Fast and Effective Turn‐on Paper‐based Phosphorescence Biosensor for Detection of Glucose in Serum

In this study, a turn‐on paper‐based optical analytical system with a rapid, sensitive and quantitative response for glucose was developed. The luminescence sensing material, crystalline iridium(III)‐Zn(II) coordination polymers, or Ir‐Zn_e, was grown electrochemically on stainless steel mesh and then deposited on filter paper. This sensing substrate was subsequently built up under glucose oxidase encapsulated in hydrogel and then immobilized on egg membrane with the layer‐by‐layer method. Once the glucose solution was dropped onto the paper, the oxygen content was depleted simultaneously with a concomitant increase in the phosphorescence of Ir‐Zn_e. The detection limit for glucose was 0.05 mM. The linear dynamic range for the determination of glucose was 0.05–8.0 mM with a correlation coefficient (R²) of 0.9956 (y=68.11 [glucose]?14.72). The response time was about 0.12 s, and the sample volume was less than 5 μL. The effects of mesh size, buffer concentration, pH, enzyme concentration, temperature, and interference, and the stability of the biosensor, have also been studied in detail. Finally, the biosensor was successfully applied to the determination of glucose in human serum.     

Pencil‐Drawn Dual Electrode Detectors to Discriminate Between Analytes Comigrating on Paper‐Based Fluidic Devices but Undergoing Electrochemical Processes with Different Reversibility

A simple method is described to discriminate between analytes comigrating under on‐plate separation conditions, whose electrochemical behavior displays different reversible characters. It is based on the use of dual electrode detectors pencil‐drawn at the end of paper‐based fluidic channels defined by hydrophobic barriers. Simultaneous detection of comigrating species is achieved by applying to the upstream pencil‐drawn working electrode a potential for the oxidation (or reduction) of both analytes, while to the downstream pencil‐drawn working electrode a potential is imposed for the reverse process involving the product of the sole analyte undergoing a reversible enough electrochemical process. The performance of these inexpensive devices was preliminarily optimized by adopting hexacyanoferrate(II) as prototype species undergoing a reversible anodic process at carbon electrodes. They were then used as dual electrode detectors for thin‐layer chromatographic runs conducted on paper‐based microfluidic devices. Two types of synthetic solutions, one containing different contents of dopamine (DA) and ascorbic acid (AA) and the other of paracetamol (PA) and AA, were chosen as model samples. This choice was prompted us by the fact that in both cases these analytes comigrated under the adopted experimental conditions and required similar enough oxidation potentials. Nevertheless, DA and PA underwent reversible enough anodic processes while an irreversible electrochemical reaction is involved in the AA oxidation. Satisfactory results were found for both couples of target analytes, whose simultaneous detection was achieved within 230 s and was characterized by good enough repeatability and sensitivity. In particular, this approach appears to be well suited for the rapid and inexpensive assembling of electrochemical detectors for flow analysis systems.     

Development of Electrochemical Paper‐based Glucose Sensor Using Cellulose‐4‐aminophenylboronic Acid‐modified Screen‐printed Carbon Electrode

The present work describes the fabrication of paper‐based analytical devices (μPADs) by immobilization of glucose oxidase onto the screen printed carbon electrodes (SPCEs) for the electrochemical glucose detection. The sensitivity towards glucose was improved by using a SPCE prepared from homemade carbon ink mixed with cellulose acetate. In addition, 4‐aminophenylboronic acid (4‐APBA) was used as a redox mediator giving a lower detection potential for improvement selectivity. Under optimized condition, the detection limit was 0.86 mM. The proposed device was applied in real samples. This μPAD has many advantages including low sample consumption, rapid analysis method, and low device cost.     

Graphene Quantum Dots‐based Electrochemical Biosensor for Catecholamine Neurotransmitters Detection

An useful electrochemical sensing approach was developed for epinephrine (EP) detection based on graphene quantum dots (GQDs) and laccase modified glassy carbon electrodes (GC). The miniature GC biosensor was designed and constructed via the immobilization of laccase in an electroactive layer of the electrode coated with carbon nanoparticles. This sensing arrangement utilized the catalytic oxidation of EP to epinephrine quinone. The detection process was based on the oxidation of catecholamine in the presence of the enzyme – laccase. With the optimized conditions, the analytical performance demonstrated a high degree of sensitivity −2.9 μA mM⁻¹ cm⁻², selectivity in a broad linear range (1–120×10⁻⁶ M) with detection limit of 83 nM. Moreover, the method was successfully applied for EP determination in labeled pharmacological samples.     

