Graphene and Carbon Nanotube-based Electrochemical Sensing Platforms for Dopamine

Dopamine (DA) is an important neurotransmitter, which is created and released from the central nervous system. It plays a crucial role in human activities, like cognition, emotions, and response to anything. Maladjustment of DA in human blood serum results in different neural diseases, like Parkinson's and Schizophrenia. Consequently, researchers have started working on DA detection in blood serum, which is undoubtedly a hot research area. Electrochemical sensing techniques are more promising to detect DA in real samples. However, utilizing conventional electrodes for selective determination of DA encounters numerous problems due to the coexistence of other materials, such as uric acid and ascorbic acid, which have an oxidation potential close to DA. To overcome such problems, researchers have put their focus on the modification of bare electrodes. The aim of this review is to present recent advances in modifications of most used bare electrodes with carbonaceous materials, especially graphene, its derivatives, and carbon nanotubes, for electrochemical detection of DA. A brief discussion about the mechanistic phenomena at the electrode interface has also been included in this review.     

三维网络结构NiCo2S4@NiCo2O4复合电极的制备及其性能

超级电容器具有更大的功率密度、优秀的循环稳定性、极快的充放电速度、超长的循环寿命以及环境友好等突出特点,其性能与构件关系密切,其中最根本的就是组成它的电极材料。本研究主要采用传统的水热法制备出钴酸镍(NiCo₂O₄)电极材料,进而通过离子交换(二次水热)制得镍钴硫(NiCo₂S₄),最后利用化学浴沉积(CBD)法使其与钴酸镍复合,得到最终所需的三维网络结构NiCo₂S₄@NiCo₂O₄复合电极。经过表面形貌表征、循环伏安测试、恒电流充放电测试以及比电容计算分析等可以证明:三维网络结构NiCo₂S₄@NiCo₂O₄复合电极的比电容及循环稳定性等远远优于复合前单一的纯NiCo₂O₄电极材料,具有极大应用前景。     

In-situ preparation and electrochromic properties of TiO2/PTPA-HTAN core-shell nanocomposite film

A new star-shaped structure conjugated microporous polymers, poly (2,8,14-tri[4-diphenyl-benzene]-hexaazatrinaphthylene) (PTPA-HATN), was designed and in-situ electrochemically polymerized on the surfaces of FTO electrodes with a directional alignment TiO₂ nanorod array to obtain TiO₂/PTPA-HATN core-shell nanocomposite films. Compared with the PTPA-HATN film, the TiO₂/PTPA-HATN composite film exhibits higher optical contrast and faster response time, with contrast of 57% at 783 nm, coloring time of 3.62 s and discoloring time of 2.55 s (43%, 4.63 s and 4.77 s for PTPA-HATN film, respectively). After 400 cycles, the contrast of nanocomposite film decreased by 28%, while the PTPA-HATN film basically lost its electrochromic properties. A simple three-layer EC prototype device based on TiO₂/PTPA-HATN nanocomposite film constructed with hydrogel electrolyte clearly shows color changes at different voltages. On the one hand, the formation of core-shell porous nanostructure of TiO₂/PTPA-HATN composite film provides a larger ion doping/de-doping interface, shortening the average diffusion length of ions. On the other hand, the large indented polymer-nanorods contact interface makes it difficult for the polymer to detach from the electrode, thus significantly improving the cyclic stability of the composite film.     

Photocatalytically Renewable Micro‐electrochemical Sensor for Real‐Time Monitoring of Cells

Electrode fouling and passivation is a substantial and inevitable limitation in electrochemical biosensing, and it is a great challenge to efficiently remove the contaminant without changing the surface structure and electrochemical performance. Herein, we propose a versatile and efficient strategy based on photocatalytic cleaning to construct renewable electrochemical sensors for cell analysis. This kind of sensor was fabricated by controllable assembly of reduced graphene oxide (RGO) and TiO₂ to form a sandwiching RGO@TiO₂ structure, followed by deposition of Au nanoparticles (NPs) onto the RGO shell. The Au NPs‐RGO composite shell provides high electrochemical performance. Meanwhile, the encapsulated TiO₂ ensures an excellent photocatalytic cleaning property. Application of this renewable microsensor for detection of nitric oxide (NO) release from cells demonstrates the great potential of this strategy in electrode regeneration and biosensing.     

Electrodes/Electrolyte Interfaces in the Presence of a Surface‐Modified Photopolymer Electrolyte: Application in Dye‐Sensitized Solar Cells

Since hundreds of studies on photoanodes and cathodes show that the electrode/electrolyte interfaces represent a key aspect at the base of dye‐sensitized solar cell (DSSC) performances, it is reported here that these interfaces can be managed by a smart design of the spatial composition of quasi‐solid electrolytes. By means of a cheap, rapid, and green process of photoinduced polymerization, composition‐tailored polymer electrolyte membranes (PEMs) with siloxane‐enriched surfaces are prepared, and their properties are thoroughly described. When assembled in DSSCs, the interfacial action promoted by the composition‐tailored PEMs enhances the photocurrent and fill factor values, thus increasing the global photovoltaic conversion efficiency with respect to the non‐modified PEMs. Moreover, the presence of the siloxane‐chain‐enriched surface increases the hydrophobicity and reduces the water vapor permeation into the device, thus enhancing the cell′s durability.     

