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1.
This paper reports the results of the chemical composition modeling for an atmospheric pressure DC air discharge with water cathode. The modeling was based on the combined solution of Boltzmann equation for electrons, equations of vibrational kinetics for ground states of N2, O2, H2O and NO molecules, equations of chemical kinetics and plasma conductivity equation. Calculations were carried out using experimental values of E/N and gas temperatures for the discharge currents range of 20–50 mA. The effect of H2O concentration on the plasma composition was studied. The main particles of plasma were shown to be O2(a1Δ, b1Σ), O(3P), NO, NO2, HNO3, H2O2 and OH. Effective vibrational temperatures of molecules were higher than gas temperature and they did not depend on the discharge current. Distribution functions on vibrational levels for N2, O2, H2O and NO ground states were non-equilibrium ones.  相似文献   

2.
In the present work, hemoglobin (Hb) was entrapped into the nanosheets of a pre-exfoliated layered material HNb3O8. UV–vis spectra analysis displayed that no significant denaturation occurred to the entrapped protein. Electrochemical results showed that the entrapment of Hb into layered HNb3O8 enhanced the direct electron transfer ability between protein molecules and electrode. A pair of well-defined redox peaks was observed at ?0.39 and ?0.34 V on the glassy carbon electrode modified with the Hb/HNb3O8 composite. The electrode reactions showed a surface-controlled process with a single electron transfer at the scan rate of 50–400 mV/s, and the electron transfer rate was very fast. The entrapped Hb retained its biological activity well and the sensor constructed by the Hb/HNb3O8-composite-modified electrode displayed excellent response to the reduction of hydrogen peroxide (H2O2) with wide linear range, low detection limit, and good stability.  相似文献   

3.
MnxOy/SBA-15 catalysts were prepared via the impregnation method and utilized for toluene removal in dielectric barrier discharge plasma at atmospheric pressure and room temperature. The catalysts were characterized by X-ray diffraction, N2 adsorption–desorption, Raman spectroscopy, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction, and O2 temperature-programmed desorption methods. The characterization results indicated that manganese loading did not influence the 2D-hexagonal mesoporous structure of SBA-15. The catalyst had various oxidation states of manganese (Mn2+, Mn3+, and Mn4+), with Mn3+ being the dominant oxidation state. Toluene removal was investigated in the environment of pure N2 and 80 % N2 + 20 % O2 plasma, showing that the toluene removal efficiency and CO2 selectivity were noticeably increased by MnxOy/SBA-15, especially in the presence of 5 % Mn/SBA-15. This activity was closely related to the high dispersion of 5 % Mn on SBA-15 and the lowest reduction temperature exhibited by this catalyst. Mn loading increased the yield of CO2 in the N2 plasma and promoted the deep oxidation of toluene. During toluene oxidation, oxygen exchange might follow a pathway, wherein bulk oxygen was released from the MnxOy/SBA-15 surface; gas-phase O2 subsequently filled up the vacancies created on the oxide. Each of the manganese oxidation states played an important role; Mn2O3 was considered as a bridge for oxygen exchange between the gas phase and the catalyst, and Mn3O4 mediated transfer of oxygen between the catalyst and toluene.  相似文献   

