Bioelectrochemical sensor based on PQQ-dependent glucose dehydrogenase

Bioelectrochemical responses of pyrroloquinoline quinone (PQQ) dependent glucose dehydrogenase (PQQ-GDH) have been studied with the use of two principal electrode configurations: (i) glassy carbon electrode, coated with Nafion layer, containing sorbed N-methylphenazonium (NMP), and overcoated by an enzyme layer, crosslinked by glutaraldehyde, and (ii) glassy carbon electrode, containing an electropolymerized layer of either Toluidine blue, or o-phenylenediamine, or pyrrole, and overcoated by a crosslinked enzyme layer. When operated within the potential window of 0.0–0.3 V, Nafion-coated and NMP-soaked bioelectrode shows an anodic current response to glucose without the presence of electron transfer mediator in solution. The current–concentration profile obtained resemble to that, typical for enzyme catalyzed reaction. Other configurations studied showed bioelectrochemical response to glucose only in the presence of soluble mediator NMP. Without any mediator, no electrochemical responses have been registered. It indicates that direct electron transfer between PQQ-GDH and all types of electrodes modified during current work is undetectable.     

Docking of Fatty Acids into the WIF Domain of the Human Wnt Inhibitory Factor-1

Palmitoylated Wnt proteins comprise a conserved family of secreted signaling molecules associated with variety of human cancers. WIF domain of the human WIF (Wnt inhibitory factor)-1 is sufficient for Wnt binding and signaling inhibition. Detailed interactions between Wnt and WIF-1 are not known. Computational docking was employed to identify a possible fatty acid binding site in the WIF domain. A putative binding site was identified inside the domain. WIF domain exhibited the highest affinity for C16:0–C18:0 (−22 kJ/mol free energy of binding) fatty acids. The results suggest a role of the WIF domain as a palmitoyl binding domain required for WIF-1 binding to palmitoylated Wnt and signaling inhibition. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A semi-global reaction rate model based on experimental data for the self-hydrolysis kinetics of aqueous sodium borohydride

This work studied the self-hydrolysis kinetics of aqueous sodium borohydride (NaBH₄) for hydrogen generation and storage purposes. Two semi-global rate expressions of sodium borohydride and hydrogen ion consumption were derived from an extensive series of batch process experiments where the following parameters were systematically varied: solution temperature (298 K–348 K), NaBH₄ concentration (0.5 wt% to 25.0 wt%), and sodium hydroxide (NaOH) concentration (0.0 wt% to 4.0 wt%). Transient hydrogen generation rates and transient solution pH were measured during the hydrolysis experiments. Given initial conditions (temperature, NaBH₄ concentration, and H⁺ concentration), the two coupled semi-global rate equations can be integrated to obtain the transient time history of H₂ generation (or NaBH₄ consumption) and solution pH (or H⁺ concentration). Comparing analytical results of transient hydrogen generation rate and transient solution pH with experimental data, good agreement was reached for many conditions, especially for elevated solution pH values, levels at which NaBH₄ solutions are used practically.     

Plasma hemoglobin measurement techniques for the in vitro evaluation of blood damage caused by medical devices

A sensitive measure of the in vitro blood damage potential of a medical device is the rate at which hemoglobin is released into the plasma from red blood cells flowing through the device. Presently there is no one widely accepted method for measuring the plasma hemoglobin concentration. Nine currently used assays, classified as either direct optical or added chemical techniques, were evaluated for accuracy, reproducibility, sensitivity, interference effects, and ease of use by adding hemoglobin (1-200 mg/dl) to saline, lipid, and bilirubin solutions and to normal cow plasma. Most of the assays displayed good linearity, accuracy, and reproducibility down to 1 mg/dl when interferents were absent. However, representative of the effects caused by interferents, the endogenous hemoglobin concentration of a typical cow plasma sample measured by the 9 techniques ranged from -2 to 39 mg/dl. Although used by fewer organizations, some of the direct optical spectrophotometric methods (e.g., the Cripps and Harboe baseline correction methods) are safer, easier, and more precise and accurate than the chemical addition methods used to measure plasma hemoglobin concentration from in vitro blood damage testing of medical devices.     

