A wearable sweat electrochemical aptasensor based on the Ni-Co MOF nanosheet-decorated CNTs/PU film for monitoring of stress biomarker.

Monitoring cortisol, a hormone released by the adrenal cortex in response to stress, is essential to evaluate the endocrine response to stress stimuli. While the current cortisol sensing methods require large laboratory settings, complex assay, and professional personnel. Herein, a novel flexible and wearable electrochemical aptasensor based on a Ni-Co metal-organic frameworks (MOF) nanosheet-decorated carbon nanotubes (CNTs)/polyurethane (PU) film is developed for rapid and reliable detection of cortisol in sweat. First, the CNTs/PU (CP) film was prepared by a modified wet spinning technology, and the CNTs/polyvinyl alcohol (PVA) solution was thermally deposited on the surface of CP film to form the highly flexible CNTs/PVA/CP (CCP) film with excellent conductivity. Then aminated Ni-Co MOF nanosheet prepared by a facile solvothermal method was conjugated with streptavidin and modified on the CCP film. Biofunctional MOF can effectively capture cortisol aptamer due to its excellent specific surface area. In addition, the MOF with peroxidase activity can catalytic oxidization of hydroquinone (HQ) by hydrogen peroxide (H2O2), which could amplify the peak current signal. The catalytic activity of Ni-Co MOF was substantially suppressed in the HQ/H2O2 system due to the formation of the aptamer-cortisol complex, which reduced the current signal, thereby realizing highly sensitive and selective detection of cortisol. The sensor has a linear range of 0.1-100 ng/mL and a detection limit of 0.032 ng/mL. Meanwhile, the sensor showed high accuracy for cortisol detection under mechanical deformation conditions. More importantly, the prepared MOF/CCP film based three-electrode was assembled with the polydimethylsiloxane (PDMS) substrate, and the sweat-cloth was used as the sweat collection channel to fabricate a wearable sensor patch for monitoring of cortisol in volunteers' sweat in the morning and evening. This flexible and non-invasive sweat cortisol aptasensor shows great potential for quantitative stress monitoring and management.

Determination of ribavirin by molecularly imprinted electrochemical sensors using pyrro-1-propionyl-alaninoyl-chitooligosaccharide and pyrrole as bifunctional monomers on Prussian blue-gold nanocomposite films.

Herein, we developed a highly sensitive imprinted electrochemical sensor for the trace detection of ribavirin (RBV) using pyrrole (PYR) and pyrro-1-propionyl-alaninoyl-chitooligosaccharides (PPACO) as bifunctional monomers on Prussian blue-gold nanocomposite films. PPACO had strong molecular effect on RBV molecule and was selected by quantitative calculations. After the deposition of the Prussian blue-gold nanocomposite on a glassy carbon electrode (GCE) surface, a 4-aminothiophenol layer successfully self-assembled on the surface. Subsequently, the molecularly imprinted membrane (MIM) was subjected to electrochemical polymerization on the electrode surface using RBV as the template and PPACO and PYR as the two monomers. After eluting the RBV molecules from the MIM, the fabricated RBV-MIM/Fn-Au-PB/GCE exhibited the specific adsorption of RBV. Under optimal conditions, differential pulse voltammetry (DPV) was used to measure the performance of the synthesized sensor, which exhibited a linear relationship between the decreasing peak current and RBV concentration from 0.015 to 3.5 µM with a low detection limit of 3 nM (S/N = 3). As a proof of concept, RBV-MIM/Fn-Au-PB/GCE was also applied to monitor the RBV content in RBV granules. It showed a satisfactory recovery (96.5-99.2%) with a relative standard deviation of less than 3.5% (n = 5), and thus, we believe it has potential for practical applications.

An integrated and flexible PDMS/Au film-based electrochemical immunosensor via Fe-Co MOF as a signal amplifier for alpha fetoprotein detection.

