A GdW10@PDA-CAT Sensitizer with High-Z Effect and Self-Supplied Oxygen for Hypoxic-Tumor Radiotherapy

Anticancer treatment is largely affected by the hypoxic tumor microenvironment (TME), which causes the resistance of the tumor to radiotherapy. Combining radiosensitizer compounds and O₂ self-enriched moieties is an emerging strategy in hypoxic-tumor treatments. Herein, we engineered GdW₁₀@PDA-CAT (K₃Na₄H₂GdW₁₀O₃₆·2H₂O, GdW₁₀, polydopamine, PDA, catalase, CAT) composites as a radiosensitizer for the TME-manipulated enhancement of radiotherapy. In the composites, Gd (Z = 64) and W (Z = 74), as the high Z elements, make X-ray gather in tumor cells, thereby enhancing DNA damage induced by radiation. CAT can convert H₂O₂ to O₂ and H₂O to enhance the X-ray effect under hypoxic TME. CAT and PDA modification enhances the biocompatibility of the composites. Our results showed that GdW₁₀@PDA-CAT composites increased the efficiency of radiotherapy in HT29 cells in culture. This polyoxometalates and O₂ self-supplement composites provide a promising radiosensitizer for the radiotherapy field.     

Antioxidant Activity of Acanthopanax senticosus Flavonoids in H2O2-Induced RAW 264.7 Cells and DSS-Induced Colitis in Mice

The redox reaction is a normal process of biological metabolism in the body that leads to the production of free radicals. Under conditions such as pathogenic infection, stress, and drug exposure, free radicals can exceed normal levels, causing protein denaturation, DNA damage, and the oxidation of the cell membrane, which, in turn, causes inflammation. Acanthopanax senticosus (A. senticosus) flavonoids are the main bioactive ingredients with antioxidant function. H₂O₂-treated RAW 264.7 cells and DSS-induced colitis in mice were used to evaluate the antioxidant properties of A. senticosus flavonoids. The results show that A. senticosus flavonoids can significantly downregulate the levels of ROS and MDA in H₂O₂-treated RAW 264.7 cells and increase the levels of CAT, SOD, and GPx. A. senticosus flavonoids can also increase the body weights of DSS-induced colitis mice, increase the DAI index, and ameliorate the shortening of the colon. ELISA experiments confirmed that A. senticosus flavonoids could reduce the level of MDA in the mouse serum and increase the levels of SOD, CAT, and GPx. Histopathology showed that the tissue pathological changes in the A. senticosus flavonoid group were significantly lower than those in the DSS group. The Western blot experiments showed that the antioxidant capacity of A. senticosus flavonoids was accomplished through the Nrf2 pathway. In conclusion, A. senticosus flavonoids can relieve oxidative stress in vivo and in vitro and protect cells or tissues from oxidative damage.     

Enhanced DNA Oxidative Damage by Acrylonitrile and Protecting DNA from Damage with an Outer Catalase Layer: an Electrochemical Study

In the present article, an in vitro model system to mimic the transformation of acrylonitrile (ACN) from nontoxic to toxic in DNA damage and the protective function of catalase (Cat) against DNA damage in real biosystems was investigated electrochemically with (CS/DNA)₃‐AQDS and (CS/DNA)₃‐AQDS‐Cat multilayer films, where CS and AQDS represent chitosan and electroactive probe 9,10‐anthraquinone‐2,6‐disulfonate, respectively. The electroactive AQDS was loaded into (CS/DNA)₃ layer‐by‐layer films mainly by intercalation of AQDS into the double‐helix structure of DNA and acted as the probe to detect the damage of DNA in the films. While only ACN could not induce DNA damage, the enhancement of ACN on DNA damage in the presence of Fenton reagents (Fe(II)/EDTA/H₂O₂) was observed. In addition, Cat in the (CS/DNA)₃‐AQDS‐Cat films could protect DNA from damage to a considerable extent in both Fenton and Fenton+ACN solutions because of the high efficiency of Cat in decomposition of H₂O₂.     

