有序介孔碳/石墨烯/镍泡沫的制备及其对多巴胺的高灵敏度和高选择性检测

柔性生物传感器在可穿戴电子设备中有着广泛的应用前景. 为了获得柔性电化学多巴胺传感器,作者在本工作中首先在镍泡沫表面通过化学气相沉积生长石墨烯,随后通过高温碳化嵌段共聚物与酚醛树脂在石墨烯表面共组装形成的薄膜制备了有序介孔碳/石墨烯/镍泡沫（OMC/G/Ni）复合材料. 其中,镍泡沫可以为复合材料提供具有高导电性和良好柔韧性的金属骨架,而具有垂直排列介孔阵列的有序介孔碳层为复合材料提供了高的电活性表面积,且有利于活性位点的暴露. 值得注意的是,夹在有序介孔碳层和镍泡沫之间的石墨烯极大地增强了各组分之间的相容性,有利于进一步提升复合材料的电化学性能. 作为电化学传感器中的工作电极,OMC/G/Ni体现出优异的多巴胺检测能力. 不但具有宽的线性检测范围（0.05 ~ 58.75 μmol·L^-1）和低检测限（0.019 μmol·L^-1）,还具有良好的选择性、重现性和稳定性. 此外,OMC/G/Ni在弯曲状态下依旧能够保持对多巴胺的高检测能力,证明了其在柔性生物传感器中的应用潜力.     

Flexible strain sensor with ridge-like microstructures for wearable applications

The flexible stretchable sensors have great potential for implementation in various applications, such as intelligent soft robots, health monitoring, and motion detection. However, most of the flexible stretchable sensors with microstructures and high sensitivities are fabricated by expensive templates and complex processes. In consideration of large-scale fabrication, a low cost and efficient way is in great demand. Herein, electroless plating on Nafion films with decent swelling ratios are proposed to fabricate stretchable sensors with wrinkle-structured electrodes. By adding isopropanol (IPA) to the electroless plating process, the H₂O-IPA sensor with larger swelling ratio shows deeper surface wrinkles, higher surface roughness, and better sensitivity to strain. At the same time, the H₂O-IPA sensor exhibit good durability (500 cycles). By mounting the sensor on the joint of human finger, the motion of the finger bending and even the bending degree can be accurately detected, indicating the potential use in the field of wearable devices and soft electronic skins.     

A Novel Flexible Electrochemical Ascorbic Acid Sensor Constructed by Ferrocene Methanol doped Multi-walled Carbon Nanotube Yarn

An ascorbic acid (AA) electrochemical sensor was fabricated by ferrocene methanol (Fc−OH) modified multi-walled carbon nanotube yarn (CNTY). The prepared sensor (Fc−OH/CNTY) exhibited outstanding flexibility, highly stretchability, excellent bendability and obviously electrocatalytic activity for oxidation of ascorbic acid. The morphology of Fc−OH/CNTY was evaluated by scanning electron microscope. The electrochemical behaviour of Fc−OH/CNTY sensor was studied by cyclic voltammetry and amperometry measurements. Moreover, the influence of Fc−OH concentration, applied potential and electrolyte solution pH were also investigated to obtain the best sensor performance. The prepared sensor exhibited a wide linear range from 3 μM to 3.0 mM toward AA, and a detection limit of 1.32 μM (S/N=3). It also possessed a good lifetime and a fast response speed (2.83 s). In addition, the Fc−OH/CNTY sensor remained 90 % and 60 % of its initial activity after 100 and 500 times bending, respectively, which indicated a potential application on flexible, implantable and/or wearable electrochemical sensors.     

Bimetallic CuCo Derived from Prussian Blue Analogue for Nonenzymatic Glucose Sensing

Bimetallic CuCo composites are prepared by calcinating copper hexacyanocobaltate precursor in N₂ atmosphere. The CuCo modified electrodes are fabricated for nonenzymatic glucose sensing in the alkaline electrolyte. The glucose can be directly electro-oxidized on the surface of the electrode catalyst mediated by the redox couples of Cu and Co. The optimal glucose sensor exhibits a high sensitivity (567 μA ⋅ mM⁻¹ ⋅ cm⁻²) in the range up to 825 μM with a detection limit of 3 μM and acceptable selectivity. The sensor can also be applied in serum samples. This work provides a facile and easily-scalable synthesis method of electrocatalysts for nonenzymatic glucose sensors.     