Ultrasensitive determination of tumor marker (TM) is of great significance in cancer prevention and diagnosis. Traditional TM detection methods involve large instrumentation and professional manipulation, which complicate the assay procedures and increase the cost of investment. To resolve these problems, an integrated electrochemical immunosensor based on the flexible polydimethylsiloxane/gold (PDMS/Au) film with Fe-Co metal-organic framework (Fe-Co MOF) as a signal amplifier was fabricated for ultrasensitive determination of alpha fetoprotein (AFP). First, gold layer was deposited on the hydrophilic PDMS film to form the flexible three-electrode system, and then the thiolated aptamer for AFP was immobilized. Afterward, the aminated Fe-Co MOF possessing high peroxidase-like activity and large specific surface area was prepared by a facile solvothermal method, and subsequently the biofunctionalized MOF could effectively capture biotin antibody (Ab) to form MOF-Ab as a signal probe and amplify the electrochemical signal remarkably, thereby realizing highly sensitive detection of AFP with a wide linear range of 0.01-300 ng/mL and a low detection limit of 0.71 pg/mL. In addition, the PDMS based-immunosensor showed good accuracy for assaying of AFP in clinical serum samples. The integrated and flexible electrochemical immunosensor based on the Fe-Co MOF as a signal amplifier demonstrates great potential for application in the personalized point-of-care (POC) clinical diagnosis.

Polymer surface ligand and silica coating induced highly stable perovskite nanocrystals with enhanced aqueous fluorescence for efficient Hg2+ and glutathione detection.

The poor stability and aqueous-quenching of fluorescence of perovskite nanocrystals (NCs) hinder their application in bio-detection and bio-imaging. Herein, through the synergistic effects of polymer surface ligand and silica encapsulation, highly stable and enhanced aqueous fluorescent CsPbBr3-mPEG@SiO2 NCs were synthesized and used as a novel "on-off-on" fluorescent probe for highly sensitive and selective detection of mercury ions (Hg2+) and glutathione (GSH) in aqueous solutions. The effects of the methoxypolyethylene glycol amine (mPEG-NH2) ligand and silica encapsulation on the stability and aqueous fluorescence of the CsPbBr3 NCs were studied. It indicated that the aqueous fluorescence of perovskite NCs was increased by 2.59 times. The water stability was also greatly improved, with the NCs maintaining 73% of their original fluorescence after storage for 30 days in water. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FT-IR) analyses further demonstrated that the NCs were successfully passivated by mPEG-NH2 and silica. The fluorescence of the CsPbBr3-mPEG@SiO2 nanocrystals was effectively quenched by Hg2+ which is attributed to the electron transfer process between NCs and Hg2+. Then, through the interaction between Hg2+ and GSH, the restoration of fluorescence for CsPbBr3-mPEG@SiO2 was realized. The "on-off-on" fluorescent probe can be used for the detection of Hg2+ and GSH with a low detection limit of 0.08 nM and 0.19 µM, respectively. It also shows a fast response time and high accuracy for practical sample detection. The simple and sensitive fluorescent probe of CsPbBr3-mPEG@SiO2 shows great potential in environmental and biological sensing.

A Dual-emitting Two-dimensional Nickel-based Metal-organic Framework Nanosheets: Eu3+/Ag+ Functionalization Synthesis and Ratiometric Sensing in Aqueous Solution.

Using two-dimensional (2D) nickel-based metal organic framework (Ni-MOF) nanosheets as a matrix, Eu3+ and Ag+ were incorporated to synthesize Ag/Eu@Ni-MOF with double luminescence centers of Eu3+ ion (615 nm) and organic ligand (524 nm). And a ratiometric luminescence sensor is constructed based on Ag/Eu@Ni-MOF for sensitive detection of biothiols in aqueous solutions. The dual-emissive fluorescence properties can be tuned by changing the amounts of Ag+ ions doping. The results of temperature and pH effects on the fluorescence of Ag/Eu@Ni-MOF indicates that the Ag/Eu@Ni-MOF is a temperature-sensitive material and the fluorescence of Ag/Eu@Ni-MOF can keep stable over a wide pH range. Due to the binding of -SH in cysteine (Cys) and glutathione (GSH) with Ag+, the ligand luminescence was significantly inhibited by weakening the Ag + influence on the energy transfer process in the MOFs. Therefore, ratiometric fluorescent sensing of biomolecular thiols was realized based on the dual-emission Ag/Eu@Ni-MOF. More importantly, the fluorescence color change can be observed with naked eyes to realize visual detection. The ratiometric fluorescent sensor exhibits high performance for Cys and GSH detection with a wide linear range of 5-250 µM and a relatively low detection limit of 0.20 µM and 0.17 µM, respectively. Furthermore, the biothiols content in human serum was determined with satisfactory results. It proves the Ni-MOF nanosheets can be used as a stable matrix for construction luminescent MOFs for the first time, and validate the great potential of Ag/Eu@Ni-MOF as a ratiometric fluorescent probe for point-of-care testing (POCT) in disease diagnosis.

