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Detonation nanodiamond possesses facile surface functional groups and can be chemically processed for many engineering applications. In this work, we demonstrate the functionalization of nanoscale diamond particles with aryl organics using Suzuki coupling reactions. In route one, hydrogenated nanodiamond is derivatized with aryl diazonium to form the bromophenyl-nanodiamond complex, this is subsequently reacted with phenyl boronic acid to generate the biphenyl adduct. In route two, the nanodiamond is first derivatized with boronic acid groups to form the boronic acid-nanodiamond complex, this is followed by Suzuki cross coupling with arenediazonium tetrafluroborate salts to generate the biphenyl product. Good chemoselectivity can be obtained in both routes. The efficiencies of the Suzuki coupling reaction can be further improved by performing the chemistry in a microreactor where electro-osmotic flow accelerates the mixing of reactants. Using the Suzuki coupling reactions, we can functionalize nanodiamond with trifluoroaryls and increase the solubilities of nanodiamond in ethanol and hexane. Fluorescent nanodiamond can be generated by the Suzuki coupling of pyrene to nanodiamond.

Boron doped diamond (BDD) thin film was found to exhibit higher photocurrent conversion efficiencies and photostability compared to commonly used transparent conducting oxides (ITO and FTO) owing to the matching energy levels and strong C-C bonding at the organic/diamond interface.

A solution-gate field effect transistor (SGFET) has been fabricated on few-layer graphene (FLG). The ideally polarizable graphene/aqueous electrolyte interface allows the capacitive charging of the surface by hydroxyl (OH-) and hydroxonium ions (H3O+). The conductivity versus gate potential curve exhibits "V" shaped ambipolar transfer characteristics of graphene, with hole and electron mobilities of 3600 cm2/Vs and 2100 cm2/Vs, respectively. The shift of the negative gate potential with pH shows a supra-Nernstian response of 99 meV/pH. Our work points to the potential application of graphene in ultrafast and ultralow noise chemical or biological sensors.

Arsenic(II) sulfide nanocrystals were fabricated by a wet process from its bulk through cluster-mediate transformation. The bulk arsenic(II) sulfide can be easily dissolved in ethylenediamine to form a solution-like cluster (As4S4-NH2C2H4NH2)). The cluster can be transformed to nanocrystals assisted by consumption of ethylenediamine in protic polar solvents with mild thermal treatment. The nanocrystals show size-dependent fluorescence ranging from UV to the blue, two photon fluorescence as well as cytotoxic effects on cancer cells.

Cycloaddition of allyl organics on the dimer rows of a clean C(100)-2x1 diamond surface can be used for the controlled functionalization of such a surface. Sticking probability measurements confirm that appreciable uptake of acetylene and butadiene occur on the clean diamond surface at room temperature. The change in electron affinity of the surface as a function of the coverage of the organic molecules is investigated with periodic DFT calculations. The presence of C-H dipoles on these adsorbates modify the surface charge density and gives rise to an induced dipolar layer that modifies the electrostatic potential outside the surface. There is a significant reduction of up to 2.5 eV in electron affinity following the chemisorption of ethylene. Therefore, the adsorbed molecules play the same role as surface hydrogen in inducing the NEA condition on the clean diamond. The change in electron affinity does not scale linearly with the coverage of the organic molecules, because the spatial profile of the C-H dipoles as well as the orientation of the molecules on the surface have a predominant effect on the surface charge density.

We investigate the interface between a C(60) fullerite film, C(60)F(36), and diamond (100) by using core-level photoemission spectroscopy, cyclic voltammetry (CV), and high-resolution electron energy loss spectroscopy (HREELS). We show that C(60) can be covalently bonded to reconstructed C(100)-2x1 and that the bonded interface is sufficiently robust to exhibit characteristic C(60) redox peaks in solution. The bare diamond surface can be passivated against oxidation and hydrogenation by covalently bound C(60). However, C(60)F(36) is not as stable as C(60) and desorbs below 300 degrees C (the latter species being stable up to 500 degrees C on the diamond surface). Neither C(60) fullerite nor C(60)F(36) form reactive interfaces on the hydrogenated surface-they both desorb below 300 degrees C. The surface transfer doping process of hydrogenated diamond by C(60)F(36) is the most evident one among all the adsorbate systems studied (with a coverage-dependent band bending induced by C(60)F(36)).

