Interfacial Photopolymerization Research Articles

Interfacial Photopolymerization: A Method for Light-Based Printing of Thermoplastics.

Ultraviolet (UV) printing of photopolymers is a widely adopted manufacturing method because of its high resolution and throughput. However, available printable photopolymers are typically thermosets, resulting in challenges in postprocessing and recycling of printed structures. Here, we present a new process called interfacial photopolymerization (IPP) which enables photopolymerization printing of linear chain polymers. In IPP, a polymer film is formed at the interface between two immiscible liquids, one containing a chain-growth monomer and the other containing a photoinitiator. We demonstrate the integration of IPP in a proof-of-concept projection system for printing of polyacrylonitrile (PAN) films and rudimentary multi-layer shapes . IPP shows in-plane and out-of-plane resolutions comparable to conventional photoprinting methods. Cohesive PAN films with number-average molecular weights greater than 15 kg mol-1 are obtained, and to our knowledge this is the first report of photopolymerization printing of PAN. A macrokinetics model of IPP is developed to elucidate the transport and reaction rates involved and evaluate how reaction parameters affect film thickness and print speed. Last, demonstration of IPP in a multilayer scheme suggests its suitabiliy for three-dimensional printing of linear-chain polymers.

An analytic model of two-level compressive buckling with applications in the assembly of free-standing 3D mesostructures.

Recently developed methods for mechanically-guided assembly exploit stress release in prestretched elastomeric substrates to guide the controlled formation of complex three-dimensional (3D) mesostructures in advanced functional materials and integrated electronic devices. The techniques of interfacial photopolymerization allow for realization of such 3D mesostructures in free-standing forms, separated from their elastomeric substrate, via formation of an integrated base layer. Theoretical models for the complex modes of deformation associated with this scheme are essential in the optimal design of the process parameters. Here, we present an analytic finite-deformation model of an isolated double-ribbon structure to describe the buckling process and morphology change of the assembled mesostructures upon removal of the substrate. As validated by finite element analyses (FEA), this analytic model can accurately predict the profiles of the double-ribbon structure with a range of different design parameters. We further illustrate the extension of this model to the analyses of 3D mesostructures with different geometries. Inspired by analytic results for flexible base structures, combined experimental results and numerical simulations demonstrate that mechanical interactions between the two different layers can be leveraged to achieve hierarchical assembly of 3D mesostructures. These findings could be useful in further advances in designs of free-standing 3D mesostructures based on mechanically-guided assembly.

Three-dimensional mesostructures as high-temperature growth templates, electronic cellular scaffolds, and self-propelled microrobots

Recent work demonstrates that processes of stress release in prestrained elastomeric substrates can guide the assembly of sophisticated 3D micro/nanostructures in advanced materials. Reported application examples include soft electronic components, tunable electromagnetic and optical devices, vibrational metrology platforms, and other unusual technologies, each enabled by uniquely engineered 3D architectures. A significant disadvantage of these systems is that the elastomeric substrates, while essential to the assembly process, can impose significant engineering constraints in terms of operating temperatures and levels of dimensional stability; they also prevent the realization of 3D structures in freestanding forms. Here, we introduce concepts in interfacial photopolymerization, nonlinear mechanics, and physical transfer that bypass these limitations. The results enable 3D mesostructures in fully or partially freestanding forms, with additional capabilities in integration onto nearly any class of substrate, from planar, hard inorganic materials to textured, soft biological tissues, all via mechanisms quantitatively described by theoretical modeling. Illustrations of these ideas include their use in 3D structures as frameworks for templated growth of organized lamellae from AgCl-KCl eutectics and of atomic layers of WSe2 from vapor-phase precursors, as open-architecture electronic scaffolds for formation of dorsal root ganglion (DRG) neural networks, and as catalyst supports for propulsive systems in 3D microswimmers with geometrically controlled dynamics. Taken together, these methodologies establish a set of enabling options in 3D micro/nanomanufacturing that lie outside of the scope of existing alternatives.

Bactericidal Hydrogels via Surface Functionalization with Cecropin A.

