Azide photochemistry for facile modification of graphitic surfaces : preparation of DNA-coated carbon nanotubes for biosensing

A facile, two-step method for chemically attaching single-stranded DNA to graphitic surfaces, represented here by carbon nanotubes, is reported. In the first step, an azide-containing compound, N-5-azido-nitrobenzoyloxy succinimide (ANB-NOS), is used to form photo-adducts on the graphitic surfaces in a solid-state photochemical reaction, resulting in active ester groups being oriented for the subsequent reactions. In the second step, pre-synthesized DNA strands bearing a terminal amine group are coupled in an aqueous solution with the active esters on the photo-adducts. The versatility of the method is demonstrated by attaching pre-synthesized DNA to surfaces of carbon nanotubes in two platforms—as vertically-aligned multi-walled carbon nanotubes on a solid support and as tangled single-walled carbon nanotubes in mats. The reaction products at various stages were characterized by x-ray photoelectron spectroscopy. Two different assays were used to check that the DNA strands attached to the carbon nanotubes were able to bind their partner strands with complementary base sequences. The first assay, using partner DNA strands tethered to gold nanoparticles, enabled the sites of DNA attachment to the carbon nanotubes to be identified in TEM images. The second assay, using radioactively labelled partner DNA strands, quantified the density of functional DNA strands attached to the carbon nanotubes. The diversity of potential applications for these DNA-modified carbon-nanotube platforms is exemplified here by the successful use of a DNA-modified single-walled carbon-nanotube mat as an electrode for the specific detection of metal ions.

Facilitated heterogeneous photodegradation of dissolved organic matter by particulate iron

The photochemical degradation of dissolved organic matter (DOM) derived from the leaves of River Red Gum (Eucalyptus camaldulensis) was examined, with a particular focus on the photochemical generation of CO₂, consumption of O₂, and the effect of particulate iron minerals on these photochemical reactions. Solutions of leaf leachate were irradiated with ultraviolet and visible light in the presence and absence of amorphous iron oxides. Addition of fresh iron oxide was found to increase the rate of photodegradation of the organic matter by up to an order of magnitude compared to the reactions without added iron oxide. The ratio of CO₂ produced to O₂ consumed was ~1:1 in both the presence and absence of iron oxyhydroxide. The reactivity of the iron oxides was dependent on the preparation method and decreased with increased storage time. These results suggest that photochemical reactions on particle surfaces should be considered when examining carbon transformation in aquatic ecosystems, especially at sites with potential for the production of iron oxyhydroxides.

Directional water-transport fabrics achieved by wettablity gradient from superhydrophobicity to hydrophilicity

In this study, we demonstrate that fabrics having a wettability gradient from superhydrophobic to hydrophilic through the thickness direction show a novel directional water transfer effect: water can transfer only from the superhydrophobic to the hydrophilic side, but not in the opposite direction unless an external force is applied. A sol-gel technology was used to prepare a superhydrophobic coating on fabrics, and the coated fabrics showed water contact-angle as high as 165°. When the coated fabric was subjected to a photochemistry treatment from one fabric side, the irradiated surface turned hydrophilic permanently, while the back side still maintained the superhydrophobicity. The treated fabric can transfer water droplet rapidly from hydrophobic to hydrophilic side, and the pressure allowing water breakthrough the fabric is different considerably between the two fabric sides. The directional water transfer effect is also affected by the wettability gradient. Such a directional water transfer coating may be useful to develop new functional fabrics for defence applications.

Unidirectional water transfer effect from fabrics having a superhydrophobic-to-hydrophillic gradient

In this study, we demonstrate that fabrics having a wettability gradient from superhydrophobic to hydrophilic through the thickness direction show a novel directional water transfer effect: water can transfer from the superhydrophobic to the hydrophilic side, but not in the opposite direction unless an external force is applied. A sol-gel technology was used to prepare a nano-structured superhydrophobic coating on fabrics, and the coated fabrics showed water contact-angle as high as 165 degrees. When the coated fabric was subjected to a photochemistry treatment from one fabric side, the irradiated surface turned hydrophilic permanently, while the back side still maintained the superhydrophobicity. The treated fabric can transfer water droplet rapidly from hydrophobic to hydrophilic side, and the pressure allowing water breakthrough the fabric are different considerably between the two fabric sides. The directional water transfer effect is affected by the wettability gradient. Such a directional water transfer coating may be useful to develop new functional fabrics for defence applications.

Photoreactive azido-containing silica nanoparticle/polycation multilayers : durable superhydrophobic coating on cotton fabrics

In this study, we report the functionalization of silica nanoparticles with highly photoreactive phenyl azido groups and their utility as a negatively charged building block for layer-by-layer (LbL) electrostatic assembly to produce a stable silica nanoparticle coating. Azido-terminated silica nanoparticles were prepared by the functionalization of bare silica nanoparticles with 3-aminopropyltrimethoxysilane followed by the reaction with 4-azidobenzoic acid. The azido functionalization was confirmed by FTIR and XPS. Poly(allylamine hydrochloride) was also grafted with phenyl azido groups and used as photoreactive polycations for LbL assembly. For the photoreactive silica nanoparticle/polycation multilayers, UV irradiation can induce the covalent cross-linking within the multilayers as well as the anchoring of the multilayer film onto the organic substrate, through azido photochemical reactions including C–H insertion/abstraction reactions with surrounding molecules and dimerization of azido groups. Our results show that the stability of the silica nanoparticle/polycation multilayer film was greatly improved after UV irradiation. Combined with a fluoroalkylsilane post-treatment, the photoreactive LbL multilayers were used as a coating for superhydrophobic modification of cotton fabrics. Herein the LbL assembly method enables us to tailor the number of the coated silica nanoparticles through the assembly cycles. The superhydrophobicity of cotton fabrics was durable against acids, bases, and organic solvents, as well as repeated machine wash. Because of the unique azido photochemistry, the approach used here to anchor silica nanoparticles is applicable to almost any organic substrate.

Unidirectional water transfer effect from fabrics having a superhydrophobic-to-hydophilic gradient

In this study, we demonstrate that fabrics having a wettability gradient from superhydrophobic to hydrophilic through the thickness direction show a novel directional water transfer effect: water can transfer from the superhydrophobic to the hydrophilic side, but not in the opposite direction unless an external force is applied. A sol–gel technology was used to prepare a nano-structured superhydrophobic coating on fabrics, and the coated fabrics showed water contact-angle as high as 165 degrees. When the coated fabric was subjected to a photochemistry treatment from one fabric side, the irradiated surface turned hydrophilic permanently, while the back side still maintained the superhydrophobicity. The treated fabric can transfer water droplet rapidly from hydrophobic to hydrophilic side, and the pressure allowing water breakthrough the fabric are different considerably between the two fabric sides. The directional water transfer effect is affected by the wettability gradient. Such a directional water transfer coating may be useful to develop new functional fabrics for defence applications.

Brønsted acid-mediated radical processes in organic synthesis

This highlight focuses on recent applications of Brønsted acid-mediated radical processes across a range of reaction manifolds, including transition metal-based catalysis, photochemistry, and polymer science. A brief overview of significant research developments in the area and a discussion of the key mechanistic features of notable transformations are provided.