture Collection 30-2020
Micro-computed tomography instrument Scanco
Image analysis software (Analyze) Mayo Clinic
Tensile tester Instron 5848
Micrometer Multitoyo 293-340
Calipers Fisher Scientific 14-648-17

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Kaplan, J., Grinstaff, M. Fabricating Superhydrophobic Polymeric Materials for Biomedical Applications. J. Vis. Exp. (102), e53117, doi:10.3791/53117 (2015).

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