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Source Information for the following slides: 1) B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004).
Pain Leads Art Professor to Remove "Third Eye" Camera From Head An assistant arts professor at New York University, needed to remove the camera he had installed into the back of his head earlier this month because his body rejected the foreign object. Perhaps one of the primary problems: • The camera, which was implanted between his skin and his skull in a L.A. tattoo shop…. Biocompatability • Titanium posts… • •
‐water insoluble, three dimensional network of polymeric chains that are crosslinked by chemical or physical bonding; ‐polymers capable of swelling substantially in aqueous conditions (e.g. hydrophilic) ‐polymeric network in which water is dispersed throughout the structure
Cross‐links may be physical or chemical:
– by reaction of one or more monomers with pendant functional groups – hydrogen or ionic bonding, or – van der Waals interactions
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2/21/2011 6 . • When the content of water exceeds 95% of the total weight (or volume). • By definition. water must constitute at least 10% of the total weight (or volume) for a materials to be a hydrogel.Hydrogels • One or more highly electronegative atoms which results in charge asymmetry favoring hydrogen bonding with water. • Because of their hydrophilic nature dry materials absorb water. the hydrogel is said to be superabsorbant.
Classification based on preparation method – homopolymer hydrogels (one type of hydrophilic mer) – copolymer hydrogels (two types of mers. making intermeshing network of polymer1 and polymer2) . at least one hydrophilic) – multipolymer hydrogels (more than three types of mers) – interpenetrating polymeric hydrogels (swelling a network of polmer1 in mer2.
Hydrogels • Classification based on ionic charges – – – – neutral hydrogels anionic hydrogels cationic hydrogels ampholytic hydrogels • Classification based on structure – amorphous hydrogels (chains randomly arranged) – semicrystalline hydrogels (dense regions of ordered macromolecules. i.e. crystallites) – hydrogen‐bonded hydrogels 8 .
Preparation of Hydrogels 2/21/2011 Hoffman. S. Rev. Adv. 43. 2002.. Drug Deliv. A. 3 9 .
The unique property of these gels is there ability to maintain their original shape during and after swelling.Hydrogels: • • • • • In a chemically cross‐linked hydrogel. all of the polymer chains are connected by covalent bonds to form a network. thus Can be viewed as one one molecule of large size. Two forces become equal at some point and equilibrium is reached 2/21/2011 10 . and. The thermodynamically driven swelling force is counterbalanced by the retractive force of the crosslinked structure.
s is the polymer volume fraction of the gel • weight degree of swelling: ratio of the weight of swollen sample to that of the dry sample (q) 2/21/2011 11 . s Volume of swollen gel Vgel where v 2 .Hydrogels: Swelling • Degree of swelling can be quantified by: • ratio of sample volume in the swollen state to volume in the dry state (Q) Vp Volume of polymer 1/ Q v2.
Hydrogels: Swelling Why is the degree of swelling important? solute diffusion coefficient through the hydrogel surface properties and surface mobility optical properties (particularly for contact lens applications) mechanical properties 2/21/2011 12 .
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s 2 .Structural Characteristics M c (Molecular weight between crosslinks) Defines the average molecular weight between two consecutive junctions. s ) 2. 2 1 2 ( / V1 ) ln(1 2. s 1 2. s 1/ 3 2 Mc Mc .water interaction parameter is the reciprocal of the amorphous polymer density (specific volume of polymer) Crosslink density 1 x Mc . s / 2) where 1 is polymer .
Hydrogels •Crosslink structure: A) ideal network with tetrafunctional covalent crosslinks (rarely observed) B) multifunctional junctions C) molecular entanglements (could be permanent or semi‐permanent) Mc: Molecular weight between crosslinks 15 .
Hydrogels •Defects in crosslink structure: D) unreacted functionality E) chain loops •Note that neither of the two configurations contribute to mechanical strength or physical properties of the network 16 .
Highly compressed in secretory vessicle and expand rapidly and dramatically on release – Can undergo volumetric phase transitions in response to ionic concentrations (Ca++. H+).Important features of hydrogels – Usually comprised of highly polyionic polymers – Often exhibit large volumetric changes eg. .. hydrophobic • attractive. hydrogen binding. – Volume is determined by combination of attractive and repulsive forces: • repulsive electrostatic. cross‐linking 2/21/2011 17 . temperature.
