Generalized platform for antibody detection using the antibody catalyzed water oxidation pathway.

Infectious diseases, such as influenza, present a prominent global problem including the constant threat of pandemics that initiate in avian or other species and then pass to humans. We report a new sensor that can be specifically functionalized to detect antibodies associated with a wide range of infectious diseases in multiple species. This biosensor is based on electrochemical detection of hydrogen peroxide generated through the intrinsic catalytic activity of all antibodies: the antibody catalyzed water oxidation pathway (ACWOP). Our platform includes a polymer brush-modified surface where specific antibodies bind to conjugated haptens with high affinity and specificity. Hydrogen peroxide provides an electrochemical signal that is mediated by Resorufin/Amplex Red. We characterize the biosensor platform, using model anti-DNP antibodies, with the ultimate goal of designing a versatile device that is inexpensive, portable, reliable, and fast. We demonstrate detection of antibodies at concentrations that fall well within clinically relevant levels.

Polymer Brushes as Functional, Patterned Surfaces for Nanobiotechnology.

Polymer brushes have many desirable characteristics such as the ability to tether molecules to a substrate or change the properties of a surface. Patterning of polymer films has been an area of great interest due to the broad range of applications including bio-related and medicinal research. Consequently, we have investigated patterning techniques for polymer brushes which allow for two different functionalities on the same surface. This method has been applied to a biosensor device which requires both polymer brushes and a photosensitizer to be polymerized on a patterned gold substrate. Additionally, the nature of patterned polymer brushes as removable thin films was explored. An etching process has enabled us to lift off very thin membranes for further characterization with the potential of using them as Janus membranes for biological applications.

One-dimensional magnetic inorganic-organic hybrid nanomaterials.

One-dimensional (1D) magnetic inorganic-organic hybrid nanomaterials bear both the intrinsic magnetic properties of the inorganic components and the functionality and responsiveness of their organic part. In this tutorial review, we first emphasize various synthetic strategies for this type of materials: (i) template-directed synthesis employs different preformed templates such as channels in solids, mesostructures self-assembled from block copolymers, cylindrical polymer brushes, 1D biological templates and other existing 1D templates; (ii) electrospinning, which provides a simple and efficient technique that can lead to a potential large-scale production; (iii) 1D conjugation of building blocks which combines the physical attraction of magnetic nanoparticles in a magnetic field with chemical crosslinking and stabilization. The properties, functions and the future trends of these materials are also briefly introduced. It is foreseeable that these hybrid materials will play more and more important roles in the ever-advancing miniaturization of functional devices.

Patterning of conjugated polymers for organic optoelectronic devices.

Conjugated polymers have been attracting more and more attention because they possess various novel electrical, magnetical, and optical properties, which render them useful in modern organic optoelectronic devices. Due to their organic nature, conjugated polymers are light-weight and can be fabricated into flexible appliances. Significant research efforts have been devoted to developing new organic materials to make them competitive with their conventional inorganic counterparts. It is foreseeable that when large-scale industrial manufacture of the devices made from organic conjugated polymers is feasible, they would be much cheaper and have more functions. On one hand, in order to improve the performance of organic optoelectronic devices, it is essential to tune their surface morphologies by techniques such as patterning. On the other hand, patterning is the routine requirement for device processing. In this review, the recent progress in the patterning of conjugated polymers for high-performance optoelectronic devices is summarized. Patterning based on the bottom-up and top-down methods are introduced. Emerging new patterning strategies and future trends for conventional patterning techniques are discussed.

Patterning of polymer brushes. A direct approach to complex, sub-surface structures.

We report a unique method to directly fabricate complex polymer brush structures with nanometer scale features by means of electron beam lithography. Polymer brushes for direct patterning were grown from surface-anchored initiator sites using atom transfer radical polymerization. Selected monomers (poly(2-hydroxyethyl methacrylate) and poly(methyl methacrylate)) were used based on their ability to readily scission when exposed to radiation. Single step direct patterning of polymer brushes is attractive as this eliminates many process steps, reducing the possibility of contamination and possibly improving resolution. In addition, we report a method to form subsurface polymer brush channels with nanometer-scale features. With the chains tethered to a surface, a diblock copolymer brush with a negative tone upper layer (polystyrene) and a positive tone under layer (poly(methyl methacrylate)) or (poly(2-hydroxyethyl methacrylate) were patterned to create channels. In the work presented, the direct electron beam patterning behavior of the brushes was studied and fabrication of nanochannels was demonstrated. Imaging of the nanopatterned surfaces was carried out using atomic force microscopy and fluorescence microscopy.

Manipulating the morphologies of cylindrical polyelectrolyte brushes by forming interpolyelectrolyte complexes with oppositely charged linear polyelectrolytes: an AFM study.