The immobilization of antimicrobial peptides (AMPs) to surfaces, enabling their utilization in biosensor and antibacterial/antifouling coating applications, is typically performed using rigid, solid support materials such as glass or gold and may require lengthy, temperamental protocols. Here, we employ a hydrogel immobilization platform to afford facile fabrication and surface functionalization while offering improved biocompatibility for evaluating the influence of linker length, surface density, and AMP conjugation site on retained peptide activity. Rapid, interfacial photo-polymerization using the radical-mediated thiol-ene addition mechanism was used to generate cross-linked, polymeric coatings bearing residual thiol moieties on prefabricated poly(ethylene glycol) (PEG)-based hydrogel supports. The photo-polymerized coatings were 60 μm thick and contained 0.55 nmol of unreacted free thiols, corresponding to a concentration of 410 μM, for use as cecropin A (CPA) immobilization handles via thiol-maleimide conjugation, where the CPA-bound maleimide moiety was localized at either the carboxyl terminus or midsequence between Ala22 and Gly23. Surface presentation of the thiol handles was controlled by varying the thiolated PEG monomer (PEGSH) used in the photo-polymerizable formulation. Bactericidal activity of CPA functionalized hydrogels against E. coli K235 indicated that CPA immobilized at the carboxyl terminus killed 94 ± 6% of the inoculated pathogens when coatings were prepared with high molecular weight PEGSH and 99 ± 1% when prepared with low molecular weight PEGSH. E. coli cell death demonstrated a stronger dependence on peptide concentration than PEG linker length or degree of thiol functionalization, with activity ranging from 34 ± 13% to 99 ± 1% bacterial cells killed as the prefunctionalization thiol concentration in the coatings was increased from 90 to 990 μM. Finally, the immobilization site on the surface-bound CPA strongly affected antibacterial activity; when midsequence modified CPA was bound to a hydrogel coating bearing 990 μM thiol, only 20 ± 4% of the E. coli population was killed.

Modeling of PEG Hydrogel Membranes for Biomedical Applications

AbstractA mathematical model has been developed for surface‐initiated photopolymerization of PEG‐DA forming cross‐linked hydrogel membranes on the surface of a substrate. The existing model was extended to apply the NF technique, which made it possible to describe the progression of photopolymerization through gelation, and to calculate gelation time, cross‐link density of the gel and soluble phases. The model provides a tool for understanding and studying the kinetics of interfacial photopolymerization reactions, which are important in processes such as cell encapsulation by hydrogel membranes formed through free radical photopolymerization. It will also be useful for applications in tissue engineering, where protein gradients are required for optimizing engineered tissue formation.magnified image

Interfacial photopolymerization of β‐cell clusters: Approaches to reduce coating thickness using ionic and lipophilic dyes

Interfacial photopolymerization of β‐cell clusters: Approaches to reduce coating thickness using ionic and lipophilic dyes

Interfacial photopolymerization of ?-cell clusters: Approaches to reduce coating thickness using ionic and lipophilic dyes

Microencapsulation of insulin-secreting cells is a potential therapy for Type I diabetes. Critical requirements for therapeutic use are the high number of beta-cells to be implanted and a fast insulin diffusion through the encapsulating membrane. The use of thin, conformal coating for beta-cell encapsulation may be a way to reach these goals by decreasing the capsule void volume. This study focuses on the production of very thin membranes by interfacial photopolymerization of beta-cell clusters. Two types of photosensitizing dyes were used: Eosin Y, which stains the cell surface as well as the cytoplasm, and a lipophilic-derivatized eosin that specifically stains the cell membrane. The fraction of encapsulated clusters and membrane thickness were studied as a function of irradiation parameters. In the case of Eosin Y, the fraction of encapsulated clusters is found to depend mainly on an optimal light dose for and above which complete encapsulation is obtained. We found that the membrane thickness decreased with decreasing irradiation time, but does not depend on irradiation intensity. Using Eosin Y, 16 microm thick coatings were obtained, together with a high fraction of encapsulated clusters. The coating thickness was further reduced to 10 microm by using the lipophilic-derivatized eosin photoinitiator. Cell viability and functionality were studied following the encapsulation process using vital staining and measurement of insulin secretion. Cell viability and functionality were preserved following the encapsulation process with Eosin Y and for sufficiently low lipophilic dye concentration. Although it still requires further improvement, the method proposed here provides a promising route to obtain thinner coatings, down to a few microns.

Intraarterial protein delivery via intimally-adherent bilayer hydrogels

Arterial structure plays an important role in drug delivery from intraarterial depots. The internal elastic lamina forms a major diffusive resistance to the transport of macromolecular drugs from intimally-adherent hydrogel depots to the arterial media. The objectives of this study were to develop an approach by which to form a bilayer hydrogel depot with a higher permeability intimally-adherent layer, containing the drug, and a lower permeability luminal layer, and to evaluate ex vivo whether this luminal layer could enhance the delivery of a protein to the arterial media. Sequential interfacial photopolymerization of polyethyleneglycol diacrylate precursors (molecular weight 4000 for the luminal layer, 10,000 for the intimal layer) with eosin Y and triethanolamine as an initiation system was employed to form these bilayer hydrogels. Horseradish peroxidase was used as a model protein, and delivery to the arterial media was measured in rat carotid arteries ex vivo. The lower permeability luminal layer served to enhance delivery of the model protein into the arterial media for delivery periods at least up to 72 h. Thus, it was possible to compensate for the diffusional resistance of the internal elastic lamina on the one side of the hydrogel depot with a second diffusional resistance on the other side of the hydrogel.

