[Show abstract][Hide abstract] ABSTRACT: In this study development of impedimetric sensor based on oxygen terminated boron-doped nanocrystalline diamond (B:NCD:O) modified with theophylline imprinted polypyrrole is described. Hydrogen peroxide induced chemical formation of polypyrrole molecularly imprinted by theophylline was applied for the modification of conducting silicon substrate covered by B:NCD:O film. Non-imprinted polypyrrole layer was formed on similar substrate in order to prove efficiency of imprinted polypyrrole. Electrochemical impedance spectroscopy was applied for the evaluation of analyte-induced changes in electrochemical capacitance/resistance. The impact of polymerization duration on the capacitance of impedimetric sensor was estimated. A different impedance behavior was observed at different ratio of polymerized monomer and template molecule in the polymerization media. The influence of ethanol as additive to polymerization media on registered changes in capacitance/resistance was evaluated. Degradation of sensor stored in buffer solution was evaluated.
[Show abstract][Hide abstract] ABSTRACT: Correction for ‘Diamond functionalization with light-harvesting molecular wires: improved surface coverage by optimized Suzuki cross-coupling conditions’ by W. S. Yeap et al., RSC Adv., 2014, 4, 42044–42053.
[Show abstract][Hide abstract] ABSTRACT: In this article, we report on a label-free real-time method based on heat transfer resistivity for thermal monitoring of DNA denaturation and its potential to quantify DNA fragments with a specific sequence of interest. Probe DNA, consisting of a 36-mer fragment was covalently immobilized on a nanocrystalline diamond surface, created by chemical vapor deposition on a silicon substrate. Various concentrations of full matched 29-mer target DNA fragments were hybridized with this probe DNA. We observed that the change in heat transfer resistance upon denaturation depends on the concentration of target DNA used during the hybridization, which allowed to determine the dose response curve. Therefore, these results illustrate the potential of this technique to quantify the concentration of a specific DNA fragment and to quantify the hybridization efficiency to its probe.
Diamond and Related Materials 09/2014; · 1.71 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The modification of the diamond surface with organic molecules is a crucial aspect to be considered for any bio-application of this material. There is a great interest in broadening the range of linker molecules which can be covalently bound to the diamond surface. In the case of protein immobilization, the hydropathicity of the surface has a major influence on the protein conformation and, thus, on the functionality of proteins immobilized at surfaces. For electrochemical applications, particular attention has to be devoted to avoid that the charge transfer between the electrode and the redox center embedded in the protein is hindered by a thick insulating linker layer. This paper reports on the grafting of 6-phosphonohexanoic acid on OH-terminated diamond surfaces, serving as linkers to tether electro-active proteins onto diamond surfaces. X-ray photoelectron spectroscopy (XPS) confirms the formation of a stable layer on the surface. The charge transfer between electro-active molecules and the substrate is studied by electrochemical characterization of the redox activity of aminomethylferrocene and cytochrome c covalently bound to the substrate through this linker. Our work demonstrates that OH-terminated diamond functionalized with 6-phosphonohexanoic acid is a suitable platform to interface redox-proteins, which are fundamental building blocks for many bioelectronics applications.
[Show abstract][Hide abstract] ABSTRACT: A straightforward protocol for the covalent functionalization of boron-doped diamond electrodes with either ferrocene or single-stranded deoxyribonucleic acid (DNA) is reported. The functionalization method is based on a combination of diazonium salt electrografting and click chemistry. An azide-terminated organic layer is first electrografted onto the diamond surface by electrochemical reduction of 4-azidophenyldiazonium chloride. The azidophenyl-modified surface then reacts rapidly and efficiently with molecules bearing a terminal alkyne moiety by means of CuI-catalyzed alkyne–azide cycloaddition. Covalent attachment of ferrocene moieties was analyzed by X-ray photoelectron spectroscopy and cyclic voltammetry, whereas impedance spectroscopy was applied for the characterization of the immobilized DNA.