We present a study on water-soluble interpolyelectrolyte complexes (IPECs) formed by cationic cylindrical polyelectrolyte brushes (CPBs) and linear anionic poly(sodium styrenesulfonate) (PSSNa) using atomic force microscopy (AFM). The IPECs were prepared by dialysis of salt-containing solutions of the two polymeric components. The morphologies of the IPECs could be tuned by changing the charge ratio between the two polyelectrolytes, Z(-/+). Addition of increasing numbers of short PSSNa chains induced morphology changes of host CPBs from worms through intermediate pearl-necklace structures to fully collapsed spheres. Extremely long guest PSSNa caused the full collapse of the brushes to spheres even at very low charge ratios without intermediate states. In both cases we observe "disproportionation", that is, inhomogeneous distribution of the PSS chains between the CPB for Z(-/+) < 1. Unexpected micrometer-scale core-shell cylindrical objects were found by directly mixing CPBs with long PSSNa, which might be nonequilibrium structures caused by the kinetically controlled IPEC formation.

Direct Synthesis of Poly(potassium 3-sulfopropyl methacrylate) Cylindrical Polymer Brushes via ATRP Using a Supramolecular Complex With Crown Ether.

A supramolecular complex between an ionic monomer 3-sulfopropyl methacrylate (SPMAK) and crown ether 18-crown-6 (18C6) has been employed to prepare a strong anionic cylindrical polyelectrolyte brush poly(potassium 3-sulfopropyl methacrylate) (PSPMAK) by atom transfer radical polymerization (ATRP) in polar solvent dimethyl sulfoxide (DMSO). This strategy solved the problem of the solubilities of the incompatible hydrophobic poly-initiator and hydrophilic ionic monomer. The formation of the PSPMAK brush is well proven by (1) H NMR, aqueous gel permeation chromatography (GPC), dynamic light scattering (DLS), static light scattering (SLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo-TEM) measurements. Cleavage of the side chains and further analysis reveal that the initiating efficiency of the polymerization is as low as 0.35.

Switching the morphologies of cylindrical polycation brushes by ionic and supramolecular inclusion complexes.

Cylindrical polycation brushes form an ionic complex with surfactant sodium dodecyl sulfate (SDS) in aqueous solution, which causes a worm-to-sphere collapse of the brush. Alpha- and beta-cyclodextrin (CD) returns the brush to the worm-like conformation by forming a supramolecular inclusion complex with SDS. When beta-CD was employed for the inclusion complex, addition of 1-adamantylammonium chloride releases SDS by forming a stronger inclusion complex, causing the recollapse of the brush to spheres.

Water-soluble organo-silica hybrid nanowires.

There has been growing interest in the past decade in one-dimensional (1D) nanostructures, such as nanowires, nanotubes or nanorods, owing to their size-dependent optical and electronic properties and their potential application as building blocks, interconnects and functional components for assembling nanodevices. Significant progress has been made; however, the strict control of the distinctive geometry at extremely small size for 1D structures remains a great challenge in this field. The anisotropic nature of cylindrical polymer brushes has been applied to template 1D nanostructured materials, such as metal, semiconductor or magnetic nanowires. Here, by constructing the cylindrical polymer brushes themselves with a precursor-containing monomer, we successfully synthesized hybrid nanowires with a silsesquioxane core and a shell made up from oligo(ethylene glycol) methacrylate units, which are soluble in water and many organic solvents. The length and diameter of these rigid wires are tunable by the degrees of polymerization of both the backbone and the side chain. They show lyotropic liquid-crystalline behaviour and can be pyrolysed to silica nanowires. This approach provides a route to the controlled fabrication of inorganic or hybrid silica nanostructures by living polymerization techniques.

Influence of counterion valency on the conformational behavior of cylindrical polyelectrolyte brushes.

Using a dissipative particle dynamics approach, we study the conformations and interactions of a cylindrical polyelectrolyte brush (CPB) with added salt. The effects of counterion valency on the conformational behaviors of the CPB are analyzed in detail by considering various parameters like the distribution of bond lengths, the mean distance between two grafting points, the order parameter of side chains, etc. The lyotropic behavior of the CPB is also investigated through examining the backbone persistence. Our simulations demonstrate that the presence of the multivalent counterions can induce the collapse of the CPB, leading to various conformations. We identify a horseshoe to helical to coil-like conformation transition with increasing counterion valency. An important factor for the collapse of the CPB is the fact that the strong condensation of counterions induced by the higher electrostatic correlations decreases the osmotic pressure inside the brush. It is found that the ratio of the backbone persistence to the diameter of the CPB, l(p)/d, can only be affected to a slight extent by changing the counterion valency and the side chain length. These results may provide a valuable guideline that can be used to tailor the microstructure of the systems and to yield desired macroscopic behaviors.

Undulated multicompartment cylinders by the controlled and directed stacking of polymer micelles with a compartmentalized corona.

