Surface-initiated Photopolymerization Research Articles

Application of the Numerical Fractionation Approach to the Design of Biofunctional PEG Hydrogel Membranes

A mathematical model is described for surface-initiated photopolymerization of PEG-DA forming crosslinked biofunctional PEG hydrogel membranes based on the NF technique. The model includes an additional monomer with biological functionality, which is a common experimental strategy for the design of ECM mimics in tissue engineering in order to direct signaling pathways, and considers concentration-dependent VP propagation and reaction diffusion termination. The influence of these features on the crosslink density of the soluble and gel phases, the progression through gelation, sol/gel fraction, and molecular weight distribution of biofunctional PEG hydrogel are studied using the NF model. This model may be useful for specific applications of tissue engineering.

RGDS-functionalized polyethylene glycol hydrogel-coated magnetic iron oxide nanoparticles enhance specific intracellular uptake by HeLa cells

The objective of this study was to develop thin, biocompatible, and biofunctional hydrogel-coated small-sized nanoparticles that exhibit favorable stability, viability, and specific cellular uptake. This article reports the coating of magnetic iron oxide nanoparticles (MIONPs) with covalently cross-linked biofunctional polyethylene glycol (PEG) hydrogel. Silanized MIONPs were derivatized with eosin Y, and the covalently cross-linked biofunctional PEG hydrogel coating was achieved via surface-initiated photopolymerization of PEG diacrylate in aqueous solution. The thickness of the PEG hydrogel coating, between 23 and 126 nm, was tuned with laser exposure time. PEG hydrogel-coated MIONPs were further functionalized with the fibronectin-derived arginine-glycine-aspartic acid-serine (RGDS) sequence, in order to achieve a biofunctional PEG hydrogel layer around the nanoparticles. RGDS-bound PEG hydrogel-coated MIONPs showed a 17-fold higher uptake by the human cervical cancer HeLa cell line than that of amine-coated MIONPs. This novel method allows for the coating of MIONPs with nano-thin biofunctional hydrogel layers that may prevent undesirable cell and protein adhesion and may allow for cellular uptake in target tissues in a specific manner. These findings indicate that the further biofunctional PEG hydrogel coating of MIONPs is a promising platform for enhanced specific cell targeting in biomedical imaging and cancer therapy.

Synthesis of multifunctional polymer brush surfaces via sequential and orthogonal thiol-click reactions

Fabrication of multifunctional surfaces with complexity approaching that found in nature requires the application of a modular approach to surface engineering. We describe a versatile post-polymerization modification strategy to synthesize multifunctional polymer brush surfaces via combination of surface-initiated photopolymerization (SIP) and orthogonal thiol-click reactions. Specifically, we demonstrate two routes to multifunctional brush surfaces: in the first approach, alkyne-functionalized homopolymer brushes are modified with multiple thiolsvia a statistical, radical-mediated thiol-yne co-click reaction; and in the second approach, statistical copolymer brushes carrying two distinctly-addressable reactive moieties are sequentially modified via orthogonal base-catalyzed thiol-X (where X represents an isocyanate, epoxy, or α-bromoester) and radical-mediated thiol-yne reactions. In both cases, we show that surface properties, in the form of wettability, can be easily tuned over a wide range by judicious choice of brush composition and thiol functionality.

Design of molecularly imprinted polymer grafts with embedded gold nanoparticles through the interfacial chemistry of aryl diazonium salts

A novel strategy is described for the preparation of highly sensitive molecularly imprinted (MIPs) sensors for dopamine. It combines mercaptobenzene diazonium salt as a coupling agent for immobilizing gold nanoparticles to gold electrodes and benzoyl benzene diazonium salt as photoinitiator of radical polymerization at the said gold nanoparticle-decorated gold electrodes. The MIP films were prepared by surface-initiated photopolymerization (SIPP) of methacrylic acid (MAA) as functional monomer (F) for dopamine (DA) the template molecule (T), and ethylene glycol dimethacrylate (EGDMA), the crosslinker (C). Dimethylaniline was employed as a hydrogen donor. The specificity and selectivity were demonstrated by square wave voltammetry (SWV). The detection limit was 0.35 nmol L-1 (0.054 ng mL−1). The sensor layers are stable and adherent to the surface through aryl layers. The originality and advantage of the process lie in the use of aryl diazonium salt as coupling agents for anchroring nanoparticles and MIP layers to the electrode surface in a simple and efficient way which ensures high sensing performance together with good surface-MIP adhesion. The same strategy can be extended to a broad range of templates.