[Show abstract][Hide abstract] ABSTRACT: Hydrogen and oxygen surface-terminated nanocrystalline diamond (NCD) films are studied by the contactless time-resolved microwave conductivity (TRMC) technique and X-ray photoelectron spectroscopy (XPS). The opto-electronic properties of undoped NCD films are strongly affected by the type of surface termination. Upon changing the surface termination from oxygen to hydrogen, the TRMC signal rises dramatically. For an estimated quantum yield of 1 for sub-bandgap optical excitation the hole mobility of the hydrogen-terminated undoped NCD was found to be ~0.27 cm2/Vs with a lifetime exceeding 1 µs. Assuming a similar mobility for the oxygen-terminated undoped NCD a lifetime of ~100 ps was derived. Analysis of the valence band spectra obtained by XPS suggests that upon oxidation of undoped NCD the surface Fermi level shifts (towards an increased work function). This shift originates from the size and direction of the electronic dipole moment of the surface atoms, and leads to different types of band bending at the diamond/air interface in the presence of a water film. In the case of boron-doped NCD no shift of the work function is observed, which can be rationalized by pinning of the Fermi level. This is confirmed by TRMC results of boron-doped NCD, which show no dependency on the surface termination. We suggest that photo-excited electrons in boron-doped NCD occupy non-ionized boron dopants, leaving relatively long-lived mobile holes in the valence band.
[Show abstract][Hide abstract] ABSTRACT: N3 dye molecules [cis-bis(isothiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)] are covalently attached onto boron-doped nanocrystalline diamond (B:NCD) thin films through a combination of coupling chemistries, i.e. diazonium, Suzuki and EDC-NHS. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS), and near-edge X-ray absorption fine structure spectroscopy (NEXAFS) are used to verify the covalent bonding of the dye on the B:NCD surface (as compared to a hydrogen-terminated reference). The spectroscopic results confirm the presence of a dense N3 chromophore layer and the positions of the frontier orbitals of the dye relative to the band edge of the B:NCD thin film are inferred as well. Proof of concept photoelectrochemical measurements show a strong increase in photocurrent as compared to non-dye-functionalized B:NCD films. This study opens up the possibility to apply N3-sensitized B:NCD thin films as hole conductors in dye-sensitized solar cells.
[Show abstract][Hide abstract] ABSTRACT: We report on the use of the heat transfer method, a novel surface-sensitive technique based on heat transfer through solid–liquid interfaces, to detect phase transitions of model lipid membranes. We selected the lipid DPPC because of its rich phase behavior in an experimentally accessible temperature range. The vesicles were adsorbed on nanocrystalline diamond films, known as a versatile platform material for biosensing with outstanding heat-conduction properties. Complementary Peltier-element-based adiabatic scanning calorimetry (pASC) and quartz crystal microbalance with dissipation monitoring (QCM-D) measurements were carried out to monitor the phase transitions in multilamellar and small unilamellar vesicles, respectively. The heat-transfer measurements revealed reversible jumps upon heating and cooling in the thermal resistance in the vicinity of the expected transition temperature and they agree qualitatively with molecular simulations of the thermal conductivity across a lipid bilayer. The results show the capability of the heat transfer method to detect the main phase transition in DPPC, opening new perspectives for the study of more complex lipid systems and different solid platforms. This work confirms QCM-D as a useful tool for the assessment of the structural changes upon the phase conversion and shows the capability of pASC to provide high-resolution thermodynamic information on biophysical systems.Temperature profile of the heat transfer resistance Rth during the main phase transition of a DPPC supported vesicle layer adsorbed on a hydrogen-terminated nanocrystalline diamond substrate. The arrows indicate the sense of the run: heating (red solid line) and cooling (blue solid line).