In vitro and in vivo performance of porcine islets encapsulated in interfacially photopolymerized poly(ethylene glycol) diacrylate membranes.

The usefulness of interfacial photopolymerization of poly(ethylene glycol) (PEG) diacrylate at a variety of concentrations and molecular weights to form hydrogel membranes for encapsulating porcine islets of Langerhans was investigated. The results from this study show in vitro and in vivo function of PEG-encapsulated porcine islets and the ability of PEG membranes to prevent immune rejection in a discordant xenograft model. Encapsulated islets demonstrated an average viability of 85% during the first week after encapsulation, slightly but significantly lower than unencapsulated controls. Encapsulated porcine islets were shown to be glucose responsive using static glucose stimulation and perifusion assays. Higher rates of insulin release were observed for porcine islets encapsulated in lower concentrations of PEG diacrylate (10-13%), not significantly reduced relative to unencapsulated controls, than were observed in islets encapsulated in higher concentrations (25%) of PEG diacrylate. Perifusion results showed biphasic insulin release from encapsulated islets in response to glucose stimulation. Streptozotocin-induced diabetic athymic mice maintained normoglycemia for up to 110 days after the implantation of 5,000-8,000 encapsulated porcine islet equivalents into the peritoneal cavity. Normoglycemia was also confirmed in these animals using glucose tolerance tests. PEG diacrylate-encapsulated porcine islets were shown to be viable and contain insulin after 30 days in the peritoneal cavity of Sprague-Dawley rats, a discordant xenograft model. From these studies, we conclude that PEG diacrylate encapsulation of porcine islets by interfacial photopolymerization shows promise for use as a method of xenoprotection toward a bioartificial endocrine pancreas.

A sensitivity study of the key parameters in the interfacial photopolymerization of poly(ethylene glycol) diacrylate upon porcine islets.

A method has been defined to interfacially photopolymerize poly(ethylene glycol) diacrylates (PEG diacrylates) to form a crosslinked hydrogel membrane upon the surfaces of porcine islets of Langerhans to serve as an immune barrier for allo- and xenotransplantation. A sensitivity study of six key parameters in the interfacial photopolymerization process was performed to aid in determination of the optimal encapsulation conditions, leading to the most uniform hydrogel membranes and viable islets. The key parameters included the concentrations of the components of the initiation scheme, namely eosin Y, triethanolamine, and 1-vinyl 2-pyrrolidinone. Other parameters investigated included the duration and flux of laser irradiation and the PEG diacrylate molecular weight. Each parameter was doubled and halved from the standard conditions used in the encapsulation process while holding all the remaining parameters at the standard conditions. The effects of changing each parameter on islet viability, encapsulation efficiency, and gel thickness were quantified. Islet viability was sensitive to the duration of laser illumination, viability significantly increasing as the duration was reduced. Encapsulation efficiency was sensitive to the concentrations of eosin Y, triethanolamine, and 1-vinyl 2-pyrrolidinone, to the laser flux, and to the PEG diacrylate molecular weight. Increasing the concentration of eosin Y significantly improved the encapsulation efficiency, while decreasing the concentration of 1-vinyl 2-pyrrolidinone and increasing the concentration of triethanolamine had the greatest effects in significantly reducing the encapsulation efficiency. Gel thickness was sensitive to the concentrations of triethanolamine and 1-vinyl 2-pyrrolidinone, to the duration of laser illumination, and to the PEG diacrylate molecular weight. Increasing the PEG diacrylate molecular weight significantly increased the gel thickness, while decreasing the concentration of 1-vinyl 2-pyrrolidinone and increasing the concentration of triethanolamine had the greatest effects in significantly reducing the gel thickness. From this sensitivity study, conditions were determined to encapsulate porcine islets, resulting in greater than 90% islet viability and greater than 90% encapsulation efficiency.

Characterization of the formation of interfacially photopolymerized thin hydrogels in contact with arterial tissue

The aim of this study was to examine the conditions under which an interfacial photopolymerization process results in hydrogel barriers. Visible light initiated interfacial photopolymerization of a polyoxyethylene glycol (PEG)-co-poly(α-hydroxy acid) copolymer based on PEG 8000 macromonomer was performed on porcine aortic tissue, resulting in conformai hydrogel barriers. The process conditions were optimized in vitro for the formation of a 5–100 μm thick barrier.