2/21/2011 18 .Xerogels • Dried hydrogels • Usually clear and swelling in water takes a long time. • A useful property in controlled drug delivery. • The swelling behavior is due to slow diffusion of water through the compact polymer chains.
Chitosan 2/21/2011 19 .
Applications Pharmaceutical applications – monomer composition and relative amounts of multi‐polymer hydrogels can be varied to alter the diffusion characteristic and – permeability of the gel containing pharmaceutical agents Methods for drug delivery – drug gets trapped in the hydrogel during polymerization – drug introduced during swelling in water – Release occurs by outflow of drug from the gel and inflow of water to the gel 2/21/2011 20 .
Drug delivery 2/21/2011 21 .
Examples of biological hydrogels: – – – – – – – – Jello (a collagen gel ~ 97% water) Extracellular matrix components Polysaccharides DNA/RNA Blood clot Mucin ‐ lining the stomach. bronchial tubes. intestines Gycocalyx ‐ lining epithelial cells of blood vessels Sinus secretions 22 2/21/2011 .
Fibrin Hydrogel (Blood Clot) 2/21/2011 23 .
Function of a biological hydrogel – – – – – Decreased permeability to large molecules Structural strength (for epithelial cell walls) Capture and clearance of foreign substances Decreased resistance to sliding/gliding High internal viscosity (low washout) 2/21/2011 24 .
Hydrogel Forming Polymers Natural H O 2C HO O HO O OH HO O NH O O n poly(s odium alginate) NaO 2 C HO OH O O n poly(hyaluronic acid) Synthetic O O n O n NH O n poly(lactic acid) poly(N ‐ is opropyl acrylamide) poly(ethylene g lycol) 2/21/2011 25 .
Hydrogels Highly swollen hydrogels: • • • • • cellulose derivatives poly(vinyl alcohol) poly(N‐vinyl 2‐pyrrolidone). PNVP poly(ethylene glycol) poly(hydroxyethyl methacrylate). PHEMA and derivatives Moderately or poorly swollen hydrogels: One may copolymerize a higly hydrophilic monomer with other less hydrophilic monomers to achieve desired swelling properties 2/21/2011 26 .
Hylauronic Acid 2/21/2011 27 .
Polyelectrolyte Hydrogels 2/21/2011 28 .
Alginate gels β linkage α linkage 2/21/2011 29 .
Alginate gels 2/21/2011 30 .
Enzyme Immobilization 2/21/2011 31 .
Cell Encapsulation 2/21/2011 32 .
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Applications in Biomaterials and Tissue Engineering • • • • • • Cell Encapsulation Drug delivery Surface modification Enzyme Immobilization Biosensors Lab on a chip 2/21/2011 35 .
Hydrogels: PHEMA • • • • • • • • The most widely used hydrogel water content similar to living tissues inert to biological processes shows resistance to degradation permeable to metabolites not absorbed by the body withstands sterilization by heat prepared in various shaped and forms 2/21/2011 36 .
drainage tubes and gloves • non‐toxic 2/21/2011 37 .Hydrogels: Applications • • • • Biomedical use due to bio‐ and blood‐compatibility Pharmaceutical use due to hydrophilicity (controlled/sustained drug release) Earliest biomedical application contact lenses • good mechanical stability • favorable refractive index • high oxygen permeability • needs hygienic maintenance • unable to correct for astigmatism lubricating surface coating • used with catheters.
Corning® Ultra Low Attachment Products Unique hydrogel surface inhibits cell attachment 2/21/2011 38 .
Ocular Drug Delivery 2/21/2011 39 .
flexible wound cover – permeable to water and metabolites – low‐strength • • • • artificial kidney membranes artificial skin maxillofacial and sexual organ reconstruction materials vocal cord replacement 2/21/2011 40 . • Gelperm®) – non‐antigenic. Hydron®.Applications • artificial tendon and cartilage • wound healing dressings (Vigilon®.
Applications Pharmaceutical applications – monomer composition and relative amounts of multi‐polymer hydrogels can be varied to alter the diffusion characteristic and – permeability of the gel containing pharmaceutical agents Methods for drug delivery – drug gets trapped in the hydrogel during polymerization – drug introduced during swelling in water – Release occurs by outflow of drug from the gel and inflow of water to the gel 2/21/2011 41 .
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Contact lens • PMMA • HEMA • Fabrication methods – Computer assisted cutting (lathe)‐PMMA rods – Spin casting‐polymerization – Molding‐polymerization 2/21/2011 44 .
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