Flexible paper-based Ni-MOF composite/AuNPs/CNTs film electrode for HIV DNA detection.

It is very important to develop a rapid, simple, low cost point-of-care (POC) method for the early diagnosis of pathogens. In this work, a flexible paper-based electrode based on nickel metal-organic framework (Ni-MOF) composite/Au nanoparticles/carbon nanotubes/polyvinyl alcohol (Ni-Au composite/CNT/PVA) was constructed to detect target human immunodeficiency virus (HIV) DNA by DNA hybridization using methylene blue (MB) as a redox indicator. The CNT/PVA and Ni-Au composite were deposited on the cellulose membrane by vacuum filtration and drop-coating method in turn to obtain Ni-Au composite/CNT/PVA (CCP) film electrode. Compared to the CNT/PVA film electrode, CCP film electrode makes a higher loading of the probe DNA for its large specific surface area and conjugated π-electron system that can provide hydrogen bond sources to achieve interactions between MOF and single-stranded DNA, which improves the sensitivity for detecting target DNA. The variation of peak current for MB molecules adsorbed onto DNA before and after hybridization with HIV DNA was monitored. Electrochemical results proved that the CCP film maintained stable electrochemical property even after bending 200 times or stretching under different strains from 0% to 20%. The flexible paper electrode showed excellent sensing performance with a linear range of 10 nM-1 µM and a low detection limit of 0.13 nM. The target HIV DNA was successfully detected even in complex serum samples using the flexible CCP film electrode. Therefore, the simple and inexpensive flexible paper-based MOF composite film electrode can also be utilized for other pathogens POC diagnosis.

A highly-specific photoelectrochemical platform based on carbon nanodots and polymers functionalized organic-inorganic perovskite for cholesterol sensing.

Herein, we reported the introduction of carbon nanodots (CNDs) and polyvinylidene fluoride (PVDF) as additives into perovskite CH3NH3PbI3 through in situ synthesis to prepare PVDF-CH3NH3PbI3@CNDs composite, which demonstrated improved water tolerance and mechanical stability. The application of PVDF-CH3NH3PbI3@CNDs for photoelectrochemical sensing was then explored. A molecularly imprinted polymer (MIP) that could specifically recognize cholesterol (CHO) was anchored to PVDF-CH3NH3PbI3@CNDs via a simple thermal polymerization process, followed by elution with hexane. A label-free and sensitive photoelectrochemical method for CHO detection was achieved by using the MIPs@PVDF-CH3NH3PbI3@CNDs platform. The detection limit for CHO was 2.1 × 10-14 mol/L, lower than most of the existing CHO detection methods. In our perception, this platform can be extended to numerous other analytes. This research result may provide a new understanding to improve the performance and broaden the application range of organic-inorganic perovskites.

A near-infrared fluorescent sensor based on the architecture of low-toxic Ag2S quantum dot and MnO2 nanosheet for sensing glutathione in human serum sample.

Near-infrared (NIR) emitting Ag2S quantum dots (QDs) are excellent fluorescent nanoprobes for bioassays with low toxicity. A novel fluorescent sensing platform which employing NIR fluorescent Ag2S QDs and MnO2 2D nanosheets as NIR emitters and quenchers is designed for rapid and selective determination of glutathione (GSH). A facile and efficient approach was demonstrated for the synthesis of NIR fluorescent Ag2S QDs with the emission of 845 nm. Then the NIR fluorescent nanoprobe of Ag2S QDs-MnO2 nanosheets is obtained by adsorbing Ag2S QDs onto the surface of MnO2 nanosheets which have atomically thick two-dimensional structure and high specific surface area. And the NIR fluorescence of Ag2S QDs is quenched by the MnO2 nanosheets. The presence of GSH could reduce MnO2 to Mn2+ that results in the restoration of NIR fluorescence for Ag2S QDs. The NIR fluorescent nanoprobe could be used for highly selective detection of GSH. Also a low detection limit of 60 µmol/L was obtained. Because NIR fluorescence of the Ag2S QDs can efficiently reduce the interferences from background scattering and autofluorescence. The NIR fluorescent nanoprobe was directly applied to monitor the GSH level in human serum sample with high accuracy and precision.