4.
Nitrite has recently been recognized as a storage form of NO in blood and as playing a key role in hypoxic vasodilation. The nitrite ion is readily reduced to NO by hemoglobin in red blood cells, which, as it happens, also presents a conundrum. Given NO’s enormous affinity for ferrous heme, a key question concerns how it escapes capture by hemoglobin as it diffuses out of the red cells and to the endothelium, where vasodilation takes place. Dinitrogen trioxide (N2O3) has been proposed as a vehicle that transports NO to the endothelium, where it dissociates to NO and NO2. Although N2O3 formation might be readily explained by the reaction Hb‐Fe3++NO2?+NO?Hb‐Fe2++N2O3, the exact manner in which methemoglobin (Hb‐Fe3+), nitrite and NO interact with one another is unclear. Both an “Hb‐Fe3+‐NO2?+NO” pathway and an “Hb‐Fe3+‐NO+NO2?” pathway have been proposed. Neither pathway has been established experimentally. Nor has there been any attempt until now to theoretically model N2O3 formation, the so‐called nitrite anhydrase reaction. Both pathways have been examined here in a detailed density functional theory (DFT, B3LYP/TZP) study and both have been found to be feasible based on energetics criteria. Modeling the “Hb‐Fe3+‐NO2?+NO” pathway proved complex. Not only are multiple linkage‐isomeric (N‐ and O‐coordinated) structures conceivable for methemoglobin–nitrite, multiple isomeric forms are also possible for N2O3 (the lowest‐energy state has an N? N‐bonded nitronitrosyl structure, O2N? NO). We considered multiple spin states of methemoglobin–nitrite as well as ferromagnetic and antiferromagnetic coupling of the Fe3+ and NO spins. Together, the isomerism and spin variables result in a diabolically complex combinatorial space of reaction pathways. Fortunately, transition states could be successfully calculated for the vast majority of these reaction channels, both MS=0 and MS=1. For a six‐coordinate Fe3+O‐nitrito starting geometry, which is plausible for methemoglobin–nitrite, we found that N2O3 formation entails barriers of about 17–20 kcal mol?1, which is reasonable for a physiologically relevant reaction. For the “Hb‐Fe3+‐NO+NO2?” pathway, which was also found to be energetically reasonable, our calculations indicate a two‐step mechanism. The first step involves transfer of an electron from NO2? to the Fe3+–heme–NO center ({FeNO}6) , resulting in formation of nitrogen dioxide and an Fe2+–heme–NO center ({FeNO}7). Subsequent formation of N2O3 entails a barrier of only 8.1 kcal mol?1. From an energetics point of view, the nitrite anhydrase reaction thus is a reasonable proposition. Although it is tempting to interpret our results as favoring the “{FeNO}6+NO2?” pathway over the “Fe3+‐nitrite+NO” pathway, both pathways should be considered energetically reasonable for a biological reaction and it seems inadvisable to favor a unique reaction channel based solely on quantum chemical modeling.  相似文献   

5.
This paper reports the results of the experimental study of parameters for a DC oxygen discharge with water cathode in the pressure range of 0.1–1 bar and the discharge current of 40 mA. The radius of positive column, the cathode voltage drop, the cathode current density and the electric field strength were measured. Rotational temperatures of N2 (C3Πu, V = 0) and OH (A2Σ, V = 0) and absolute line intensities of atomic oxygen with wave length of 845 and 777 nm were determined as well. Plasma composition modeling was carried out by the combined solution of the Boltzmann equation for electrons, the equations of vibrational kinetics for ground states of N2, O2, H2O molecules, and the equations of chemical kinetics, and the plasma conductivity equation. Calculations were carried out taking into consideration the discharge radial heterogeneity and using experimental values of E/N and gas temperatures. The main particles being formed in plasma were shown to be ·OH, H2O2, O(3P), O2(a1Δg), O2(b1Σ g + ), H(1S). On the basis of this calculation and experimental values of line intensities, the populating mechanism of (3p 3P) level of atomic oxygen was discussed. The comparison of some properties of discharges in O2, N2 and air was done.  相似文献   

6.
By utilizing a fully floating double electrical probe system, the conductivity of a linear atmospheric pressure plasma jet, utilizing nitrogen as process gas, was measured. The floating probe makes it possible to measure currents in the nanoamp range, in an environment where capacitive coupling of the probes to the powered electrodes is on the order of several kilovolts. Using a chemical kinetic model, the production of reactive nitrogen oxide and hydrogen-containing species through admixture of ambient humid air is determined and compared to the measured gas conductivity. The chemical kinetic model predicts an enhanced diffusion coefficient for admixture of O2 and H2O from ambient air of 2.7 cm2 s?1, compared to a literature value of 0.21 cm2 s?1, which is attributed to rapid mixing between the plasma jets and the surrounding air. The dominant charge carriers contributing to the conductivity, aside from electrons, are NO+, NO2 ? and NO3 ?. Upon admixture of O2 and H2O, the dominant neutral products formed in the N2 plasma jet are O, NO and N2O, while O2(1Δg) singlet oxygen is the only dominant excited species.  相似文献   

