Enhancing quality evaluation in traditional Chinese medicine: Utilizing dual wavelength fusion fingerprint, electrochemical fingerprint, and DSC fingerprint.

Developing a reliable and effective quality evaluation system for traditional Chinese medicine (TCM) is both challenging and crucial for its advancement. This study employs fingerprinting techniques to establish precise and comprehensive quality control for TCM, taking Xuezhikang capsules as an example and aiming to facilitate the internationalization of TCM. The "double wavelength absorption coefficient ratio fingerprint" and "Reliability theory" are developed to determine the fingerprint peak purity and fingerprint reliability respectively. Subsequently, the dual-wavelength fusion fingerprint was obtained to avoid the limitations of a single wavelength. In addition, an electrochemical fingerprint (ECFP) was obtained to assess the similarity of electroactive components in the sample, and the Differential Scanning Calorimetry quantized fingerprint (DSC QFP) was introduced for thermal analysis. Fingerprint-efficacy correlations between PL-EC* and dual-wavelength fusion fingerprint (DWFFP) provided valuable insights that there are 76.6 % of the fingerprint compounds exhibited electroactivity. Finally, samples were classified into grades 1∼3 by combining DWFFP, ECFP and DSC QFP through the mean method, meeting the evaluation standard (SL-M > 0.9, PL-M between 80 % and 120 %). This study provides valuable information for ensuring the quality of TCM products, which represents a significant step forward in enhancing the reliability and authenticity of TCM products.

Highly selective and sensitive molecularly imprinted sensors for the electrochemical assay of quercetin in methanol extracts of Rubus sanctus and Fragaria vesca.

Quercetin (QUE) is a powerful antioxidant and one of the common phenolic compounds found in plants, vegetables, and fruits, which has shown many pharmacological activities. The complex nature of the matrix in which QUE is found and its importance and potential uses in diverse applications force the researchers to develop selective and sensitive sensors. In the present work, a novel molecularly imprinted polymer (MIP)-based electrochemical sensor was fabricated for the selective and sensitive determination of the QUE in plant extracts and food supplements. Tryptophan methacrylate (TrpMA) was chosen as the functional monomer, whereas the photopolymerization (PP) method was applied using a glassy carbon electrode (GCE). Electrochemical and morphological characterizations of the developed sensor (TrpMA@QUE/MIP-GCE) were performed using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). The linear range of the developed sensor was determined to be in the range of 1.0-25 pM, while the limit of detection (LOD) was calculated to be 0.235 pM. In conclusion, The TrpMA@QUE/MIP-GCE sensor might be classified as a promising platform for selective and sensitive determination of QUE not only in plant extracts but also in commercial food supplements because of its reliability, reproducibility, repeatability, stability, and fast response time.

Determination of the total antioxidant capacity of the Chinese tea based on a novel "peroxidase/zirconium phosphonate"composite electrochemical sensor.

In this work, a novel zirconium phosphonate (ZrPR1R2) was prepared by decorating both the aminoethoxy- group (R1) and the carboxypropyl- group (R2) on the zirconium phosphate layers in order to manipulate further the immobilization of the peroxidase (POD), and an antioxidant biosensor with higher sensitivity was constructed by dropping the POD/ZrPR1R2 composite onto the glassy carbon electrode surface. The activity of the POD/ZrPR1R2 composite was detected by Uv-vis spectra. The direct electrochemical behavior, the electrocatalytic response to dissolved oxygen and hydrogen peroxide, as well as the ability to detect total antioxidant capacity in tea sample were investigated by the methods of cyclic voltammetry. The results indicated that the immobilization of POD in ZrPR1R2 nanosheets matrix enhanced the enzymatic activity, and achieved the fast and direct electron transfer between POD and glassy carbon electrode. Moreover, the POD/ZrPR1R2 composite modified electrode show the electrocatalytic response to hydrogen peroxide in the linear range of 8.8×10-8 to 8.8×10-7 mol L-1, with the detection limit of 3.3×10-8 mol L-1. Attributing to the sensitive response to dissolved oxygen, the total antioxidant capacity can be detected directly in the real tea water by this POD/ZrPR1R2 composite modified electrode.

