Acoustic Doppler velocimetry (ADV) data on flow-vegetation interaction with natural-like and rigid model plants in hydraulic flumes.

Vegetation, generally present along river margins and floodplains, governs key hydrodynamic processes in riverine systems. Despite the flow-influencing mechanisms exhibited by natural vegetation and driven by its complex morphology and flexibility, vegetation has been conventionally simulated by using rigid cylinders. This article presents a dataset obtained from hydraulic experiments performed for investigating the flow-vegetation interaction in partly vegetated channels. Vegetation was simulated by using both natural-like and rigid model plants. Specifically, two sets of experiments are described: in the first, vegetation was simulated with natural-like flexible foliated plants standing on a grassy bed; in the second, rigid cylinders were used. Experiments with rigid cylinders were designed to be compared against tests with natural-like plants, as to explore the effects of vegetation representation. The following experimental data were produced: 3D instantaneous velocity measured by acoustic Doppler velocimetry, vegetation motion video recordings, and auxiliary data including detailed vegetation characterization. These experiments are unique both for the use of natural-like flexible woody vegetation in hydraulic experiments and for the similarity achieved between the resulting observed vegetated shear layers. These data are expected to be useful in vegetated flows model development and validation, and represent a unique benchmark for the interpretation of the flow-vegetation interaction in partly vegetated channels.

Hydromorphologically-driven variability of thermal and oxygen conditions at the block ramp hydraulic structure: The Porebianka River, Polish Carpathians.

Growing anthropopressure in mountain streams aimed at limiting erosion and flood protection often caused adverse effects on the natural environment. In recent years, great attention has been paid to the restoration and conservation of natural habitats in mountain streams using environmentally friendly solutions such as the Block Ramp (BR) Hydraulic Structures. In this study we investigated the factors responsible for spatial variability in thermal and oxygen conditions at the single BR structure in the growing season, and the relation between water temperature and dissolved oxygen (DO) concentration. This has been done by measurements of hydraulic characteristics along with physicochemical properties of water, such as water temperature and DO concentration, at two different discharges. The redundancy analysis has been applied in order to describe the relationships among hydraulic parameters and physicochemical variables, and extract potential sources of water temperature and DO variability within the BR hydraulic structure. Results have shown that DO and water temperature distributions within the BR hydraulic structure depend on discharge conditions and are associated with the submergence of the block ramp. The highest heterogeneity in hydraulic, DO and water temperature conditions occurs at low flow and is associated with the presence of crevices between protruding cobbles at the block ramp. The lowest variability, in turn, occurs at high discharge, when the block ramp is completely submerged. The results indicated that thermal and oxygen conditions within the BR hydraulic structure are independent of hydraulic parameters at low flow. Moreover, the relation between DO concentration and water temperature is positive at low flow indicating potential impact of biological processes. On the contrary, at high discharge both, the DO concentrations and water temperature within the BR structure, depend on bed shear velocity and maximum Reynolds number.

Liquid crystal membranes for serum-compatible diabetes management-assisting subcutaneously implanted amperometric glucose sensors.

