Graphene-modified electrode. Determination of hydrogen peroxide at high concentrations

A gold electrode partially coated by graphene multilayer is developed and tested with respect to high concentrations of hydrogen peroxide. The effective use of conventional electrode materials for the determination of such an analyte by anodic oxidation or cathodic reduction is prevented by the occurrence of adsorptions fouling the electrode surface. This prevents reliable and repeatable voltammetric curves for being recorded and serious problems arise in quantitative analysis via amperometry. The gold–graphene electrode is shown to be effective in quantitative evaluation, by cathodic reduction, of hydrogen peroxide at concentration levels that are of interest in an industrial. Acid, neutral, and basic pH values have been tested through correct adjustment of a Britton Robinson buffer. The experiments have been performed both by cyclic voltammetry and with amperometry at constant potential in unstirred solution. The latter technique has been employed in drawing a calibration linear plot. In particular, the performances of the developed electrode system have been compared with those of both pure gold and pure graphene electrode materials. The bi-component electrode was more sensitive; co-catalytic action by the combination of the two components is hypothesised. The system is stable over many potential cycles, as checked by surface-enhanced Raman spectra recorded over time.     

Boron nitride nanotube-based amphiphilic hybrid nanomaterials for superior encapsulation of hydrophobic cargos

We report an organic-inorganic hybrid core-shell nanomaterial obtained by conjugation of an amphiphilic monomethoxy-poly(ethylene glycol)-b-poly(epsilon-caprolactone) diblock copolymer to hydroxylated boron nitride nanotubes (BNNTs). The extent of copolymer grafting reached 64% w/w, an exceptionally high value. The hybrid materials exhibit excellent physical stability in water and an outstanding loading capacity (31.3% w/w) for curcumin, a hydrophobic drug. Moreover, they present good compatibility with the Caco2 cell line, a model of intestinal epithelium. Our findings demonstrate the potential of multifunctional hybrid BNNTs to serve as a platform for complex amphiphilic nanoparticle architectures with improved features.     

Aqueous dispersion, surface thiolation, and direct self-assembly of carbon nanotubes on gold

We report the efficient aqueous dispersion of pristine HiPco single-walled carbon nanotubes (SWNTs) with ionic liquid (IL)-based surfactants 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), the thiolation of nanotube sidewalls with 2, and the controlled self-assembly of positively charged SWNT-1,2 composites on gold. Optical absorption spectra and resonance Raman (RR) data of obtained aqueous SWNT-1,2 dispersions are consistent with debundled and noncovalently functionalized nanotubes whose electronic properties have not been disturbed. Additionally, the dispersion of pristine nanotube material with surfactants 1 and 2 leads to a high degree of purification from carbonaceous particles. The chiralities of the 14 smallest semiconducting HiPco SWNTs in resonance with Raman excitation at 1064 nm (1.165 eV) were determined in SWNT-2 aqueous dispersion using UV-vis-NIR and RR spectra. X-ray photoelectron spectroscopy (XPS) and surface-enhanced resonance Raman scattering (SERRS) spectroscopy of SWNT-2 submonolayers on gold verified the encapsulation of individualized SWNTs with IL surfactants, the cleavage of S-S disulfide bonds formed in aqueous SWNT-2 suspensions, and the direct chemisorption of the SWNT-2 composite on bare gold via the Au-S bond. Aqueous dispersions of SWNTs with IL-based surfactants add biofunctionality to carbon nanotubes by imparting the positive surface charge necessary for interactions with cell membranes. Our technique, which purifies pristine nanotube material and produces water-soluble, positively charged nanotubes with pendent surface-active thiol groups, may also be translated to other carbon nanotubes and carbon nanostructures. Self-assembled, positively charged submonolayers of SWNTs can be further used for applications in cell biology and sensor technology.     

Hydrolysis products of water treatment chemical aluminium sulfate octadecahydrate by electrospray ionization mass spectrometry

Hydrolysis and speciation of aluminium sulfate octadecahydrate Al₂(SO₄₎₃·18H₂O${\text{Al}}_2({\text{SO}}_4{)}_3·18{\text{H}}_2\text{O}$ was studied by electrospray time of flight mass spectrometry (ESI TOF MS). Several novel polymeric species were determined. Highly charged polymers, characterized by other methods, such as the Keggin cation [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺ and the octameric aluminium hydroxide cluster [Al₈(OH)₁₄(H₂O)₁₈](SO₄)₅ 16H₂O, were found using ESI-MS as the anions [Al₁₃O₄(OH)₂₅(SO₄)₄]²⁻ and [Al₈O(OH)₁₄(SO₄)₅(H₂O)₄]²⁻. All the main species identified contained sulfate or hydrogen sulfate. The compositions of the determined ions mimicked those of several stable mineral forms.     