Stretchable Electrochemical Biosensing Platform Based on Ni-MOF Composite/Au Nanoparticle-Coated Carbon Nanotubes for Real-Time Monitoring of Dopamine Released from Living Cells.

Existing electrochemical biosensing platforms, using traditional rigid and unstretchable electrodes, cannot monitor the biological signaling molecules released by cells in a mechanically deformed state in real time. Here, a stretchable and flexible electrochemical sensor was developed based on nickel metal-organic framework composite/Au nanoparticle-coated carbon nanotubes (Ni-MOF composite/AuNPs/CNTs) for sensitive detection of dopamine (DA) released by C6 living cells in real time. A Ni-MOF composite was obtained by introducing Ni, NiO, and a carbon frame onto the surface of two-dimensional (2D) Ni-MOF nanosheets using an efficient one-step calcination method. The hybrid of Ni-MOF composite/AuNPs/CNTs that deposited on the poly(dimethylsiloxane) (PDMS) film endowed the sensor with excellent electrochemical performance with a wide linear range of 50 nM to 15 µM and a high sensitivity of 1250 mA/(cm2 M) and also provided the sensor with desirable stability against mechanical deformation. Furthermore, the stretchable electrode also displayed good cellular compatibility while C6 living cells can be cultured and proliferated on it with strong adhesion. Then, the DA released by C6 living cells with chemical induction in both natural and stretched states was monitored using our stretchable and flexible electrochemical sensor in real time. This indicates that our new design of flexible Ni-MOF composite/AuNPs/CNTs/PDMS (NACP) film electrodes provides more opportunities for the detection of chemical signals released from cells and soft living organisms even under mechanically deformed states.

A flexible rGO electrode: a new platform for the direct voltammetric detection of salicylic acid.

Flexible sensors are of considerable interest for the development of wearable smart miniature devices. This work reported a flexible electrochemical platform based on reduced graphene oxide (rGO) for the detection of salicylic acid (SA). The free-standing and flexible rGO electrode was prepared via a simple extruded process. Dynamic mechanical deformation and bending studies illustrated the resilience and compliance of the flexible electrode against extreme mechanical deformations. Quantitative analysis of SA was performed by using differential pulse voltammetry (DPV) with this flexible rGO electrode. Linearity ranges for SA were obtained from 1.0 × 10-10 M to 1.0 × 10-5 M with the detection limit of 2.3 × 10-11 M (S/N = 3). This strategy provided a new insight into the design and application of flexible electrodes. It will extend the applications of rGO in sensing, bio-electronics and lab-on-chip devices.

Dual Functional Molecular Imprinted Polymer-Modified Organometal Lead Halide Perovskite: Synthesis and Application for Photoelectrochemical Sensing of Salicylic Acid.

This work reports the synthesis of dual functional molecularly imprinted polymer (MIP)-modified organometal lead halide perovskite (CH3NH3PbI3) and its application for photoelectrochemical (PEC) bioanalysis of salicylic acid (SA). Specifically, the CH3NH3PbI3 was encapsulated into the MIPs via a simple thermal polymerization process on the indium tin oxide (ITO) glass, and the as-obtained MIPs/CH3NH3PbI3/ITO electrode was characterized by various techniques, which revealed that the MIPs could not only stabilize CH3NH3PbI3 but also improve the electron-hole separation efficiency of CH3NH3PbI3 under light illumination. In the detection of model analyte SA, the PEC sensor, with numerous amounts of recognition sites to SA, exhibited desirable performance in terms of good sensitivity, selectivity, stability, and feasibility for real sample analysis. This work not only featured the use of MIPs/CH3NH3PbI3 for PEC detection of SA but also provided a new horizon for the design and implementation of functional polymers/perovskite materials in the field of PEC sensors and biosensors.