Like a bamboo rod: Long, bamboo-like undulated cylinders with distinct branch points and end groups (see picture) were obtained by the stacking of block terpolymer micelles that contain a fluorinated polybutadiene core and a compartmentalized corona of poly(4-tert-butoxystyrene) and poly(tert-butyl methacrylate). Stacking of the polymer micelles, which can be reversed, occurred when the solvent was changed from dioxane to ethanol.

Introduction of the exogenous NADH coenzyme regeneration system and its influence on intracellular metabolic flux of Paenibacillus polymyxa.

The NAD(+)-dependent formate dehydrogenase (FDH) gene from Candida boidinii was introduced into Paenibacillus polymyxa ZJ-9. The effects of this exogenous gene on the growth of the recombinant strain P. polymyxa XG-1, FDH activity, intracellular NADH and NAD(+) level and the synthesis of R,R-2,3-butanediol (R,R-2,3-BD) were determined. Results from the fermentation in the 7.5L bioreactor showed that the exogenous FDH was highly expressed in the recombinant strain. The titers of NADH, lactic acid, ethanol, NADH/NAD(+), and CO2 excretion rate (CER) of the recombinant strain increased considerably, while acetoin and formic acid decreased significantly. The highest titers of R,R-2,3-BD by the recombinant strain in batch and fed-batch fermentation were 36.8g/L and 51.3g/L, increased 10.2% and 8.0% compared with the parent strain, respectively. This study confirmed that coenzyme regeneration system can manipulate substance metabolism in bacteria, and is an efficient way for promoting the synthesis of NADH-dependent products.

Gene cloning, expression, and characterization of an exo-inulinase from Paenibacillus polymyxa ZJ-9.

An inulinase-producing strain, Paenibacillus polymyxa ZJ-9, was isolated from natural sources to produce R,R-2,3-butanediol via one-step fermentation of raw inulin extracted from Jerusalem artichoke tubers. The inulinase gene from P. polymyxa ZJ-9 was cloned and overexpressed in Escherichia coli BL21 (DE3), and the purified recombinant inulinase was estimated to be approximately 56 kDa by both sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and gel filtration chromatography. This result suggests that the active form of the inulinase is probably a monomer. Terminal hydrolysis fructose units from the inulin indicate that enzymes are exo-inulinase. The purified recombinant enzyme showed maximum activity at 25 °C and pH 6.0, which indicate its extreme suitability for industrial applications. Zn(2+), Fe(2+), and Mg(2+) stimulated the activity of the purified enzyme, whereas Co(2+), Cu(2+), and Ni(2+) inhibited enzyme activity. The K m and V max values for inulin hydrolysis were 1.72 mM and 21.69 µmol min(-1) mg(-1) protein, respectively. The same parameters toward sucrose were 41.09 mM and 78.7 µmol min(-1) mg(-1) protein, respectively. Considering its substrate specificity and other enzymatic characteristics, we believe that this inulinase gene from P. polymyxa ZJ-9 could be transformed into other special bacterial strains to allow inulin conversion to other biochemicals and bioenergy through one-step fermentation.

Alignment of tellurium nanorods via a magnetization-alignment-demagnetization ("MAD") process assisted by an external magnetic field.

Tellurium (Te) nanorods have been successfully aligned on a solid substrate via a magnetization-alignment-demagnetization ("MAD") process in the presence of an external magnetic field. Te nanorods carrying a poly(tert-butyl methacrylate) shell were first converted into magnetic nanocylinders by assembling magnetite nanoparticles on their surface via a hydrophobic interaction in THF. We demonstrate that, below a critical concentration of the nanoparticles, this assembly process is able to quantitatively tune the magnetite nanoparticles' density on the nanorods in terms of their stoichiometric ratio. Due to the polymer and surfactant on their surface, the formed magnetic nanocylinders are soluble in THF and aligned when dried on a solid substrate in the presence of an external magnetic field. The demagnetization of the prealigned nanocylinders was achieved via an acid-etching process, leaving Te nanorods in an aligned state. This MAD process can be extended as a general procedure for other nonmagnetic 1-D nanostructures. Additionally, the nonetched magnetic nanocylinders can be potentially applied in field of magnetorheology.

Interaction of cylindrical polymer brushes in dilute and semi-dilute solution.

We present a systematic study of flexible cylindrical brush-shaped macromolecules in a good solvent by small-angle neutron scattering (SANS), static light scattering (SLS), and by dynamic light scattering (DLS) in dilute and semi-dilute solution. The SLS and SANS data extrapolated to infinite dilution lead to the shape of the polymer that can be modeled in terms of a worm-like chain with a contour length of 380 nm and a persistence length of 17.5 nm. SANS data taken at higher polymer concentration were evaluated by using the polymer reference interaction site model (PRISM). We find that the persistence length reduce from 17.5 nm at infinite dilution to 5.3 nm at the highest concentration (volume fraction 0.038). This is comparable with the decrease of the persistence length in semi-dilute concentration predicted theoretically for polyelectrolytes. This finding reveals a softening of stiffness of the polymer brushes caused by their mutual interaction.