Physica Status Solidi (A) Applications and Materials 05/2014; · 1.53 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: In this contribution we report on a novel method for the growth of laterally patterned synthetic diamond films with submicron feature sizes. The lateral patterning is induced by depositing a nanodiamond-based seeding layer prior to the chemical vapor deposition of the diamond films. The seeding layer is prepared by a microfluidic approach, based on soft lithography with PDMS moulds, used in the microcontact printing. These moulds are prepared by electron-beam lithography of photoresist on silicon substrates. The master moulds are reusable, allowing for cheap, high-throughput manufacturing, and the resulting diamond microstructures exhibit an outstanding smoothness and structural reproducibility. Possible applications are expected in the fields of diamond electronics, micro-electro-mechanical systems (MEMS) as well as bio- and chemosensors. The abstract figure shows the SU-8 master mould (left). The resulting diamond structure (right) is shown, after chemical vapor deposition. The purple color originates from the settings of the optical microscope, used to get a high-contrast image.
Physica Status Solidi (A) Applications and Materials 05/2014; · 1.53 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The production of boron-doped diamond nanoparticles enables the application of this material for a broad range of fields, such as electrochemistry, thermal management, and fundamental superconductivity research. Here we present the production of highly boron-doped diamond nanoparticles using boron-doped CVD diamond films as a starting material. In a multistep milling process followed by purification and surface oxidation we obtained diamond nanoparticles of 10-60 nm with a boron content of approximately 2.3 × 10(21) cm(-3). Aberration-corrected HRTEM reveals the presence of defects within individual diamond grains, as well as a very thin nondiamond carbon layer at the particle surface. The boron K-edge electron energy-loss near-edge fine structure demonstrates that the B atoms are tetrahedrally embedded into the diamond lattice. The boron-doped diamond nanoparticles have been used to nucleate growth of a boron-doped diamond film by CVD that does not contain an insulating seeding layer.
[Show abstract][Hide abstract] ABSTRACT: Nanostructured boron-doped diamond has been investigated as a sensitive impedimetric electrode for the detection of immunoglobulin G (IgG). The immunosensor was constructed in a three-step process: (i) reactive ion etching of flat boron-doped diamond (BDD) interfaces to synthesize BDD nanowires (BDD NWs), (ii) electrochemical deposition of nickel nanoparticles (Ni NPs) on the BDD NWs, and (iii) immobilization of biotin-tagged anti-IgG onto the Ni NPs. Electrochemical impedance spectroscopy (EIS) was used to follow the binding of IgG at different concentrations without the use of any additional label. A detection limit of 0.3 ng mL(-1) (2 nM) with a dynamic range up to 300 ng mL(-1) (2 μM) was obtained with the interface. Moreover, the study demonstrated that this immunosensor exhibits good stability over time and allows regeneration by incubation in ethylenediaminetetraacetic acid (EDTA) aqueous solution.
[Show abstract][Hide abstract] ABSTRACT: Glass and diamond are suitable materials for harsh environments. Here, a procedure for fabricating ultra-thin nanocrystalline diamond membranes on glass, acting as an electrically insulating substrate, is presented. In order to investigate the pressure sensing properties of such membranes, a circular, highly conductive boron-doped nanocrystalline diamond membrane with a resistivity of 38 mΩ cm, a thickness of 150 nm, and a diameter of 555 μm is fabricated in the middle of a Hall bar structure. During the application of a positive differential pressure under the membrane (0–0.7 bar), four point piezoresistive effect measurements are performed. From these measurements, it can be concluded that the resistance response of the membrane, as a function of differential pressure, is highly linear and sensitive.
[Show abstract][Hide abstract] ABSTRACT: Surface conductivity in hydrogen-terminated single crystal diamond is an intriguing phenomenon for fundamental reasons as well as for application driven research. Surface conductivity is also observed in hydrogen-terminated nanocrystalline diamond although the electronic transport mechanisms remain unclear. In this work, the piezoresistive properties of intrinsic surface conductive nanocrystalline diamond are investigated. A gauge factor of 35 is calculated from bulging a diamond membrane of 350 nm thick, with a diameter of 656 μm and a sheet resistance of 1.45 MΩ/sq. The large piezoresistive effect is reasoned to originate directly from strain-induced changes in the resistivity of the grain boundaries. Additionally, we ascribe a small time-dependent fraction of the piezoresistive effect to charge trapping of charge carriers at grain boundaries. In conclusion, time-dependent piezoresistive effect measurements act as a tool for deeper understanding the complex electronic transport mechanisms induced by grain boundaries in a polycrystalline material or nanocomposite.