A promising voltammetric biosensor based on glutamate dehydrogenase/Fe3O4/graphene/chitosan nanobiocomposite for sensitive ammonium determination in PM2.5.

A novel NH4+ voltammetric electrochemical biosensor was constructed by immobilizing glutamate dehydrogenase (GLDH)/Fe3O4/graphene (GR)/chitosan (CS) nanobiocomposite onto a glassy carbon electrode (GCE). On the GLDH/Fe3O4/GR/CS/GCE, GLDH catalyzed the reversible reaction, i.e., the reductive amination of α-ketoglutaric acid and the oxidative deamination of L-glutamate. The electrons produced in the enzymatic reactions were transferred to the surface of the electrode via the [Fe(CN)6]3-/4- couple, which helped for the amplification of the electrochemical signal. The electrochemical detection of NH4+ was based on the fact that the enhanced response current was proportional to the NH4+ concentration. Owing to the combination of the advantages of the synergistic effects of Fe3O4 nanospheres, GR and CS, a promising platform for NH4+ sensing was provided. Under optimum conditions, the introduced biosensor had a linear range of 0.4-2.0 µM for NH4+ with the detection and quantification limits of 0.08 and 0.27 µM, respectively. Moreover, the biosensor exhibited good sensitivity and excellent reproducibility. It could retain 91.8% of its original response after two weeks of storage at 4 °C, suggesting satisfactory stability. Additionally, the proposed biosensor was successfully applied to detect NH4+ levels in PM2.5 samples, indicating its feasibility for application in NH4+monitoring in the environmental fields.

Facile one-step solvothermal synthesis of active carbon/BiOI microspheres with enhanced visible light-driven photocatalytic activity in the reduction of Cr(vi).

Active carbon/BiOI microspheres were first prepared using a facile one-step solvothermal route from Bi(NO3)3·5H2O, KI, active carbon, and ethylene glycol. The phase structure, morphology, and optical properties of the as-prepared products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy, and UV-visible diffuse reflectance spectra. HRTEM mapping results showed that within the composites, active carbon particles dispersed well onto BiOI spheres. The apparent variations in binding energies and photocurrent measurement results verified that the interactions between both components are strong. As a consequence, these active carbon/BiOI composites exhibit an enhanced photocatalytic reduction activity of Cr(vi) under visible light (λ > 420 nm) irradiation when compared with pure BiOI. This work can strengthen the application of BiOI-based micromaterials in treating wastewater contaminated by highly toxic and intractable Cr(vi).

Visible-light-induced photo-Fenton process for the facile degradation of metronidazole by Fe/Si codoped TiO2.

This work investigated the feasibility and efficiency of a heterogeneous photo-Fenton catalyst, Fe/Si codoped TiO2, for the degradation of metronidazole (MNZ) under visible light irradiation. The Fe/Si codoped TiO2 was prepared via a facile and simple sol-gel solvothermal process followed by annealing at 480 °C for 4 hours. High resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) measurements revealed that the photo-Fenton process did not change the structure, textural and surface morphologies of this catalyst. Elemental mapping results indicated the good dispersion of Fe and Si ions in TiO2. Nitrogen adsorption and desorption measurements indicated that Si doping increased the surface area of the catalysts. The Fe and Si doping narrowed the band gap of TiO2. They also facilitated the transfer of photo-generated electrons from TiO2 to Fe(iii). Under visible light irradiation and the optimum operating conditions, MNZ could be completely degraded in 50 min by this catalyst within a wide pH range. Hydroxyl radicals and holes were verified to be responsible for degrading MNZ. The leaching of iron ions was less than 0.047 ppm even after illuminating the catalyst for 6 hours, indicating the good stability of the Fe/Si codoped TiO2. The as-prepared catalysts with excellent catalytic activity, and remarkable reusability and stability could provide a new insight into the preparation of photocatalysts and have wide applications for antibiotics removal.

A novel sensor for the detection of acetamiprid in vegetables based on its photocatalytic degradation compound.