In-situ growth of vertically aligned nickel cobalt sulfide nanowires on carbon nanotube fibers for high capacitance all-solid-state asymmetric fiber-supercapacitors

Fiber-supercapacitors(FSCs)are promising power sources for miniature portable and wearable electronic devices.However,the development and practical application of these FSCs have been severely hindered by their low volumetric capacitance and narrow operating voltage.In this work,vertically aligned nickel cobalt sulfide(Ni Co_2S_4)nanowires grown on carbon nanotube(CNT)fibers were achieved through an in-situ two-step hydrothermal reaction method.The as-prepared Ni Co_2S_4@CNT fiber electrode exhibits a high volumetric capacitance of 2332 F cm~(-3),benefiting from its superior electric conductivity,large surface area,and rich Faradic redox reaction sites.Furthermore,a Ni Co_2S_4@CNT//VN@CNT(vanadium nitride nanosheets grown on CNT fibers)asymmetric fiber-supercapacitor(AFSC)was successfully fabricated.The device exhibits an operating voltage up to 1.6 V and a high volumetric energy density of 30.64m Wh cm~(-3).The device also possesses outstanding flexibility as evidenced by no obvious performance degradation under various bending angles and maintaining high capacitance after 5000 bending cycles.This work promotes the practical application of flexible wearable energy-storage devices.     

二次刻蚀聚酰亚胺负载CuxO纳米复合物薄膜电极用于葡萄糖的快速测定

本文采用激光刻蚀聚酰亚胺薄膜为载体, 浸泡吸附铜离子后经过二次刻蚀还原得到含有Cu(0)、Cu(I)和Cu(II)的纳米复合物薄膜电极(SLEPI/Cu_xO-FE). 通过表征可知,SLEPI/Cu_xO-FE具有大比表面积、丰富的活性位点以及良好的电催化性能. 实验结果表明,该电极对葡萄糖具有良好的电化学响应,并具有较好的稳定性和重现性,有望应用于葡萄糖的低成本检测.     

Highly Sensitive Hydrazine Sensor Based on Co(OH)2 Nanoflakes Electrochemically Deposited on MWCNTs

We delineate the electrochemical preparation of cobalt hydroxide nanoflakes Co(OH)₂ NFs on multi‐walled carbon nanotubes (MWCNTs) by potentiostatic methods. The preparation was done on the surface of glassy carbon electrode (GCE). The prepared nanocomposite was characterized by field emission scanning electron microscopy (FESEM), X‐ray diffraction spectroscopy (XRD) and X‐ray photo electron spectroscopy (XPS). The resulting f‐ MWCNTs/Co(OH)₂ NFs modified GCE exhibits a good electrocatalytic activity for the oxidation of hydrazine in terms of decreasing over potential and increasing peak current. The modified electrode holds good in the linear range from 0.5 to 15.5 μM with limit of detection as 87.5 nM. The sensitivity of our modified electrode is calculated to be 5733 μA/mM cm‐2. Remarkably, the obtained LOD value of our sensor is very lower compared to the recommended concentration of hydrazine in water by World health organization (WHO) and Environmental protective agency (EPA). The modified electrode detects hydrazine selectively even in the presence of common interferants. Various water samples were chosen to study the practical feasibility of our sensor. The sensor also exhibited an appreciable stability, repeatability and reproducibility.     

Wearable electrochemical sensors for in situ analysis in marine environments

The development of wearable screen-printed electrochemical sensors on underwater garments comprised of the synthetic rubber neoprene is reported. These wearable sensors are able to determine the presence of environmental pollutants and security threats in marine environments. Owing to its unique elastic and superhydrophobic morphology, neoprene is an attractive substrate for thick-film electrochemical sensors for aquatic environments and offers high-resolution printing with no apparent defects. The neoprene-based sensor was evaluated for the voltammetric detection of trace heavy metal contaminants and nitroaromatic explosives in seawater samples. We also describe the first example of enzyme (tyrosinase) immobilization on a wearable substrate towards the amperometric biosensing of phenolic contaminants in seawater. Furthermore, the integration of a miniaturized potentiostat directly on the underwater garment is demonstrated. The wearable sensor-potentiostat microsystem provides a visual indication and alert if the levels of harmful contaminants have exceeded a pre-defined threshold. The concept discussed here is well-suited for integration into dry- and wetsuits worn by divers and recreational surfers/swimmers, thereby providing them with the ability to continuously assess their surroundings for environmental contaminants and security hazards.     

