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1.
Bare (unmodified) and crown ether (CE)-modified Fe3O4 magnetic nanoparticles (MNPs) were investigated for the rapid extraction of 226Ra from water samples. It involved synthesizing the MNPs, introducing them into the sample solutions, ultrasonicating and agitating the suspension, magnetically separating the nanoparticles from solution, and measuring the 226Ra content in the supernatant. Experimental parameters such as salt choice, salt concentration and pH were optimized to achieve maximum extraction of 226Ra onto the MNPs. 226Ra content was determined using a Hidex 300SL liquid scintillation counter with α/β separation capability, or a gamma spectrometric detection system. The bare Fe3O4 nanoparticles showed significant pH dependence for the extraction of 226Ra from an aqueous solution over a pH range of 2–10. They gave an extraction of 95 ± 1 and 98 ± 1 % at pH 9 in 0.1 M NaCl and 0.1 M NaClO4, respectively, whereas an extraction of 8–24 % was obtained, over the pH ranges from 2 to 5. The CE-modified MNPs yielded extraction efficiencies as high as 99 ± 1 % in the presence of 0.01 M picric acid at pH 4. This study demonstrates that the surface functionalization of Fe3O4 MNPs with suitable ligand modification can offer a selective mode of extraction for 226Ra in the presence of its daughter progenies.  相似文献   

2.
Despite the rapid development of nanomaterials and nanotechnology, it is still desirable to develop novel nanoparticle-based techniques which are cost-effective, timesaving, and environment-friendly, and with ease of operation and procedural simplicity, for assay of target analytes. In the work discussed in this paper, the dye fluorescein isothiocyanate (FITC) was conjugated to 1,6-hexanediamine (HDA)-capped iron oxide magnetic nanoparticles (FITC–HDA Fe3O4 MNPs), and the product was characterized. HDA ligands on the surface of Fe3O4 MNPs can bind 2,4,6-trinitrotoluene (TNT) to form TNT anions by acid–base pairing interaction. Formation of TNT anions, and captured TNT substantially affect the emission of FITC on the surface of the Fe3O4 MNPs, resulting in quenching of the fluorescence at 519 nm. A novel FITC–HDA Fe3O4 MNPs-based probe featuring chemosensing and magnetic separation has therefore been constructed. i.e. FITC–HDA Fe3O4 MNPs had a highly selective fluorescence response and enabled magnetic separation of TNT from other nitroaromatic compounds by quenching of the emission of FITC and capture of TNT in aqueous solution. Very good linearity was observed for TNT concentrations in the range 0.05–1.5 μmol?L?1, with a detection limit of 37.2 nmol?L?1 and RSD of 4.7 % (n?=?7). Approximately 12 % of the total amount of TNT was captured. The proposed methods are well-suited to trace detection and capture of TNT in aqueous solution.
Figure
Iron oxide magnetic nanoparticles-based selective fluorescent response and magnetic separation probe for 2,4,6-trinitrotoluene  相似文献   

3.
In the present study, application of Fe3O4 magnetic nanoparticles (MNPs) coated with diethyldithiocarbamate as a solid-phase sorbent for extraction of trace amounts of cadmium (Cd2+) and nickel (Ni2+) ions by the aid of ultrasound was investigated. The analytes were determined by inductively coupled plasma-optical emission spectroscopy. Fe3O4 MNPs were prepared by solvothermal method and characterized with dynamic light scattering, scanning electron microscope and X-ray diffraction. Response surface methodology was used for optimization of the extraction process and modeling the data. The optimal conditions obtained were as follows: chelating agent, 1.2 g L?1; pH, 6.13; sonication time, 13 min and Fe3O4 MNPs, 10.3 mg. The calibration curves were linear over the concentration range of 1–1,000 μg L?1 for Cd2+ and 2.5–1,000 for Ni2+ with the determination coefficients (R 2) of 0.9997 and 0.9995, respectively. The limits of detection were 0.27 μg L?1 for Cd2+ and 0.76 μg L?1 for Ni2+. The relative standard deviations (n = 7, C = 200 μg L?1) for determination of Cd2+ and Ni2+ were 2.0 and 2.7 %, respectively. The relative recoveries of the analytes from tap, river and lagoon waters and rice samples at the spiking level of 10 μg L?1 were obtained in the range of 95–105 %.  相似文献   