Behavior of acetonitrile confined to mesoporous silica gels as studied by 129Xe NMR: a novel method for determining the pore sizes

129Xe NMR spectra of xenon dissolved in acetonitrile confined into three mesoporous silica gels with nominal pore diameters of 40, 60, and 100 A have been measured over the temperature range 170-245 K. The spectra consist of a number of lines, which contain detailed information on the system. The most interesting result is that the chemical shift of a particular signal observed below the melting point of confined acetonitrile is highly sensitive to the pore size, and hence its shape is sensitive to the pore size distribution function. This signal originates from the xenon atoms sited in very small cavities built up inside the pores during the freezing transition. It can be used to determine the size or even the size distribution function of the pores. In addition, the emergence of this signal reveals the phase transition temperature of acetonitrile inside the pores, which can also be used to determine the size of the pores. The difference in the chemical shifts of two other signals, which arise from xenon dissolved in bulk and confined acetonitrile, provides still another novel method for determining the size of the pores.     

Optimal shape design in a fibre orientation model

We study a 2D model of the orientation distribution of fibres in a paper machine headbox. The goal is to control the orientation of fibres at the outlet by shape variations. The mathematical formulation leads to an optimization problem with control in coefficients of a linear convection-diffusion equation as the state problem. Existence of solutions both to the state and the optimization problem is analyzed and sensitivity analysis is performed. Further, discretization is done and a numerical example is shown. This research was supported by the Charles University Grant Agency under Contract 6/2005/R, MSM 0021620839 (MŠMT ČR), and the Academy of Finland, Grant #204741.     

Binary tree approach to scaling in unimodal maps

Ge, Rusjan, and Zweifel introduced a binary tree which represents all the periodic windows in the chaotic regime of iterated one-dimensional unimodal maps. We consider the scaling behavior in a modified tree which takes into account the self-similarity of the window structure. A nonuniversal geometric convergence of the associated superstable parameter values towards a Misiurewicz point is observed for almost all binary sequences with periodic tails. For these sequences the window period grows arithmetically down the binary tree. There are an infinite number of exceptional sequences, however, for which the growth of the window period is faster. Numerical studies with a quadratic maximum suggest more rapid than geometric scaling of the superstable parameter values for such sequences.     

Nonadiabatic charge pumping in a hybrid single-electron transistor

We study theoretically current quantization in the charge turnstile based on the superconductor-normal-metal single-electron transistor. The quantization accuracy is limited by either Andreev reflection or by Cooper-pair-electron cotunneling. The rates of these processes are calculated in the "above-the-threshold" regime when they compete directly with the lowest-order tunneling. By shaping the ac gate voltage drive it should be possible to achieve the metrological accuracy of 10;{-8}, while maintaining the quantized current on the level of 30 pA, just by one turnstile with realistic parameters using aluminum as a superconductor.     

Preoperative localization of the sensorimotor area using independent component analysis of resting-state fMRI

Analysis of resting-state functional magnetic resonance imaging (fMRI) data is based on detecting low-frequency signal fluctuations in functionally connected brain areas. These synchronous fluctuations in resting-state networks have been observed in several studies with healthy subjects. In this study, we explored if independent component analysis (ICA) can be used to localize the sensorimotor area from resting-state fMRI data in patients with brain tumors. Finger-tapping activation task and resting-state blood-oxygenation-level-dependent fMRI data were acquired from 8 patients with brain tumors and 10 healthy volunteers. Sensorimotor task independent components (IC_task) were used to verify resting-state independent components (IC_rest) individually. In addition, sensorimotor IC_rests were compared between the groups and no significant differences were detected in volume, spatial correlation or temporal correlation. These results show that it is possible to localize a sensorimotor area from resting-state data using ICA in patients with brain tumors. This offers a complementary method for assessing the sensorimotor area in subjects with brain tumors who have difficulties in performing motor paradigms.