Carbon felt-based bioelectrocatalytic flow-through detectors: Highly sensitive amperometric determination of H2O2 based on a direct electrochemistry of covalently modified horseradish peroxidase using cyanuric chloride as a linking agent

Horseradish peroxidase (HRP) was chemically modified using cyanuric chloride (CC) as a linking agent onto a carbon felt (CF), which is a microelectrode ensemble of micro carbon fiber (>7 μm, diameter) with a random three-dimensional structure. The resulting HRP-modified CF (HRP-ccCF) exhibited well-defined redox waves based on the HRP heme Fe^III/Fe^II redox couple at −0.23 V vs. Ag/AgCl (at pH 7.0), while the HRP-adsorbed CF (HRP-CF) showed no apparent redox couple in the same potential range, indicating that the chemical modification of HRP via CC facilitated the direct electron transfer (DET) between HRP and CF. The apparent heterogeneous electron transfer rate constant k_s was estimated to be 35 s⁻¹. Cyclic voltammetry and electrochemical impedance spectroscopy revealed that the interfacial properties (i.e., structure, morphology of enzyme-layer) of covalently modified HRP (HRP-ccCF) and physically adsorbed HRP (HRP-CF) are different, resulting in the difference in the electron transfer properties. The HRP-ccCF was successfully used as a working electrode unit in bioelectrocatalytic flow-through detector for highly sensitive amperometric determination of H₂O₂. Under the optimized conditions (i.e., applied potential, 0 V vs. Ag/AgCl; carrier flow rate, 3.25 ml/min; and carrier pH 7.0), the cathodic peak current of H₂O₂ linearly increased up to 3 μM (sensitivity, 1.94 μA/μM; the detection limit, 0.08 μM [S/N = 3]) with sample through-put of ca. 90 samples/h.     

Electrochemical studies of bovine serum albumin immobilization onto the poly-o-phenylenediamine and carbon-coated nickel composite film and its interaction with papaverine

A biosensor based on bovine serum albumin (BSA) and poly-o-phenylenediamine (PoPD)/carbon-coated nickel (C-Ni) nanobiocomposite film modified electrode has been developed to study the interaction of BSA with papaverine (PAP). The well-dispersed C-Ni nanoparticles were dripped onto the glassy carbon electrode (GCE) surface firstly, and PoPD films were subsequently electropolymerized by cyclic voltammetry (CV) to prepare PoPD/C-Ni/GCE. Finally, the BSA was easily immobilized on the PoPD films via electrostatic adsorption. The morphology and the electrochemical properties of the fabricated composite electrodes were examined by scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS), respectively. The interaction of PAP with BSA was monitored by differential pulse voltammetry (DPV), using PoPD as the electrochemical indicator. The binding constant (K), obtained by DPV, was 1.7 × 10⁴ L/mol, which was consistent with the fluorescence analysis. This constructed biosensor also exhibited a fine linear correlation with PAP concentration range of 2.5 × 10⁻⁹-4.5 × 10⁻⁵ mol/L and a detection limit of 8.3 × 10⁻¹⁰ mol/L was achieved by DPV.     

Modification of the oxygen diffusivity in limiting current oxygen sensors

Effect of sacrificial carbon on microstructure of protective layer and sensing properties of limiting current oxygen sensors were studied. Graphite and carbon nanofiber with different concentrations were examined as sacrificial layer. Therefore, several YSZ-based electrochemical gas sensors were fabricated with dissimilarity in the diffusivity of the layer covering their measuring electrodes.Gas sensors were tested as potentiometric and amperometric devices under O₂-N₂ mixtures, and synthetic gases similar to the exhaust gas mixtures from combustion engines. Sensors with low diffusivity (low concentration of sacrificial material) exhibit more abrupt and O₂-sensitive potentiometric responses. Indeed, less O₂-linear amperometric responses and higher response times are their characteristics. Sensors with high diffusion in their layers (high concentration of sacrificial material) show a less abrupt step-drop potentiometric response but a more linear O₂ dependence for the amperometric response and, in general, lower response times.Results suggest that the configuration of the diffusive layer shall be controlled in terms of the expected performance of the sensor, as an amperometric or potentiometric device. The controlling parameters are discussed and given in this study.     