A photoelectrochemical aptasensor for omethoate determination based on a photocatalysis of CeO2@MnO2 heterojunction for glucose oxidation.

In the present work, we developed a photoelectrochemical aptasensor to determine omethoate (OMT) based on the dual signal amplification of CeO2@MnO2 photocatalysis for glucose oxidation and exonuclease I-assisted cyclic catalytic hydrolysis. CeO2@MnO2 heterojunction material prepared by hydrothermal method was linked with captured DNA (cDNA) and then assembled on the ITO conductive glass to form ITO/CeO2@MnO2-cDNA, which exhibited significant photocurrent response and good photocatalytic performance for glucose oxidation under visible light irradiation, providing the feasibility for sensitive determining OMT. After binding with the aptamer of OMT (apt), the formation of rigid double stranded cDNA/apt kept CeO2@MnO2 away from ITO surface, which ensured a low photocurrent background for the constructed ITO/CeO2@MnO2-cDNA/apt aptasensor. In the presence of target OMT, the restoration of the cDNA hairpin structure and the exonuclease I-assisted cyclic catalytic hydrolysis led to the generation and amplification of measurement photocurrent signals, and allowed the aptasensor to have an ideal quantitative range of 0.01-10.0 nM and low detection limit of 0.0027 nM. Moreover, the aptasensor has been applied for selective determination of OMT in real samples with good precision of the relative standard deviation less than 6.2 % and good accuracy of the recoveries from 93 % to 108 %. What's more, the aptasensor can be used for other target determination only by replacing the captured DNA and corresponding aptamer.

A novel electrochemical sensor based on a molecularly imprinted polymer for highly selective and sensitive determination of rutin from herbal supplements and plant extracts.

Rutin (RUT), a natural flavonoid with various beneficial pharmacological actions such as cardioprotective, antioxidant, anti-inflammatory, neuroprotective, etc., is found in the content of many plants that are consumed daily. Due to the healthful effects, RUT is also included in the composition of various herbal supplement samples. Therefore, it is highly important to develop a sensor with high selectivity and sensitivity to determine RUT in complex samples. In this study, it was aimed to take advantage of the cheap, easy, and sensitive nature of electrochemistry and, in addition, to improve the selectivity. For this purpose, the functional monomer selected in the fabricated molecularly imprinted polymer (MIP) was N-methacryloyl-L-aspartic acid (MA-Asp) while photopolymerization (PP) was applied as the polymerization route. After completing critical optimization steps, the developed sensor (MA-Asp@RUT/MIP-GCE) was characterized electrochemically and morphologically. As a result of analytical performance evaluation in standard solution, the linear response of the sensor was found in the concentration range between 1 and 10 pM with a detection limit of 0.269 pM. The recovery studies from plant extract and commercial herbal supplement samples emphasized accuracy and applicability. In imprinting factor studies figuring out quite good selectivity, molecules with a structure similar to RUT were selected as competitors to prove the affinity of the sensor against RUT. Consequently, the MA-Asp@RUT/MIP-GCE sensor offers a more sensitive and selective method thanks to its indirect analysis approach and also stands out with the diversity of its real sample application compared to other available studies.

Ultrasensitive electrochemiluminescence biosensor based on dual quenching effects of silver nanoclusters and multiple cycling amplification for detection of ATP.