Additive Manufacturing of SiOC,SiC, and Si3N4 Ceramic 3D Microstructures

Herein, the fabrication of hard ceramic SiOC 3D microstructures by precursor synthesis, laser lithography, and pyrolysis combination is proposed. Precursors are hybrid organosilicon materials prepared via sol–gel method using trimethoxymethylsilane and 3-(trimethoxysilyl)propyl methacrylate, which has an acrylate functional group enabling laser photopolymerization process. Hard 3D ceramic structures (hardness up to ≈15 GPa, reduced elastic modulus ≈105 GPa) from soft organometallic derivatives are obtained after high-temperature pyrolysis under nitrogen atmosphere. The advantage of the proposed method is the absence of shrinkage defects leading to a uniform repetitive decrease in the volume of printed microstructures. In contrast to slurry-based printing technology, the proposed method is focused on homogeneous monolithic molecular resins resulting in visual smooth surfaces of prepared microstructures. Moreover, the printing resolution of the proposed method is substantially improved through the absence of predispersed ceramic microparticles in mixtures, which is a necessary element in a slurry-based technology.     

Relationships Between Strain and Recombination in Intermediate Growth Stages of GaN

Using metalorganic chemical vapor deposition, we heteroepitaxially grew undoped gallium nitride epilayers on sapphire. Assessing the epilayers at different growth stages, we investigated changes in epilayer strain and the lifetime of minority nonequilibrium charge carriers. The in-plane compressive strain was evaluated by x-ray diffraction and bandgap photoluminescence. The epilayer thickness ranged from 200 nm (islets) to 3.5 μm (continuous structure). The carrier lifetimes, measured using a light-induced transient grating technique, revealed a correlation between strain and the density of edge-type threading dislocations. This dislocation density was 10⁹ cm^?2 to 10¹¹ cm^?2, corresponding to the dominant mechanism for nonradiative carrier recombination. How the carrier lifetime depended on the growth stage differed between the surface and interfacial measurements. On the surface side, the carrier lifetime increased monotonically up to ~500 ps with thickness; on the interface side, the lifetime changed little with thickness, except in the thickest sample, where the carrier lifetime increased with thickness. We attributed this behavior to defect healing aided by long-term annealing, leading to mutual lateral motion and annihilation of mixed threading dislocations.     

Modification of alumina matrices through chemical etching and electroless deposition of nano-Au array for amperometric sensing

Simple nanoporous alumina matrix modification procedure, in which the electrically highly insulating alumina barrier layer at the bottom of the pores is replaced with the conductive layer of the gold beds, was described. This modification makes possible the direct electron exchange between the underlying aluminum support and the redox species encapsulated in the alumina pores, thus, providing the generic platform for the nanoporous alumina sensors (biosensors) with the direct amperometric signal readout fabrication. Electronic supplementary material   Supplementary material is available in the online version of this article at (doi: ) and is accessible for authorized users.     

Synthesis of new hole-transporting molecular glasses with pendant carbazolyl-based hydrazone moieties

Synthesis, thermal, optical and photoelectrical properties of new hole-transporting molecular glasses with pendant carbazolyl-based hydrazone moieties, linked by aliphatic linking fragments, are reported. Electron photoemission spectra of the synthesized derivatives have been recorded and the ionization potentials have been established. The hole drift mobility values in compositions of the designed structures with bisphenol Z polycarbonate exceed 10^?5 cm² V^?1 s^?1 at an electric field 10⁶ V/cm.     

Antibacterial performance of polydopamine-modified polymer surfaces containing passive and active components

A growing number of device-related nosocomial infections, elevated hospitalization costs, and patient morbidity necessitate the development of novel antibacterial strategies for clinical devices. We have previously demonstrated a simple, aqueous polydopamine dip-coating method to functionalize surfaces for a wide variety of uses. Here, we extend this strategy with the goal of imparting antifouling and antimicrobial properties to substrates, exploiting the ability of polydopamine to immobilize polymers and induce metal nanoparticle formation. Polydopamine was deposited as a thin adherent film of 4 nm thickness from alkaline aqueous solution onto polycarbonate substrates, followed by grafting of antifouling polymer polyethylene glycol and in situ deposition of silver nanoparticles onto the polydopamine coated polycarbonate substrates. Elemental and morphological surface analyses confirmed successful grafting of polyethylene glycol brushes onto polydopamine-coated substrates, as well as spontaneous silver nanoparticle formation for polydopamine-coated substrates incubated in silver-nitrate solutions. Sustained silver release was observed over at least 7 days from silver-coated substrates, and the release kinetics could be modulated via additional polydopamine overlayers. In vitro functional assays employing gram negative and positive strains demonstrated dual fouling resistance and antibacterial properties of the coatings due to the fouling resistance of grafted polyethylene glycol and antibacterial effect of silver, respectively. Polycarbonate substrates coated only with silver using a method similar to existing commercial coatings provided an antibacterial effect but failed to inhibit bacterial attachment. Taking into account the previously demonstrated substrate versatility of polydopamine coatings, our findings suggest that this strategy could be implemented on a variety of substrate materials to simultaneously improve antifouling and antimicrobial performance.