Low potential detection of glutamate based on the electrocatalytic oxidation of NADH at thionine/single-walled carbon nanotubes composite modified electrode

A glutamate biosensor based on the electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH), which was generated by the enzymatic reaction, was developed via employing a single-walled carbon nanotubes/thionine (Th-SWNTs) nanocomposite as a mediator and an enzyme immobilization matrix. The biosensor, which was fabricated by immobilizing glutamate dehydrogenase (GIDH) on the surface of Th-SWNTs, exhibited a rapid response (ca. 5 s), a low detection limit (0.1 mu M), a wide and useful linear range (0.5-400 mu M), high sensitivity (137.3 +/- 15.7) mu A mM(-1) cm(-2), higher biological affinity, as well as good stability and repeatability. In addition, the common interfering species, such as ascorbic acid, uric acid, and 4-acetamidophenol, did not cause any interference due to the use of a low operating potential (190 mV vs. NHE). The biosensor can be used to quantify the concentration of glutamate in the physiological level. The Th-SWNTs system represents a simple and effective approach to the integration of dehydrogenase and electrodes, which can provide analytical access to a large group of enzymes for wide range of bioelectrochemical applications including biosensors and biofuel cells.

Fabrication and characterization of microstructured and pH sensitive interpenetrating networks hydrogel films and application in drug delivery field

Novel microstructured and pH sensitive poly(acryliac acid-co-2-hydroxyethyl methacrylate)/poly(vinyl alcohol) (P(AA-co-HEMA)/PVA) interpenetrating network (IPN) hydrogel films were prepared by radical precipitation copolymerization and sequential IPN technology. The first P(AA-co-HEMA) network was synthesized in the present of IPN aqueous solution by radical initiating, then followed by condensation reaction (Glutaraldehyde as crosslinking agent) within the resultant latex, it formed multiple IPN microstructured hydrogel film. The film samples were characterized by IR, SEM and DSC. Swelling and deswelling behaviors and mechanical property showed the novel multiple IPN nanostuctured film had rapid response and good mechanical property. The IPN films were studied as controlled drug delivery material in different pH buffer solution using cationic compound, crystal violet as a model drug.

Preparation and Characterization of Nanostructured and High Transparent Hydrogel Films with pH Sensitivity and Application

Novel nanostructured, high transparent, and pH sensitive poly(2-hydroxyethyl methacrylate-co-methacryliac acid)/poly(vinyl alcohol) (P(HEMA-co-MA)/PVA) interpenetrating polymer network (IPN) hydrogel films were prepared by precipitation copolymerization of aqueous phase and sequential IPN technology. The first P(HEMA-co-MA) network was synthesized in aqueous solution of PVA, then followed by aldol condensation reaction, it formed multiple IPN nanostructured hydrogel film. The film samples were characterized by IR, SEM, DSC, and UV-vis spectrum. The transmittance arrived at 93%. Swelling and deswelling behaviors showed the multiple IPN nanostructured film had rapid response. The mechanical properties of all the IPN films improved than that of PVA film. Using crystal violet as a model drug, the release behaviors of the films were studied.

Electrocatalytic oxidation of catechol at multi-walled carbon nanotubes modified electrode

In 0.05 mol/L phosphate buffer solution (pH 7.0), carbon nanotubes modified electrode exhibits rapid response, strong catalytic activity with high stability toward the electrochemical oxidation of catechol. The electrochemical behavior of catechol on both the multi-walled and single-walled carbon nanotubes modified electrode was investigated. The experimental conditions, such as pH of the solution and scan rate were optimized. The currents (measured by constant potential amperometry) increase linearly with the concentrations of catechol in the range of 2.0 x 10(-5) - 1.2 x 10(-3) mol/L. Moreover, at the multi-walled carbon nanotubes modified electrode the electrochemical responses of catechol and ascorbic acid can be separated clearly.

Phenolphthalein immobilized membrane for an optical pH sensor

A phenolphthalein immobilized cellulose membrane for an optical pH sensor was described. The phenolphthalein was first reacted with the formaldehyde to produce a series of prepolymers with many hydroxymethyl groups. In this paper, the prepolymers was abbreviated to phenolphthalein-formaldehyde (PPF). Then the PPF was covalently immobilized to the diacetylcellulose membrane via hydroxymethyl groups. Finally the membrane was hydrolyzed in the 0.1 M NaOH solution for 24 h to reduce the response time. Advantageous features of the pH-sensitive membrane include (a) a large dynamic range from pH 8.0 to 12.50, or even broader, (b) rapid response time (2-30 s), (c) easy of fabrication, and (d) a promising material for determination of high pH values. The immobilized PPF has a broader dynamic range from 8.0 to 12.50 than the free phenolphthalein from pH 8.0 to 11.0, and this was due to the newly produced methylenes in our investigation.

Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor

A new amperometric biosensor for hydrogen peroxide was developed based on cross-linking horseradish peroxidase (HRP) by glutaraldehyde with multiwall carbon nanotubes/chitosan (MWNTs/chitosan) composite film coated on a glassy carbon electrode. MWNTs were firstly dissolved in a chitosan solution. Then the morphology of MWNTs/chitosan composite film was characterized by field-emission scanning electron microscopy. The results showed that MWNTs were well soluble in chitosan and robust films could be formed on the surface. HRP was cross-linked by glutaraldehyde with MWNTs/chitosan film to prepare a hydrogen peroxide biosensor. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for H2O2 in the absence of a mediator. The linear range of detection towards H2O2 (applied potential: -0.2 V) was from 1.67 x 10(-5) to 7.40 x 10(-4) M with correction coefficient of 0.998. The biosensor had good repeatability and stability for the determination of H2O2. There were no interferences from ascorbic acid, glucose, citrate acid and lactic acid.

CHOLESTEROL SENSOR-BASED ON ELECTRODEPOSITION OF CATALYTIC PALLADIUM PARTICLES

A layer of palladium particles was electrodeposited on a glassy carbon electrode. The dispersed Pd particles resulted in a large decrease in overvoltage for the electrochemical oxidation of H2O2 down to +0.4 V vs. Ag/AgCl, based on which a new kind of cholesterol sensor was fabricated. Cholesterol oxidase was immobilized on the Pd-dispersed electrode by cross-linking with glutaraldehyde and a layer of poly(o-phenylenediamine) (PPD) film was electropolymerized on the enzyme layer. The sensor shows a linear response in the concentration range 0.05-4.50 mmol l-1 with a rapid response of less than 20 s. The polymer film can prevent interference from uric acid and ascorbic acid and also increases the thermal stability of the sensor. The sensor can be used for 200 assays without an obvious decrease in activity.

Suspended particulate matter fluxes through the Straits of Dover, English Channel: observations and modelling

Suspended Particulate Matter (SPM) concentrations at various levels within the water column, together with salinity and temperature, were measured using water samples collected from six stations across the Straits of Dover. The sampling programme covered a 16-month period, undertaken during 23 cruises. On the basis of the spatial variability in the concentrations, the water bodies are divided by several boundaries, controlled by tidal and wind conditions. Within the water column, SPM concentrations were higher near the sea bed than in the surface waters. Throughout the cross-section, maximum concentrations occurred adjacent to the coastlines. Temporal variability in the SPM concentration exists on daily and seasonal scales within the coastal waters (4.2 to 74.5 mg L-1): resuspension processes, in response to semi-diurnal tidal cycles (with a period of around 12.4 h) and spring-neap cycles (with a period of 15 days) make significant contributions. Distinctive seasonal/annual concentration changes have also been observed. In the offshore waters, such variability is much less significant (0.9 to 6.0 mg L-1). In the summer the English Coastal Zone is associated with relatively high SPM concentrations: the Central Zone has a low and stable SPM concentration between these zones, there is a Transitional Zone, where there is a rapid response of SPM concentration to wind forcing. Finally, the French Coastal Zone is characterized by variable (sometimes high) SPM concentrations. Because of the zonation, SPM fluxes within the Dover Strait are controlled by different transport mechanisms. Within the Central Zone, the flux can be represented by the product of mean water discharges and SPM concentrations. However, within the coastal zones fluctuations in SPM concentrations on various time-scales must be considered. In order to calculate the maximum and minimum SPM fluxes, 10 cells were divided in the strait. A simple modelling calculation has been proposed for this complex area. The effect of spring-neap tidal cycles and seasonal changes can contribute significantly to the overall flux, which is of the order of 20 x 10(6) t.yr(-1) (through the Dover Strait, towards the North Sea). Such an estimate is higher than most obtained previously. (C) 2000 Ifremer/CNRS/IRD/Editions scientifiques et medicales Elsevier SAS.