In this work, an electrochemiluminescence (ECL) biosensor based on dual ECL quenching effects of silver nanoclusters (Ag NCs) and multiple cycling amplification was designed to achieve ultrasensitive detection of ATP. The specific recognition of target ATP to aptamer initiated multiple cycling amplification, and a small amount of target was converted into a large number of DNA product chains (S1) by amplification. After S1 opened hairpin DNA 2 (HP2), Ag NCs approached the surface of CdS quantum dots (QDs) modified-electrode by complementary DNA, resulting in a significant decrease of ECL intensity from CdS QDs. The quenching principle is as follows. Firstly, the absorption spectrum of Ag NCs overlaps well with the ECL emission spectrum of CdS QDs, leading to effective ECL resonance energy transfer (ECL-RET); Secondly, Ag NCs could catalyze electrochemical reduction of K2S2O8, leading to consumption of ECL co-reactant and reducing ECL of QDs. The double-ECL quenching achieved ultrasensitive biosensing detection of ATP with a wide range from 1 aM to 1 pM. This present work reported new principle of double-quenching QDs ECL by Ag NCs, and developed a novel ECL biosensor by combining with multiple cycle amplification technique, which has great contribution to the development of QDs ECL and biosensing applications.

Measurement of microRNA-106b as a gastric cancer biomarker based on Zn-BTC MOF label-free genosensor.

Due to the late detection of stomach cancer, this cancer usually causes high mortality. The development of an electrochemical genosensor to measure microRNA 106b (miR-106b), as a gastric cancer biomarker, is the aim of this effort. In this regard, first, 1,3,5-benzenetricarboxylate (BTC) metal-organic frameworks (Zn-BTC MOF) were self-assembled on the glassy carbon electrode and then the probe (ssDNA) was immobilized on it. The morphology Zn-BTC MOF was characterized by SEM, FT-IR, Raman and X-Ray techniques. Zn-BTC MOF as a biosensor substrate has strong interaction with ssDNA. Quantitative measurement of miR-106b was performed by electrochemical impedance spectroscopy (EIS). To perform this measurement, the difference of the charge transfer resistances (ΔRct) of Nyquist plots of the ssDNA probe modified electrode before and after hybridization with miR-106b was obtained and used as an analytical signal. Using the suggested genosensor, it is possible to measure miR-106b in the concentration range of 1.0 fM to 1.0 µM with a detection limit of 0.65 fM under optimal conditions. Moreover, at the genosensor surface, miR-106b can be detected from a non-complementary and a single base mismatch sequence. Also, the genosensor was used to assess miR-106b in a human serum sample and obtained satisfactory results.

Platforms of graphene/MXene heterostructure for electrochemical monitoring of rutin in drug and Tartary buckwheat tea.

The use of two-dimensional heterostructure composite as electrode modification material has become a new strategy to improve the electrocatalytic activity and electroactive sites of electrochemical sensor. Herein, a soluble heterostructure, namely rGO-PSS@MXene, was designed and synthesized by integrating poly (sodium p-styrenesulfonate)-functionalized reduced graphene oxide into MXene nanosheets via ultrasonic method. The interactive heterostructure can effectively alleviate the self-stacking of MXene and rGO, endowing them with superior electron transfer capacity and large specific surface area, thereby producing prominent synergistic electrocatalytic effect towards rutin. In addition, the excellent enrichment effect of rGO-PSS@MXene for rutin also plays an important role through the electrostatic and π-π stacking interactions. The electrochemical characteristics of rutin on the sensor were examined in detail and a sensitive sensing method was proposed. Under optimized conditions, the method showed satisfactory linear relationship for rutin in the concentration range of 0.005-10.0 µM, with limit of detection of 1.8 nM (S/N = 3). The quantitative validation results in herbal medicine and commercial Tartary buckwheat tea were highly consistent with the labeled quantity and the results of HPLC determination, respectively, suggesting the sensor possessed excellent selectivity and accuracy. This proposed strategy for rutin determination is expected to expand the application of MXene heterostructure in electrochemical sensors, and is envisioned as a promising candidate for quality monitoring of drugs and foods.

Low-Cost Plant-Based Metal and Metal Oxide Nanoparticle Synthesis and Their Use in Optical and Electrochemical (Bio)Sensors.