Paper‐Based Electronic Tongue

We present a low cost paper‐based electronic tongue capable of discriminating forged water samples. System comprises of 4 paper‐based potentiometric sensors (sensitive to Cl^?, Na⁺/K⁺, Ca²⁺/Mg²⁺, ) and a traditional Ag/AgCl reference electrode. Different electrode materials and methods of insulation were tested with best results obtained for pencil graphite and lamination. The presented electronic tongue was able to distinguish tap and lake water from mineral water samples (PCA – Principal Component Analysis and KNN ? K‐nearest neighbour). In total 14 different water samples were used in this study. Sensors presented good signal repeatability, selectivity and reasonable sensitivity.     

Nonenzymatic Electrochemical Biosensor Based on Novel Hydrophilic Ferrocene‐terminated Hyperbranched Polymer and its Application in Glucose Detection

We designed a novel water soluble topological structure polymer‐ferrocene‐ terminated hyperbranched polyurethane (HPU‐Fc) with good water solubility. The redox behaviors and the electrochemical kinetics parameters of HPU‐Fcs were explored by cyclic voltammetry (CV) according to electrochemical principle. The topological structure polymer was applied for the design and engineering of non‐enzymatic glucose sensor. The designed sensor showed good response to glucose concentration with good stability, favorable accuracy and high selectivity. The electrode was also used to detect glucose in blood samples, and the glucose contents detected by the electrode were in good agreement with those from the hospital where a common automatic biochemical analyzer (HF240–300) was used. This finding makes HPU‐Fc a promising biosensor for directly sensing glucose.     

Paper‐based solid‐phase microextraction for analysis of 8‐hydroxy‐2’‐deoxyguanosine in urine sample by CE‐LIF

An easy‐to‐do paper‐based solid‐phase microextraction (p‐SPME) was developed for determination of 8‐hydroxy‐2’‐deoxyguanosine (8‐OHdG) in urine sample by CE‐LIF. Small piece of filter paper was used as a solid phase to extract 8‐OHdG from urine sample. Its primary mechanism is based on the hydrogen‐bonding interaction between 8‐OHdG and cellulose molecules. The effects of the pH of the sample solution, extraction time, and temperature on the peak area of the analyte were investigated in order to obtain the optimal p‐SPME conditions. Comparing with the untreated sample, the p‐SPME can significantly reduce the interference to the separation of 8‐OHdG by CE‐LIF. Meanwhile, the p‐SPEM can provide more than three times concentrated effect. The developed method was evaluated according to an FDA guideline for biological analysis. The precisions (RSD%, n = 5) of the peak area and migration time of the analyte at three different concentrations were within 3.02–5.82% and 0.92–1.58%, respectively. The limit of identification of the method is about 5 nM according to the significant difference between two sets of the samples with and without spiking the standard (Student's t ‐test, p < 0.05). Good linearity was obtained in the range of 10–1000 nM (R ²>0.99) based on the standard addition. The recoveries at three different concentrations were within 99.8–103.5%. The results of the real sample analysis are consistent with those reported in our previous paper (Electrophoresis 2014, 35, 1873–1879).     

A Facile Graphene Nanosheets‐based Electrochemical Sensor for Sensitive Detection of Honokiol in Traditional Chinese Medicine

The sensitive detection of honokiol was performed using a graphene nanosheets‐based electrochemical sensor by cyclic voltammogram and a differential pulse anodic stripping voltammogram. Several important parameters such as deposition cycle of reduced graphene oxide, the acidity of the running buffer, accumulation potential and accumulation time were investigated to acquire the optimum conditions. The sensor was further applied to quantification of honokiol in the concentration range from 0.005 to 10 µM with a low detection limit of 1.7 nM. Finally, the sensor successfully determined the content of honokiol in Ageratum Liquid with a satisfied recovery of 98.2 %～99.1 %.     