7.
In this study, hydrogen production from water splitting in N2 using an atmospheric pressure rotating gliding arc plasma was investigated. The effect of input H2O concentration and total flow rate on the performance of the plasma water splitting process (e.g., H2 and O2 yield, H2 production rate, and energy yield of H2) was investigated. N2 showed a pronouncedly facilitating effect on the H2O splitting and H2 production process due to the reactions of the excited N2 species [e.g., electronically excited metastable N2(A)] with the H2O molecules. The maximum H2 production rate reached up to 41.3 μmols?1, which is much higher than that of other typical non-thermal plasmas (e.g., ~0.2 μmols?1 for a dielectric barrier discharge). Optical emission diagnostics has shown that in addition to the NO, N2, and N2 + that were observed in the pure N2 spectra, strong OH and NH emission lines also appeared in the H2O/N2 spectra. OH radical is considered as a key intermediate species that could contribute to the formation of H2, O2, and H2O2. The increase of the H2O concentration could lead to a continuous enhancement of the OH intensity. The rotational temperature of N2 + dropped drastically from 2875 ± 125 to 1725 ± 25 K with the addition of 1 % (mol/mol) H2O into the N2 plasma.  相似文献   

8.
The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities than a specified cutoff sensitivity of 1%. Theactive reactions exert a significant influence on main plasma parameters,such as velocity, temperature, and species concentrations. The sensitivityanalysis for the specified systems shows that two NO reactions, known asZel'dovich reactions (N2+ONO+N andNO+OO2+N),(1) are both active in a nitrogenplasma jet. On the other hand, the latter is not active and may be omittedin a nitrogen–hydrogen plasma jet. A nitrogen–hydrogen plasmajet requires contribution of two active charge exchange reactions:N2+N+N+ 2+N andN+H+N+ +H, while only the former is needed in a nitrogen plasmajet. The dissociation reactions are all active in both plasma jets, exceptthe dissociation of OH.  相似文献   

9.
《Electroanalysis》2006,18(22):2210-2217
A novel method to immobilize hemoglobin (Hb) in a polymer grown from dopamine (DA) oxidation was proposed. The growth of the polymeric films during DA oxidation at the Prussian blue (PB) modified Au electrode in weak alkaline phosphate buffer (pH 9.18) and the immobilization of Hb into the polymeric films during their growth were traced by the electrochemical quartz crystal impedance analysis (EQCIA) method. A hydrogen peroxide (H2O2) biosensor was thus constructed, and effects of experimental parameters on the sensor performance, including the applied potential, solution pH and electroactive interferents, were examined. At an optimal potential of ?0.25 V vs. SCE, the current response of the biosensor in the selected phosphate buffer (pH 5.29) was linear with the concentration of H2O2 from 0.01 to 4.5 mM, with a lower limit of detection of 0.5 μM (S/N=3), short response time (within 10 s) and good anti‐interferent ability. The Michaelis constant (Kmapp) was estimated to be 3.80 mM. Compared with the separate film of PB or Hb, the composite film of Hb and PB exhibited a higher catalytic activity toward the reduction of H2O2, as a result of the additive effect of the chemical and biological catalyses.  相似文献   