Technological progress has led to the development of analytical tools that promise a huge socio-economic impact on our daily lives and an improved quality of life for all. The use of plant extract synthesized nanoparticles in the development and fabrication of optical or electrochemical (bio)sensors presents major advantages. Besides their low-cost fabrication and scalability, these nanoparticles may have a dual role, serving as a transducer component and as a recognition element, the latter requiring their functionalization with specific components. Different approaches, such as surface modification techniques to facilitate precise biomolecule attachment, thereby augmenting recognition capabilities, or fine tuning functional groups on nanoparticle surfaces are preferred for ensuring stable biomolecule conjugation while preserving bioactivity. Size optimization, maximizing surface area, and tailored nanoparticle shapes increase the potential for robust interactions and enhance the transduction. This article specifically aims to illustrate the adaptability and effectiveness of these biosensing platforms in identifying precise biological targets along with their far-reaching implications across various domains, spanning healthcare diagnostics, environmental monitoring, and diverse bioanalytical fields. By exploring these applications, the article highlights the significance of prioritizing the use of natural resources for nanoparticle synthesis. This emphasis aligns with the worldwide goal of envisioning sustainable and customized biosensing solutions, emphasizing heightened sensitivity and selectivity.

Target-triggered cascade signal amplification in nanochannels: An ingenious strategy for ultrasensitive photoelectrochemical DNA bioanalysis.

Artificial solid-state nanochannels have aroused intense interests in biosensors and bioelectronics because of their special architectures. Herein, we pioneered an ingenious approach of target-triggered cascade signal amplification in porous anodic aluminum oxide (AAO) nanochannels for ultrasensitive photoelectrochemical (PEC) DNA bioanalysis. In the design, AAO nanochannels were modified initially with capture DNA (cDNA) and then incorporated with a photoelectrode, yielding the desired architecture of highly ordered nanoarrays on top of the signal transducer. For target DNA (tDNA) probing, exonuclease III (Exo-III) mediated target recycling (ETR) was first activated to generate plenty of output DNA (oDNA) fragments. After oDNA and the conjugate of Au-labeled probe DNA (Au-pDNA) were anchored within the nanochannels via DNA hybridization, in-situ synthesis of Ag shells on tethered Au nanoparticles was conducted. The resulting large-sized Au@Ag core-shell nanostructure within the nanochannels would cause conspicuous blocking effect to hinder the transportation of electrons accessing the photoelectrode. Since the signal inhibition was directly related to tDNA concentration, an innovative nanochannels PEC DNA assay was exploited and qualified for ultrasensitive detection. The anti-interference ability of this platform was also emphasized by the split AAO membrane for biological incubation without participation of the photoelectrode. This featured nanochannels PEC strategy with cascade amplification launched a novel detecting platform for trace levels of DNA, and it could spark more inspiration for a follow-up exploration of other smart nanochannels PEC bioassays.

Proximity hybridization induced bipedal DNA walker for label-free electrochemical detection of apolipoprotein A4 based on DNA meditated Ag nanoparticles growth.

Apolipoprotein A4 (Apo-A4) is considered as a prospective molecular biomarker for diagnosis of depression due to its neurosynaptic toxicity. Here, we propose a neighboring hybridization induced catalyzed hairpin assembly (CHA) driven bipedal DNA walker that mediates hybridization of Ag nanoparticles (Ag NPs) with DNA probes for highly sensitive electrochemical quantitative detection of Apo-A4. Driven by CHA, this bipedal DNA walker can spread all over the surface of the sensor, induce the HP1-HP2 double chain structure, make the surface of the sensor negatively charged, and adsorb a large number of Ag ions. After chemical reduction with hydroquinone, the Ag NPs formed provide signal tracers for electrochemical dissolution analysis of the target. The Ag NPs formed by chemical reduction of hydroquinone can provide signal traces for electrochemical stripping analysis of target thrombin. The linear range of this method is from 10 pg mL-1 to 1000 ng mL-1, and the detection limit is 5.1 pg mL-1. This enzyme-free and labeling detection method provides a new strategy for rapid clinical detection of Apo-A4 and accurate identification of depression.