Amperometric Sniffer for Volatile Amines Based on Paper‐Supported Room Temperature Ionic Liquids Enabling Rapid Assessment of Fish Spoilage

A gas sensors based on a room temperature ionic liquid (RTIL) supported on paper is proposed as amperometric sniffer for monitoring volatile amines (VAs) released from fish samples, in order to gain indication of their state of turning spoiled. It was used as a paper electrochemical detector (PED) for a flow injection system in which controlled headspace volumes in equilibrium with ice‐stored fish samples were directly injected. The performance of this RTIL‐PED sensor was preliminarily tested on synthetic samples of trimethylamine (TMA), dimethylamine (DMA), methylamine (MA) and ammonia (i.e. the main species responsible for the typical flavor of spoiled fish), thus verifying that only TMA, DMA and MA can be detected because NH₃ oxidation occurred beyond the solvent discharge. This notwithstanding, detection of the sole TMA, DMA and MA as a whole turned out to be well suited for the rapid assessment of fish spoilage, since during storage the release enhancement for these amines is largely predominant over that of NH₃. Repeatable (8 % RSD) sharp peaks were detected for all amines above over a wide range (5–1000 nmol) and a detection limit of a little more than 3 nmol was inferred for a signal‐to‐noise ratio of 3. This approach was applied to the detection of VAs released from real fish samples (sardines), in parallel to the determination of their total volatile basic nitrogen (TVBN), which is a conventional indicator frequently adopted for the chemical quality assessment of fish. A substantially satisfactory agreement was found by comparing the data achieved by these two approaches.     

Electrochemical Estrogen Receptor α based Biosensor for Label‐Free Detection of Estradiol

We describe a new electrochemical biosensor based on estrogen receptor α (ER‐α) for label‐free detection of 17β‐estradiol, a model of endocrine‐disrupting compounds. ER‐α is coupled onto the gold electrode through its 6‐His tag and NTA‐copper complex. After interaction of estradiol with ER‐α, the biosensor presents a well‐defined peak at +500 mV due to estradiol oxidation (E17 peak). The linear range of detection is from 1 fM to 1 nM and the detection limit is 1 fM. Good selectivity was obtained for interfering substances at nanomolar level, for concentration of E17 up to 0.1 pM. The E17 was detected in hospital effluents.     

Photopatternable Carbon Electrodes for Chip‐Based Electrochemical Detection

Presented is the preparation and initial characterization of carbonaceous electrodes prepared using photolithographic techniques. The electrodes were created using a graphite doped photoresist mixture which allowed for direct electrode patterning. The electrodes were tested using cyclic voltammetry with a Fe(CN) test solution and were found to exhibit a linear response as per the Randles–Sevick relation. The feasibility of using these electrodes to conduct biological assays was demonstrated with p‐aminophenol, a common analyte in electrochemical ELISAs, using differential pulse voltammetry.     

Open‐circuit Electrochemical Polymerization for the Sensitive Detection of Phenols

We report on a novel electrochemical method for electro‐polymerizing phenols under open‐circuit conditions. The method developed here is simple, sensitive, rapid, and overcomes the well‐documented surface fouling of carbon electrodes by phenols. A pre‐charged disposable graphite pencil electrode (pCGPE) was found to be useful for both phenol sampling and sensing. The pCGPE was prepared by charging the surface of a graphite pencil electrode by applying a cyclic voltammetry electrochemical treatment in a NaOH solution. Phenol sampling was accomplished by immersing the pCGPE into a phenol solution. This method permitted phenol detection with a detection limit of 4.17 nM (0.39 ppt).     

A MgO Nanoparticles Composite Matrix‐Based Electrochemical Biosensor for Hydrogen Peroxide with High Sensitivity

A novel horseradish peroxidase (HRP) electrochemical biosensor based on a MgO nanoparticles (nano‐MgO)‐chitosan (chit) composite matrix was developed. The morphology of nano‐MgO‐chit nanocomposite was examined by scanning electron microscopy (SEM). The interaction between nano‐MgO‐chit nanocomposite matrix and enzyme was characterized with UV‐vis spectra. This proposed composite material combined the advantages of inorganic nanoparticles and organic polymer chit. The HRP immobilized in the nanocomposite matrix displayed excellent electrocatalytic activity to the reduction of H₂O₂ in the presence of hydroquinone as a mediator. The effects of the experimental variables such as solution pH and the working potential were investigated using steady‐state amperometry. The present biosensor (HRP‐modified electrode) had a fast response towards H₂O₂ (less than 10 s), and excellent linear relationships were obtained in the concentration range of 0.1–1300 μM, with a detection limit of 0.05 μM (S/N=3). Moreover, the stability and reproducibility of this biosensor were evaluated with satisfactory results.     

