Meichuan Liu

A highly selective electrochemical impedance spectroscopy-based aptasensor for sensitive detection of acetamiprid

A simple aptasensor for sensitive and selective detection of acetamiprid has been developed based on electrochemical impedance spectroscopy (EIS). To improve sensitivity of the aptasensor, gold nanoparticles (AuNPs) were electrodeposited on the bare gold electrode surface by cycle voltammetry (CV), which was employed as a platform for aptamer immobilization. With the addition of acetamiprid, the formation of acetamiprid-aptamer complex on the AuNPs-deposited electrode surface resulted in an increase of electron transfer resistance (Ret). The change of Ret strongly depends on acetamiprid concentration, which is applied for acetamiprid quantification. A wide linear range was obtained from 5 to 600nM with a low detection limit of 1nM. The control experiments performed by employing the pesticides that may coexist or have similar structure with acetamiprid demonstrate that the aptasensor has only specific recognition to acetamiprid, resulting in high selectivity of the aptasensor. The dissociation constant, Kd of 23.41nM for acetamiprid-aptamer complex has been determined from the differential capacitance (Cd) by assuming a Langmuir isotherm, which indicates strong interaction between acetamiprid and aptamer, further proving high selectivity of the aptasensor. Besides, the applicability of the developed aptasensor has been successfully evaluated by determining acetamiprid in the real samples, wastewater and tomatoes.

A femtomolar level and highly selective 17β-estradiol photoelectrochemical aptasensor applied in environmental water samples analysis.

Driven by the urgent demand of determining low level of 17β-estradiol (E2) present in environment, a novel and ultrasensitive photoelectrochemical (PEC) sensing platform based on anti-E2 aptamer as the biorecognition element was developed onto CdSe nanoparticles-modified TiO2 nanotube arrays. The designed PEC aptasensor exhibits excellent performances in determination of E2 with a wide linear range of 0.05-15 pM. The detection limit of 33 fM is lower than the previous reports. The aptasensor manifests outstanding selectivity to E2 while used to detect seven other endocrine disrupting compounds that have similar structure or coexist with E2. The superior sensing behavior toward E2 can be attributed to the appropriate PEC sensing interface resulting from the preponderant tubular microstructure and excellent photoelectrical activity, the large packing density of aptamer on the sensing interface, as well as the high affinity of the aptamer to E2. The PEC aptasensor was applied successfully to determine E2 in environmental water samples without complicate sample pretreatments, and the analytical results showed good agreement with that determined by HPLC. Thus, a simple and rapid PEC technique for detection low level of E2 was established, having promising potential in monitoring environmental water pollution.

High-Yield and Selective Photoelectrocatalytic Reduction of CO2 to Formate by Metallic Copper Decorated Co3O4 Nanotube Arrays

Carbon dioxide (CO2) reduction to useful chemicals is of great significance to global climate and energy supply. In this study, CO2 has been photoelectrocatalytically reduced to formate at metallic Cu nanoparticles (Cu NPs) decorated Co3O4 nanotube arrays (NTs) with high yield and high selectivity of nearly 100%. Noticeably, up to 6.75 mmol·L(–1)·cm(–2) of formate was produced in an 8 h photoelectrochemical process, representing one of the highest yields among those in the literature. The results of scanning electron microscopy, transmission electron microscopy and photoelectrochemical characterization demonstrated that the enhanced production of formate was attributable to the self-supported Co3O4 NTs/Co structure and the interface band structure of Co3O4 NTs and metallic Cu NPs. Furthermore, a possible two-electron reduction mechanism on the selective PEC CO2 reduction to formate at the Cu–Co3O4 NTs was explored. The first electron reduction intermediate, CO2 ads•–, was adsorbed on Cu in the form of Cu–O. With the carbon atom suspended in solution, CO2 ads•– is readily protonated to form the HCOO– radical. And HCOO– as a product rapidly desorbs from the copper surface with a second electron transfer to the adsorbed species.

A simple, stable and picomole level lead sensor fabricated on DNA-based carbon hybridized TiO2 nanotube arrays.