4.
Fluorine? tin oxide (FTO) nanostructure was developed on the surface of a glass plate using spray payroliziz method. A new electrochemical biosensor was fabricated based on a layer by layer process. In this process chitosan? Fe3O4 (CH? Fe3O4) nanocomposite film was prepared at the surface of FTO electrode by dip? coating method. In the next step, the glucose oxidase (GOx) was immobilized on the CH? Fe3O4/FTO nanocomposite electrode. The GOx/CH? Fe3O4/FTO bioelectrode has a linear range of 10–270 µM and a detection limit of 5 µM. The highest sensitivity was obtained at 1.2 µA mM?1 cm?2.  相似文献   

5.
The effect of the structure of a mixture of industrially produced iron and iron oxide on the decomposition of trichloroethylene (TCE) was investigated by gas chromatography, scanning electron microscopy, Fourier transform infrared spectroscopy, energy dispersive X-ray analysis, X-ray diffractometry, and 57Fe-Mössbauer spectroscopy. The concentration of 10 mg L?1 TCE aqueous solution decreased to 0.41, 0.52, 0.26, and 0.09 mg L?1 when stirred for 7 days with iron–iron oxide mixtures having mass ratios of 2:8, 3:7, 4:6, and 5:5, respectively. The Mössbauer spectra of the mixtures after leaching were composed of two sextets with respective isomer shifts (δ) and internal magnetic fields (H) of 0.29±0.01 mm s?1 and 48.8±0.1 T, and 0.64±0.01 mm s?1 and 45.5±0.1 T, attributed to the Fe3+ species in tetrahedral (T d) and the Fe2+ and Fe3+ mixed species (Fe2.5+) in octahedral (O h) sites, respectively. Mössbauer spectra of a 3:7 mass ratio iron–iron oxide mixture showed a gradual decrease in the absorption area (A) of zero valent iron (Fe0) from 40.6. to 12.6, 13.2, 3.8 2.8, and 1.0±0.5 % and an increase in A of Fe3O4 from 31.8 to 59.4, 71.4, 93.2, 95.6, and 98.0±0.5 % after leaching with 10 mg L?1 TCE aqueous solution for 1, 2, 3, 7, and 10 days, respectively. Consistent values of the first-order rate constant were calculated as 0.32 day?1 for Fe0 oxidation, 0.34 day?1 for Fe3O4 production, and 0.30 day?1 for TCE decomposition, which indicates that the oxidation of Fe0 was the rate-controlling factor for Fe3O4 production and TCE decomposition. It is concluded from the experimental results that an iron–iron oxide mixture is very effective for the decomposition of TCE.  相似文献   

6.
Human saliva quantitative monitoring of clarithromycin (CLA) by chemiluminescence (CL) with flow injection analysis was proposed for the first time, which was based on the quenching effect of CLA on luminol–bovine serum albumin (BSA) CL system with a linear range from 7.5?×?10?4 to 2.0 ng/ml. This proposed approach, offering a maximum sample throughput of 100 h?1, was successfully applied to the quantitative monitoring of CLA levels in human saliva during 24 h after a single oral dose of 250 mg intake, with recoveries of 95.2~109.0 % and relative standard deviations lower than 6.5 % (N?=?7). Results showed that CLA reached maximum concentration of 2.28?±?0.02 μg/ml at approximately 3 h, and the total elimination ratio was 99.6 % in 24 h. The pharmacokinetic parameters including absorption rate constant (0.058?±?0.006 h?1), elimination rate constant (0.149?±?0.009 h?1) and elimination half-life time (4.66?±?0.08 h) were obtained. A comparison of human saliva and urine monitoring was also given. The mechanism study of BSA–CLA interaction revealed the binding of CLA to BSA is an entropy driven and spontaneous process through hydrophobic interaction, with binding constant K BSA–CLA of 4.78?×?106 l/mol and the number of binding sites n of 0.82 by flow injection–chemiluminescence model. Molecular docking analysis further showed CLA might be in subdomain IIA of BSA, with K BSA–CLA of 6.82?×?105 l/mol and ΔG of ?33.28 kJ/mol.  相似文献   

