Revealing the supramolecular nature of side-chain terpyridine-functionalized polymer networks.

Nowadays, finely controlling the mechanical properties of polymeric materials is possible by incorporating supramolecular motifs into their architecture. In this context, the synthesis of a side-chain terpyridine-functionalized poly(2-(dimethylamino)ethyl methacrylate) is reported via reversible addition-fragmentation chain transfer polymerization. By addition of transition metal ions, concentrated aqueous solutions of this polymer turn into metallo-supramolecular hydrogels whose dynamic mechanical properties are investigated by rotational rheometry. Hence, the possibility for the material to relax mechanical constrains via dissociation of transient cross-links is brought into light. In addition, the complex phenomena occurring under large oscillatory shear are interpreted in the context of transient networks.

Temperature- and light-responsive smart polymer materials.

Stimuli-responsive polymers have been attracting great interest within the scientific community for several decades. The unique feature to respond to small changes in the environmental conditions has made this class of materials very promising for several applications in the field of nanoscience, nanotechnology and nanomedicine. So far, several different chemical, physical or biochemical stimuli have been investigated within natural or synthetic polymers. Very interesting and appealing seems to be the combination of several stimuli to tune the properties of these materials in manifold ways. Within this present review, we want to highlight the recent progress in the field of synthetic stimuli-responsive polymers combining temperature and light responsiveness.

Hydrogen peroxide sensors for cellular imaging based on horse radish peroxidase reconstituted on polymer-functionalized TiO2 nanorods.

We describe the reconstitution of apo-horse radish peroxidase (apo-HRP) onto TiO(2) nanorods functionalized with a multifunctional polymer. After functionalization, the horse radish peroxidase (HRP) functionalized TiO(2) nanorods were well dispersible in aqueous solution, catalytically active and biocompatible, and they could be used to quantify and image H(2)O(2) which is a harmful secondary product of cellular metabolism. The shape, size and structure of TiO(2) nanorods (anatase) were analyzed by transmission electron microscopy (TEM), high resolution TEM (HRTEM), electron diffraction (ED) and X-ray diffraction (XRD). The surface functionalization, HRP reconstitution and catalytic activity were confirmed by UV-Vis, FT-IR, CLSM and atomic force microscopy (AFM). Biocompatibility and cellular internalization of active HRP reconstituted TiO(2) nanorods were confirmed by a classical MTT cytotoxicity assay and confocal laser scanning microscopy (CLSM) imaging, respectively. The intracellular localization allowed H(2)O(2) detection, imaging and quantification in HeLa cells. The polymer functionalized hybrid system creates a complete sensor including a "cell positioning system" in each single particle. The flexible synthetic concept with functionalization by post-polymerization modification allows introduction of various dyes for sensitisation at different wavelengths and introduction of various anchor groups for anchoring on different particles.

Multi-responsive copolymers: using thermo-, light- and redox stimuli as three independent inputs towards polymeric information processing.

We report on triple responsive polymers, exhibiting a distinct and reversible lower critical solution temperature in water that can be altered by light and redox stimuli, and we suggest their evaluation for molecular information processing.

Chemical mimicry: hierarchical 1D TiO2@ZrO2 core-shell structures reminiscent of sponge spicules by the synergistic effect of silicatein-α and silintaphin-1.

In nature, mineralization of hard tissues occurs due to the synergistic effect of components present in the organic matrix of these tissues, with templating and catalytic effects. In Suberites domuncula, a well-studied example of the class of demosponges, silica formation is mediated and templated by an axial proteinaceous filament with silicatein-α, one of the main components. But so far, the effect of other organic constituents from the proteinaceous filament on the catalytic effect of silicatein-α has not been studied in detail. Here we describe the synthesis of core-shell TiO(2)@SiO(2) and TiO(2)@ZrO(2) nanofibers via grafting of silicatein-α onto a TiO(2) nanowire backbone followed by a coassembly of silintaphin-1 through its specifically interacting domains. We show for the first time a linker-free, one-step funtionalization of metal oxides with silicatein-α using glutamate tag. In the presence of silintaphin-1 silicatein-α facilitates the formation of a dense layer of SiO(2) or ZrO(2) on the TiO(2)@protein backbone template. The immobilization of silicatein-α onto TiO(2) probes was characterized by atomic force microscopy (AFM), optical light microscopy, and high-resolution transmission electron microscopy (HRTEM). The coassembly of silicatein-α and silintaphin-1 may contribute to biomimetic approaches that pursue a controlled formation of patterned biosilica-based biomaterials.