10.
A self-supported nanoporous cobalt phosphide (CoP) nanowire arrays on the carbon cloth (CC) as an active matrix was fabricated and utilized as an interface for the construction of hemoglobin (Hb)-based biosensors. This matrix was wrapped in a thin aluminum sheet by handmade. Moreover, the electrochemistry and electrocatalytic properties of Hb were investigated on such a matrix. The results revealed that the self-supported nanoporous CoP nanowire arrays on CC significantly enhanced the electrochemical responses of Hb. In the meantime, the immobilized Hb remained its good bioactivity and high catalytic activity to hydrogen peroxide (H2O2). This matrix is thus a suitable platform to develop highly sensitive enzyme-based biosensor, which has the linear range of H2O2 concentration from 2 to 2670 μM with a detection limit of 0.7 μM (S/N?=?3). Consequently, it is desirable to explore the possibility of developing a kind of simpler and cheaper matrix electrode.  相似文献   

11.
The emission of greenhouse gases, such as N2O and fluorinated gases, has been increasingly regulated in the semiconductor industry. Pressure effects on the abatement of N2O and CF4 were investigated in a low-pressure plasma reactor by using Fourier transform infrared (FTIR) spectroscopy. The destruction and removal efficiency (DRE) of N2O and CF4 was significantly lowered below 0.2 Torr. When the pressure was increased, the DRE of CF4 with H2O as the reactant gas increased continuously, but that with O2 or without any reactant gas first increased and then decreased. A larger electrode length yielded a higher DRE of N2O and CF4, especially at lower pressures. To understand this phenomenon, the electrical waveforms for the discharge in N2O were analyzed in conjunction with its optical emission profiles, and the rotational temperatures for different electrode lengths were compared using the N2 + ion band (λ = 391.4 nm). They provided insights into the mechanism involved in terms of plasma property and gas residence time.  相似文献   

12.
We have studied the trans-membrane electron transfer in human red blood cells (RBCs) immobilized in a chitosan film on a glassy carbon electrode (GCE). Electron transfer results from the presence of hemoglobin (Hb) in the RBCs. The electron transfer rate (k s) of Hb in RBCs is 0.42 s?1, and <1.13 s?1 for Hb directly immobilized in the chitosan film. Only Hb molecules in RBCs that are closest to the plasma membrane and the surface of the electrode can undergo electron transfer to the electrode. The immobilized RBCs displayed sensitive electrocatalytic response to oxygen and hydrogen peroxide. It is believed that this cellular biosensor is of potential significance in studies on the physiological status of RBCs based on observing their electron transfer on the modified electrode.
The transmembrane electron transfer rate of Hb in RBCs is slower than hemoglobin molecules directly immobilized on the chitosan film. Only those hemoglobin in RBCs closest to the plasma membrane and electrode could exchange electrons with the electrode. The immobilized RBCs showed sensitive electrocatalytic response to O2 and H2O2.  相似文献   

13.
A high‐speed darkfield microscope has been developed to monitor the rapid rotation of single gold nanorods (AuNRs) and used to study the spatiotemporal heterogeneity of chemical reactions in free solution. A wide range of viscosities from 237 cP to 0.8 cP could be detected conveniently. We studied H2O2 decomposition reactions that were catalyzed by AuNRs coated with Pt nanodots (AuNR@PtNDs) and observed two different rotational states. The two states and their transitions are related to the production and the amalgamation of O2 nanobubbles on the nanorod surface depending on H2O2 concentration. In addition, the local fluidic environment of pure water was found to be non‐uniform in time and space. This technique could be applied to study other chemical and biochemical reactions in solution.  相似文献   

14.
CARS Diagnostic and Modeling of a Dielectric Barrier Discharge   总被引:1,自引:0,他引:1  
Baeva  M.  Dogan  A.  Ehlbeck  J.  Pott  A.  Uhlenbusch  J. 《Plasma Chemistry and Plasma Processing》1999,19(4):445-466
Dielectric barrier discharges (DBD) with planar- and knife-shaped electrodes are operated in N2O2NO mixtures under a pressure of 20 and 98 kPa. They are excited by means of consecutive unipolar or bipolar high-voltage pulse packages of 10 kV at a pulse repetition rate of 1 and 2 kHz. The rotational and vibrational excitation of N 2 molecules and the reduction of nitric oxide (NO) in the discharge have been investigated using coherent anti-Stokes Raman scattering (CARS) technique. Rotational (gas) temperatures near the room temperature and vibrational temperatures of about 800 K at atmospheric pressure and 1400 K at a pressure of 20 kPa are observed. Therefore, chemical reactions of NO with vibrationally excited N 2 are probably insignificant. One-dimensional kinetic models are developed that balance 35 chemical reactions between 10 species and deliver equations for the population density of excited vibrational levels of N 2 together with a solution of the Boltzmann equation for the electrons. A good agreement between measured vibrational temperatures of N 2 , the concentration of NO, and calculated data is achieved. Modeling of the plasma discharge verifies that a DBD operated with a N2NO mixture reduces the NO content, the simultaneous presence of O 2 , already 1%, is enough to prevent the NO reduction.  相似文献   