7.
The catalytic activity of heme peptides is an area of intense investigation. They are utilized for exploring the fine details of structural and functional properties of an active site, and to create minimized and industrial catalysts. The peroxidase activity and kinetics of suicide-inactivation of microperoxidase-11/FSM16 as a heterogeneous nanobiocatalyst in oxidation reaction of guaiacol were studied in the presence of high concentration of hydrogen peroxide (2?mM), as its natural suicide-substrate. The substrate concentration was first-order in relation to aromatic substrate (AH), and the ratio of suicide-substrate (H2O2) was kept much higher than the benign substrate (guaiacol). The results of kinetic analysis confirmed a similar mechanism for suicide-peroxide inactivation of horseradish peroxidase (HRP), microperoxidase (MP-11) and MP-11/NH2-FSM16. Inactivation kinetic parameters, including intact activity of MP-11/NH2-FSM16, ??i, and the apparent inactivation rate constant (k i) were obtained as 0.229?±?0.009?min?1 and 0.651?±?0.041?min?1 at [H2O2]?=?2.0?mM, respectively, in 5.0?mM phosphate buffer solution (PBS; pH 7.0) at 27?°C. Our results indicated that covalent immobilization of microperoxidase onto NH2-FSM16 protected the heme group against peroxide inactivation resulting in generation of an efficient peroxide-resistant heterogeneous nanobiocatalyst.  相似文献   

8.
The direct electron transfer of glucose oxidase (GOx) was achieved based on the immobilization of CdSe@CdS quantum dots on glassy carbon electrode by multi-wall carbon nanotubes (MWNTs)-chitosan (Chit) film. The immobilized GOx displayed a pair of well-defined and reversible redox peaks with a formal potential (E θ’) of ?0.459 V (versus Ag/AgCl) in 0.1 M pH 7.0 phosphate buffer solution. The apparent heterogeneous electron transfer rate constants (k s) of GOx confined in MWNTs-Chit/CdSe@CdS membrane were evaluated as 1.56 s?1 according to Laviron's equation. The surface concentration (Γ*) of the electroactive GOx in the MWNTs-Chit film was estimated to be (6.52?±?0.01)?×?10?11?mol?cm?2. Meanwhile, the catalytic ability of GOx toward the oxidation of glucose was studied. Its apparent Michaelis–Menten constant for glucose was 0.46?±?0.01 mM, showing a good affinity. The linear range for glucose determination was from 1.6?×?10?4 to 5.6?×?10?3?M with a relatively high sensitivity of 31.13?±?0.02 μA?mM?1?cm?2 and a detection limit of 2.5?×?10?5?M (S/N=3).  相似文献   

9.
The heat capacities of 1-butyl-3-methylimidazolium lactate ionic liquids ([C4mim][Lact]) were measured with a highly accurate automatic adiabatic calorimeter over the temperature range from 79 to 406 K. And the experimental values of molar heat capacities were fitted to a polynomial equation using least square method in the appropriate temperature ranges. The standard molar heat capacity was determined to be 1734.46?±?5.12 J K?1 mol?1 at 298.15 K. The molar enthalpy and molar entropy of the transition were determined to be 15.575?±?0.045 and 64.44?±?0.14 J K?1 mol?1. Other thermodynamic properties, such as (HT???H298.15) and (ST???S298.15), were also calculated. Furthermore, when the temperature reaches 241.87 K, the strongest peaks appeared by analysis of the heat capacity curve. This phenomenon could be explained from the interionic interaction, which is the hydrogen bond between the anions and cations.  相似文献   

10.
A new copper(II) complex [Cu(adefovir)2Cl2], where adefovir = adefovir dipivoxil drug, was synthesized and characterized by using different physicochemical methods. Binding interaction of this complex with calf thymus DNA (ct-DNA) has been investigated by multi-spectroscopic techniques and molecular modeling study. The complex displays significant binding properties of ct-DNA. The results of fluorescence and UV–vis absorption spectroscopy indicated that, this complex interacted with ct-DNA in a groove-binding mode, and the binding constant was 4.3(±0.2) × 104 M?1. The fluorimeteric studies showed that the reaction between the complex and ct-DNA is exothermic (ΔH = 73.91 kJ M?1; ΔS = 357.83 J M?1 K?1). Furthermore, the complex induces detectable changes in the CD spectrum of ct-DNA and slightly increases its viscosity which verified the groove-binding mode. The molecular modeling results illustrated that the complex strongly binds to the groove of DNA by relative binding energy of the docked structure ?5.74 kcal M?1. All experimental and molecular modeling results showed that the Cu(II) complex binds to DNA by a groove-binding mode.  相似文献   