Signal "On-Amplified-Off" Strategy Based on Hafnium Dioxide Nanomaterials as Electrochemiluminescence Emitters for Progesterone Detection.

When consumed, excess progesterone (P4)─found in food and the environment─can lead to severe illnesses in humans. Therefore, quantitative analysis of P4 is critical for identifying its hazardous levels. In this study, a novel signal "on-amplified-off" P4 detection mode was proposed, which was based on the utilization of hafnium oxide (HfO2) as a unique electrochemiluminescence (ECL) emitter, produced by calcining UiO-66(Hf). This is the first time that HfO2 has been used as an ECL emitter. HfO2 displayed excellent conductivity and a high specific surface area, allowing it to connect with numerous aptamers and produce a "signal-on" effect. Ni-doped ZnO (Ni-ZnO) acted as a coreaction accelerator, enhancing the ECL strength of HfO2 by generating more tripropylamine radicals. cDNA was labeled with Ni-ZnO, and Ni-ZnO was linked to the aptamer via base complementary pairing, affording "signal-amplified". The presence of the target molecule P4 instigated a specific binding process with the aptamer, triggering the shedding of cDNA-Ni-ZnO and resulting in "signal-off". This novel "on-amplified-off" strategy effectively improved the sensitivity and specificity of P4 analysis, introducing a practical method for detecting biomolecules beyond the scope of this study, which holds immense potential for future applications.

Cerium-Encapsulated SbIII-SeIV-Templating Polyoxotungstate for Electrochemically Sensing Human Multidrug Resistance Gene Segment.

A tower-like SbIII-SeIV-templating polyoxotungstate [H2N(CH3)2]12Na7H3[Ce0.5/Na0.5(H2O)5]2[SbSe2W21O75]2·50H2O (1) was synthesized, whose skeleton is assembled from two prolonged lacunary Dawson [SbSe2W21O75]13- units and two [Ce0.5/Na0.5(H2O)5]2+ linkers. The uncommon [SbSe2W21O75]13- unit can be viewed as a combination of one [SeW6O21]2- group grafted onto a trivacant Dawson [SbSeW15O54]11- subunit. The conductive composite 1-Au@rGO containing 1, gold nanoparticles, and reduced graphene oxide (rGO) was conveniently prepared, using which the 1-Au@rGO-based electrochemical genosensor was constructed for detecting human multidrug resistance gene segment. This work enriches structural types of dual-heteroatom-inserted polyoxometalates and promotes the application of polyoxometalates in genosensors.

Label-Free Electrochemical Aptasensor for Sensitive Detection of Malachite Green Based on AuNPs/MWCNTs@TiO2 Nanocomposites.

This study proposes a label-free aptamer biosensor for the sensitive detection of malachite green(MG) using gold nanoparticles/multi-walled carbon nanotubes @ titanium dioxide(AuNPs/MWCNTs@TiO2). The nanocomposite provides a large surface area and good electrical conductivity, improving current transfer and acting as a platform for aptamer immobilization. The aptamer and the complementary chain(cDNA) are paired by base complementary to form the recognition element and fixed on the AuNPs by sulfhydryl group, which was modified on the cDNA. Since DNA is negatively charged, the redox probe in the electrolyte is less exposed to the electrode surface under the repulsion of the negative charge, resulting in a low-electrical signal level. When MG is present, the aptamer is detached from the cDNA and binds to MG, the DNA on the electrode surface is reduced, and the rejection of the redox probe is weakened, which leads to an enhanced electrical signal and enables the detection of MG concentration by measuring the change in the electrical signal. Under the best experimental conditions, the sensor demonstrates a good linear relationship for the detection of MG from 0.01 to 1000 ng/mL, the limit of detection (LOD)is 8.68 pg/mL. This sensor is stable, specific, and reproducible, allowing for the detection of various small-molecule pollutants by changing the aptamer, providing an effective method for detecting small-molecule pollutants.