[Show abstract][Hide abstract] ABSTRACT: Conventional neonatal diagnosis of phenylketonuria is based on the presence of abnormal levels of phenylalanine in the blood. However, for carrier detection and prenatal diagnosis, direct detection of disease-correlated mutations is needed. To speed up and simplify mutation screening in genes, new technologies are developed. In this study, a heat-transfer method is evaluated as a mutation-detection technology in entire exons of the phenylalanine hydroxylase (PAH) gene. This method is based on the change in heat-transfer resistance (Rth) upon thermal denaturation of dsDNA (double-stranded DNA) on nanocrystalline diamond. First, ssDNA (single-stranded DNA) fragments that span the size range of the PAH exons were successfully immobilized on nanocrystalline diamond. Next, it was studied whether an Rth change could be observed during the thermal denaturation of these DNA fragments after hybridization to their complementary counterpart. A clear Rth shift during the denaturation of exon 5, exon 9, and exon 12 dsDNA was observed, corresponding to lengths of up to 123 bp. Finally, Rth was shown to detect prevalent single-nucleotide polymorphisms, c.473G>A (R158Q), c.932T>C (p.L311P), and c.1222C>T (R408W), correlated with phenylketonuria, displaying an effect related to the different melting temperatures of homoduplexes and heteroduplexes.
International Journal of Nanomedicine 01/2014; 9:1629-40. · 4.20 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Graphene has potential for applications in solar cells. We show that the short circuit current density of P3HT (Poly(3-hexylthiophene-2,5-diyl):PCBM((6,6)-Phenyl C61 butyric acid methyl ester) solar cells is enhanced by 10% upon the addition of graphene, with a 15% increase in the photon to electric conversion efficiency. We discuss the performance enhancement by studying the crystallization of P3HT, as well as the electrical transport properties. We show that graphene improves the balance between electron and hole mobilities with respect to a standard P3HT:PCBM solar cell.
[Show abstract][Hide abstract] ABSTRACT: Polycrystalline aluminum nitride (AlN) thin films are exposed to hydrogen and hydrogen/methane plasmas at different conditions. The latter plays an indispensable role in the subsequent deposition of nanocrystalline diamond thin films on AlN. The changes of AlN properties are investigated by means of Fourier transform infrared (FTIR) and Raman spectroscopies as well as atomic force microscopy. The E1(TO) and E22 phonon mode frequencies blue-shift after the exposure to plasmas. The damping constant of E1(TO) phonon, calculated from FTIR transmission spectra using the factorized model of a damped oscillator, and the width of E22 peak in Raman spectra decrease with increasing substrate temperature till the decomposition of AlN thin film becomes notable. It is proven that these changes are driven by the plasmas as annealing in vacuum does not induce them.
[Show abstract][Hide abstract] ABSTRACT: A new and facile approach is presented for generating quasi-regular patterns of transition metal-based nanoparticles on flat substrates exploiting polystyrene-block-poly2vinyl pyridine (PS-b-P2VP) micelles as intermediate templates. Direct loading of such micellar nanoreactors by polar transition metal salts in solution usually results in nanoparticle ensembles exhibiting only short range order accompanied by broad distributions of particle size and inter-particle distance. Here, we demonstrate that the use of P2VP homopolymers of appropriate length as molecular carriers to transport precursor salts into the micellar cores can significantly increase the degree of lateral order within the final nanoparticle arrays combined with a decrease in spreading in particle size. Thus, a significantly extended range of materials is now available which can be exploited to study fundamental properties at the transition from clusters to solids by means of well-organized, well-separated, size-selected metal and metal oxide nanostructures.