11.
Two iron(II) complexes, [FeII(pytBuN3)2](FeCl4) (1) and [FeII(pytBuMe2N3)Cl2] (2), with sterically constrained pytBuN3 and pytBuMe2N3 chelate ligands (pytBuN3 = 2,6-bis-(aldiimino)pyridyl; pytBuMe2N3 = 2,6-bis-(ketimino)pyridyl), have been synthesized and characterized by elemental analysis, IR, UV–vis spectra, and preliminary X-ray single-crystal diffraction. The latter revealed that Fe(II) in 1 is six-coordinate by six nitrogen donors from two bisiminopyridines in a distorted octahedron. Complex 2 reacts with thiourea with a second-order rate constant k2 = (2.50 ± 0.05) × 10?3 M?1 s?1 at 296 K, and the reaction seemed to be slow. In a similar way, the interaction of 2 and DNA was studied by fluorescence and absorption spectroscopy. The results revealed that 2 caused fluorescence quenching of DNA through a dynamic quenching procedure. The binding constants KA, Kapp, and KSV as well as the number of binding sites between 2 and DNA were determined.  相似文献   

12.
Poly(2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole) (PAPT) modified glassy carbon electrode (GCE) was fabricated and used for the simultaneous determinations of dopamine (DA), uric acid (UA) and nitrite (NO2 ?) in 0.1 mol?L?1 phosphate buffer solution (PBS, pH 5.0) by using cyclic voltammetry and differential pulse voltammetry (DPV) techniques. The results showed that the PAPT modified GCE (PAPT/GCE) not only exhibited electrocatalytic activities towards the oxidation of DA, UA and NO2 ? but also could resolve the overlapped voltammetric signals of DA, UA and NO2 ? at bare GCE into three strong and well-defined oxidation peaks with enhanced current responses. The peak potential separations are 130 mV for DA–UA and 380 mV for UA–NO2 ? using DPV, which are large enough for the simultaneous determinations of DA, UA and NO2 ?. Under the optimal conditions, the anodic peak currents were correspondent linearly to the concentrations of DA, UA and NO2 ? in the ranges of 0.95–380 μmol?L?1, 2.0–1,000 μmol?L?1 and 2.0–1,200 μmol?L?1 for DA, UA and NO2 ?, respectively. The correlation coefficients were 0.9989, 0.9970 and 0.9968, and the detection limits were 0.2, 0.35 and 0.6 μmol?L?1 for DA, UA and NO2 ?, respectively. In 0.1 mol?L?1 PBS pH 5.0, the PAPT film exhibited good electrochemical activity, showing a surface-controlled electrode process with the apparent heterogeneous electron transfer rate constant (k s) of 25.9 s?1 and the charge–transfer coefficient (α) of 0.49, and thus displayed the features of an electrocatalyst. Due to its high sensitivity, good selectivity and stability, the modified electrode had been successfully applied to the determination of analytes in serum and urine samples.  相似文献   

13.
The objective of the present study was to investigate the potential use of applying polythiophene coating on magnetic Fe3O4 nanoparticles for the enhancement of asphaltene adsorption. Two stages of experimental were conducted. In the first stage, the ability of coated nanoparticles for asphaltene adsorption in synthetic asphaltene-toluene solution was evaluated. The effects of parameters such as nanoparticles concentration, initial concentration of asphaltene, and temperature were studied. In the second stage, the performance of the coated nanoparticles for the adsorption of asphaltene from crude oil was investigated under atmospheric pressure and a pressure-volume-temperature (PVT) apparatus was utilized for simulated reservoir conditions. Fe3O4 and Fe3O4-PT MNPs were synthesized using an effective co-precipitation method. The results of the first-stage tests indicated that the maximum adsorption capacity values for Fe3O4 and Fe3O4-PT MNPs were 0.79 and 1.09?mg?m?2, respectively. The optimum value of nanoparticles concentration was approximately determined as 10?g?L?1. According to the adsorption isotherms and kinetics, the Langmuir and pseudo-second-order Lagergren models were consistent with the experimental data, respectively. The average adsorption efficiencies for Fe3O4-PT and Fe3O4 MNPs were 78.98 and 65.94%, respectively. The results of the performed experiments on crude oil showed that Fe3O4-PT MNPs could adsorb asphaltenes from crude oil in a similar trend as synthetic asphaltene-toluene solution.  相似文献   