Membranes formed of thermodynamically stable cubic phase lyotropic liquid crystals (LLCs) could replace the presently used polymeric membranes, applied to reduce the flux of glucose in semicontinuous, subcutaneously implanted, user-replaced, miniature, amperometric glucose sensors, assisting in the management of diabetes. LLC-forming amphiphilic compounds set and toughen spontaneously after mixing with water, without undergoing chemical change. When applied by doctor-blading, they form membranes having three-dimensionally interconnected water channels of uniform diameter, with reproducible glucose transport-characteristics. We find that the best studied cubic phase LLCs, which are formed of monoolein and water, are not useful in their intended application because they are hydrolyzed by serum lipases. Those formed of phytantriol, a liquid at ambient temperature, and water, are not hydrolyzed but change their shape and size in a dehydration and rehydration cycle. Because glucose sensors are sterilized and stored in a sealed package in a dry atmosphere, drying and rehydration must not change the transport characteristics. A third, novel, LLC-forming, amphiphile 1-O-beta-(3,7,11,15-tetramethylhexadecyl)-d-ribopyranoside, I, was synthesized, and its phase diagram was tailored by adding Vitamin E acetate, to form a cubic phase. The phase was stable through the 20 degrees C-90 degrees C temperature range in excess of water and had the desired glucose-transport characteristics. A preferred LLC, II, was formed of water and I containing 7 wt % of Vitamin E acetate. When II was applied to a wired glucose oxidase bioelectrocatalyst, sensors of reproducible glucose-sensitivity were formed. At a 0.1 mm thickness of II, the membrane reduced the glucose flux 5-fold and increased the 90% response-time by less than 2 min. The membrane was mechanically rugged, withstanding the approximately 1 N m(-2) maximal shear stress at 5 mm diameter electrodes rotating at 4000 rpm. The activation energy for glucose permeation through II was reduced to 15.6 kJ/mol, making the sensors's current less temperature-dependent than that of the polymeric-membrane overcoated implantable glucose sensors.

Mechanical and chemical protection of a wired enzyme oxygen cathode by a cubic phase lyotropic liquid crystal.

When implanted in animals, enzyme-containing battery electrodes, biofuel cell electrodes, and biosensors are often damaged by components of the biological environment. An O2 cathode, superior to the classical platinum cathode, which would be implanted, as part of a caseless physiological pH miniature Zn-O2 battery or as part of a caseless and membraneless miniature glucose-O2 biofuel cell, is rapidly damaged by serum urate at its operating potential. The cathode is made by electrically connecting, or wiring, reaction centers of bilirubin oxidase to carbon with an electron-conducting redox hydrogel. In the physiological pH 7.3 electrolyte battery or biofuel cell, the O2 cathode should operate at, or positive of, 0.3 V (Ag/AgCl), where the urate anion, a common serum component, is electrooxidized. Because an unidentified urate electrooxidation intermediate, formed in the presence of O2, damages the wired bilirubin oxidase electrocatalyst, urate must be excluded from the cathode. Unlike O2, which permeates through both the lipid and the aqueous interconnected networks of cubic-phase lyotropic liquid crystals, urate permeates only through their continuous three-dimensional aqueous channel networks. The aqueous channels have well-defined diameters of approximately 5 nm in the monoolein/water cubic-phase liquid crystal. Through tailoring the wall charge of the aqueous channels, the anion/cation permeability ratio can be modulated. Thus, doping the monoolein of the monoolein/water liquid crystal with 1,2-dioleoyl-sn-glycero-3-phosphate makes the aqueous channel walls anionic and reduces the urate permeation in the liquid crystal. As a result, the ratio of the urate electrooxidation current to the O2 electroreduction current is reduced from 1:3 to 1:100 for 5-mm O2 cathodes rotating at 1000 rpm. Doping with 1,2-dioleoyl-sn-glycero-3-phosphate also increases the shear strength of the cubic-phase monoolein/water lyotropic liquid crystal. While the undoped liquid crystal is promptly damaged at the 0.1 N m-2 average shear stress generated by rotating the 5-mm-diameter disk cathode at 1000 rpm in a physiological aqueous solution, the 10 mol % 1,2-dioleoyl-sn-glycero-3-phosphate-doped film remains intact. The mechanical strengthening of the lyotropic liquid crystal by the two-tailed 1,2-dioleoyl-sn-glycero-3-phosphate is attributed to cross-linking hydrophobic bonds (i.e., bonds resulting of the increase in entropy upon the freeing of the translation and rotation of multiple water molecules), which is analogous to the strengthening of polymer-based plastic materials by cross-linking through covalent bonds.

Modified electrodes based on lipidic cubic phases.