Hyper-reflective cholesteric liquid crystal fabricated using surface-initiated photopolymerization

Hyper-reflective cholesteric liquid crystal fabricated using surface-initiated photopolymerization

Polymeric vesicles with well-defined poly(methyl methacrylate) (PMMA) brushes via surface-initiated photopolymerization (SIPP)

We describe a novel and general approach to fabricate polymeric vesicles with well-defined PMMA brushes by using silica particles as template through surface-initiated photopolymerization (SIPP). The crosslinked PDMAEMA layer was immobilized on the surface of silica particles, and then photoinitiated polymerization of methyl methacrylate (MMA) was used to generate PMMA brushes in the presence of thioxanthone (TX). Polymeric vesicles with well-defined PMMA brush were obtained after removing silica cores. The whole process was well traced and confirmed by TEM, SEM, FT-IR and TGA. To the best of our knowledge, this is the first report the fabrication of polymer brush on the surface of polymeric vesicles through SIPP. This robust approach is expected to have potential in fabrication and modification of polymer vesicles with different sizes and functions.

Synthesis of polymer nanograss and nanotubes by surface-initiated photopolymerization in cylindrical alumina nanopores

Functional polymer nanograss and nanotubes with active epoxy groups were synthesized by a surface-initiated photopolymerization pattern transfer method in cylindrical alumina nanopores. The nanograss structures were obtained when the neat glycidyl methacrylate (GMA) monomer or the mixture of GMA monomer and ethylene glycol dimethacrylate (EGDMA) crosslinker solution was injected into the photoinitiator-immobilized template. In contrast, uniform polymer nanotubes that completely follow the contour of the template were generated with the mixture of GMA monomer, EGDMA crosslinker and pre-synthesized poly(glycidyl methacrylate) (PGMA) polymer as the precursor material. The mechanism of the formation of polymer nanograss and nanotubes was discussed in terms of mechanical strength of polymer and polymerization shrinkage. The incorporation of the pre-synthesized polymer into the monomer solution as the precursor material allows for precompensation of the structure shrinkage induced by photopolymerization reactions. Effects of the pre-synthesized PGMA polymer percentage and the amount of the EGDMA crosslinker on the morphology of the formed polymer nanostructures were investigated respectively. FT-IR spectra confirmed the chemically immobilized photoinitiators, and chemical component, poly(GMA-co-EGDMA), of the polymer nanotubes inside the cylindrical alumina nanopores respectively. Finally, an intriguing dendritic-shaped fractal pattern was formed from concentrated crosslinked polymer nanoneedles by self-assembly and droplet evaporation.

Polyamine/DNA polyplexes with acid-degradable polymeric shell as structurally and functionally virus-mimicking nonviral vectors

Improving low transfection efficiency associated with nonviral vectors is crucial to utilize their advantages (e.g., low safety and manufacturing concerns) over viral vectors. Bioavailable polyamines (e.g., protamine sulfate [PS] and spermine [SPM]), attractively interact with nucleic acids but usually result in low transfection efficiency due to poor intracellular processes and limited complexation capability. In this study, PS/DNA and SPM/DNA polyplexes were shelled with an acid-degradable polyketal (PK) layer via surface-initiated photopolymerization. The resulting polyamine/PK core-shell nanoparticles have gene-carrying polyamine/DNA polyplex core shielded by PK shell, mimicking a viral vector consisting the gene-carrying capsid core and an outer envelope. The PK shell hydrolyzes at an endosomal pH, exposing the polyplex core that is further disassembled by heparan sulfate. Significantly enhanced transfection efficiency by the polyamine/PK core-shell nanoparticles, compared with that of corresponding polyamine/DNA polyplexes, was achieved. Confocal microscopy revealed efficient DNA release from the PS/PK core-shell nanoparticles into the nucleus and substantially increased cellular uptake of SPM/PK core-shell nanoparticles. In addition, lyophilized polyamine/PK core-shell nanoparticles showed preserved transfection capability. In conclusion, addition of an acid-degradable PK shell significantly improved cellular internalization and intracellular trafficking of polyamine/DNA polyplexes, resulting in enhanced transfection.