We demonstrate here the functionalization of detonation nanodiamond (ND) with aminophenylboronic acid (APBA) for the purpose of targeting the selective capture of glycoproteins from unfractionated protein mixtures. The reacted ND, after blending with the matrix consisting of alpha-cyano-4-hydroxy-cinnamic acid, could be applied directly for matrix-assisted laser desorption ionization (MALDI) assay. A loading capacity of approximately 350 mg of glycoprotein/g of ND could be attained on ND that has been silanized with an alkyl linker chain prior to linking with the phenylboronic acid. The role of the alkyl spacer chain is to form an exclusion shell which suppresses nonspecific binding with nonglycated proteins and to reduce steric hindrance among the bound glycoproteins. In the absence of the alkyl spacer chain, nonselective binding of proteins was obtained. This work demonstrates the usefulness of functionalized ND as a high-efficiency extraction and analysis platform for proteomics research.

A whole-cell environmental biosensor was fabricated on a diamond electrode. Unicellular microalgae Chlorella vulgaris was entrapped in the bovine serum albumin (BSA) membrane and immobilized directly onto the surface of a diamond electrode for heavy metal detection. We found that the unique surface properties of diamond reduce the electrode fouling problem commonly encountered with metal electrodes. The cell-based diamond biosensor can attain a detection limit of 0.1 ppb for Zn(2+) and Cd(2+), and exhibits higher detection sensitivity and stability compared to platinum electrodes.

We show here that a re-structured carbon nanotube (CNT) forest can be used 'as-received' for high selectivity, non-enzymatic glucose detection without the need to incorporate catalytic metal nanoparticles or an exclusion polymeric membrane. Direct amperometric sensing of glucose has been achieved by using multiply-branched CNTs prepared by growing secondary or tertiary 'offshoot' CNTs on top of the existing CNT layer. The increased roughness factor on these re-structured CNTs enhances the amperometric detection sensitivity for glucose by a factor of 20x over that of interfering species like ascorbic acid or uric acid. A sensitivity of 60 microA mM(-1) cm(-2) and a detection limit of 1 microM, with a linear detection range of 1-11 mM (R(2) = 0.999), could be attained on the re-grown CNTs. When the re-grown CNTs were subjected to further anodization in acid to introduce a highly-charged interface, the sensitivity to glucose was enhanced to 157 microA mM(-1) cm(-2).

The self-aggregation behavior of three amphiphilic graft copolymers, oligo(9,9-dihexyl)fluorence-graft-poly(ethylene oxide) (OHF-g-PEO), with different architectures was studied by dynamic and static light scattering (DLS and SLS) in combination with fluorescence spectroscopy and transmission electron microscopy (TEM). The formation of self-assembled polymeric micelles was confirmed by SLS and TEM. DLS and SLS analyses showed that the architecture of graft copolymers has a dramatic effect on critical aggregation concentration (CAC), micelle size distribution, apparent aggregation number (Nagg app), and apparent molecular weight of polymer aggregates (Mw,agg app). An architecture-dependent excimer emission, resulting from the pi-pi stacking of the oligofluorene backbones, was also observed from the photoluminescence spectra of the micelle aqueous solutions, which indicated a strong intermolecular interaction among the polymeric molecules. The excimer emission was further investigated by time-resolved fluorescence spectroscopy.

