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Surface enhanced Raman spectroscopy (SERS)-based nanosensors that offer high spatial and temporal resolution as well as high sensitivity are promising for cell endoscopy studies. This requires fabricating glass nanofibers with a dense but well-dispersed monolayer array of gold nanoparticles (AuNPs), which is a challenge on the highly curved nanofiber surface. We showed previously that this can be achieved with dip-coated block copolymer (BCP) templates, hypothesized to be brushlike. Here, we demonstrate, using small AuNPs and a concentrated THF solution of polystyrene-block-poly-(4-vinylpyridine) (PS-b-P4VP), that the effect of decreasing fiber diameter (increasing substrate curvature) on the AuNP deposition pattern parallels the effect of decreasing BCP solution concentration using flat surfaces, allowing the definitive conclusion that the BCP template at small fiber diameters is indeed in the form of an adsorbed brushlike layer. Notably, when dip-coating the fiber from concentrated BCP solution followed by incubation in a AuNP suspension, SEM images show dense clusters composed of two to four AuNPs at high fiber diameters (mm range) that transition into dense but mainly isolated AuNPs at low diameters (μm range), where the transition range depends on the BCP solution concentration and dip-coating rate. The nanothin brush-only layer at low fiber diameters down to the sub-micrometer range provides an effective template for optimal AuNP deposition that is both simple and robust against changing experimental conditions, such as BCP solution concentration and dip-coating rate, while allowing tunability of the AuNP density and gap sizes through the AuNP diameter (10–100 nm studied) and, more mildly, BCP molecular weight characteristics. These features are ideal for nanosensor applications. [ABSTRACT FROM AUTHOR]

Abstract In this study, we grafted bromo-terminated poly(N-isopropylacrylamide) (PNIPAAm) brushes onto thin gold films deposited on silicon, and then reacted with NaN3 to produce azido-terminated PNIPAAm brushes. A probe sequence of single-stranded DNA (ssDNA) with a 4-pentynoic acid succinimidyl ester unit was grafted onto the azido-terminated PNIPAAm brushes through a click reaction, resulting in the formation of block copolymer brushes. The PNIPAAm-b-ssDNA copolymer brushes formed supramolecular complexes stabilized by bio-multiple hydrogen bonds (BMHBs), which enhanced the proton transfer and thereby decreased the resistivity of the structures. In addition, the optimal operation window for DNA detection ranges from 0 to 0.2 M of NaCl concentration. Therefore, the specimens were prepared in the PBS solution at 150 mM NaCl concentration for target hybridization. The supramolecular complex state of the PNIPAAm-b-ssDNA copolymer brushes transformed into the phase-separated state after the hybridization with 0.5 ng/µL of its target DNA sequence owing to the competition between BMHBs and complementary hydrogen bonds. This phase transformation of the PNIPAAm and probe segments inhibited the proton transfer and significantly increased the resistivity at 25 °C. Moreover, there were no significant changes in the resistivity of the copolymer brushes after hybridization with the target sequence at 45 °C. These results indicated that the phase-separated state of the PNIPAAm-b-ssDNA copolymer brushes, which was generally occurred above the LCST, can be substantially generated after hybridization with its target DNA sequence. By performing the controlled experiments, in the same manner, using another sequence with lengths similar to that of the target sequence without complementarity. In addition, the sequences featuring various degrees of complementarity were exploited to verify the phase separation behavior inside the PNIPAAm-b-ssDNA copolymer thin film.