Ultraflexible Screen‐Printed Graphitic Electroanalytical Sensing Platforms

The pursuit of ultraflexible sensors has arisen from the recent implementation of electrochemical sensors into wearable clothing where extensive mechanical stress upon the sensing platform is likely to occur. Such scenarios have witnessed screen‐printed electrodes being incorporated into the waistband of undergarments for the determination of key analytes while others have reported incorporation into a neoprene wetsuit. In these conformations, the substrates which the sensors are printed upon need to be ultraflexible and capable of withstanding extensive individual mechanical stress. Therefore the composition, thickness and its combination of screen‐printed ink require extensive consideration. A common short‐coming within the field of screen‐printed derived sensors is the lack of consideration towards the substrate material employed, and is rather in favour of the development of new electrode geometries and screen‐printing inks. In this paper we explore the screen‐printing of graphite based electroanalytical sensing platforms onto graphic paper commonly used in house‐hold printers, and for the first time both tracing paper and ultraflexible polyester‐based substrates are used. These sensors are electrochemically benchmarked with the redox probes hexaammine‐ruthenium(III) chloride and potassium ferrocyanide(II). The effect of mechanical contortion upon two types of electrode substrates is also performed where it was found that these ultraflexible based polyester‐based electrodes are superior to the previously reported ultraflexible paper electrodes since they can withstand extensive mechanical contortion, yet they still give rise to useful electrochemical performances. Most importantly the ultraflexible polyester electrodes do not suffer from capillary action as observed in the case of paper‐based sensors causing the solution to wick‐up the electrode towards the electrical connections resulting in electrical shorting, therefore compromising the electrochemical measurement; as such this new substrate can be used as a replacement for paper‐based substrates and yet still be resilient to extreme mechanical contortion. A new configuration is also explored using these electrode substrate supports where the working carbon electrode contains the electrocatalyst, cobalt(II) phthalocyanine (CoPC), and is benchmarked towards the electroanalytical sensing of the model analytes citric acid and hydrazine which demonstrate excellent sensing capabilities in comparison to previously reported screen‐printed electrodes.     

A Polymer‐Based Electrochemical DNA Biosensor for Salmonella: Preparation,Characterization and Calibration

In this paper, we present the results of the use of bifunctional polymeric films of polystyrene (10.3 KD–49.5 KD) to anchor oligo sequences of various lengths (15, 35 and 70‐mer). The polymers were prepared by radical polymerization with 4,4′‐azobis(4‐cyanovaleric acid) as initiator and 3‐Carboxy PROXYL to control the molecular weight and polydispersity. They were further modified with N‐hydroxysuccinimide to anchor the (5′‐AmMC₁₂) oligos. The anchoring reaction was done on a polymer‐modified glassy carbon electrode. The probes were hybridized with their ferrocene‐labeled complementary sequences. The hybridization reaction was followed by Osteryoung square wave voltammetry (OSWV). The calibration curve showed a narrow and sharp linear range between (5.7–8.0)×10^?7 M and a detection limit around 0.55 µM.     

Electrochemical Aptasensors for Biological and Chemical Analyte Detection

Aptamers are short length, single-stranded DNA or RNA affinity molecules which interact with any desired targets such as biomarkers, cells, biological molecules, drugs or chemicals with high sensitivity. They have been extensively employed for medical applications due to having more advantages than the antibodies such as easier preparation and modification, higher stability, lower batch-to-batch variability and cost. Moreover, aptamers can be easily integrated efficiently with sensors, biosensors, actuators and other devices. In this review article, different applications of aptamers for biological and chemical molecules detection within the scope of electrochemical methods were presented with recent studies. In addition, the present status and future perspectives for highly-effective aptasensors for specific and selective analyte detection were discussed. As in stated throughout the review, combining of extraordinary properties of aptamers with the electrochemical-based biosensors could have improved the sensitivity of the assay and reduced limit of detection.     