We have applied surface plasmon resonance (SPR) spectroscopy, in combination with one-step direct binding, competition, and sandwiched assay schemes, to study thrombin binding to its DNA aptamers, with the aim to further the understanding of their interfacial binding characteristics. Using a 15-mer aptamer that binds thrombin primarily at the fibrinogen-recognition exosite as a model, we have demonstrated that introducing a DNA spacer in the aptamer enhances thrombin-binding capacity and stability, as similarly reported for hydrocarbon linkers. The bindings are aptamer surface coverage and salt concentration dependent. When free aptamers or DNA sequences complementary to the immobilized aptamer are applied after the formation of thrombin/aptamer complexes, bound thrombin is displaced to a certain extent, depending on the stability of the complexes formed under different conditions. When the 29-mer aptamer (specific to thrombin's heparin-binding exosite) is immobilized on the surface, its affinity to thrombin appears to be lower than the immobilized 15-mer aptamer, although the 29-mer aptamer is known to have a higher affinity in the solution phase. These findings underline the importance of aptamers' ability to fold into intermolecular structures and their accessibility for target capture. Using a sandwiched assay scheme followed by an additional signaling step involving biotin-streptavidin chemistry, we have observed the simultaneous binding of the 15- and 29-mer aptamers to thrombin protein at different exosites and have found that one aptamer depletes thrombin's affinity to the other when they bind together. We believe that these findings are invaluable for developing DNA aptamer-based biochips and biosensors.

The tuning of electron affinity and secondary electron emission on diamond (100) surfaces due to cycloaddition with 1,3-butadiene is investigated by photoemission experiments and density functional theory (DFT) calculations. A significant reduction in electron affinity up to 0.7 eV and enhancement of secondary electron emission were observed after 1,3-butadiene adsorption. The lowering of vacuum level via 1,3-butadiene adsorption is supported by DFT calculations. The C-H bonds in the covalently bonded organics on diamond contribute to the enhanced secondary electron emission and reduced electron affinity in a mechanism similar to that of C-H bonds on hydrogenated diamond surfaces. This combination of strong secondary emission and low electron affinity by the organic functionalization of diamond has potential applications in diamond-based molecular electronic devices.

Bulk molybdenum disulfide is known to be a nonmagnetic material. We have synthesized edge-oriented MoS2 nanosheet-like films that exhibit weak magnetism ( approximately 1-2 emu/g) and 2.5% magnetoresistance effects with a Curie temperature of 685 K. The magnetization is related to the presence of edge spins on the prismatic edges of the nanosheets. Spin-polarized calculations were performed on triangular-shaped cluster models in order to provide insight into the origin of magnetism on the edges as well as the size-property correlation in these MoS2 nanosheets. Our results imply that nanostructured films with a high density of edge spins can give rise to magnetism even though the bulk material is nonmagnetic.

The growth dynamics of bamboo-like multiwalled carbon nanotubes (BCNTs) via catalytic decomposition of C2H2 on Ni catalyst at 650 degrees C was observed in real time using an in situ ultrahigh vacuum transmission electron microscope. During BCNT growth, the shape of the catalyst particle changes constantly but remains metallic and crystalline. Graphene sheets (bamboo knots) within the nanotube preferentially nucleate on the multistep Ni-graphite edges at the point where the graphene joins the catalyst particle, where it is stabilized by both the graphene walls and the Ni catalyst surface. The growth of a complete inner graphene layer growth prior to contraction of the Ni catalyst particle due to restoring cohesive forces will result in a complete BCNT knot whereas partial growth of the inner wall will lead to an incomplete BCNT knot.

The biocompatibility of diamond was investigated with a view toward correlating surface chemistry and topography with cellular adhesion and growth. The adhesion properties of normal human dermal fibroblast (NHDF) cells on microcrystalline and ultrananocrystalline diamond (UNCD) surfaces were measured using atomic force microscopy. Cell adhesion forces increased by several times on the hydrogenated diamond surfaces after UV irradiation of the surfaces in air or after functionalization with undecylenic acid. A direct correlation between initial cell adhesion forces and the subsequent cell growth was observed. Cell adhesion forces were observed to be strongest on UV-treated UNCD, and cell growth experiments showed that UNCD was intrinsically more biocompatible than microcrystalline diamond surfaces. The surface carboxylic acid groups on the functionalized diamond surface provide tethering sites for laminin to support the growth of neuron cells. Finally, using capillary injection, a surface gradient of polyethylene glycol could be assembled on top of the diamond surface for the construction of a cell gradient.