Novel e-nose for the discrimination of volatile organic biomarkers with an array of carbon nanotubes (CNT) conductive polymer nanocomposites (CPC) sensors

We report the original design of a new type of electronic nose (e-nose) consisting of only five sensors made of hierarchically structured conductive polymer nanocomposites (CPC). Each sensor benefits from both the exceptional electrical properties of carbon nanotubes (CNT) used to build the conductive architecture and the spray layer by layer (sLbL) assembly technique, which provides the transducers with a highly specific 3D surface structure. Excellent sensitivity and selectivity were obtained by optimizing the amount of CNT with five different polymer matrices: poly(caprolactone) (PCL), poly(lactic acid) (PLA), poly(carbonate) (PC), poly(methyl methacrylate) (PMMA) and a biobased polyester (BPR). The ability of the resulting e-nose to detect nine organic solvent vapours (isopropanol, tetrahydrofuran, dichloromethane, n-heptane, cyclohexane, methanol, ethanol, water and toluene), as well as biomarkers for lung cancer detection in breath analysis, has been demonstrated. Principal component analysis (PCA) proved to be an excellent pattern recognition tool to separate vapour clusters.     

Bryophyte cover estimation in a boreal black spruce forest using airborne lidar and multispectral sensors

Bryophytes are the dominant ground cover vegetation layer in many boreal forests and in some of these forests the net primary production of bryophytes exceeds the overstory. Therefore it is necessary to quantify their spatial coverage and species composition in boreal forests to improve boreal forest carbon budget estimates. We present results from a small exploratory test using airborne lidar and multispectral remote sensing data to estimate the percentage of ground cover for mosses in a boreal black spruce forest in Manitoba, Canada. Multiple linear regression was used to fit models that combined spectral reflectance data from CASI and indices computed from the SLICER canopy height profile. Three models explained 63-79% of the measured variation of feathermoss cover while three models explained 69-92% of the measured variation of sphagnum cover. Root mean square errors ranged from 3-15% when predicting feathermoss, sphagnum, and total moss ground cover. The results from this case study warrant further testing for a wider range of boreal forest types and geographic regions.     

An assessment of photosynthetic light use efficiency from space: Modeling the atmospheric and directional impacts on PRI reflectance

Estimation of photosynthetic light use efficiency (ε) from satellite observations is an important component of climate change research. The photochemical reflectance index, a narrow waveband index based on the reflectance at 531 and 570 nm, allows sampling of the photosynthetic activity of leaves; upscaling of these measurements to landscape and global scales, however, remains challenging. Only a few studies have used spaceborne observations of PRI so far, and research has largely focused on the MODIS sensor. Its daily global coverage and the capacity to detect a narrow reflectance band at 531 nm make it the best available choice for sensing ε from space. Previous results however, have identified a number of key issues with MODIS-based observations of PRI. First, the differences between the footprint of eddy covariance (EC) measurements and the MODIS footprint, which is determined by the sensor's observation geometry make a direct comparison between both data sources challenging and second, the PRI reflectance bands are affected by atmospheric scattering effects confounding the existing physiological signal. In this study we introduce a new approach for upscaling EC based ε measurements to MODIS. First, EC-measured ε values were “translated” into a tower-level optical PRI signal using AMSPEC, an automated multi-angular, tower-based spectroradiometer instrument. AMSPEC enabled us to adjust tower-measured PRI values to the individual viewing geometry of each MODIS overpass. Second, MODIS data were atmospherically corrected using a Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm, which uses a time series approach and an image-based rather than pixel-based processing for simultaneous retrievals of atmospheric aerosol and surface bidirectional reflectance (BRDF). Using this approach, we found a strong relationship between tower-based and spaceborne reflectance measurements (r² = 0.74, p < 0.01) throughout the vegetation period of 2006. Swath (non-gridded) observations yielded stronger correlations than gridded data (r² = 0.58, p < 0.01) both of which included forward and backscatter observations. Spaceborne PRI values were strongly related to canopy shadow fractions and varied with different levels of ε. We conclude that MAIAC-corrected MODIS observations were able to track the site-level physiological changes from space throughout the observation period.     

Identification and quantification of different vapours using a single polymer chemoresistor and the novel dual transient temperature modulation technique

This paper presents a novel signal processing technique for a square wave temperature modulated carbon black/polymer composite sensor. The technique consists of only two mathematical operations: summing the off- and on-transients of the conductance signals, and subtracting the steady-state conductance signal. The technique has been verified through its application to a carbon black/polyvinylpyrrolidone composite chemoresistor. Identification of water, methanol and ethanol vapours was successfully demonstrated using the peak time of the resultant curves. Furthermore, quantification of those vapours was found to be possible using the height of the peak heights, which was linearly proportional to concentration. The technique does not require zero-gas calibration and thus is superior to previously reported techniques.     