MoS2 nanosheets supported on anodic aluminum oxide membrane: An effective interface for label-free electrochemical detection of microRNA.

The interesting adsorption affinity of two-dimensional nanosheets to single stranded over double stranded nucleic acids have stimulated the exploration of these materials in biosensing. Herein, MoS2 nanosheets decorated anodic aluminum oxide (AAO) membrane was simply prepared by suction filtration. The MoS2/AAO hybrid membrane was initially applied to the electrochemical detection of microRNA using let-7a as the model. When let-7a was incubated with its complementary DNA, double stranded DNA-RNA formed and which displayed weak adsorption capability to the hybrid membrane. And thus the steric effect combining the electrostatic repulsion of the backbone phosphate of nucleic acids for [Fe(CN)6]3- transport across the hybrid membrane varied with the concentration of let-7a. In this way, a label-free electrochemical detection method for microRNA was established by monitoring the change of the redox current of [Fe(CN)6]3-. To further improve the detection sensitivity of the method, we proposed two separate strategies focusing on the amplification of the target-induced steric hindrance with DNA nanostructure and the magnification of the electrode sensitivity for [Fe(CN)6]3- by electrode modification. By using the two strategies, the hybrid membrane based-detection method exhibited broad linear range, low detection limit and good selectivity as well as reproducibility. Therefore, this study provided a proof-of-concept for the application of two-dimensional material to nucleic acids detection.

Different Aspects of the Voltammetric Detection of Vitamins: A Review.

Vitamins comprise a group of organic chemical compounds that contribute significantly to the normal functioning of living organisms. Although they are biosynthesized in living organisms, some are also obtained from the diet to meet the needs of organisms, which is why they are characterized as essential chemical compounds. The lack, or low concentrations, of vitamins in the human body causes the development of metabolic dysfunctions, and for this reason their daily intake with food or as supplements, as well as the control of their levels, are necessary. The determination of vitamins is mainly accomplished by using analytical methods, such as chromatographic, spectroscopic, and spectrometric methods, while studies are carried out to develop new and faster methodologies and techniques for their analysis such as electroanalytical methods, the most common of which are voltammetry methods. In this work, a study is reported that was carried out on the determination of vitamins using both electroanalytical techniques, the common significant of which is the voltammetry technique that has been developed in recent years. Specifically, the present review presents a detailed bibliographic survey including, but not limited to, both electrode surfaces that have been modified with nanomaterials and serve as (bio)sensors as well as electrochemical detectors applied in the determination of vitamins.

Development of metal free carbon catalyst derived from Parthenium hysterophorus for the electrochemical detection of dopamine.

Parthenium hysterophorus, one of the seven most hazardous weeds is widely known for its allergic, respiratory and skin-related disorders. It is also known to affect biodiversity and ecology. For eradication of the weed, its effective utilization for the successful synthesis of carbon-based nanomaterial is a potent management strategy. In this study, reduced graphene oxide (rGO) was synthesized from weed leaf extract through a hydrothermal-assisted carbonization method. The crystallinity and geometry of the as-synthesized nanostructure are confirmed from the X-ray diffraction study, while the chemical architecture of the nanomaterial is ascertained through X-ray photoelectron spectroscopy. The stacking of flat graphene-like layers with a size range of ∼200-300 nm is visualized through high-resolution transmission electron microscopy images. Further, the as-synthesized carbon nanomaterial is advanced as an effective and highly sensitive electrochemical biosensor for dopamine, a vital neurotransmitter of the human brain. Nanomaterial oxidizes dopamine at a much lower potential (0.13 V) than other metal-based nanocomposites. Moreover, the obtained sensitivity (13.75 and 3.31 µA µM-1 cm-2), detection limit (0.6 and 0.8 µM), the limit of quantification (2.2 and 2.7 µM) and reproducibility calculated through cyclic voltammetry/differential pulse voltammetry respectively outcompete many metal-based nanocomposites that were previously used for the sensing of dopamine. This study boosts the research on the metal-free carbon-based nanomaterial derived from waste plant biomass.