The lipidic cubic phase can be characterized as a curved bilayer forming a three-dimensional, crystallographical, well-ordered structure that is interwoven by aqueous channels. It provides a stable, well-organized environment in which diffusion of both water-soluble and lipid-soluble compounds can take place. Cubic phases based on monoacylglycerols form readily and attract our interest due to their ability to incorporate and stabilize proteins. Their lyotropic and thermotropic phase behaviour has been thoroughly investigated. At hydration over 20%, lipidic cubic phases Ia3d and Pn3m are formed. The latter is stable in the presence of excess water, which is important when the cubic phase is considered as an electrode-modifying material. Due to high viscosity, the cubic phases can be simply smeared over solid substrates such as electrodes and used to host enzymes and synthetic catalysts, leading to new types of catalytically active modified electrodes as shown for the determination of cholesterol, CO(2), or oxygen. The efficiency of transport of small hydrophilic molecules within the film can be determined by voltametry using two types of electrodes: a normal-size electrode working in the linear diffusion regime, and an ultramicroelectrode working under spherical diffusion conditions. This allows determining both the concentration and diffusion coefficient of the electrochemically active probe in the cubic phase. The monoolein-based cubic phase matrices are useful for immobilizing enzymes on the electrode surface (e.g., laccases from Trametes sp. and Rhus vernicifera were employed for monitoring dioxygen). The electronic contact between the electrode and the enzyme was maintained using suitable electroactive probes.

Electrodes modified with monoolein cubic phases hosting laccases for the catalytic reduction of dioxygen.

An enzyme-catalyzed process has been used for dioxygen monitoring. The enzymes were two different laccases (p-diphenol:dioxygen oxidoreductases), chosen as catalysts for dioxygen reduction. The laccases were immobilized in a liquid crystalline cubic phase formed with monoolein. The structures of the cubic phases, both with and without enzymes, were established using small-angle X-ray scattering. The catalytic reduction of dioxygen was performed using a glassy carbon electrode modified with cubic phases containing the enzymes. The modified electrode was used as a dioxygen sensing system, based on the increasing reduction current of a suitable electrochemical probe in the presence of dioxygen.

Diffusion of hydrophilic probes in bicontinuous lipidic cubic phase.

The lipidic cubic phase was prepared by mixing monoolein (monooleoyl-rac-glycerol, MO) with water in 64:36% ratio and applied to the solid support-glassy carbon or platinum electrodes. Highly viscous, homogeneous and transparent cubic phase film remained stable and firmly attached to the electrode surface. In order to describe the efficiency of transport of small hydrophilic molecules within the film, we studied the diffusion of selected redox mediators along the network of aqueous channels present in the cubic phase structure. Loading times, diffusion coefficients and concentrations of the mediators in the layer were determined by voltammetry and chronocoulometry using two types of electrodes: a normal size electrode working in the linear diffusion regime and an ultramicroelectrode working under spherical diffusion conditions. In addition to the well-defined order, transparency and viscosity, the fast transport of small redox mediators through the aqueous channels of the cubic phase and along the interfacial water-lipid region is another important property of this matrix. The diffusion of the hydrophilic probes in the cubic phase was found to be more efficient than in the Nafion layers. Efficient transport of small redox mediators within the cubic phase means that not only enzymes and synthetic catalysts can be incorporated into the phase but also their fast communication with electrode surface will be enabled thanks to the simultaneous incorporation of small mobile redox mediators. This property of the cubic liquid crystalline phases based on lipids makes them especially interesting from the point of view of practical applications in biosensing and bioelectrocatalysis.

A concept for immobilizing catalytic complexes on electrodes: cubic phase layers for carbon dioxide sensing.

Liquid crystalline cubic phases formed with monoolein and Myverol have been used as matrixes to host a catalytic complex of nickel(II) and 1-hexadecyl-1,4,8,11-tetraazacyclotetradecane for the reduction of carbon dioxide. The structures of the cubic phases, both with and without the catalyst, were established using small-angle X-ray scattering. The catalytic reduction of carbon dioxide was performed using thin mercury film and glassy carbon electrodes modified with cubic phases containing the catalyst. The linear dependence of the catalytic reduction current on the carbon dioxide concentration allowed use of the modified electrodes as sensing devices both in solution and in the gas phase. The high reproducibility of the measurements makes this method of monitoring carbon dioxide levels attractive compared to other methods based on modified electrodes.