The optimization of biosensing efficiency on a diamond platform depends on the successful coupling of biomolecules on the surface, and also on effective signal transduction in the biorecognition events. In terms of biofunctionalization of diamond surfaces, surface electrochemical studies of diamond modified with undecylenic acid (UA), with and without headgroup protection, were performed. The direct photochemical coupling method employing UA was found to impart a higher density of carboxylic acid groups on the diamond surface compared to that using trifluoroethyl undecenoate (TFEU) as the protecting group during the coupling process. Non-faradic impedimetric DNA sensing revealed that lightly doped diamond gives better signal transduction sensitivity compared to highly doped diamond.

Self-assembled functionalized aromatic thiols (oligophenylenes composed of building blocks of dimethoxy-substituted phenylenes, perfluoro-substituted phenylenes, and a terminal thiol group) were used to tune the hole injection barrier (Delta(h)) of copper(II) phthalocyanine (CuPc) on Au(111). Synchrotron-based high-resolution photoemission spectroscopy study reveals a significant reduction of Delta(h) by as much as 0.75 eV from Delta(h) = 0.9 eV for CuPc/Au(111) to Delta(h) = 0.15 eV for CuPc/BOF/Au(111), where BOF represents 4-pentafluorophenyl-1-(p-thiophenyl)-2,5-dimethoxybenzene. The delocalized pi orbitals of these functionalized aromatic thiols greatly facilitate effective charge transfer (hole or electron) across the SAM interface as compared to alkanethiols, hence making this novel interface modification scheme a simple and effective way to tune the hole injection barrier. This method has potential applications in molecular electronics, organic light-emitting diodes (OLED), organic field-effect transistors (OFETs), and organic solar cells.

A SiC nanomesh is used as a nanotemplate to direct the epitaxy of C60 molecules. The epitaxial growth of C60 molecules on SiC nanomesh at room temperature is investigated by in situ scanning tunneling microscopy, revealing a typical Stranski-Krastanov mode (i.e., for the first one or two monolayers, it is a layer-by-layer growth or 2-D nucleation mode; at higher thicknesses, it changes to island growth or a 3-D nucleation mode). At submonolayer (0.04 and 0.2 ML) coverage, C60 molecules tend to aggregate to form single-layer C60 islands that mainly decorate terrace edges, leaving the uncovered SiC nanomesh almost free of C60 molecules. At 1 ML C60 coverage, a complete wetting layer of hexagonally close-packed C60 molecules forms on top of the SiC nanomesh. At higher coverage from 4.5 ML onward, the C60 stacking adopts a (111) oriented face-centered-cubic (fcc) structure. Strong bright and dim molecular contrasts have been observed on the first layer of C60 molecules, which are proposed to originate from electronic effects in a single-layer C60 island or the different coupling of C60 molecules to SiC nanomesh. These STM molecular contrast patterns completely disappear on the second and all the subsequent C60 layers. It is also found that the nanomesh can be fully recovered by annealing the C60/SiC nanomesh sample at 200 degrees C for 20 min.

Apoptosis has been well documented to play a significant role in cell loss during neurodegenerative disorders, such as stroke, Parkinson disease, and Alzheimer's disease. In addition, reactive oxygen species (ROS) has been implicated in the cellular damage during these neurodegenerative disorders. These ROS can react with cellular macromolecular through oxidation and cause the cells undergo necrosis or apoptosis. The control of the redox environment of the cell provides addition regulation in the signal transduction pathways which are redox sensitive. Recently, many researches focus on the relationship between apoptosis and oxidative stress. However, till now, there is no clear and defined mechanisms that how oxidative stress could contribute to the apoptosis. This review hopes to make clear that generation of ROS during brain injury, particularly in ischemic stroke and Alzheimer's Disease, and the fact that oxidative state plays a key role in the regulation and control of the cell survival and cell death through its interaction with cellular macromolecules and signal transduction pathway, and ultimately helps in developing an unique therapy for the treatment of these neurodegenerative disorders.