In Situ Detection of Particle Aggregation on Electrode Surfaces

Partially blocked electrodes (PBEs) are important; many applications use non‐conductive nanoparticles (NPs) to introduce new electrode functionalities. As aggregation is a problem in NP immobilization, developing an in situ method to detect aggregation is vital to characterise such modified electrodes. We present chronoamperometry as a method for detection of NP surface aggregation and semi‐quantitative sizing of the formed aggregates, based on the diffusion limited current measured at PBEs as compared with the values calculated numerically for different blocking feature sizes. In contrast to voltammetry, no approximations on electrode kinetics are needed, making chronoamperometry a more general and reliable method. Sizing is shown for two modification methods. Upon drop casting, significant aggregation is observed, while it is minimized in electrophoretic NP deposition. The aggregate sizes determined are in semi‐quantitative agreement with ex situ microscopic analysis of the PBEs.     

Non‐destructive Patterning of Carbon Electrodes by Using the Direct Mode of Scanning Electrochemical Microscopy

Patterning of glassy carbon surfaces grafted with a layer of nitrophenyl moieties was achieved by using the direct mode of scanning electrochemical microscopy (SECM) to locally reduce the nitro groups to hydroxylamine and amino functionalities. SECM and atomic force microscopy (AFM) revealed that potentiostatic pulses applied to the working electrode lead to local destruction of the glassy carbon surface, most likely caused by etchants generated at the positioned SECM tip used as the counter electrode. By applying galvanostatic pulses, and thus, limiting the current during structuring, corrosion of the carbon surface was substantially suppressed. After galvanostatic patterning, unambiguous proof of the formation of the anticipated amino moieties was possible by modulation of the pH value during the feedback mode of SECM imaging. This patterning strategy is suitable for the further bio‐modification of microstructured surfaces. Alkaline phosphatase, as a model enzyme, was locally bound to the modified areas, thus showing that the technique can be used for the development of protein microarrays.     

Photoluminescence properties of a cationic trinuclear zinc(II) complex with the tetradentate Schiff base ligand 6‐methyl‐2‐({[(pyridin‐2‐yl)methyl]imino}methyl)phenolate

Metal complexes with Schiff base ligands have been suggested as potential phosphors in electroluminescent devices. In the title complex, tetrakis[6‐methyl‐2‐({[(pyridin‐2‐yl)methyl]imino}methyl)phenolato‐1:2κ⁸N,N′,O:O;3:2κ⁸N,N′,O:O]trizinc(II) hexafluoridophosphate methanol monosolvate, [Zn₃(C₁₄H₁₃N₂O)₄](PF₆)₂·CH₃OH, the Zn^II cations adopt both six‐ and four‐coordinate geometries involving the N and O atoms of tetradentate 6‐methyl‐2‐({[(pyridin‐2‐yl)methyl]imino}methyl)phenolate ligands. Two terminal Zn^II cations adopt distorted octahedral geometries and the central Zn^II cation adopts a distorted tetrahedral geometry. The O atoms of the phenolate ligands bridge three Zn^II cations, forming a dicationic trinuclear metal cluster. The title complex exhibits a strong emission at 469 nm with a quantum yield of 15.5%.     

化学探头法与荧光光谱法测定水中溶解氧量

探讨了化学探头法和荧光光谱法测定水中溶解氧的关系。分别用F检验和t检验对两组数据进行了比较,结果表明两组数据的精密度和系统误差都没有显著差异,两种方法测定溶解氧的相对标准偏差(RSD,n=9)分别为0.35%,0.33%。进而又探讨了溶解氧与NaCl含量、温度之间的关系,结果表明溶解氧含量随NaCl含量的增加、温度的升高而逐渐降低。     

Construction of a novel electrochemical sensor based on molecularly imprinted polymers for the selective determination of chlorpyrifos in real samples

We present a novel electrochemical sensor based on an electrode modified with molecularly imprinted polymers for the detection of chlorpyrifos. The modified electrode was constructed by the synthesis of molecularly imprinted polymers by a precipitation method then coated on a glassy carbon electrode. The surface morphology of the modified electrode was characterized by using field‐emission scanning electron microscopy and transmission electron microscopy. The performance of the imprinted sensor was thoroughly investigated by using cyclic voltammetry and differential pulse voltammetry. The imprinted electrochemical sensor displayed high repeatability, stability, and selectivity towards the template molecules. Under the optimal experimental conditions, the peak current response of the imprinted electrochemical sensor was linearly related to the concentration of chlorpyrifos over the range 1 × 10⁻¹⁰–1 × 10⁻⁵ mol/L with a limit of detection of 4.08 × 10⁻⁹ mol/L (signal‐to‐noise ratio = 3). Furthermore, the proposed molecularly imprinted electrochemical sensor was applied to the determination of chlorpyrifos in the complicated matrixes of real samples with satisfactory results. Therefore, the molecularly imprinted polymers based electrochemical sensor might provide a highly selective, rapid, and cost‐effective method for chlorpyrifos determination and related analysis.