Xiaoyi Yan

Biomimetic sensor based on molecularly imprinted polymer with nitroreductase-like activity for metronidazole detection.

The utility of molecularly imprinted polymer (MIP) as electrochemical sensor often suffers from its limited catalytic efficiency. Here, we proposed an alternative approach by combining the concept of MIP with the use of mimetic enzyme. A metronidazole imprinted polymer with nitroreductase-like activity was successfully achieved via an electrochemical method, where melamine served two purposes: functional monomer of MIP and component of mimetic enzyme. During the imprinting process, the redox-active center, which is responsible for catalysis, was introduced into the imprinted cavities. Accordingly, the imprinted polymer, having both catalysis centers and recognition sites, exhibited enhanced electrocatalytic activity and selectivity. The sensing performances of this metronidazole imprinted biomimetic sensor were evaluated in detail. Results revealed that the response to metronidazole was linear in the concentration range of 0.5-1000 μM, and the detection limit was 0.12 μM (S/N=3). In addition, we applied the proposed sensor to detect metronidazole in an injection solution and the results implied its feasibility for practical application.

Synergetic catalysis based on the proline tailed metalloporphyrin with graphene sheet as efficient mimetic enzyme for ultrasensitive electrochemical detection of dopamine

In this paper, linking with the butoxycarbonyl (BOC) protection of proline, a new tailed metalloporphyrin with many useful active functions, nickel (II) 5-[4-N-(tert-Butoxycarbonyl)-l-prolinecoxylpropyloxy]phenyl-10,15,20-triphenylporphyrin (NiTBLPyP), was designed and synthesized. And the NiTBLPyP polymer (poly(NiTBLPyP)) was successfully obtained via a low-cost electrochemical method and exploited as an efficient mimic enzyme. Subsequently, a noncovalent nanohybrid of poly(NiTBLPyP) with graphene (rGO) sheet (rGO-poly(NiTBLPyP)) was prepared through π-π stacking interaction for the ultrasensitive and selective detection of DA. The nanohybrid was characterized by UV-vis spectroscopy, Fourier transform infrared spectra, Raman spectroscopy, scanning electron microscopy and electrochemical impedance spectroscopy. Due to the excellent electrocatalytic ability of poly(NiTBLPyP) film and aromatic π-π stacking interaction between poly(NiTBLPyP and rGO sheet, the obtained rGO-poly(NiTBLPyP) film exhibited a great synergistic amplification effect toward dopamine oxidation. Under optimum experimental conditions, the logarithm of catalytic currents showed a good linear relationship with that of the dopamine concentration in the range of 0.01-200 μM with a low detection limit of 1.40 nM. With good sensitivity and selectivity, the present method was applied to the determination of DA in real sample and the results was satisfactory. Thus, the rGO-poly(NiTBLPyP) film is one of the promising mimetic enzyme for electrocatalysis and relevant fields.

A novel electrochemical biomimetic sensor based on poly(Cu-AMT) with reduced graphene oxide for ultrasensitive detection of dopamine

A polymerized film of copper-2-amino-5-mercapto-1,3,4-thiadiazole (Cu(II)-AMT) complex (poly(Cu-AMT)) was successfully achieved via a simple and low-cost electrochemical methodology. Subsequently, a noncovalent nanohybrid of poly(Cu-AMT) with reduced graphene oxide (rGO) (rGO-poly(Cu-AMT)) was prepared through π-π stacking interaction as an efficient mimetic enzyme for the ultrasensitive and selective detection of dopamine (DA). The rGO-poly(Cu-AMT) nanocomposites showed considerable mimetic enzyme catalytic activity, which may be attributed to the significant promotion of the electron transfer between the substrate and graphene-based carbon materials, and also the synergistic electrocatalytic effect in mimetic enzyme between rGO sheet and poly(Cu-AMT). The electrocatalytic and sensing performances of the biomimetic sensor based on the rGO-poly(Cu-AMT) nanocomposites were evaluated in detail. The biomimetic sensor enables a reliable and sensitive determination of DA with a linear range of 0.01-40μM and a detection limit of 3.48nM at a signal-to-noise ratio of 3. In addition, we applied the proposed method to detect DA in real sample with satisfactory results. Accordingly, the rGO-poly(Cu-AMT) is one of the promising mimetic enzyme for electrocatalysis and biosensing.