北京石花洞滴水沉积的季节变化及影响因素

Because of the high resolution, stalagmite laminae can play an important role in the paleoclimate reconstructions. However, few investigations for the formation mechanisms of stalagmite lamilae have been done. Based on two-year observation on calcite growth rate at the drip sites, three-year monitoring of hydrodynamics, physics and chemistry of drip waters at different drip sites and the surrounding environments inside and outside the Beijing Shihua Cave, the seasonal variations of calcite growth rate are revealed and the results can be concluded as follows: 1. The drip waters inside the Cave are mostly sourced from the summer rain, and its minimal response-time to the atmospheric precipitation is less than one day. There are three types of response relationships between the precipitation and the drip rate variations: rapid response type, time-lag response type and stable response type. For rapid response type, the drip discharge is recharged through the flow routes along intensive fractures and interconnectivities; for time-lag response type, the drip discharge is recharged by double-porosity system composed of a high conductivity, low storage capability conduit network and a low-conductivity high-storage capability rock matrix under variable boundary conditions; for stable response type, the drip discharge is mainly recharged by seepage flow and base flow. 2. The observation shows that, inside the Cave, the growth rate of calcite is generally lower in rainy seasons and higher in dry seasons. During the rainy seasons, the drip water is characterized by a lower pH value, higher [Ca2+], [Mg2+], [SO42-] and electrical conductivity (EC) values. According to the calculations of saturation index of calcite (SIc), pCO2 of the drip water, as well as the synthetical analysis of other possible factors, the calcite growth rate is found to be principally influenced by the drip water saturation index of calcite (SIc). And the drip rate and pCO2 in the drip water and in the cave air play the secondly important roles in this process. The recharge mode of heavy rainfall events in the rainy seasons should probably be the main driving force that controls the physicochemical properties and calcite sediment of the drip waters. The abrupt decrease of sedimentary rate and the sharp peak of DOC in drip water in the rainy season probably forms the thin opaque (luminescent under ultraviolet radiation) layers observed in the stalagmites, whereas the relatively higher sedimentary rate in the dry seasons may be responsible for the thicker bright layers. The investigation elucidated here preliminarily reveals the formation mechanism of the stalagmite laminae in Beijing Shihua Cave.

冰期间冰期转换过程中陆地碳库的演化规律研究

Terrestrial carbon pool mainly consists of three parts: the active carbon pool of the vegetation，soil carbon pools and the lithosphere carbon pool of less activity. Under natural conditions，vegetation carbon pools，soil carbon exchange with atmospheric carbon pool directly，the lithosphere participate in the global carbon cycle by weathering Our research have coverd the soil organic carbon density，plant biomass (carbon density)，plant net primary productivity of past 40 ka，and the magnetic susceptibility，grain size，weathering of silicate carbon consumption of past 140 ka. This study has achieved a number of conclusions as shown below. 1 Silicate weathering CO2 consumption in the long-term fluctuations with a similar deep-sea δ18O record，demonstate that it not only can be used as one of the instructions of terrestrial carbon pool，even can be used as indicators of global environmental change; silicate weathering CO2 consumption and susceptibility shown a clear relationship between lag or lead at different times，it maybe lies on how the climate change. 2 Soil carbon pools in line with the global climate on long-term，but the relationship between soil carbon density and climate change was not obvious in short-term change，generally lags behind the changes in other climatic proxies. 3 Carbon density of vegetation and other proxy indicators of climate have good consistency. In the study period，perform the cycle of glacial and interglacial completely，but because of the ancient vegetation of accurate information is difficult to obtain，it did not reflect rapid response to climate change. 4 Cooling events is conducive to soil organic carbon accumulation but not conducive to weathering and vegetation growth. High temperature environment is not conducive to the accumulation of soil organic carbon. 5 In the deglacial time from the last glacial maximum to the Holocene，weathering carbon consumption seems earlier than vegetation and soil organic carbon in the fluctuant increase.Does it imply that the effects of silicate weathering is an important factor to the global carbon cycle and global climate change? It is worth further research.

Difterentially expressed genes of Tetrahymena thermophila in response to tributyltin (TBT) identified by suppression subtractive hybridization and real time quantitative PCR

Tributyltin (TBT) is widely used as antifouling paints, agriculture biocides, and plastic stabilizers around the world, resulting in great pollution problem in aquatic environments. However, it has been short of the biomonitor to detect TBT in freshwater. We constructed the suppression subtractive hybridization library of Tetrahymena thermophila exposed to TBT, and screened out 101 Expressed Sequence Tags whose expressions were significantly up- or down-regulated with TBT treatment. From this, a series of genes related to the TBT toxicity were discovered, such as glutathione-S-transferase gene (down-regulated), plasma membrane Ca2+ ATPase isoforms 3 gene (up-regulated) and NgoA (up-regulated). Furthermore, their expressions under different concentrations of TBT treatment (0.5-40 ppb) were detected by real time fluorescent quantitative PCR. The differentially expressed genes of T thermophila in response to TBT were identified, which provide the basic to make Tetrahymena as a sensitive, rapid and convenient TBT biomonitor in freshwater based on rDNA inducible expression system. (c) 2006 Elsevier B.V. All rights reserved.