Real-time detection of food-borne bacterial adenosine triphosphate (ATP) using dielectrophoretic force and a bioluminescence sensor

A copper hexacyanoferrate nanostructure was prepared on the surface of a disposable pencil graphite electrode. The resulting electrode exhibits an excellent electrocatalytic activity for the oxidation of L-cysteine. Cyclic voltammetry and chronoamperometry were employed to characterize the response to L-cysteine that changes linearly in the concentration range from 1 to 13 μM, with a detection limit of 0.13 μM (at an SNR of 3). Typical features of the sensor include low cost, simple preparation, fast response, good stability, selectivity, and reproducibility. It was applied to the determination of L-cysteine in urine.     

The influence of bending on the performance of flexible carbon black/polymer composite gas sensors

The performance of electronics on flexible substrates suffers under substrate bending leading to reduced device performance. In this article, we highlighted the influence of bending strain on a conductive polymer composite gas sensor and developed a model to investigate the influence of strain. We evaluated the strain influence on the resistance of a gas sensor with respect to sensitivity, filler content, cyclic loading, and electrode orientation. The sensitivity of gas sensors increased with decreasing tensile bending radii. The influence of strain was dominant for gas sensors with less carbon black concentration. Cyclic bending tests showed a decrease of sensor resistance versus time and a plastic deformation. A sensor geometry orientations effect to reduce the sensitivity to bending strain was achieved by aligning the electrode fingers parallel to the strain. A model was successfully implemented to simulate strain influences inside the polymer incorporating the Poisson ratio. We suggest a concept to achieve a strain insensitive gas sensor by creating an orientation between single particles inside the composite. Implementing this results into existing gas sensors will improve the measurement quality and reliability of sensors on flexible substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Hydrogen peroxide and glucose biosensor based on silver nanowires synthesized by polyol process

Silver nanowires synthesized through a polyol process using polyvinylpyrrolidone as protection (PVP-AgNWs) were used as a new electrode material for constructing a sensor. Hydrogen peroxide (H(2)O(2)) and glucose were used as analytes to demonstrate the sensor performance of the PVP-AgNWs. It is found that the PVP-AgNWs-modified glassy carbon electrode (PVP-AgNWs/GCE) exhibits remarkable catalytic performance toward H(2)O(2) reduction. This sensor has a fast amperometric response time of less than 2 s and the catalytic current is linear over the concentration of H(2)O(2) ranging from 20 μM to 3.62 mM (R = 0.998) with a detection limit of 2.3 μM estimated on a signal-to-noise ratio of 3. A glucose biosensor was constructed by immobilizing glucose oxidase (GOD) onto the surface of the PVP-AgNWs/GCE. The resultant glucose biosensor can be used for glucose detection in human blood serum with a sensitivity of 15.86 μA mM(-1) cm(-2) and good selectivity and stability.     

Fabrication of multiwalled carbon nanotubes/polyaniline modified Au electrode for ascorbic acid determination

An ascorbate oxidase (AsOx) (E.C.1.10.3.3) purified from Lagenaria siceraria fruit was immobilized covalently onto a carboxylated multiwalled carbon nanotubes and polyaniline (c-MWCNT/PANI) layer electrochemically deposited on the surface of an Au electrode. The diffusion coefficient of ascorbic acid was determined as 3.05 × 10(-4) cm(2) s(-1). The behavior of different electrolytes on electro-deposition was also studied. An ascorbate biosensor was fabricated using a AsOx/c-MWCNT/PANI/Au electrode as a working electrode, Ag/AgCl (3 M/saturated KCl) as standard and Pt wire as an auxiliary electrode connected through a potentiostat. Linear range, response time and detection limit were 2-206 μM, 2 s and 0.9 μM respectively. The biosensor showed optimum response at pH 5.8 and in a broader temperature range (30-45 °C), when polarized at +0.6 V. The biosensor was employed for determination of ascorbic acid level in sera, fruit juices and vitamin C tablets. The sensor was evaluated with 91% recovery of added ascorbic acid in sera and 6.5% and 11.4% within and between batch coefficients of variation respectively for five serum samples. There was a good correlation (r = 0.98) between fruit juice ascorbic acid values by the standard 2,6-dichlorophenolindophenol (DCPIP) method and the present method. The enzyme electrode was used 200 times over a period of two months, when stored at 4 °C. The biosensor has advantages over earlier enzyme sensors in that it has no leakage of enzyme, due to the covalent coupling of enzyme with the support, lower response time, wider working range, higher storage stability and no interference by serum substances.     