An electrochemical method for the indirect determination of acetamiprid was studied, using titanium dioxide photocatalysts coupled with a carbon paste electrode. The cyclic voltammetric results indicated that the photocatalytic degradation compound of acetamiprid had electroactivity in neutral solutions. The amount of acetamiprid was further indirectly determined by differential pulse anodic stripping voltammetric analysis as a sensitive detection technique. The experimental parameters were optimized with regard to the photocatalytic degradation time, pH of buffer solution, accumulation potential and accumulation time. Under optimal conditions, the proposed electrochemical method could detect acetamiprid concentrations ranging from 0.01 to 2.0µM, with a detection limit (3S/N) of 0.2nM. Moreover, the proposed method displays excellent selectivity, good reproducibility, and acceptable operational stability and can be successfully applied to acetamiprid determination in vegetable samples with satisfying results.

Fabrication of electrochemical sensor for paracetamol based on multi-walled carbon nanotubes and chitosan-copper complex by self-assembly technique.

An electrochemical sensor for paracetamol based on multi-walled carbon nanotubes and chitosan-copper complex (MWCNTs/CTS-Cu) was fabricated by self-assembly technique. The MWCNTs/CTS-Cu modified GCE showed an excellent electrocatalytic activity for the oxidation of paracetamol, and accelerated electron transfer between the electrode and paracetamol. Under optimal experimental conditions, the differential pulse peak current was linear with the concentration of paracetamol in the range of 0.1-200 µmol L(-1) with a detection limit of 0.024 µmol L(-1). The sensitivity was found to be 0.603 A/mol L(-1). The proposed sensor also showed a high selectivity for paracetamol in the presence of ascorbic acid and dopamine. Moreover, the proposed electrode revealed good reproducibility and stability. The proposed method was successfully applied for the determination of paracetamol in tablet and human serum samples.

Electrochemical detection of nitrate in PM2.5 with a copper-modified carbon fiber micro-disk electrode.

The accurate measurement of nitrate in PM2.5 is essential for a complete understanding of the effects of aerosols on human health, the impact of aerosols on the radiative balance of the earth and the role of aerosols in visibility problems. In this paper, we present a novel, quick, easy, cheap and eco-friendly electroanalytical procedure for the determination of nitrate in PM2.5 samples using a carbon-fiber micro-disk electrode (CFMDE) coupled with square-wave voltammetry (SWV). Under optimal experimental conditions the nitrate SWV response increases linearly with nitrate concentration over a range of 0.003-2.0 mmol L(-1), and the detection limit is 1.10 µmol L(-1) (S/N=3). Nitrate contents in daily PM2.5 of Yangzhou in China were detected successfully by employing this novel method, and the results were compared well with those obtained by using ion chromatography. Then, we detected nitrate in two-hour PM2.5 filter samples via the standard addition method, and the concentrations were applied in an analysis of the daily change of nitrate contained in PM2.5 of Yangzhou. The research in this work indicates that the electrochemical method opens a new opportunity for fast, portable, and sensitive analysis of components in PM2.5.

A derivative photoelectrochemical sensing platform for herbicide acetochlor based on TiO2-poly (3-hexylthiophene)-ionic liquid nanocomposite film modified electrodes.

Nonelectroactive acetochlor can be indirectly determined through the photocatalytical degradation of acetochlor. A derivative visible light photoelectrochemical sensor for indirect detection of the herbicide acetochlor using TiO2-poly(3-hexylthiophene)-ionic liquid nanocomposite is constructed. Poly(3-hexylthiophene) (P3HT) was synthesized via chemical oxidative polymerization with anhydrous FeCl3 as oxidant, 3-hexylthiophene as monomer, chloroform as solvent, and the functional TiO2 nanoparticles were facilely prepared by blending TiO2 nanoparticles and P3HT at room temperature ionic liquid, 1-Butyl-3-methylimidazolium hexafluorophosphate solution. Operational parameters, including the photolysis time, ratios of TiO2 to P3HT, bias voltage and pH of buffer solution have been optimized. Under optimal conditions, the proposed photoelectrochemical method could detect acetochlor ranging from 0.5 to 20 µmol L(-1) with a detection limit of 0.2 nmol L(-1) at a signal-to-noise ratio of 3. The assay results of acetochlor in water samples with the proposed method were in acceptable agreement with those of the gas chromatograph-mass spectrometer (GC-MS) method. The promising sensor opens a new opportunity for fast, portable, and sensitive analysis of acetochlor in environmental samples.