Schematic view of His-tagged protein binding to core-brush nanocomposites functionalized with multiple IDA-Cu ligands. We developed a modular approach for the preparation of nanoparticle-supported polymer brushes carrying repeating iminodiacetate units for affinity separation of histidine-tagged recombinant proteins. The nanoparticle-supported polymer brushes were prepared via the combination of surface-initiated atom transfer radical polymerization with Cu(I)-catalyzed azide–alkyne cycloaddition reaction. The nanocomposite materials were characterized to determine the particle size, morphology, organic content, densities of polymer chains and the affinity ligand. Protein binding assay illustrated that the iminodiacetate-rich polymer brushes enable to selectively bind histidine-tagged recombinant proteins in the presence of abundant interfering proteins. More importantly, the protein binding capacity can be tuned by adjusting the environmental temperature. The nanoparticle core-polymer brush structure enables selective binding of histidine-tagged recombinant proteins via multiple metal-coordination interactions. The soft and flexible structure of the polymer brushes was found beneficial for lowering the steric hindrance in protein binding. Taking advantage of the conformational changes of the polymer brushes at different temperatures, it is possible to modulate the protein binding on the nanocomposite by adjusting the environmental temperature. In general, the iminodiacetate-rich core-brush nano adsorbents are attractive for purifying histidine-tagged recombinant proteins practically. The synthetic approach reported here may be expanded to develop other advanced functional materials for applications in various biomedical fields ranging from biosensors to drug delivery. [ABSTRACT FROM AUTHOR]

A well-defined block copolymer brush poly(glycidyl methacrylate)-graft-(poly(methyl methacrylate)-block- poly(oligo(ethylene glycol) methyl ether methacrylate)) (PGMA-g-(PMMA-b-POEGMA)) is synthesized via grafting from an approach based on a combination of click chemistry and reversible addition-fragmentation chain transfer (RAFT) polymerization. The resulting block copolymer brushes were characterized by 1H-NMR and size exclusion chromatography (SEC). The self-assembly of the block copolymer brush was then investigated under selective solvent conditions in three systems: THF/water, THF/CH3OH, and DMSO/CHCl3. PGMA-g-(PMMA-b-POEGMA) was found to self-assemble into spherical micelle structures as analyzed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The average size of the particles was much smaller in THF/CH3OH and DMSO/CHCl3 as compared with the THF/water system. Thin film of block copolymer brushes with tunable surface properties was then prepared by the spin-coating technique. The thickness of the thin film was confirmed by scanning electron microscopy (SEM). Atom force microscopy (AFM) analysis revealed a spherical morphology when the block copolymer brush was treated with poor solvents for the backbone and hydrophobic side chains. The contact angle measurements were used to confirm the surface rearrangements of the block copolymer brushes.

A well-defined block copolymer brush poly(glycidyl methacrylate)-graft-(poly(methyl methacrylate)-block- poly(oligo(ethylene glycol) methyl ether methacrylate)) (PGMA-g-(PMMA-b-POEGMA)) is synthesized via grafting from an approach based on a combination of click chemistry and reversible addition-fragmentation chain transfer (RAFT) polymerization. The resulting block copolymer brushes were characterized by 1H-NMR and size exclusion chromatography (SEC). The self-assembly of the block copolymer brush was then investigated under selective solvent conditions in three systems: THF/water, THF/CH3OH, and DMSO/CHCl3. PGMA-g-(PMMA-b-POEGMA) was found to self-assemble into spherical micelle structures as analyzed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The average size of the particles was much smaller in THF/CH3OH and DMSO/CHCl3 as compared with the THF/water system. Thin film of block copolymer brushes with tunable surface properties was then prepared by the spin-coating technique. The thickness of the thin film was confirmed by scanning electron microscopy (SEM). Atom force microscopy (AFM) analysis revealed a spherical morphology when the block copolymer brush was treated with poor solvents for the backbone and hydrophobic side chains. The contact angle measurements were used to confirm the surface rearrangements of the block copolymer brushes. [ABSTRACT FROM AUTHOR]