Reactive surface coatings based on polysilsesquioxanes: universal method toward light-responsive surfaces.

Reactive surface coatings were used as an ideal precursor coating for the fabrication of three different photoswitchable surface coatings in parallel. Different light-responsive moieties, such as azobenzene, salicylideneaniline, and spiropyran, were immobilized on glass, polycarbonate, and steel surfaces. Independent from the underlying substrate, wettability could be switched reversibly by UV irradiation. The maximum switching range was obtained after functionalization of the reactive coating with spiropyran, resulting in a contact angle difference between the two isomeric states of almost 30°.

Double thermoresponsive block copolymers featuring a biotin end group.

A poly(oligo(ethylene glycol) monomethyl ether methacrylate)-block-poly(N-isopropyl methacrylamide) (POEGMA-b-PNIPMAM) block copolymer with a biotin end group on the PNIPMAM block as a biotarget was synthesized as a model system for temperature-controlled polymer immobilization. The synthesis was based on RAFT polymerization followed by postpolymerization modification of an activated ester precursor block and an exchange of the dithioester end group within one step. NMR, differential scanning calorimetry (DSC), dynamic light scattering (DLS), and turbidimetry measurements were performed to investigate the stimulus-responsive properties. The double thermoresponsive POEGMA-b-PNIPMAM with biotin end group showed a temperature-dependent multistage assembly behavior as it was completely soluble in water at temperatures below the LCST of both blocks, formed micellar structures above the LCST of PNIPMAM but below the LCST of POEGMA, or precipitated from solution above the LCST of both blocks. At room temperature, the polymer could be immobilized onto a streptavidin surface via its biotin end group, as shown in surface plasmon resonance (SPR) experiments. At 50 °C, at which the block copolymer formed micelles trapping the biotin target within the PNIPMAM core, no immobilization was observed, showing that the biological binding ability of the model could be controlled via external stimuli.

Thermo- and light responsive micellation of azobenzene containing block copolymers.

In this communication, the synthesis and characterization of thermo- and light responsive block copolymers is reported. PEO-b-PNIPAM polymers with azobenzene moieties were prepared and analyzed by turbidimetry, fluorescence, NMR and DLS measurements. A temperature controlled reversible formation as well as a light induced disruption and reformation of micellar structures in water was found.

Nanotube Friendly Poly(N-isopropylacrylamide).

Poly(N-ispropylacrylamide) [PNIPAM] is a widely studied polymer for use in biological applications due to its lower critical solution temperature (LCST) being so close to the human body temperature. Unfortunately, attempts to combine carbon nanotubes (CNTs) with PNIPAM have been unsuccessful due to poor interactions between these two materials. In this work, a PNIPAM copolymer with 1 mol-% pyrene side group [p-PNIPAM] was used to produce a thermoresponsive polymer capable of stabilizing both single and multi-walled carbon nanotubes (MWNTs) in water. The presence of pyrene in the polymer chain lowers the LCST less than 4 °C and the interaction with nanotubes does not show any influence on LCST. Moreover, p-PNIPAM stabilized nanotubes show a temperature-dependent dispersion in water that allows the level of nanotube exfoliation/bundling to be controlled. Cryo-TEM images, turbidity, and viscosity of these suspensions were used to characterize these thermoresponsive changes. This ability to manipulate the dispersion state of CNTs in water with p-PNIPAM will likely benefit many biological applications, such as drug delivery, optical sensors, and hydrogels.