Hybrid polyacrylamide chiral stationary phases for HPLC prepared by surface-initiated photopolymerization

Two hybrid polyacrylamide chiral stationary phases (CSPs) for HPLC have been synthesized by a new surface-initiated photo-induced radical polymerization approach of enantiopure N,N'-diacryloyl derivatives of (1R,2R)-diaminocyclohexane (CSP1) and (1R,2R)-diphenylethylenediamine (CSP2). This system is based on the activation of mesoporous silica microparticles by chemically bonded trichloroacetyl groups and dimanganese decacarbonyl as catalyst. UV irradiation was performed using a lab-made quartz photochemical reactor, ad hoc designed for the photo-induced polymerization process on the surface of microparticles. The two phases were evaluated and compared as chromatographic supports for the enantioselective HPLC of model chiral compounds. Their physico-chemical properties and chromatographic performances were also evaluated in comparison with those exhibited by the homologue CSPs obtained by the grafting-from thermal-induced process (CSP3 and CSP4). The new photopolymerization approach yielded higher grafting density than the thermal-induced one, especially in the case of the less reactive monomer (the diacryloyl derivative of (1R,2R)-diphenylethylenediamine), good chromatographic efficiency and a broad application field under normal phase and polar organic mode conditions.

Photocatalytic Antibacterial Capabilities of TiO2−Biocidal Polymer Nanocomposites Synthesized by a Surface-Initiated Photopolymerization

Novel biocidal polymer-functionalized TiO(2) nanoparticles were prepared by surface-initiated photopolymerization using titania as an initiator. Vinyl monomer mixtures of nontoxic secondary amine-containing biocidal 2-(tert-butylamino)ethyl methacrylate and antifouling ethylene glycol dimethacrylate were used for the antimicrobial polymer shell. It was shown that the synthesized TiO(2)/poly[2-(tert-butylamino)ethyl methacrylate-co-ethylene glycol dimethacrylate] core/shell nanoparticles had enhanced photocatalytic antibacterial properties compared to the pristine TiO(2) nanoparticles due to the combined antibacterial activities of light-driven anti-infective TiO(2) core and biocidal polymer shell. In the dark condition, the TiO(2)/biocidal polymer nanoparticles exhibited high antimicrobial efficiency (95.7%) against gram-positive S. aureus. Furthermore, during UV irradiation, the TiO(2)/biocidal polymer showed improved inhibition of bacterial growth against gram-negative E. coli and gram-positive S. aureus in comparison to the pristine TiO(2) nanoparticles.

Facile Approach to Patterned Binary Polymer Brush through Photolithography and Surface-Initiated Photopolymerization

Taking advantage of the photobleaching and co-initiating properties of the dendritic thioxanthone (TX) photoinitiator, we developed a general and facile approach to fabricate patterned binary polymer brushes by combining photolithography and surface-initiated photopolymerization (SIPP). The dendritic TX photoinitiator monolayer was immobilized covalently on a silicon slide surface, followed by photobleaching through a mask. The resulting slides could initiate photopolymerization of methyl methacrylate (MMA) to generate a patterned poly (methyl methacrylate) (PMMA) brush, and subsequently initiate styrene (St) in the presence of TX to obtain patterned binary poly (methyl methacrylate)-polystyrene (PMMA-PS) brushes. This general and facile method could be of use in large-scale patterned binary polymer brush fabrication.

Well-Defined PMMA Brush on Silica Particles Fabricated by Surface-Initiated Photopolymerization (SIPP)

The photochemical method is a convenient and simple way to synthesize the polymer brush on surface. We presented here a facile approach to fabricate PMMA brush on silica particles (SPs) by combination of self-assembly monolayer of hyperbranched polymeric thioxanthone (HPTX) and surface-initiated photopolymerization (SIPP). HPTX was immobilized on the surface of silica particles (SPs) through nucleophilic addition between amine and epoxy groups, and then initiated photopolymerization of MMA to generate PMMA brush on SPs at room temperature. The whole process was well-traced by FT-IR, TGA, SEM, and TEM. The results show that it is easy to create PMMA brushes of tunable thickness under UV irradiation. Especially, TEM images reveal the obvious formation of well-defined hybrid particles with SPs as the core and PMMA layers as the shell. The obtained hybrid particles can be implanted into PMMA matrix to produce PMMA composite with enhanced thermal and mechanical properties.