A nanothin block copolymer (BCP) brush-layer film adsorbed on glass nanofibers is shown to address the long-standing challenge of forming a template for the deposition of dense and well-dispersed nanoparticles on highly curved surfaces, allowing the development of an improved nanosensor for neurotransmitters. We employed a polystyrene- block-poly(4-vinylpyridine) BCP and plasmonic gold nanoparticles (AuNPs) of 52 nm in diameter for the fabrication of the nanosensor on pulled fibers with diameters down to 200 nm. The method is simple, using only solution processes and a plasma cleaning step. The templating of the AuNPs on the nanofiber surprisingly gave rise to more than 1 order of magnitude improvement in the surface-enhanced Raman scattering (SERS) performance for 4-mercaptobenzoic acid compared to the same AuNPs aggregated on identical fibers without the use of a template. We hypothesize that a wavelength-scale lens formed by the nanofiber contributes to enhancing the SERS performance to the extent that it can melt the glass nanofiber under moderate laser power. We then show the capability of this nanosensor to detect the corelease of the neurotransmitters dopamine and glutamate from living mouse brain dopaminergic neurons with a sensitivity 1 order of magnitude greater than with aggregated AuNPs. The simplicity of fabrication and the far superior performance of the BCP-templated nanofiber demonstrates the potential of this method to efficiently pattern nanoparticles on highly curved surfaces and its application as molecular nanosensors for cell physiology.

In this study, we grafted bromo-terminated poly(N-isopropylacrylamide) (PNIPAAm) brushes onto thin gold films deposited on silicon, and then reacted with NaN 3 to produce azido-terminated PNIPAAm brushes. A probe sequence of single-stranded DNA (ssDNA) with a 4-pentynoic acid succinimidyl ester unit was grafted onto the azido-terminated PNIPAAm brushes through a click reaction, resulting in the formation of block copolymer brushes. The PNIPAAm-b-ssDNA copolymer brushes formed supramolecular complexes stabilized by bio-multiple hydrogen bonds (BMHBs), which enhanced the proton transfer and thereby decreased the resistivity of the structures. In addition, the optimal operation window for DNA detection ranges from 0 to 0.2 M of NaCl concentration. Therefore, the specimens were prepared in the PBS solution at 150 mM NaCl concentration for target hybridization. The supramolecular complex state of the PNIPAAm-b-ssDNA copolymer brushes transformed into the phase-separated state after the hybridization with 0.5 ng/µL of its target DNA sequence owing to the competition between BMHBs and complementary hydrogen bonds. This phase transformation of the PNIPAAm and probe segments inhibited the proton transfer and significantly increased the resistivity at 25 °C. Moreover, there were no significant changes in the resistivity of the copolymer brushes after hybridization with the target sequence at 45 °C. These results indicated that the phase-separated state of the PNIPAAm-b-ssDNA copolymer brushes, which was generally occurred above the LCST, can be substantially generated after hybridization with its target DNA sequence. By performing the controlled experiments, in the same manner, using another sequence with lengths similar to that of the target sequence without complementarity. In addition, the sequences featuring various degrees of complementarity were exploited to verify the phase separation behavior inside the PNIPAAm-b-ssDNA copolymer thin film.

In this report, we present a novel modular approach to the immobilization of a high density of boronic acid ligands on thermoresponsive block copolymer brushes for effective enrichment of glycoproteins via their synergistic multiple covalent binding with the immobilized boronic acids. Specifically, a two-step, consecutive surface-initiated atom transfer radical polymerization (SI-ATRP) was employed to graft a flexible block copolymer brush, pNIPAm-b-pGMA, from an initiator-functionalized nanosilica surface, followed by postpolymerization modification of the pGMA moiety with sodium azide. Subsequently, an alkyne-tagged boronic acid (PCAPBA) was conjugated to the polymer brush via a Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction, leading to a silica-supported polymeric hybrid material, Si@pNIPAm-b-pBA, with a potent glycol binding affinity. The obtained core-brush nanocomposite was systematically characterized with regard to particle size, morphology, organic content, brush density, and number of immobilized boronic acids. We also studied the characteristics of glycoprotein binding of the nanocomposite under different conditions. The nanocomposite showed high binding capacities for ovalbumin (OVA) (98.0 mg g -1 ) and horseradish peroxidase (HRP) (26.8 mg g -1 ) in a basic buffer (pH 9.0) at 20 °C. More importantly, by adjusting the pH and temperature, the binding capacities of the nanocomposite can be tuned, which is meaningful for the separation of biological molecules. In general, the synthetic approach developed for the fabrication of block copolymer brushes in the nanocomposite opened new opportunities for the design of more functional hybrid materials that will be useful in bioseparation and biomedical applications.