Organophilicity of Graphene Oxide for Enhanced Wettability of ZnO Nanorods.

Interfacing two-dimensional graphene oxide (GO) platelets with one-dimensional zinc oxide nanorods (ZnO) would create mixed-dimensional heterostructures suitable for modern optoelectronic devices. However, there remains a lack in understanding of interfacial chemistry and wettability in GO-coated ZnO nanorods heterostructures. Here, we propose a hydroxyl-based dissociation-exchange mechanism to understand interfacial interactions responsible for GO adsorption onto ZnO nanorods hydrophobic substrates. The proposed mechanism initiated from mixing GO suspensions with various organics would allow us to overcome the poor wettability (θ ∼ 140.5°) of the superhydrophobic ZnO nanorods to the drop-casted GO. The addition of different classes of organics into the relatively high pH GO suspension with a volumetric ratio of 1:3 (organic-to-GO) is believed to introduce free radicals (-OH and -COOH), which consequently result in enhancing adhesion (chemisorption) between ZnO nanorods and GO platelets. The wettability study shows as high as 75% reduction in the contact angle (θ = 35.5°) when the GO suspension is mixed with alcohols (e.g., ethanol) prior to interfacing with ZnO nanorods. The interfacial chemistry developed here brings forth a scalable tool for designing graphene-coated ZnO heterojunctions for photovoltaics, photocatalysis, biosensors, and UV detectors.

Controlling surface functionality through generation of thiol groups in a self-assembled monolayer.

A lithographic method to generate reactive thiol groups on functionalized synthetic diamond for biosensor and molecular electronic applications is developed. We demonstrate that ultrananocrystalline diamond (UNCD) thin films covalently functionalized with surface-generated thiol groups allow controlled thiol-disulfide exchange surface hybridization processes. The generation of the thiol functional head groups was obtained by irradiating phenylsulfonic acid (PSA) monolayers on UNCD surfaces. The conversion of the functional headgroup of the self-assembled monolayer was verified by using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and fluorescence microscopy. Our findings indicate the selective generation of reactive thiol surface groups. Furthermore, we demonstrate the grafting of yeast cytochrome c to the thiol-modified diamond surface and the electron transfer between protein and electrode.

Induction annealing and subsequent quenching: effect on the thermoelectric properties of boron-doped nanographite ensembles.

Boron-doped nanographite ensembles (NGEs) are interesting thermoelectric nanomaterials for high temperature applications. Rapid induction annealing and quenching has been applied to boron-doped NGEs using a relatively low-cost, highly reliable, laboratory built furnace to show that substantial improvements in thermoelectric power factors can be achieved using this methodology. Details of the design and performance of this compact induction furnace as well as results of the thermoelectric measurements will be reported here.

Potential impact of ZT = 4 thermoelectric materials on solar thermal energy conversion technologies.

State-of-the-art methodologies for the conversion of solar thermal power to electricity are based on conventional electromagnetic induction techniques. If appropriate ZT = 4 thermoelectric materials were available, it is likely that conversion efficiencies of 30-40% could be achieved. The availability of all solid state electricity generation would be a long awaited development in part because of the elimination of moving parts. This paper presents a preliminary examination of the potential performance of ZT = 4 power generators in comparison with Stirling engines taking into account specific mass, volume and cost as well as system reliability. High-performance thermoelectrics appear to have distinct advantages over magnetic induction technologies.

Ultrananocrystalline diamond thin films functionalized with therapeutically active collagen networks.

The fabrication of biologically amenable interfaces in medicine bridges translational technologies with their surrounding biological environment. Functionalized nanomaterials catalyze this coalescence through the creation of biomimetic and active substrates upon which a spectrum of therapeutic elements can be delivered to adherent cells to address biomolecular processes in cancer, inflammation, etc. Here, we demonstrate the robust functionalization of ultrananocrystalline diamond (UNCD) with type I collagen and dexamethasone (Dex), an anti-inflammatory drug, to fabricate a hybrid therapeutically active substrate for localized drug delivery. UNCD oxidation coupled with a pH-mediated collagen adsorption process generated a comprehensive interface between the two materials, and subsequent Dex integration, activity, and elution were confirmed through inflammatory gene expression assays. These studies confer a translational relevance to the biofunctionalized UNCD in its role as an active therapeutic network for potent regulation of cellular activity toward applications in nanomedicine.

Structured polymer grafts on diamond.

In this work, a facile method for the preparation of structured and functional polymer grafts on diamond surfaces is described. Uniform poly(styrene) (PS) grafts with a thickness of approximately 110 nm were created directly onto oxidized ultrananocrystalline diamond (UNCD) surfaces by the self-initiated photografting and photopolymerization of bulk styrene with UV irradiation. The stable covalent bonding of the PS grafts allows polymer analogue reactions with drastic reaction conditions without noticeable detachment of the polymer coating. Thus, various functionalities, such as nitro, sulfonic, and aminomethyl groups have been successfully incorporated to the polymer grafts. Furthermore, the reactivity contrast between hydrogenated and oxidized UNCD surfaces allows for the preparation of structured polymer grafts. Finally, we have demonstrated the good reactivity and accessibility of the incorporated pendant functional groups.

Chemical grafting of biphenyl self-assembled monolayers on ultrananocrystalline diamond.

We have investigated the formation of self-assembled monolayers (SAMs) of 4'-nitro-1,1-biphenyl-4-diazonium tetrafluoroborate (NBD) onto ultrananocrystalline diamond (UNCD) thin films. In contrast to the common approach to modify diamond and diamond-like substrates by electrografting, the SAM was formed from the saturated solution of NBD in acetonitrile by pure chemical grafting. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and near edge X-ray absorption fine structure spectroscopy (NEXAFS) have been used to verify the direct covalent attachment of the 4'-nitro-1,1-biphenyl (NB) SAM on the diamond substrate via stable C-C bonds and to estimate the monolayer packing density. The results confirm the presence of a very stable, homogeneous and dense monolayer. Additionally, the terminal nitro group of the NB SAM can be readily converted into an amino group by X-ray irradiation as well as electrochemistry. This opens the possibility of in situ electrochemical modification as well as the creation of chemical patterns (chemical lithography) in the SAM on UNCD substrates and enables a variety of consecutive chemical functionalization for sensing and molecular electronics applications.

DNA-modified nanocrystalline diamond thin-films as stable, biologically active substrates.

Diamond, because of its electrical and chemical properties, may be a suitable material for integrated sensing and signal processing. But methods to control chemical or biological modifications on diamond surfaces have not been established. Here, we show that nanocrystalline diamond thin-films covalently modified with DNA oligonucleotides provide an extremely stable, highly selective platform in subsequent surface hybridization processes. We used a photochemical modification scheme to chemically modify clean, H-terminated nanocrystalline diamond surfaces grown on silicon substrates, producing a homogeneous layer of amine groups that serve as sites for DNA attachment. After linking DNA to the amine groups, hybridization reactions with fluorescently tagged complementary and non-complementary oligonucleotides showed no detectable non-specific adsorption, with extremely good selectivity between matched and mismatched sequences. Comparison of DNA-modified ultra-nanocrystalline diamond films with other commonly used surfaces for biological modification, such as gold, silicon, glass and glassy carbon, showed that diamond is unique in its ability to achieve very high stability and sensitivity while also being compatible with microelectronics processing technologies. These results suggest that diamond thin-films may be a nearly ideal substrate for integration of microelectronics with biological modification and sensing.