It has been well documented that oxidative stress is involved in stroke. Currently, many neuroprotective strategies have been targeted at molecules that are able to act as an oxidant to intervene with free-radical mediated apoptosis in the ischemic penumbra. In particular, natural products which contain antioxidant properties have undoubtedly efficacious for stroke treatment. In the current study, therapeutic effects of Ginkgo biloba extract (EGb) against cerebral protection in Wistar rats underwent middle cerebral artery occlusion (MCAO) was evaluated. A comparison study was conducted by using Losartan, an antihypertensive drug. Gene expression levels of pro-apoptotic genes (AT2 receptor, Fas, Bax and Bcl-xS) have shown to have significant reduction by EGb- and Losartan-treated groups as compared to vehicle group. Significant reduction of immunoreactivity of protein production of these genes, together with least nuclear green fluorescence observed in TUNEL, EGb, as an antioxidant drug, is concluded to have potent and promising therapeutic effect for stroke treatment.

Electrochemistry and electrochemical surface plasmon resonance (SPR) spectroscopy have been applied to study the electrochemical deposition and the redox transition of poly(4-nitro-1,2-phenylenediamine) (P4NoPD) on gold disk. It was shown that SPR can be the signal transducer for the different redox states of P4NoPD. Using a model biomolecular system, involving streptavidin, biotinylated DNA, and its complementary target DNA, it was found that the presence of nitro groups in P4NoPD allows the biorecognition events to be modulated by voltages. There is minimal nonspecific binding of biomolecules on oxidized (+0.2 V) or as-prepared P4NoPD, and binding occurs more significantly on the reduced P4NoPD (-0.2 to -0.6 V) with the presence of amine groups. The electrochemical deposition of P4NoPD film was also conducted on boron-doped diamond (BDD) electrode. The stability of the reduced P4NoPD film on gold and BDD was comparatively evaluated by electrochemical impedance spectroscopy (EIS). The result showed that BDD allows the electrochemical reduction of the P4NoPD film at wider cathodic limits than gold.

The adsorption of allyl alcohol, acrylic acid, and allyl chloride, as well as unsaturated organic molecules such as acetylene and 1,3 butadiene, on reconstructed diamond (100) 2 x 1 have been investigated using high-resolution electron energy loss (HREELS) spectroscopy and synchrotron radiation spectroscopy. The cycloadditions of these organic molecules produce chemically adsorbed adlayers with varying degree of coverages on the clean diamond. The organic adsorbed surface has a lowered electron affinity and shows a secondary electron yield that varies between 12 and 40% of the yield obtained from a fully hydrogenated diamond surface. The diamond surface can be functionalized with hydroxyl, carboxylic, and chlorine functionalities by the adsorption of these allyl organics. The [2 + 2] adduct of acetylene on the diamond (100) 2 x 1 surface can be observed. 1,3-butadiene attains a higher coverage as well as forms a thermally more stable adlayer on the diamond surface compared to the other organic molecules, due to its ability to undergo [4 + 2] cycloaddition.

The growth dynamics of a single-walled carbon nanotube (SWNT) is observed in real-time using an in situ ultrahigh vacuum transmission electron microscope at 650 degrees C. SWNTs preferentially grow on smaller sized catalyst particles (diameter

We demonstrate a simple way of fabricating bulk quantities of molybdenum disulfide (MoS2) porous nanotubules (NTs) by templated deposition from a single source precursor based on tetrakis(diethylaminodithiocarbomato)molybdate(IV). Bulk quantities of crystalline MoS2 NTs that consist of agglomerates of nested nanocapsules were obtained by this one-step evaporation method. We found that MoS2 NTs show good optical limiting behavior with 532-and 1064-nm nanosecond laser pulses, and the size-effect of the NTs on optical transmission was observed.