15.
We report on a novel electrochemical biosensor that was fabricated by immobilizing hemoglobin (Hb) onto the surface of a gold electrode modified with a chitosan@Fe3O4 nano-composite. The Fe3O4 nanoparticles were prepared by co-precipitation and have an average size of 25 nm. They were dispersed in chitosan solution to obtain the chitosan@Fe3O4 nano-composite particles with an average diameter of 35 nm as verified by transmission electron microscopy. X-ray diffraction patterns and Fourier transform IR spectroscopy confirmed that the crystallite structure of the Fe3O4 particles in the nano-composite has remained unchanged. At pH 7.0, Hb gives a pair of redox peaks with a potential of about ?0.21 V and ?0.36 V. The Hb on the film maintained its biological activity and displays good electrocatalytic reduction activity towards hydrogen peroxide. The linear range for the determination of H2O2 is from 2.3 μM to 9.6 mM, with a detection limit at 1.1 μM concentration (at S/N?=?3). The apparent Michaelis-Menten constant is 3.7 mM and indicates the high affinity of Hb for H2O2. This biosensor also exhibits good reproducibility and long-term stability. Thus, it is expected to possess potential applications in the development of the third-generation electrochemical biosensors.
Figure
The chitosan@Fe3O4 nano-composite particles was prepaired and characterized. It was immobilized onto the surface of a gold electrode to form hemoglobin modified biosensor. This biosensor displays good electrocatalytic reduction activity towards hydrogen peroxide. It also exhibits good reproducibility and long-term stability. It is expected to detect BOD and COD in water.  相似文献   

16.
Electrospun hemoglobin (Hb) microbelts were used as a novel precursor to produce a new class of carbon nanofibers (Hb‐CNFs) containing Fe species (Fe2O3 and/or Fe‐N4 moiety). The Hb‐CNFs modified glassy carbon electrode (Hb‐CNFs/GCE) exhibits significant oxidation/reduction towards H2O2. The observed H2O2 oxidation/reduction starting at ca. +0.26 V and +0.15 V (vs. Ag/AgCl) are significantly lower than the values observed at other CNFs modified GCE. The Hb‐CNFs/GCE was also applied to the amperometric detection of H2O2 and the results showed fast response, high sensitivity, excellent reproducibility, good selectivity, and wide dynamic range with good limit of detection.  相似文献   

17.
Excitation of electronic states of the N2 molecule by electron impact is recognized as an essential process in nitrogen plasmas that strongly impacts their chemical reactivity and other properties. Many surface and coating technologies are based on radio-frequency plasma discharges in nitrogen. In this paper the electron impact excitation rate coefficients for singlet and triplet electronic states of the N2 molecule have been calculated in non-equilibrium conditions in the presence of a radio-frequency electric field. A Monte Carlo simulation has been performed in order to determine non-equilibrium electron energy distribution functions within one period of the electric field. By using these distribution functions, the excitation rate coefficients have been obtained in the frequency range from 13.56 up to 500 MHz, at reduced electric field values from 200 to 700 Td.  相似文献   