PNIPAM Copolymers Containing Light-Responsive Chromophores: A Method Toward Molecular Logic Gates.

A series of thermo-responsive PNIPAM copolymers containing different amounts of fulgimide moieties has been synthesized via a polymer analogous reaction of poly(pentafluorophenyl acrylate). All copolymers were designed to exhibit a lower critical solution temperature (LCST) in water, which was only weakly dependent on the amount of incorporated chromophoric fulgimide groups. The copolymers showed a photocyclization of the fulgimide side groups upon irradiation with UV-light accompanied with a color change. The closed form of the chromophore had a halftime of 136 min for the visible reisomerization and did not affect the LCST of the polymer. This led to the realization of a logic "NOT A" for the fulgimide containing PNIPAM, while a corresponding azobenzene containing PNIPAM resulted in a different logic "A implies B".

Synthesis of hetero-telechelic alpha,omega bio-functionalized polymers.

Reversible addition-fragmentation chain transfer (RAFT) polymerization was used to synthesize poly[diethylene glycol monomethylether methacrylate] (PDEGMA) (M(n) = 6250 g/mol, PDI = 1.14) with a pentafluorophenyl (PFP) activated ester and a dithioester end group. The hormone thyroxin (T4) was quantitatively attached to the PFP activated ester alpha end group via its amino group. The omega-terminal dithioester was not harmed by this reaction and was subsequently aminolyzed in the presence of N-biotinylaminoethyl methanethiosulfonate, yielding a polymer with a thyroxin and a biotin end group with very high heterotelechelic functionality. The polymer was characterized by (1)H, (13)C, and (19)F NMR, UV-vis, and IR spectroscopy and gel permeation chromatography. The thyroxin transport protein prealbumin with two thyroxin binding sites and streptavidin, which has four biotin binding sites, was conjugated using the biotarget labeled polymer, resulting in the formation of a protein-polymer network, confirming the heterotelechelic nature of the polymer. Polymer-protein microgel formation was observed with dynamic light scattering. To realize a directed protein assembly, prealbumin was immobilized onto a surface, exposing one of its two thyroxin binding groups and thus allowing the conjugation with the thyroxin alpha end group of the heterotelechelic polymer. The biotin omega end group of the attached polymer layer enabled the subsequent immobilization of streptavidin, yielding a defined multilayer system of two proteins connected with the synthetic polymer (efficiency of streptavidin immobilization 81% based on prealbumin). Without the polymer, no streptavidin immobilization occurred. The layer depositions were monitored by surface plasmon resonance. The synthetic approach of combining PFP activated esters with functional MTS reagents presents a powerful method for obtaining well-defined heterotelechelic (bio-) functionalized polymers.

Temperature controlled dispersion of carbon nanotubes in water with pyrene-functionalized poly(N-cyclopropylacrylamide).

Despite their immense potential, the ability to control the dispersion and microstructure of carbon nanotubes remains a hurdle for their widespread use. Poly(N-cyclopropylacrylamide), containing 5 mol % pyrene-bearing repeat units (p-PNCPA), is shown to vary the dispersion state of single-walled carbon nanotubes (SWNTs) in water. This is a thermo-responsive polymer whose conformation changes with temperature, which in turn leads to changes in the nanotube dispersion state. Cryo-TEM micrographs show that SWNTs stabilized using p-PNCPA transitions from a more exfoliated to a more bundled state as the aqueous suspension temperature is raised above the lower critical solution temperature (LCST) of the polymer (approximately 30 degrees C). Viscosity measurements on SWNT/p-PNCPA aqueous suspensions show shear thinning and near Newtonian behavior at 10 and 50 degrees C, respectively. Drying of these suspensions produces composites whose microstructure and electrical conductivity vary with drying temperature. This behavior has significant implications for the processing of carbon nanotubes and tailoring of composite properties. Such stimuli-controlled dispersion of carbon nanotubes could have a variety of applications in nanoelectronics, sensing, and drug and gene delivery systems.