An electrochemical lead sensor is developed on DNA-based vertically aligned conductive carbon hybridized TiO(2) nanotube arrays (DNA/C-TiO(2) NTs). The designed DNA/C-TiO(2) NTs sensor is superior in determination of lead with high sensitivity, selectivity and repeatability, as well as wide pH adaptability, fast electro-accumulation capacity for lead and easy regeneration. Such remarkable characteristics for lead sensing are attributed to the immobilization of abundant target biomolecules, DNA, and the enhanced bioelectrochemical activity. The controllable carbon hybridization of the TiO(2) NTs increases the conductivity of the electrode, while retaining the tubular structure, biocompatibility, and hydrophilicity. The results show that the lead sensor possesses a wide linear calibration ranging from 0.01 to 160 nM with the detection limitation at a picomole level (3.3 pM). The application of the present sensor is realized for determination of Pb(2+) in real water samples.

Fabrication of a Novel and Simple Microcystin-LR Photoelectrochemical Sensor with High Sensitivity and Selectivity

Microcystin-LR (MC-LR), an inert electrochemical species, is difficult to be detected by a simple and direct electrochemical method. In the present work, a novel photoelectrochemical sensor is developed on highly ordered and vertically aligned TiO(2) nanotubes (TiO(2) NTs) with convenient surface modification of molecularly imprinted polymer (MIP) (denoted as MIP@TiO(2) NTs) for highly sensitive and selective determination of MC-LR in solutions. Molecularly imprinted polypyrrole (PPy) of MC-LR is chosen as the recognition element. The designed MIP@TiO(2) NTs photoelectrochemical sensor presents excellent applicability in MC-LR determination, with linear range from 0.5 to 100 μg L(-1) and limit of detection of 0.1 μg L(-1). Moreover, the sensor exhibits outstanding selectivity while used in coexisting systems containing 2,4-dichorophenoxyacetic acid, atrazine, paraquat, or monosultap with high concentration, 100 times that of MC-LR. The sensor presents good photoelectric conversion efficiency and detection sensitivity, as well as broad linear detection range, mainly because of the high specific surface area and photoelectric activity of TiO(2) NTs and the π bond delocalized electron system of PPy that promotes the separation of electron-holes. The prominent selectivity is from the MIP by forming multiple hydrogen bonds between PPy and MC-LR. Mechanisms for photoelectrochemical analysis and selective recognition are also discussed.

Highly efficient and mild electrochemical incineration: mechanism and kinetic process of refractory aromatic hydrocarbon pollutants on superhydrophobic PbO2 anode.

Aqueous aromatic hydrocarbons are chemically stable, high toxic refractory pollutants that can only be oxidized to phenols and quinone on either Pt or traditional PbO(2) electrodes. In this study, a novel method for the electrochemical incineration of benzene homologues on superhydrophobic PbO(2) electrode (hydrophobic-PbO(2)) was proposed under mild conditions. Hydrophobic-PbO(2) can achieve the complete mineralization of aromatic hydrocarbons and exhibit high removal effect, rapid oxidation rate, and low energy consumption. The kinetics of the electrochemical incineration was also investigated, and the results revealed that the cleavage of the benzene ring is a key factor affecting the incineration efficiency. Moreover, on hydrophobic-PbO(2), the decay of intermediates was rapid, and low concentrations of aromatics were accumulated during the reaction. The removal of the initial pollutants and the effects of oxidative cleavage were related to the number of methyl groups on the benzene ring. Specifically, the results of physical experiments and quantum calculations revealed that the charge density of carbon atoms increases with an increase in the number of methyl groups, which promotes the electrophilic attack of ·OH.

Mechanism of enhanced electrochemical oxidation of 2,4-dichlorophenoxyacetic acid with in situ microwave activated boron-doped diamond and platinum anodes.

Remarkable enhancement in degradation effect is achieved at in situ activated boron-doped diamond (BDD) and Pt anodes with different extent through electrochemical oxidation (EC) of 2,4-dichlorophenoxyacetic acid (2,4-D) with microwave (MW) radiation in a flow system. Results show that when EC is activated with MW radiation, the complete mineralization time of 2,4-D at the BDD is reduced quickly from 10 to 4 h while Chemical oxygen demand (COD) removal at Pt is increased from 37.7 to 58.3% at 10 h; the initial current efficiency is both improved about 1.5 times while the pseudo-first-order rate constant is increased by 153 and 119% at the BDD and Pt, respectively. To gain insight into the higher efficiency in microwave activated EC, the mechanism has therefore been systematically evaluated from the essence of electrochemical reaction and the accumulated hydroxyl radical concentration. 2,4-Dichlorophenol, catechol, benquinone, and maleic and oxalic acids are the main intermediates on the Pt anode measured by high performance liquid chromatography (HPLC), while the intermediates on the BDD electrode include 2,4-dichlorophenol, hydroquinone, and maleic and oxalic acids. The reaction pathway with microwave radiation is the same as that in a conventional electrochemical oxidation on both electrodes. While less and lower aromatic intermediates produce at the BDD with MW, which suggests the higher ring-open ratio and the faster oxidation of carboxylic acids. With microwave radiation, the ring-open ratio at the BDD is increased to 98.8% from 85.6%; the value at Pt is increased to 67.3% from 35.9%. So microwave radiation can activate the electrochemical oxidation, which leads to the higher efficiency. This promotion is mainly due to the higher accumulated hydroxyl radical concentration and the effects by microwave radiation. All the results prove that the BDD electrode presents much better mineralization performance with MW. To the best of our knowledge, it is the first time the systematic analysis of the mechanism of microwave activated EC has been reported.