Electron transfer at the molecule-metal interface of self-assembled monolayers of 1,1';4',1''-terphenyl-4''-thiol (BBB) and its partially fluorinated counterpart (BFF: p-thiophenyl-nonafluorobiphenyl) on Au(111) is investigated by core-hole clock spectroscopy. Ultrafast electron transfer at the BBB/Au(111) interface in the low-femtosecond regime (on the same time scale as the C 1s core-hole lifetime, approximately 6 fs) was observed. In contrast, for BFF/Au(111), the interface electron transfer was forbidden during the core-hole decay. This strongly suggests that fluorination of phenyl rings significantly enhances the localization of the excited electrons in the LUMO.

The impedimetric sensing of DNA hybridization on polyaniline/polyacrylate (PANI/PAA)-modified boron-doped diamond (BDD) electrode has been investigated. An ultrathin film of PANI-PAA copolymer was electropolymerized onto the diamond surfaces to provide carboxylic groups for tethering to DNA sensing probes. The electrochemical impedance and the intrinsic electroactivity of the polymer-diamond interface were analyzed after the hybridization reaction with target and non-target DNA. The impedance measurement shows changes in the impedance modulus as well as electron-transfer resistance at the stage of probe DNA immobilization (single-strand), as well as after hybridization with target DNA (double-strand). DNA hybridization increases the capacitance of the polymer-DNA layer and reduces the overall impedance of the DNA-polymer-diamond stack significantly. The polymer-modified BDD electrode shows no detectable nonspecific adsorption, with good selectivity between the complementary DNA targets and the one-base mismatch targets. The detection limit was measured to be 2 x 10(-8) M at 1000 Hz. Denaturing test on the hybridized probe and subsequent reuse of the probe indicates chemical robustness of the sensor. Our results suggest that electropolymerization followed by the immobilization of biomolecules is a simple and effective way of creating a functional biomolecular scaffold on the diamond surface. In addition, label-free electrochemical impedance method can provide direct and noninvasive sensing of DNA hybridization on BDD.

[structure: see text] Novel solution-processable blue light-emitting materials Blue A-D, bearing a polyphenylphenyl dendron, have been synthesized and characterized. The energy levels and band gaps can be facilely tuned by changing the central aromatic ring of the molecules. A highly efficient deep blue light-emitting OLED device based on Blue C with a maximum current efficiency of 2.2 cd/A has been achieved using PVK as the host material through a solution process.

We have synthesized edge-oriented MoS2 nanosheets by the evaporation of a single source precursor based on Mo(IV)-tetrakis(diethylaminodithiocarbomato). The surface chemistry of the MoS2 nanosheets has been studied in order to evaluate the chemical reactivities of the basal planes and edges. By irradiating the MoS2 nanosheet with a scanning infrared laser, micron-scale lithographical structures can be created due to laser-induced oxidation of MoS2 to form nanocrystalline MoO3. Preferential reactivities of the MoS2 basal edges in an electrochemical environment and during vapor phase deposition have been demonstrated. Functionalization of the basal plane with 1-pyrene acetic acid allows the immobilization of DNA and immunoglobins on the MoS2 basal plane.

The biochemical properties of boron-doped diamond (BDD), carbon nanofiber, fullerene, and multiwalled carbon nanotube (MWCNT) electrodes have been investigated comparatively. Physiochemical factors which affect the biosensing properties such as surface hydrophobicities, effective surface area, and intrinsic material properties are studied. Voltammetric responses of the as-grown thin film electrode and surface-modified electrode to biomolecules such as L-ascorbic acid (L-AA), dopamine (DA), and uric acid are examined. As-grown MWCNT electrodes exhibit selective voltammetric responses to the different biomolecules and faster electron-transfer kinetics compared to BDD. The selective response is due to the considerably lower anodic potential of L-AA on MWCNT (-48 mVvs Ag/AgCl compared to 575 mV on BDD). This electrocatalytic response can be replicated on a nonselective carbon nanofiber electrode by coating it with gold nanoparticles. BDD has no intrinsic selective response to L-AA, and surface modification by anodic polarization is necessary for resolving L-AA and DA.