居住小区价格与公共服务网络可达性的相关性研究

提出了居住小区公共服务网络的概念,考虑居住小区与各类公共服务节点之间的最短路径、最快路径、次短路径和次快路径等四个指标,以皮尔逊积矩相关系数评估各类公共服务节点可达性与居住小区住房价格的相关性,建立了计算模型,从而识别出对居住小区住房价格影响较大的因素,以武汉市居住小区公共服务网络为例进行了实证分析.结果表明,本方法能够效识别对居住小区价格有重要影响的公共服务要素,为居住小区规划和公共服务优化配置提供决策支持.     

Characterizing 3D vegetation structure from space: Mission requirements

Human and natural forces are rapidly modifying the global distribution and structure of terrestrial ecosystems on which all of life depends, altering the global carbon cycle, affecting our climate now and for the foreseeable future, causing steep reductions in species diversity, and endangering Earth's sustainability.To understand changes and trends in terrestrial ecosystems and their functioning as carbon sources and sinks, and to characterize the impact of their changes on climate, habitat and biodiversity, new space assets are urgently needed to produce high spatial resolution global maps of the three-dimensional (3D) structure of vegetation, its biomass above ground, the carbon stored within and the implications for atmospheric green house gas concentrations and climate. These needs were articulated in a 2007 National Research Council (NRC) report (NRC, 2007) recommending a new satellite mission, DESDynI, carrying an L-band Polarized Synthetic Aperture Radar (Pol-SAR) and a multi-beam lidar (Light RAnging And Detection) operating at 1064 nm. The objectives of this paper are to articulate the importance of these new, multi-year, 3D vegetation structure and biomass measurements, to briefly review the feasibility of radar and lidar remote sensing technology to meet these requirements, to define the data products and measurement requirements, and to consider implications of mission durations. The paper addresses these objectives by synthesizing research results and other input from a broad community of terrestrial ecology, carbon cycle, and remote sensing scientists and working groups. We conclude that:

(1)

Current global biomass and 3-D vegetation structure information is unsuitable for both science and management and policy. The only existing global datasets of biomass are approximations based on combining land cover type and representative carbon values, instead of measurements of actual biomass. Current measurement attempts based on radar and multispectral data have low explanatory power outside low biomass areas. There is no current capability for repeatable disturbance and regrowth estimates.

(2)

The science and policy needs for information on vegetation 3D structure can be successfully addressed by a mission capable of producing (i) a first global inventory of forest biomass with a spatial resolution 1 km or finer and unprecedented accuracy (ii) annual global disturbance maps at a spatial resolution of 1 ha with subsequent biomass accumulation rates at resolutions of 1 km or finer, and (iii) transects of vertical and horizontal forest structure with 30 m along-transect measurements globally at 25 m spatial resolution, essential for habitat characterization.

We also show from the literature that lidar profile samples together with wall-to-wall L-band quad-pol-SAR imagery and ecosystem dynamics models can work together to satisfy these vegetation 3D structure and biomass measurement requirements. Finally we argue that the technology readiness levels of combined pol-SAR and lidar instruments are adequate for space flight. Remaining to be worked out, are the particulars of a lidar/pol-SAR mission design that is feasible and at a minimum satisfies the information and measurement requirement articulated herein.     

Buyer-supplier games: Optimization over the core

In a buyer-supplier game, a special type of assignment game, a distinguished player, called the buyer, wishes to purchase some combinatorial structure. A set of players, called suppliers, offer various components of the structure for sale. Any combinatorial minimization problem can be transformed into a buyer-supplier game. While most previous work has been concerned with characterizing the core of buyer-supplier games, in this paper we study optimization over the set of core vectors. We give a polynomial time algorithm for optimizing over the core of any buyer-supplier game for which the underlying minimization problem is solvable in polynomial time. In addition, we show that it is hard to determine whether a given vector belongs to the core if the base minimization problem is not solvable in polynomial time. Finally, we introduce and study the concept of focus point price, which answers the question: If we are constrained to play in equilibrium, how much can we lose by playing the wrong equilibrium?