Synthesis of Ferrocene Based Naphthoquinones and its Application as Novel Non‐enzymatic Hydrogen Peroxide

At present, a highly sensitive hydrogen peroxide (H₂O₂) sensor is fabricated by ferrocene based naphthaquinone derivatives as 2,3‐Diferrocenyl‐1,4‐naphthoquinone and 2‐bromo‐3‐ferrocenyl‐1,4‐naphthoquinone. These ferrocene based naphthaquinone derivatives are characterized by H‐NMR and C‐NMR. The electrochemical properties of these ferrocene based naphthaquinone are investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) on modified glassy carbon electrode (GCE). The modified electrode with ferrocene based naphthaquinone derivatives exhibits an improved voltammetric response to the H₂O₂ redox reaction. 2‐bromo‐3‐ferrocenyl‐1,4‐naphthoquinone show excellent non‐enzymatic sensing ability towards H₂O₂ response with a detection limitation of 2.7 μmol/L a wide detection range from 10 μM to 400 μM in H₂O₂ detection. The sensor also exhibits short response time (1 s) and good sensitivity of 71.4 μA mM^?1 cm^?2 and stability. Furthermore, the DPV method exhibited very high sensitivity (18999 μA mM^?1 cm^?2) and low detection limit (0.66 μM) compared to the CA method. Ferrocene based naphthaquinone derivative based sensors have a lower cost and high stability. Thus, this novel non‐enzyme sensor has potential application in H₂O₂ detection.     

Highly Selective Nanostructured Electrochemical Sensor Utilizing Densely Packed Ultrathin Gold Nanowires Film

The number of studies conducted about nonenzymatic electrochemical sensors has increased in recent years due to the development of more stable and robust electrodes using noble metals. One of the key aspects for achieving high sensing performance including detection limit and sensitivity is the design of electrode architecture. Herein, we report a new electrochemical sensing platform featuring ultrathin standing gold nanowires (AuNWs) for nonenzymatic detection of hydrogen peroxide (H₂O₂). The use of AuNWs resulted in an increased electron transfer efficiency due to the higher active surface area compared to traditional gold film electrodes. This sensor demonstrates good selectivity, reproducibility, a linear range up to 49.5 mM of H₂O₂ with a sensitivity of 0.185±0.003 mAmM^?1cm^?2 and a limit of detection of 111 μM. The biological relevance of this sensor was tested in cell culture media to illustrate the performance of the proposed sensing electrode in complex biological media.     

一步原位还原法制备WS2@Au量子点复合物及其传感应用

电化学传感器界面改造是提升其检测性能的重要途径.其中,增强电化学传感界面的生物相容性和导电性,是电化学传感器发展遇到的一个重大挑战.本文基于一步原位还原法制备的WS2@Au量子点(WS2@AuQDs),对玻碳电极表面进行功能化,用于氧化还原酶的固定,实现了高性能生物传感的构建.借助WS2@Au QDs良好的生物相容性及...     

A novel palygorskite-modified carbon paste amperometric sensor for catechol determination

A palygorskite-modified carbon paste electrode (CPE) was constructed using graphite powder mixed with palygorskite particles. Compared with the unmodified CPE, the resulting palygorskite-modified CPE remarkably increases the peak currents of catechol, and greatly lowers the peak potential separation. Therefore, the palygorskite exhibits catalytic activity to catechol and significantly improves the determining sensitivity. The electrocatalytic activity of palygorskite is attributed to its high adsorption capability and the –OH groups on its surface, which plays an important role in the electron transfer between the modified CPE and the catechol in the solution. The sensor shows a linear response range between 5 and 100 μM catechol with a correlation coefficient of 0.998. The detection limit was calculated as 0.57 μM (s/n = 3).     

Back‐to‐Back Screen‐Printed Electroanalytical Sensors: Extending the Potential Applications of the Simplistic Design

In our previous paper (Analyst, 2014 , 139, 5339) we introduced the concept of the back‐to‐back electrochemical design where the commonly overlooked back of screen‐printed electrodes are utilised to provide electroanalytical enhancements in screen‐printed electroanalytical sensors. In this configuration the overall sensor comprises of a flexible polyester substrate which has a total of two working, counter and reference electrodes present on the sensor, with a set of electrodes on each side of the substrate. The sensors are designed to allow for a commonly shared electrical connection to the potentiostat and do not require any specialised connections. In this paper we demonstrate proof‐of‐concept extending the electroanalytical utility of the back‐to‐back screen‐printed electrode sensors to bulk modified single‐walled carbon‐nanotubes and electrocatalytic cobalt phthalocyanine microband electrodes. The electroanalytical applications of these novel electrode configuration are exemplified towards the sensing of dopamine, capsaicin and hydrazine. This paper demonstrates the versatility of the back‐to‐back configuration where different surface modifications can be readily employed giving rise to enhancements in sensor performance.     