14.
《Analytical letters》2012,45(15):2496-2508
Abstract

A biosensor for hydrogen peroxide was fabricated by co-immobilizing cadmium telluride (CdTe) nanoparticles, chitosan, and hemoglobin (Hb) matrix. There was a pair of nearly reversible redox peaks around ?0.360 V, and the electrochemical behavior of Hb was a surface-controlled process, with an electron-transfer rate constant of 1.36 s?1 and surface coverage of 2.62 × 10?10 mol cm?2. Fourier transform infrared (FT-IR) spectra and ultraviolet–visible (UV-vis) spectra indicated that Hb sustained its natural conformation. It was demonstrated that Hb in the matrix kept its bioactivity and exhibited catalytic ability toward H2O2, with a response ranging from 7.44 × 10?6 to 6.95 × 10?4 M and a detection limit of 2.23 × 10?6 M.  相似文献   

15.
Two types of magnetite (Fe3O4) nanoparticles were investigated as adsorbents for the simultaneous removal of Pb(II), Cd(II), and As(III) metal ions from aqueous solution. Magnetite nanoparticles were prepared by two synthesis procedures, both using water as solvent, and are referred to as conventional Fe3O4 nanoparticles and green Fe3O4 nanoparticles. The latter used Citrus limon (lemon) aqueous peel extract as the surfactant. Box–Behnken experimental design was used to investigate the effects of parameters such as initial concentration (20–150?mg?L?1), pH (2–9), and biomass dosage (1–5?g?L?1) on the removal of Pb(II), Cd(II), and As(III) ions. The optimum parameters for removal of the studied metal ions from aqueous solutions, including the initial ion concentration (20?mg?L?1), pH (5.5) and adsorbent dose (5?g?L?1), were determined. The pseudosecond-order model exhibited the best fit for the kinetic studies, while adsorption equilibrium isotherms were best described by Langmuir and Freundlich models. The optimum conditions were applied for the treatment wastewater. The removal efficiencies of Pb(II), Cd(II), and As(III) using the conventional and green synthesized Fe3O4 nanoparticles were 59.4?±?4.3, 18.7?±?1.9 and 17.5?±?1.6, and 98.8?±?5.6, 46.0?±?1.3, and 48.2?±?2.6%, respectively. These results demonstrate the potential of magnetite nanoparticles synthesized using C. limon peel extract as highly efficient adsorbents for the removal of Pb(II), Cd(II), and As(III) ions from aqueous solution.  相似文献   

16.
In this study, the potential of MOF (Mil-101-Cr)-coated Fe3O4 magnetic nanoparticles (Fe3O4-MOF MNPs) for asphaltene adsorption was investigated for the first time and the results were compared with magnetic Fe3O4 nanoparticles (Fe3O4 MNPs). The coprecipitation method was used for the synthesis of both nanoparticles and were verified using x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FE-SEM). The initial asphaltene concentration, nanoparticles concentration, and temperature were the investigated parameters that influenced the adsorption capacity. Increasing the asphaltene concentration, decreasing the mass of nanoparticles, and reducing the temperature could enhance the maximum asphaltene adsorption capacities of 0.79 for Fe3O4 MNPs and 0.98?mg?m?2 for Fe3O4-MOF MNPs. Adsorption isotherms tests showed that the Langmuir model was in agreement with the experimental data. In addition, the evaluation of adsorption kinetics demonstrated that the pseudo-second-order Lagergren model predicted the results more precisely. The amount of asphaltene adsorption for Fe3O4-MOF MNPs was higher than that for Fe3O4 MNPs. These results recommend the application of MOF as an appropriate and effective coating for enhancing asphaltene adsorption.  相似文献   