Boosted Sensor Performance by Surface Modification of Bifunctional rht-Type Metal–Organic Framework with Nanosized Electrochemically Reduced Graphene Oxide

The surface and interface could be designed to enhance properties of electrocatalysts, and they are regarded as the key characteristics. This report describes surface modification of a bifunctional rht-type metal-organic framework (MOF, Cu-TDPAT) with nanosized electrochemically reduced graphene oxide (n-ERGO). The hybrid strategy results in a Cu-TDPAT-n-ERGO sensor with sensitive and selective response toward hydrogen peroxide (H2O2). Compared with Cu-TDPAT, Cu-TDPAT-n-ERGO exhibits significantly enhanced electrocatalytic activities, highlighting the importance of n-ERGO in boosting their electrocatalytic activity. The sensor shows a wide linear detection range (4-12 000 μM), and the detection limit is 0.17 μM (S/N = 3) which is even lower than horseradish peroxidase or recently published noble metal nanomaterial based biosensors. Moreover, the sensor displays decent stability, excellent anti-interference performance, and applicability in human serum and urine samples. Such good sensing performance can be explained by the synergetic effect of bifunctional Cu-TDPAT (open metal sites and Lewis basic sites) and n-ERGO (excellent conductive property). It is expected that rht-type MOF-based composites can provide wider application potential for the construction of bioelectronics devices, biofuel cells, and biosensors.

Fabrication of Novel Electrochemical Biosensor Based on Graphene Nanohybrid to Detect H2O2 Released from Living Cells with Ultrahigh Performance

In this paper, a new class of metal-free nanocarbon catalyst-nitrogen (N) and sulfur (S) codoped graphene quantum dot/graphene (NS-GQD/G) hybrid nanosheets-was designed and synthesized for sensitive detection of hydrogen peroxide (H2O2). NS-GQD/G was prepared through two steps. First, graphene quantum dots (GQDs) were self-assembled on graphene nanoplatelets via hydrothermal treatment to constitute hybrid nanosheets, followed by a thermal annealing procedure using the hybrid nanosheets and thiourea to form the NS-GQD/G hybrid nanosheets. This hybrid material possessed high specific surface area, numerous doping sites and edges, and high electrical conductivity, which leads to ultrahigh performance toward H2O2 electrocatalysis reduction. Under the optimal experimental conditions, the proposed H2O2 sensor displayed an extended linear response in the range from 0.4 μM to 33 mM with a low detection limit of 26 nM (S/N = 3). In addition to desirable selectivity, ideal reproducibility, and long-time stability, this H2O2 sensor exhibited desirable performance in detecting H2O2 in the human serum samples and that released from Raw 264.7 cells. Therefore, the novel NS-GQD/G nanocomposite was a promising metal-free material in the fields of electrochemical sensing and bioanalysis.

Petal-like graphene–Ag composites with highly exposed active edge sites were designed and constructed for electrochemical determination of metronidazole

Petal-like graphene–Ag (p-GR–Ag) composites with highly exposed active edge sites were designed and constructed in this work. Petal-like graphene (p-GR) was prepared using a HCl assisted hydrothermal method, which was made of basal planes and highly reactive edge planes to provide more active sites. Then the p-GR can be intentionally utilized as nucleation sites for subsequent Ag nanoparticles (NPs) deposition via modified silver mirror reaction. The composites were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical methods. The combination of zero-dimensional (0D) Ag NPs on a two-dimensional (2D) graphene (GR) support that came into being three-dimensional (3D) structure created a sensor for electrochemical detection of metronidazole. The designed sensor exhibited well bimodal linear behaviour in the metronidazole concentration range between 0.05 to 10 μM and 10 to 4500 μM with a detection limit of 28 nM (S/N = 3). The mechanism and the heterogeneous electron transfer kinetics constant of the metronidazole reduction were discussed in the light of the rotating disk electrode (RDE) experiments. Moreover, validation of the applicability of the prepared sensor was carried out by detecting metronidazole in human urine and local lake water samples.

Catalytic amplification based on hole-transporting materials as efficient metal-free electrocatalysts for non-enzymatic glucose sensing

Hole-transporting materials with tunable structures and properties are mainly applied in organic light-emitting diodes as transport layer. But their catalytic properties as signal amplifiers in biological assays are seldom reported. In this paper, a starburst molecule, 4,4,4″-tri(N-carbazolyl)-triphenylamine (TCT), containing a triphenylamine as the central core and three carbazoles as the peripheral functional groups was designed and synthesized. Subsequently, the hole-transporting material based on the TCT polymer, poly(TCT) (PTCT), was achieved via a low-cost electrochemical method and exploited as an efficient metal-free electrocatalyst for non-enzymatic glucose detection. Here, this hole-transporting material served three purposes: electrochemical recognition (owing to hydrogen bonding interaction and the biomimetic microenvironment created by the polymer), electrocatalysis (owing to the hole-transporting capability of triphenylamine and the catalytic property of carbazole), and signal amplification (owing to energy migration along the conductive polymer backbone). The electrocatalytic and sensing performances of the sensor based on PTCT were evaluated in detail. Results revealed that the PTCT film could efficiently catalyze the oxidation of glucose at a less-positive potential (+0.20 V) in the absence of any enzymes. The response to glucose was linear in the concentration range of 1.0-6000 μM, and the detection limit was 0.20 μM. With good stability and selectivity, the proposed sensor could be feasibly applied to detect glucose in practical samples. The encouraging sensing performances suggest that the hole-transporting material is one of the promising biomimetic catalysts for electrocatalysis and relevant fields.