Electrochemical incineration of high concentration azo dye wastewater on the in situ activated platinum electrode with sustained microwave radiation

In this study, an in situ microwave activated platinum electrode was developed for the first time to completely incinerate the azo dye simulated wastewater containing methyl orange. The experiments were carried out in a circulating system under atmospheric pressure. Azo bond of methyl orange was partly broken on Pt, certain decoloration was reached, and the total organic carbon was not removed effectively without microwave activation. However, methyl orange was mineralized completely and efficiently on the in situ microwave activated Pt. 2,5-Dinitrophenol, p-nitrophenol, hydroquinone, benzoquinone, maleic and oxalic acids are the main intermediates during degradation of methyl orange. Aromatic products are the main substances leading to the poisoning of Pt and decrease of electrochemical oxidation efficiency, so methyl orange removal can not be carried out thoroughly. However, the intermediates were broke down quickly with in situ microwave activation promoting the mineralization of methyl orange on Pt.

Ultrasound enhanced electrochemical oxidation of phenol and phthalic acid on boron-doped diamond electrode.

The enhancement on degradation of two typical organic pollutants, phenol (Ph) and phthalic acid (PA) on boron-doped diamond (BDD) electrode is particularly investigated in this study. Results show that ultrasound (US) has remarkable influence on electrochemical (EC) oxidation of the two pollutants including degradation efficiency, EC oxidation energy consumption, mass transport and electrochemical reaction. With US, the enhancement on degradation efficiency and decreasing of EC oxidation energy consumption of Ph are more obvious. US can also efficiently reduce the average electrochemical oxidation energy consumption (AE), decreasing by 74 and 69% for Ph and PA, respectively. Mass transport process can be greatly accelerated by US. The mass transport coefficients of Ph and PA both reach 2.0 x 10(-5)ms(-1) in ultrasound-assisted electrochemical (US-EC) process, from 5.4 x 10(-6) and 6.7 x 10(-6) ms(-1) in EC, increasing by 270 and 199%, respectively. The reaction amount of Ph decreases by 79% with US, from 6.49 x 10(-10) to 1.39 x 10(-10) mol cm(-2). For PA, the reaction amount decreases from 1.25x10(-11) to 3.11 x 10(-12) mol cm(-2) with US. The oxidation peak current increases by 32% for Ph. While for PA, there is no direct oxidation happened in US-EC process.

Fabrication of a novel atrazine biosensor and its subpart-per-trillion levels sensitive performance.

The present study describes an atrazine biosensor with the detection limit of 0.1 part-per-trillion (ppt). The atrazine biosensor is fabricated on tyrosinase-immobilized vertical growth TiO(2) nanotubes (Tyr/TiO(2)-NTs), based on the inhibition of tyrosinase by atrazine. The designed Tyr/TiO(2)-NTs present excellent applicability in atrazine determination, with high sensitivity and stability, and rapid response. The outstanding sensing characteristics for atrazine is attributed to the appropriate bioelectrochemical interface of Tyr/TiO(2)-NTs, resulting from the preponderant tubular structure, excellent biocompatibility, and hydrophilicity of TiO(2)-NTs. The atrazine biosensor possesses a wide detection range from 0.2 ppt to 2 part-per-billion (ppb). The practical application of the biosensor is realized for the determination of atrazine and the analysis of its transport in soil samples. A new method for determination of atrazine in soil samples is thus established, which greatly simplifies the preparation procedure of sample and is helpful to evaluate the pollution risk of atrazine to soil, groundwater, and surface water.