18.
In this paper, we demonstrate the development of plasmonically active PMMA optical fiber probes by the attachment of gold nanoparticles to the probe surface functionalized by means of flowing post-discharges from dielectric barrier discharge (DBD) plasmas for the first time. Polymer optical fiber (POF) probes (U shape to improve absorbance sensitivity) were subjected to reactive gas atmospheres in the post-discharge region of a coaxial DBD plasma reactor run at atmospheric pressure in different gases (Ar, Ar + 10 % O2, O2, N2, N2 + 0.5 % H2). Plasma treatments in Ar or N2 gave rise to water-stable electrophilic functional groups on PMMA surface, whereas the amine groups generated by N2-containing plasmas were not stable. Subsequently, PMMA surfaces were treated with hexamethylene diamine (HMDA) to obtain stable amine groups through the reaction of electrophilic groups. Gold nanoflowers (AuNF, 37 nm, peak 570 nm) binding to the amine functionalized fiber probes was monitored in real-time by recording the optical absorbance changes at 570 nm with the help of a UV–vis spectrometer. Absorbance response from Ar or N2 plasma treated probes are 100 and 60 times, respectively, that of untreated control probes. A 25 fold improvement in absorbance response was obtained for Ar plasma treated POF in comparison with only HMDA treated POF. The shelf life of the hence fabricated plasmonically active probes was found to be at least 3 months. In addition, plasmonic activity of U-bent fiber probes treated in Ar plasma is better than the conventional wet-chemical activation by environmentally hazardous acid pre-treatment approaches.  相似文献   

19.
Plasma–liquid interaction has already been a hotspot in the research field of plasma medicine. Aqueous reactive oxygen species (ROS) generated in this process are widely accepted playing a crucial role in plasma biomedical effects. In this paper, chemistry pathways among various aqueous ROS induced by He + O2 plasmas are investigated by a numerical model. Simulation results show that these aqueous ROS can be classified into two groups according to their production ways: the group of species including O, 1O2 and e directly produced in plasma, and the other group of species including O2 ?, H2O2, O3, etc. produced by liquid reactions. A key reaction chain of e → O2 ? → HO2(→ HO2 ?) → H2O2 is found to be important in the plasma-induced liquid chemistry. Furthermore, impacts of changes in plasma and solution conditions on aqueous ROS concentrations are studied as well. It is found that changes in plasma conditions (O2 ratio in the discharge gas/power density) can globally influence the concentrations of almost every aqueous ROS, while conditions changes of the treated liquid (pH/dissolved oxygen) only partially influence the concentrations of some specific species including O2 ?/HO2, O3 ?/HO3 and H2O2. The revelations of the liquid chemistry pathways and the dependence of ROS dosage on the treatment conditions offer a better understanding on the plasma–liquid interactions, as well as provide optimized dosage control approaches for biomedical applications.  相似文献   

20.
《Analytical letters》2012,45(5):818-830
A facile strategy to construct an amperometric biosensor was described for the determination of hydrogen peroxide (H2O2). This biosensor relied on an electrospinning gold nanoparticle-chitosan-poly(vinyl alcohol) composite nanofibers modified ITO electrode, followed by immobilization of hemoglobin (Hb) on the surface. The introduction of nanofibers and gold nanoparticles in the modification of electrode surface not only enhanced the surface area of the modified electrode for enzyme immobilization but also facilitated the electron transfer rate. Under optimum conditions, the sensor was characterized in terms of its morphology by scanning electron microscopy and its electroactivity by cyclic voltammetry and chronoamperometry. Scanning electron microscopy revealed that the obtained nanofibers were uniform. The chronoamperometric behavior of the modified electrode indicated that the immobilized Hb retained electrochemical activity inside the electrospinning fibrous membranes. The electrode responded linearly to H2O2 in a wider concentration range of 5.6 × 10?7 M to 5.2 × 10?2 M with a low detection limit (S/N = 3) of 1.98 × 10?7 M and a short response time of ~4 s, suggesting a much better performance than that of other sensors. Moreover, the biosensor achieved bulk production and exhibited superior properties for the sensitive determination of H2O2, studied namely, long-term stability, good reproducibility, and high selectivity.  相似文献   

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