Molecularly Imprinted Electrochemical Sensor for the Detection of Organophosphorus Pesticide Profenofos

The presence of profenofos (PFF) in food has been strictly limited by legislation due to its genotoxic and toxic effects on health. It is therefore very important to establish simple and rapid analytical methods to detect traces of this insecticide. A reusable molecularly imprinted polypyrrole MIP(O-PPy) on a glassy carbon electrode (GCE) has been developed to measure PFF. The PPy was polymerized by cyclic voltammetry (CV) in the presence of template molecules (PFF) in an acidic solution on a GCE. The various experimental parameters such as film thickness, analyte/monomer ratio, and removal/rebinding requirements were examined and optimized. The signal of the redox probe (ferrocyanide/ferrocyanide) was used for the electrochemical detections. All steps of the sensor manufacturing, removal/rebinding of template molecules, and response to different PFF concentrations were tested by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). The MIP sensor was able to detect PFF in the linear ranges of 1.0×10⁻⁹ to 1.0×10⁻⁶ M and 1.0×10⁻⁹ to 5.0×10⁻⁶ M, with detection limits, a signal-to-noise ratio (S/N) of three was used to estimate LOD, of about 1 nM using DPV and EIS, respectively. The MIP (PPy) GCE provided excellent PFF recognition performance and was successfully used to quantify PFF in sweet pepper samples, yielding recoveries not greater than 108 %.     

Electrochemistry on Paper‐based Analytical Devices: A Review

Even though they were introduced less than a decade ago, electrochemical paper‐based devices (ePADs) have attracted widespread attention because of their inherent advantages in many applications. ePADs combine the advantages of microfluidic paper‐based devices (low cost, ease of use, equipment free pumping, etc.) for sample handling and processing with the advantages of sensitive and selective detection provided by electrochemistry. As a result, ePADs provide simplicity, portability, reproducibility, low cost and high selectivity and sensitivity for analytical measurements in a variety of applications ranging from clinical diagnostics to environmental sensing. Herein, recent advances in ePAD development and application are reviewed, focusing on electrode fabrication techniques and examples of applications specially focused on environmental monitoring, biological applications and clinical assays. Finally, a summary and prospective directions for ePAD research are also provided.     

3D Multilayered paper‐ and thread/paper‐based microfluidic devices for bioassays

In this paper we describe the fabrication of novel 3D microfluidic paper‐based analytical devices (3D‐μPADs) and a 3D microfluidic thread/paper‐based analytical device (3D‐μTPAD) to detect glucose and BSA through colorimetric assays. The 3D‐μPAD and 3D‐μTPAD consisted of three (wax, heat pressed wax‐printed paper, single‐sided tape) and four (hole‐punched single‐sided tape, blank chromatography circles, heat‐pressed wax‐printed paper, hole‐punched single‐sided tape containing trifurcated thread) layers, respectively. The saturation curves for each assay were generated for all platforms. For the glucose assay, a solution of glucose oxidase (GOx), horseradish peroxidase, and potassium iodide was flowed through each platform and, upon contact with glucose, generated a yellow‐brown color indicative of the oxidation of iodide to iodine. For the protein assay, BSA was flowed through each device and, upon contact with citrate buffer and tetrabromophenol blue, resulted in a color change from yellow to blue. The devices were dried, scanned, and analyzed yielding a correlation between either yellow intensity and glucose concentration or cyan intensity and BSA concentration. A similar glucose assay, using unknown concentrations of glucose in artificial urine, was conducted and, when compared to the saturation curve, showed good correlation between the theoretical and actual concentrations (percent differences <10%). The development of 3D‐μPADs and 3D‐μTPADs can further facilitate the use of these platforms for colorimetric bioassays.     

Facile Fabrication of a Graphene‐based Electrochemical Biosensor for Glucose Detection

A simple and effective glucose biosensor based on immobilization of glucose oxidase (GOD) in graphene (GR)/Nafion film was constructed. The results indicated that the immobilized GOD can maintain its native structure and bioactivity, and the GR/Nafion film provides a favorable microenvironment for GOD immobilization and promotes the direct electron transfer between the electrode substrate and the redox center of GOD. The electrode reaction of the immobilized GOD shows a reversible and surface‐controlled process with the large electron transfer rate constant (k_s) of 3.42±0.08 s^?1. Based on the oxygen consumption during the oxidation process of glucose catalyzed by the immobilized GOD, the as‐prepared GOD/GR/Nafion/GCE electrode exhibits a linear range from 0.5 to 14 mmol·L^?1 with a detection limit of 0.03 mmol·L^?1. Moreover, it displays a good reproducibility and long‐term stability.