17.
A yolk–shell-structured sphere composed of a superparamagnetic Fe3O4 core and a carbon shell (Fe3O4@HCS) was etched from Fe3O4@SiO2@carbon by NaOH, which was synthesized through the layer-by-layer coating of Fe3O4. This yolk–shell composite has a shell thickness of ca. 27 nm and a high specific surface area of 213.2 m2 g?1. Its performance for the magnetic removal of tetracycline hydrochloride from water was systematically examined. A high equilibrium adsorption capacity of ca. 49.0 mg g?1 was determined. Moreover, the adsorbent can be regenerated within 10 min through a photo-Fenton reaction. A stable adsorption capacity of 44.3 mg g?1 with a fluctuation <10% is preserved after 5 consecutive adsorption–degradation cycles, demonstrating its promising application potential in the decontamination of sewage water polluted by antibiotics.  相似文献   

18.
Novel magnetic polyurethane flexible foam nanocomposites were synthesized by incorporation of aminopropyltriethoxysilane (APTS) functionalized magnetite nanoparticles (MNPs) via one-shot method. The functionalized MNPs (Fe3O4@APTS) were synthesized by co-precipitation of the Fe2+ and Fe3+ with NH4OH and further functionalization with APTS onto the surface of MNPs by sol–gel method. The magnetic core-shell NPs were used up to 3.0 % in the foam formulation and the magnetic nanocomposites prepared successfully. The results of thermogravimetric analysis (TGA) showed an increasing in thermal stability of polyurethane nanocomposite foam at initial, 5 and 10 %, and maximum thermal decomposition temperatures by incorporation of Fe3O4@APTS. In addition SEM images revealed the uniformity of the foam structures and decreasing in pore sizes. Furthermore, VSM result showed super paramagnetic behavior for Fe3O4@APTS-PU nanocomposites.  相似文献   

19.
The electrochemical properties of LaY2Ni9 alloy used as an anode in nickel-metal hydride batteries were investigated at ambient and at different temperatures. Several techniques, such as the galvanostatic charging and discharging, the constant potential discharge, and the potentiodynamic polarization, were applied to characterize these electrochemical properties. The discharge capacity of the LaY2Ni9 alloy increases to reach 258 mAh g?1 after 5 cycles and decreases to 140 mAh g?1 after 100 cycles then stabilizes around this same value indicating good cycling held. The hydrogen diffusion coefficient D H in the bulky alloy is estimated to be (1.02?±?0.11)?×?10?11 cm2 s?1 correlated with the good stability of electrochemical capacity after 100 cycles. The evolution of the ratio \( \frac{D_{\mathrm{H}}}{a^2} \) and the corrosion current density and potential are correlated with the evolution of the electrochemical capacity during the activation and for a long cycling. The enthalpy, the entropy, and the apparent activation energy of the LaY2Ni9 hydride formation are evaluated. The calculated results show that the enthalpy change, the entropy change, and the activation energy are (?42.64?±?1.08), (56.85?±?2.11), and (14.84?±?0.35)?kJ mol?1, respectively.  相似文献   

20.
Multi-phase anaerobic reactor for H2 and CH4 production from paperboard mill wastewater was studied. The reactor was operated at hydraulic retention times (HRTs) of 12, 18, 24, and 36 h, and organic loading rates (OLRs) of 2.2, 1.5, 1.1, and 0.75 kg chemical oxygen demand (COD)/m3 day, respectively. HRT of 12 h and OLR of 2.2 kg COD/m3 day provided maximum hydrogen yield of 42.76?±?14.5 ml/g CODremoved and volumetric substrate uptake rate (?rS) of 16.51?±?4.43 mg COD/L h. This corresponded to the highest soluble COD/total COD (SCOD/TCOD) ratio of 56.25?±?3.3 % and the maximum volatile fatty acid (VFA) yield (YVFA) of 0.21?±?0.03 g VFA/g COD, confirming that H2 was mainly produced through SCOD conversion. The highest methane yield (18.78?±?3.8 ml/g CODremoved) and ?rS of 21.74?±?1.34 mgCOD/L h were achieved at an HRT of 36 h and OLR of 0.75 kg COD/m3 day. The maximum hydrogen production rate (HPR) and methane production rate (MPR) were achieved at carbon to nitrogen (C/N) ratio of 47.9 and 14.3, respectively. This implies the important effect of C/N ratio on the distinction between the dominant microorganism bioactivities responsible for H2 and CH4 production.  相似文献   

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