Signal amplification biosensor based on DNA for ultrasensitive electrochemical determination of metronidazole

An ultrasensitive biosensor based on a glassy carbon electrode (GCE) modified with poly(diallyldimethylammonium chloride)-functionalized graphene (PDDA-GN) and DNA assemblies mainly containing double helix and hairpin structures (DNA) has been employed to detect metronidazole. Due to the excellent synergistic electrocatalytical effect between the PDDA-GN and the DNA, the biosensor remarkably enhanced the electrocatalytic activity compared with the bare GCE toward the reduction of metronidazole in phosphate buffer solution (PBS) (pH = 6.0). The electrode materials were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy (TEM). The electrochemical properties of this composite film (PDDA-GN/DNA) were evaluated by means of cyclic voltammetry (CV) and linear sweep voltammetry (LSV). Under the optimized conditions, the fabricated biosensor showed remarkable signal amplification performance and a linear response to metronidazole in the range of 0.05–100 μM and 400–9500 μM, with a limit of detection as low as 24 nM (signal-to-noise ratio of 3). Moreover, the biosensor displayed excellent stability, reproducibility, and selectivity ability. Furthermore, this biosensor was applied to the detection of metronidazole in urine and lake water with satisfactory results.

Catalytic activity of biomimetic model of cytochrome P450 in oxidation of dopamine

The introduction of electron-withdrawing group into porphyrin molecule as cytochrome P450 model can tune the energy level and have an effect on the electronic structure. In this work, linking with the strong electron-withdrawing fluorine atoms, a starburst dendritic molecule, 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron (III) chloride (FeTFPP), containing a saddle-shaped porphyrin as the central core and four pentafluorophenyl rings as the peripheral functional groups was successfully synthesized. Subsequently, the macrocyclic conjugate polymer film of FeTFPP was achieved via a low-cost electrochemical method and exploited as an efficient mimetic enzyme. Furthermore, a biomimetic sensor was constructed by the poly(FeTFPP) film and graphene (rGO) sheet (rGO-poly(FeTFPP)) for selective and sensitive detection of dopamine (DA). Here, the FeTFPP polymer performs three functions: electrochemical recognition (owing to the hydrogen bonding between the strongly electronegative fluorine atoms and DA), biomimetic microenvironment (owing to interaction between porphyrin core and DA), electrocatalysis (owing to remarkable catalytic ability of iron (III) ion). Under optimum conditions, the response to DA was linear in the concentration range between 0.05 to 300μM, and the detection limit was 0.023μM. In addition, we applied the rGO-poly(FeTFPP) film to detect DA in real samples and the results implied its feasibility for practical application. As a result, it is believed that the rGO-poly(FeTFPP) film is one of the promising biomimetic catalysts for electrocatalysis and relevant fields.

A multidimensional design of charge transfer interfaces via D–A–D linking fashion for electrophysiological sensing of neurotransmitters

Donor-Acceptor (D-A) structure like host-guest pair serves as an organic charge-transfer (C-T) material with pregnant electrochemical and photochemical properties. Phenothiazine, a conjugated nitrogen-sulfur heterocyclic compound with broad pharmaceutical profile, is a strong electron donating system and applied in the synthesis of various classic antipsychotic drugs. In this proposal, a novel D-A molecule, 2,3-bis(4-(10H-phenothiazin-10-yl)phenyl)fumaronitrile (PTBFN), containig a diphenylfumaronitrile as the electrophilic central core and two phenothiazines as the peripheral electron donor functional groups is first designed and synthesized. Subsequently, the C-T layer based on the PTBFN polymer, poly(PTBFN), is obtained via a straightforward electrochemical method and used as an efficient electrocatalyst for dopamine (DA) detection. The logarithm of oxidation peak currents present an outstanding linear response to that of the DA concentration varying from 0.005 to 350μM with a detection limit down to 0.70nM, wherein the interferences of uric acid (UA) and ascorbic acid (AA) could be eliminated effectively. Moreover, the biosensor displays decent stability, excellent selectivity for different interfering compounds and applicability in real samples analysis. The favorable sensing performance suggests that the nontrivial D-A architecture is one of the promising bioaffinity catalysts for electrocatalysis and expected to provide wider application potential for biosensing construction and medical diagnostics.