A portable electrochemical immunosensor for ovarian cancer uses hierarchical microporous carbon material from waste coffee grounds.

A simple label-free electrochemical immunosensor for ovarian cancer (OC) detection was developed using a hierarchical microporous carbon material fabricated from waste coffee grounds (WCG). The analysis method exploited near-field communication (NFC) and a smartphone-based potentiostat. Waste coffee grounds were pyrolyzed with potassium hydroxide and used to modify a screen-printed electrode. The modified screen-printed electrode was decorated with gold nanoparticles (AuNPs) to capture a specific antibody. The modification and immobilization processes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The sensor had an effective dynamic range of 0.5 to 50.0 U mL-1 of cancer antigen 125 (CA125) tumor marker with a correlation coefficient of 0.9995. The limit of detection (LOD) was 0.4 U mL-1. A comparison of the results obtained from human serum analysis with the proposed immunosensor and the results obtained from the clinical method confirmed the accuracy and precision of the proposed immunosensor.

Ultrasensitive electrochemical sensing platform for miRNA-21 detection based on manganese dioxide-gold nanoparticle nanoconjugates coupled with hybridization chain reaction and horseradish peroxidase signal amplification.

In this study, an ultrasensitive electrochemical miRNA-21 biosensor is described. Manganese dioxide-gold nanoparticle (MnO2-Au NP) nanoconjugates were employed as sensing base materials, miRNA-21 was selected as a model analyte, and hybridization chain reaction (HCR) was employed to form long DNA concatemers using two different oligonucleotides with a complementary sequence. Thus, lots of biotin were loaded on DNA concatemers and one of them was labelled with biotin at its 3' terminal. The biosensor was designed as follows: a sulfhydryl-hairpin probe (HP) was first dropped on the surface of the glassy carbon electrode (GCE) modified with MnO2-Au NP nanoconjugates (HP/MnO2-AuNPs/GCE). After it was treated with MCH, the modified electrode was hybridized with miRNA-21, resulting in the loop of HP being opened to form a vertical structure. Subsequently, the modified electrode (miRNA-21/HP/MCH/MnO2-AuNPs/GCE) was incubated with DNA concatemers to form a sandwich structure of HP-miRNA-21-DNA concatemers on the modified electrode surface. Finally, the streptavidin-HRP conjugates were linked to the sandwich structure by specific recognition interaction between biotin and avidin. Differential pulse voltammetry (DPV) was used to measure the electrochemical response of the biosensor in the phosphate-buffered solution (0.10 M PBS, pH 7.0) containing 2.0 mM hydroquinone (HQ) and 1.8 mM H2O2. As a result, a larger reductive signal was obtained at a potential of -0.17 V (vs. SCE). Various experimental conditions were optimized, including solution pH, incubation time, and the amount of DNA concatemers. Under optimal conditions, the biosensor showed good sensing performance, such as a wide linear response range (0.1 fM and 100 nM) and low detection limit (0.063 fM, at S/N = 3). Meanwhile, the biosensor can discriminate single base matched miRNA-21, indicating that the biosensor had good selectivity.

In situ synthesized eRAFT polymers for highly sensitive electrochemical determination of AFB1 in foods and herbs.

An electrochemical sensor based on environmentally friendly eRAFT polymerization was developed for the detection of aflatoxin B1 (AFB1) in food and herbal medicine. Two biological probes, aptamer (Ap) and antibody (Ab), were used to specifically recognize AFB1, and a large number of ferrocene polymers were grafted on the electrode surface by eRAFT polymerization, which greatly improved the specificity and sensitivity of the sensor. The detection limit of AFB1 was 37.34 fg/mL. In addition, the recovery rate was 95.69% to 107.65% and the RSD was 0.84% to 4.92% by detecting 9 spiked samples. The delighted reliability of this method was verified by HPLC-FL.