“Clicking” Polymer Brushes with Thiol-yne Chemistry: Indoors and Out

Thiol-yne click chemistry is demonstrated as a modular platform for rapid and practical fabrication of highly functional, multicomponent surfaces under ambient conditions. The principle is illustrated using a postmodification strategy in which poly(propargyl methacrylate) brushes were generated via surface-initiated photopolymerization and sequentially functionalized using the radical-mediated thiol-yne reaction. Brush surfaces expressing a three-dimensional configuration of "yne" functionalities were modified with high efficiency and short reaction times using a library of commercially available thiols, including functional thiols that demonstrate applicability for pH responsive surfaces and for bioconjugation. Sequential thiol-yne reactions in conjunction with simple UV photolithography were also applied to afford micropatterned, multicomponent surfaces. The practicality of the platform was further demonstrated by carrying out thiol-yne surface reactions in sunlight, suggesting the possibility of large scale modifications using renewable energy resources. Considering the mild reaction conditions, rapid throughput, and compatibility with orthogonal chemistries, we expect this platform to find widespread use among the materials science community.

Buried, Covalently Attached RGD Peptide Motifs in Poly(methacrylic acid) Brush Layers: The Effect of Brush Structure on Cell Adhesion

Iniferter-mediated surface-initiated photopolymerization was used to graft poly(methacrylic acid) (PMAA) brush layers obtained from surface-attached iniferters in self-assembled monolayers to a gold surface. The tethered chains were subsequently functionalized with the cell-adhesive arginine-glycine-aspartic acid (RGD) motif. The modified brushes were extended by reinitiating the polymerization to obtain an additional layer of PMAA, thereby burying the peptide-functionalized segments inside the brush structure. Contact angle measurements and Fourier transform infrared (FTIR) spectroscopy were employed to characterize the wettability and the chemical properties of these platforms. Time of flight secondary ion mass spectroscopy (TOF-SIMS) measurements were performed to monitor the chemical composition of the polymer layer as a function of the distance to the gold surface and obtain information concerning the depth of the RGD motifs inside the brush structure. The brush thickness was evaluated as a function of the polymerization (i.e., UV-irradiation) time with atomic force microscopy (AFM) and ellipsometry. Cell adhesion tests employing human osteoblasts were performed on substrates with the RGD peptides exposed at the surface as well as covered by a PMAA top brush layer. Immunofluorescence studies demonstrated a variation of the cell morphology as a function of the position of the peptide units along the grafted chains.

Three-Dimensional Patterning of Poly(Ethylene Glycol) Hydrogels Through Surface-Initiated Photopolymerization

Photopolymerizable hydrogels have been investigated extensively for biomedical applications, specifically in the area of tissue engineering. While fabrication approaches have shown promise in designing hydrogel scaffolds that guide cell function, the ability to spatially control localization in three-dimensions has been limited. We have developed a method for generating two-dimensional and three-dimensional (3D) patterns within multilayered poly(ethylene glycol) diacrylate (PEG-DA) hydrogels. Covalently attached hydrogel layers are formed using precursor solutions with a 10:1 mole ratio of PEG-DA to PEG-aminoacrylate (Acr-PEG-NH2). Upon illumination of the precursor with visible light (wavelength = 514 nm), a hydrogel layer forms with pendant amine groups induced by the presence of Acr-PEG-NH2 macromer. Pendant amine groups are further functionalized with free carboxyl groups present on the visible light photoinitiator eosin, allowing for the formation of subsequent hydrogel layers. Using noncontact photolithography, the prepolymer solution is polymerized through a photomask, resulting in hydrogel structures with distinct pattern formation in each layer. Unreacted regions immobilized with eosin can be subsequently filled with a different PEG hydrogel. The technique presented shows a great potential for tissue engineering applications, for biosensors, and in the formation of cell and protein patterning for biotechnology.

Visual Detection of Labeled Oligonucleotides Using Visible-Light-Polymerization-Based Amplification

DNA biochip technology holds potential for highly parallel, rapid, and sensitive genetic diagnostic screening of target pathogens and disease biomarkers. A primary limitation involves a simultaneous, sequence-specific identification of low copy number target polynucleotides using a clinically appropriate detection methodology that implements only inexpensive detection instrumentation. Here, a rapid (20 min), nonenzymatic method of signal amplification utilizing surface-initiated photopolymerization is presented in glass microarray format. Visible light photoinitiators covalently coupled to streptavidin were used to bind biotin-labeled capture sequences. Amplification was achieved through subsequent contact with a monomer solution and the appropriate light exposure to generate 20-240-nm-thick hydrogel layers exclusively from spots containing the biotin-labeled DNA. An amplification factor of 10(6) to 10(7) was observed as well as a detectable response generated from as low as approximately 10(4) labeled oligonucleotides using minimal instrumentation, such as an optical microscope or CCD camera.

