Effects of interfacial interactions and interpenetrating brushes on the electrospinning of cellulose nanocrystals-polystyrene fibers.

This study investigated the electrospinning of polystyrene solutions using added unmodified and modified (with grafted nitrobenzene and trifluoromethyl benzene functionalities and polystyrene brushes) cellulose nanocrystals (CNCs). A strong correlation existed between the formation of beads on the fibers and the degree of dispersion of CNC particles in the electrospinning mixtures. Agglomerates of CNC particles always concentrated in the form of beads. The best dispersion in N,N dimethylformamide (DMF) mixtures was obtained using CNC-2 surfaces that were modified using trifluoromethyl benzene functional groups. Using CNC-2 also resulted in both uniform and bead-free electrospun fibers. Despite good dispersion in DMF, the use of grafted polystyrene (PS) chains with CNC-g resulted in beads above a 1.0% concentration level. This result is attributed to more favorable interactions between the CNC-g brushes during the DMF solvent evaporation stage of electrospinning. The electrospinning of CNC/PS nanocomposites at very low CNC concentrations (<1.0%) showed strong adhesion bonds at the polymer-CNC interfaces. Excellent mechanical properties were also produced by using interpenetrating networks of surface brushes.

Transition Metal Ions Enable the Transition from Electrospun Prolamin Protein Fibers to Nitrogen-Doped Freestanding Carbon Films for Flexible Supercapacitors.

Flexible carbon ultrafine fibers are highly desirable in energy storage and conversion devices. Our previous finding showed that electrospun hordein/zein fibers stabilized by Ca2+ were successfully transferred into nitrogen-doped carbon ultrafine fibers for supercapacitors. However, their relatively brittle nature needed to be improved. Inspired by this stabilizing effect of Ca2+, in this work, four transition metal divalent cations were used to assist the formation of flexible hordein/zein-derived carbon ultrafine fibers. Without alteration of the electrospinnability, adequate amounts of zinc acetate and cobalt acetate supported the fibrous structure during pyrolysis. This resulted in flexible freestanding carbon films consisting of well-defined fibers with nitrogen-doped graphitic layers and hierarchical pores. These carbon films were easily cut into small square pieces and directly applied as working electrode in the three-electrode testing system without the need for polymer binders or conducting agents. Notably, the hz-Zn0.3-p electrode, synthesized with 0.3 mol/L Zn2+ and post-acid treatment, exhibited a specific capacitance of 393 F/g (at 1 A/g), a large rate capability (72.3% remained at 20 A/g), and a capacitance retention of ∼98% after 2000 charging-discharging cycles at 10 A/g. These superior electrochemical properties were attributed to the synergistic effects of the well-developed graphitic layers induced by Zn2+, the nitrogen-decorated carbon structure, and the interconnected channels generated by HCl treatment. This research advances potential applications for prolamin proteins as nitrogen-containing raw materials in developing carbon structures for high-performance supercapacitors.

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays.

Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings.

Diazonium-derived aryl films on gold nanoparticles: evidence for a carbon-gold covalent bond.

Tailoring the surface chemistry of metallic nanoparticles is generally a key step for their use in a wide range of applications. There are few examples of organic films covalently bound to metal nanoparticles. We demonstrate here that aryl films are formed on gold nanoparticles from the spontaneous reduction of diazonium salts. The structure and the bonding of the film is probed with surface-enhanced Raman scattering (SERS). Extinction spectroscopy and SERS show that a nitrobenzene film forms on gold nanoparticles from the corresponding diazonium salt. Comparison of the SERS spectrum with spectra computed from density functional theory models reveals a band characteristic of a Au-C stretch. The observation of this stretch is direct evidence of a covalent bond. A similar band is observed in high-resolution electron energy loss spectra of nitrobenzene layers on planar gold. The bonding of these types of films through a covalent interaction on gold is consistent with their enhanced stability observed in other studies. These findings provide motivation for the use of diazonium-derived films on gold and other metals in applications where high stability and/or strong adsorbate-substrate coupling are required.

Fabrication and characterization of graphitic carbon nanostructures with controllable size, shape, and position.

The incorporation of carbon materials in micro- and nanoscale devices is being widely investigated due to the promise of enhanced functionality. Challenges in the positioning and addressability of carbon nanotubes provide the motivation for the development of new processes to produce nanoscale carbon materials. Here, the fabrication of conducting, nanometer-sized carbon structures using a combination of electron beam lithography (EBL) and carbonisation is reported. EBL is used to directly write predefined nanometer-sized patterns in a thin layer of negative resist in controllable locations. Careful heat treatment results in carbon nanostructures with the size, shape, and location originally defined by EBL. The pyrolysis process results in significant shrinkage of the structures in the vertical direction and minimal loss in the horizontal direction. Characterization of the carbonized material indicates a structure consisting of both amorphous and graphitized carbon with low levels of oxygen. The resistivity of the material is similar to other disordered carbon materials and the resistivity is maintained from the bulk to the nanoscale. This is demonstrated by fabricating a nanoscale structure with predictable resistance. The ability to fabricate these conductive structures with known dimensions and in predefined locations can be exploited for a number of applications. Their use as nanoband electrodes is also demonstrated.