Graphene Paper Decorated with a 2D Array of Dendritic Platinum Nanoparticles for Ultrasensitive Electrochemical Detection of Dopamine Secreted by Live Cells

To circumvent the bottlenecks of non‐flexibility, low sensitivity, and narrow workable detection range of conventional biosensors for biological molecule detection (e.g., dopamine (DA) secreted by living cells), a new hybrid flexible electrochemical biosensor has been created by decorating closely packed dendritic Pt nanoparticles (NPs) on freestanding graphene paper. This innovative structural integration of ultrathin graphene paper and uniform 2D arrays of dendritic NPs by tailored wet chemical synthesis has been achieved by a modular strategy through a facile and delicately controlled oil–water interfacial assembly method, whereby the uniform distribution of catalytic dendritic NPs on the graphene paper is maximized. In this way, the performance is improved by several orders of magnitude. The developed hybrid electrode shows a high sensitivity of 2 μA cm^?2 μm ^?1, up to about 33 times higher than those of conventional sensors, a low detection limit of 5 nm, and a wide linear range of 87 nm to 100 μm . These combined features enable the ultrasensitive detection of DA released from pheochromocytoma (PC 12) cells. The unique features of this flexible sensor can be attributed to the well‐tailored uniform 2D array of dendritic Pt NPs and the modular electrode assembly at the oil–water interface. Its excellent performance holds much promise for the future development of optimized flexible electrochemical sensors for a diverse range of electroactive molecules to better serve society.     

Highly Ordered 3D Porous Graphene Sponge for Wearable Piezoresistive Pressure Sensor Applications

Wearable sensors with excellent flexibility and sensitivity have emerged as a promising field for healthcare, electronic skin, and so forth. Three-dimensional (3D) graphene sponges (GS) have emerged as high-performance piezoresistive sensors; however, problems, such as limited flexibility, high cost, and low sensitivity, remain. Meanwhile, device-level wearable pressure sensors with GS have rarely been demonstrated. In this work, highly ordered 3D porous graphene sponges (OPGSs) were first successfully prepared and controlled through an emulsion method, and then a device-level wearable pressure sensor with high flexibility and sensitivity was assembled with a gold electrode and polydimethylsiloxane into a reliable package. The pH values were carefully controlled to form a stable emulsion and the OPGSs showed a highly ordered 3D structure with ultralow density, high porosity, and conductivity; this resulted in a gauge factor of 0.79–1.46, with 50 % compression strain and excellent long-term reproducibility over 500 cycles of compression–relaxation. Moreover, the well-packaged pressure sensor devices exhibited ultrahigh sensitivity to detect human motions, such as wrist bending, elbow bending, finger bending, and palm flexing. Thus, the developed pressure sensors exhibited great potential in the fields of human-interactive applications, biomechanical systems, electronic skin, and so forth.     

Ferrite Nanocomposite Based Electrochemical Sensor: Characterization,Voltammetric and Amperometric Studies for Electrocatalytic Detection of Formaldehyde in Aqueous Media

Development of nanocomposite based electrochemical sensors for detection of toxic chemicals describes an environmentally benign strategy for monitoring the health of ecosystem. Herein, we reported in situ preparation of graphitic carbon nitride (g-C₃N₄) decorated Ag₂S/NiFe₂O₄ nanocomposite sensor by facile precipitation method. The electrochemical studies demonstrated efficient electrocatalytic activity of ternary nanocomposite pasted glassy carbon electrode (g-C₃N₄@Ag₂S/NiFe₂O₄/GCE) for selective detection of formaldehyde. Moreover, fabricated sensor exhibit rapid amperometric response with excellent selectivity, remarkable sensitivity (1681 μA mmol L⁻¹ cm⁻²) and lower detection limit (LOD: 1.63 μmol L⁻¹). It is noteworthy to mention that sensor exhibits good operational and long-term storage stability.