Morphology Control of Structured Polymer Brushes

The surface-initiated photopolymerization (SIPP) of vinyl monomers on structured self-assembled monolayers, as defined by two-dimensional (2D) initiator templates for polymer growth, is investigated. The 2D templates are prepared by electron-beam chemical lithography (EBCL) of 4'-nitro-4-mercaptobiphenyl (NBT) and chemical conversion to an asymmetric azo initiator (4'-azomethylmalonodinitrile-1,1'-biphenyl-4-thiol). Ex situ kinetic studies of the SIPP process reveal a linear increase in the thickness of the polymer layer with the irradiation/polymerization time. The effect of the applied electron dosage during the EBCL process upon the final thickness of the polymer layer is also studied. The correlation between the electron-induced conversion of the 4'-nitro to the 4'-amino group and the layer thickness of the resulting polymer brush indicates that the polymer-brush grafting density can be directly controlled by the EBCL process. NBT-based template arrays are used for the combinatorial study of the influence of the lateral structure size and the irradiation dosage on the morphology of the resulting polymer-brush layer. Analysis of the array topography reveals the dependence of the thickness of the dry polymer layer on both electron dosage and structure size. This unique combination of EBCL as a lithographic technique to locally manipulate the surface chemistry and SIPP to amplify the created differences allows the preparation of defined polymer-brush layers of controlled morphologies.

Nanostructured Polymer Brushes

Nanopatterned polymer brushes with sub-50-nm resolution were prepared by a combination of electron-beam chemical lithography (EBCL) of self-assembled monolayers (SAMs) and surface-initiated photopolymerization (SIPP). As a further development of our previous work, selective EBCL was performed with a highly focused electron beam and not via a mask, to region-selectively convert a SAM of 4'-nitro-1,1'-biphenyl-4-thiol to defined areas of crosslinked 4'-amino-1,1'-biphenyl-4-thiol. These "written" structures were then used to prepare surface-bonded, asymmetric, azo initiator sites of 4'-azomethylmalonodinitrile-1,1'-biphenyl-4-thiol. In the presence of bulk styrene, SIPP amplified the primary structures of line widths from 500 to 10 nm to polystyrene structures of line widths 530 nm down to approximately 45 nm at a brush height of 10 or 7 nm, respectively, as measured by scanning electron microscopy and atomic force microscopy (AFM). The relative position of individual structures was within a tolerance of a few nanometers, as verified by AFM. At line-to-line spacings down to 50-70 nm, individual polymer brush structures are still observable. Below this threshold, neighboring structures merge due to chain overlap.

Weak Polyelectrolyte Brush Arrays Fabricated by Combining Electron-Beam Lithography with Surface-Initiated Photopolymerization

We present a simple “top-down/bottom-up” strategy to fabricate nano- and micropatterned polymer brush arrays composed of pH- and salt-sensitive, weak polyelectrolyte copolymers [poly(N-isopropylacrylamide-co-methacrylic acid, 3:1, poly(NIPAAM-co-MAA)]. In our approach, a silicon surface is first patterned with gold, using “lift-off” electron-beam lithography (“top-down”), and the resulting pattern is then amplified by surface-initiated photopolymerization by conventional, UV-light-induced free radical polymerization (“bottom-up”) from an immobilized 2,2‘-azobisisobutyronitrile (AIBN) type initiator. The use of pH- and ionic-strength-sensitive comonomers in the copolymer brush enables large, externally triggered conformational changes of the micro- and nanopatterned polymer brushes. We observed that the height of nanopatterned ionized polymer brushes increases with increasing feature size of the pattern. The design and fabrication of surfaces with conformationally switchable, patterned polymeric structures is important for sensing and actuation applications on the micro- and nanoscales.

Surface-Initiated Photopolymerization of Poly(ethylene glycol) Methyl Ether Methacrylate on a Diethyldithiocarbamate-Mediated Polymer Substrate

Grafting efficiency and graft conversion have been investigated for poly(ethylene glycol) methyl ether methacrylate (m-PEGMA) polymerized on the surface of diethyldithiocarbamate-containing polymer...