Growth and antioxidant system of the cyanobacterium Synechococcus elongatus in response to microcystin-RR

Microcystins, one type of the cyanobacterial toxins, show a broad range of hazardous effects on other organisms. Most of the researches on the toxic effects of microcystins have involved in animals and higher plants. Little work, however, has been done on evaluating the mechanisms of microcystin toxicity on algae. In this study, the toxicological effects of microcystin-RR (MC-RR) on the cyanobacterium Synechococcus elongatus were investigated. For this purpose, six physio-biochemical parameters (cell optical density, reactive oxygen species (ROS), malondialdehyde (MDA), glutathione (GSH), glutathione peroxidase (GSH-Px) and glutathione S-transferase (GST)) were tested in algal cells when exposed to 100 mug(-1) microcystin-RR. The results showed that the growth of Synechococcus elongatus ( expressed as optical density) was significantly inhibited compared with the control. At the same time, the treated algae exhibited a pronounced increase in production of ROS and MDA after 6 days exposure to microcystin-RR. Signi. cant changes in GSH levels and GSH-Px, GSH activities were also detected in algal cells, with higher values being observed in the toxin treated algae after 6 days exposure. GST activities in the treated algae exhibited a decline after exposure and rapid augmentation on day 3, thereafter, they kept at a high level when compared to the control group. GSH contents and GSH-Px activities were also significantly raised in the toxin-treated algae cells from day 3, but they showed a sharp decrease on day 4, which was the onward of cell proliferation. These results suggested that oxidative stress manifested by elevated ROS levels and MDA contents might be responsible for the toxicity of microcystin to Synechococcus elongatus and the algal cells could improve their antioxidant ability through the enhancement of enzymatic and non-enzymatic preventive substances.

On the chemical synthesis and drug delivery response of folate receptor-activated, polyethylene glycol-functionalized magnetite nanoparticles

We describe here the chemical synthesis and in vitro drug delivery response of polyethylene glycol (PEG)-functionalized magnetite (Fe3O4) nanoparticles, which were activated with a stable ligand, folic acid, and conjugated with an anticancer drug, doxorubicin. The functionalization and conjugation steps in the chemical synthesis were confirmed using Fourier transform infrared spectroscopy. The drug-release behavior of PEG-functionalized and folic acid-doxorubicin-conjugated magnetic nanoparticles was characterized by two stages involving an initial rapid release, followed by a controlled release. (C) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The involvement of HSP22 from bay scallop Argopecten irradians in response to heavy metal stress

Heat shock protein 22 (HSP22) is an important member of small heat shock protein (sHSP) subfamily which plays a key role in the process of protecting cells, facilitating the folding of nascent peptides, and responding to stress. In the present study, the cDNA of HSP22 was cloned from Argopecten irradians (designated as AiHSP22) by rapid amplification cDNA end (RACE) based on the expressed sequence tags (ESTs). The full-length cDNA of AiHSP22 was of 1,112 bp, with an open reading frame of 588 bp encoding a polypeptide of 195 amino acids. The deduced amino acid sequence of AiHSP22 showed high similarity to previously identified HSP22s. The expression patterns of AiHSP22 mRNA in different tissues and in haemocytes of scallops exposed to Cd2+, Pb2+ or Cu2+ were investigated by real-time quantitative RT-PCR. The mRNA of AiHSP22 was constitutively expressed in all examined tissues, including haemocyte, muscle, kidney, gonad, gill and heart. The expression level in heart and muscle was higher than that in other tissues. The mRNA level of AiHSP22 in haemocytes was up-regulated after a 10 days exposure of scallops to Cu2+, Pb2+ and Cd2+. However, the expression of AiHSP22 did not increase linearly along with the rise of heavy metal concentration. Different concentrations of the same metal resulted in different effects on AiHSP22 expression. The sensitive response of AiHSP22 to Cu2+, Pb2+ and Cd2+ stress indicated that it could be developed as an indicator of exposure to heavy metals for the pollution monitoring programs in aquatic environment.

Experimental warming causes large and rapid species loss, dampened by simulated grazing, on the Tibetan Plateau

We investigated the independent and combined effects of experimental warming and grazing on plant species diversity on the north-eastern Tibetan Plateau, a region highly vulnerable to ongoing climate and land use changes. Experimental warming caused a 26-36% decrease in species richness, a response that was generally dampened by experimental grazing. Higher species losses occurred at the drier sites where N was less available. Moreover, we observed an indirect effect of climate change on species richness as mediated by plant-plant interactions. Heat stress and warming-induced litter accumulation are potential explanations for the species' responses to experimental warming. This is the first reported experimental evidence that climate warming could cause dramatic declines in plant species diversity in high elevation ecosystems over short time frames and supports model predictions of species losses with anthropogenic climate change.