Photochemistry and Photophysics of Liquid Interfaces by Second Harmonic Spectroscopy

The study of photochemical and photophysical processes at various liquid interfaces using second harmonic generation methods is described. Among the topics discussed are the dynamics of photoinduced structure changes, the transport of charge across an interface, the rotational motions of interfacial molecules, intermolecular energy transfer within the interface, interfacial photopolymerization, and photoprocesses at a semiconductor/liquid interface.

Interfacial polymerization of thin polymer films onto the surface of a microporous hollow-fiber membrane

Two methods for synthesizing thin films of chemically selective polymers onto the surface of microporous hollow-fiber membranes are described. The first involves interfacial redox polymerization and yields thin films of electronically conductive polymers (e.g., polypyrrole,poly ( N-methylpyrrole), poly-aniline) on the outside surface of the hollow-fiber membrane. The second method entails interfacial photopolymerization of styrenic monomers on the surface of the hollow-fiber membrane. Such coated hollow-fiber membranes are potentially useful in membrane-based separation technologies such as pervaporation and industrial gas separations. We also investigated the transport properties of the coated hollow-fiber membranes described here using a simple pervaporation-type experiment.

Modification of islet of langerhans surfaces with immunoprotective poly(ethylene glycol) coatings via interfacial photopolymerization

Poly(ethylene glycol) (PEG) has been used previously to alter immune interactions and systemic clearance of therapeutic proteins. We present herein chemical approaches for the conceptually similar treatment of therapeutic cells and tissues whereby immune and cell adhesive interactions may be reduced or interrupted, in the context of the transplantation of xenogeneic islets of Langerhans for the treatment of insulin-dependent diabetes mellitus. Visible-light-initiated interfacial photopolymerization of multifunctional PEG-based macromers was performed directly upon the surface of rat islets of Langerhans to produce conformal barrier hydrogel coatings with thickness of order 10 microm. The islets continued to be normal in ultrastructure and function as reflected by response to a glucose challenge in vitro.

Inhibition of thrombosis and intimal thickening by in situ photopolymerization of thin hydrogel barriers.

Thin hydrogel barriers formed on the inner surface of injured arteries by interfacial photopolymerization dramatically reduced thrombosis and intimal thickening in rat and rabbit models of vascular injury. This polymerization technique allowed the synthesis of a thin hydrogel barrier that conformed to the vessel wall, directly blocking contact between blood and the damaged vessel. The illumination conditions could be varied to control the thickness of the barrier from 10 microns to > 50 microns. The hydrogel was designed to degrade by nonenzymatic hydrolysis. In rats in which the carotid artery had been severely injured by crushing, treatment with the hydrogel barrier completely eliminated thrombosis (P < 0.01) and preserved long-term patency (P < 0.01). Treatment in a rabbit model of balloon injury inhibited thrombosis (P < 0.02) and reduced long-term intimal thickening by approximately 80% (P < 0.003). These results suggest that blood-borne signals acting in the early phases of healing play an important role in stimulating thickening of the intima.

Interfacial photopolymerization of poly(ethylene glycol)-based hydrogels upon alginate-poly( l-lysine) microcapsules for enhanced biocompatibility

The biocompatibility of microcapsules made by the co-acervation of alginate and poly( l-lysine) (PLL) was enhanced by coating the surface of these microcapsules with a poly(ethylene glycol) (PEG)-based hydrogel. The hydrogel was formed by an interfacial photopolymerization technique using visible light from an argon ion laser. The light absorbing chromophore, eosin Y, was immobilized on the microcapsule surface. This restricted the formation of the PEG hydrogel to the surface of the microcapsule. The presence of the PEG gel on the surface was confirmed by fluorescent dextran entrapment, by direct visualization after dissolution of the underlying membrane and by electron spectroscopy for chemical analysis. The biological response of such microcapsules was evaluated by intraperitoneal implantation in mice. The PEG-coated microcapsules were found to be less inflammatory and were seen not to elicit a fibrotic response, as was the case with alginate-PLL microcapsules.

Composite membranes from photochemical synthesis of ultrathin polymer films

THERE has recently been a resurgence of interest in synthetic membranes and membrane-based processes1–12. This is motivated by a wide variety of technological applications, such as chemical separations1–7, bioreactors and sensors8,9, energy conversion10,11 and drug-delivery systems12. Many of these technologies require the ability to prepare extremely thin, defect-free synthetic (generally polymeric) films, which are supported on microporous supports to form composite membranes. Here we describe a method for producing composite membranes of this sort that incorporate high-quality polymer films less than 50-nm thick. The method involves interfacial photopolymerization of a thin polymer film on the surface of the microporous substrate. We have been able to use this technique to synthesize a variety of functionalized ultrathin films based on electroactive, photoactive and ion-exchange polymers. We demonstrate the method here with composite membranes that show exceptional gas-transport properties.