Biodegradable Polycaprolactone (PCL) Nanosphere Encapsulating Superoxide Dismutase and Catalase Enzymes

Biodegradable polycaprolactone (PCL) nanosphere encapsulating superoxide dismutase (SOD) and catalase (CAT) were successfully synthesized using double emulsion (w/o/w) solvent evaporation technique. Characterization of the nanosphere using dynamic light scattering, field emission scanning electron microscope, and Fourier transform infrared spectroscopy revealed a spherical-shaped nanosphere in a size range of 812?±?64 nm with moderate protein encapsulation efficiency of 55.42?±?3.7 % and high in vitro protein release. Human skin HaCat cells were used for analyzing antioxidative properties of SOD- and CAT-encapsulated PCL nanospheres. Oxidative stress condition in HaCat cells was optimized with exposure to hydrogen peroxide (H₂O₂; 1 mM) as external stress factor and verified through reactive oxygen species (ROS) analysis using H₂DCFDA dye. PCL nanosphere encapsulating SOD and CAT together indicated better antioxidative defense against H₂O₂-induced oxidative stress in human skin HaCat cells in comparison to PCL encapsulating either SOD or CAT alone as well as against direct supplement of SOD and CAT protein solution. Increase in HaCat cells SOD and CAT activities after treatment hints toward uptake of PCL nanosphere into the human skin HaCat cells. The result signifies the role of PCL-encapsulating SOD and CAT nanosphere in alleviating oxidative stress.     

Functionalization of graphene with Prussian blue and its application for amperometric sensing of H2O2

As a two-dimensional carbon material with high surface area and conductivity, graphene shows great promise for designing composite nanomaterials to achieve high-performance electrochemical devices. In this work, we prepared graphene-based nanocomposite material by electrochemically depositing Prussian blue (PB) nanoparticles on the surface of graphene. Fourier transform infrared spectra, SEM, and cyclic voltammetry were used to characterize the successful immobilization of PB. Compared with PB films and graphene sheets, the PB–graphene composite films showed the largest current response to the reduction of H₂O₂, probably due to the synergistic effects between graphene sheets and PB nanoparticles. Therefore, a fast and highly sensitive amperometric sensor for H₂O₂ was obtained with a detection sensitivity of 1.6 μA μM^?1 H₂O₂ per cm² and a linear response range of 50～5,000 μM. The detection limit of H₂O₂ was 20 nM at a signal-to-noise ratio of 3. These obtained results are much better than those reported for carbon nanotubes-based amperometric sensors.     

Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

We report a supramolecular strategy for promoting the selective reduction of O₂ for direct electrosynthesis of H₂O₂. We utilized cobalt tetraphenylporphyrin (Co‐TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co‐PB‐1(6) bearing six Co‐TPP subunits connected through twenty‐four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co‐rPB‐1(6). Both Co‐PB‐1(6) and Co‐rPB‐1(6) cages produce 90–100 % H₂O₂ from electrochemical ORR catalysis in neutral pH water, whereas the Co‐TPP monomer gives a 50 % mixture of H₂O₂ and H₂O. Bimolecular pathways have been implicated in facilitating H₂O formation, therefore, we attribute this high H₂O₂ selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.     

A novel Prussian blue‐magnetite composite synthesized by self‐template method and its application in reduction of hydrogen peroxide

A novel Prussian blue (PB)‐Fe₃O₄ composite has been prepared for the first time by self‐template method using PB as the precursor. According to this method, Fe₃O₄ nanoparticles distributed uniformly on the surface of PB cube. The feed ratio of sodium acetate to PB has been proved to be a key factor for magnetic properties and electro‐catalysis properties of the composite. Under the experimental conditions, the saturation magnetization value (Ms) of PB‐Fe₃O₄–2 composite was 22 emug^?1, while the Ms value of other samples reduced. The composites also showed a good peroxidase‐like activity for the oxidation of substrate 3,3,5,5‐tetramethylbenzidine (TMB) in the presence of H₂O₂. The catalytic reduction of hydrogen peroxide capacity was PB‐Fe₃O₄–1> PB‐Fe₃O₄–2> PB‐Fe₃O₄–3> PB‐Fe₃O₄–0, which confirmed the Fe(II) centres in PB surface and Fe₃O₄ nanoparticles had synergistic effect on catalytic reduction of hydrogen peroxide.     

Synergetic effect of Prussian blue film with gold nanoparticle graphite–wax composite electrode for the enzyme-free ultrasensitive hydrogen peroxide sensor

Enzyme-free amperometric ultrasensitive determination of hydrogen peroxide (H₂O₂) was investigated using a Prussian blue (PB) film-modified gold nanoparticles (AuNPs) graphite–wax composite electrode. A stable PB film was obtained on graphite surface through 2-aminoethanethiol (AET)-capped AuNPs by a simple approach. Field emission scanning electron microscope studies results in formation of PB nanoparticle in the size range of 60–80 nm. Surface modification of PB film on AET–AuNPs–GW composite electrode was confirmed by Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy studies. Highly sensitive determination of H₂O₂ at a peak potential of ?0.10 V (vs. SCE) in 0.1 M KCl PBS, pH?=?7.0) at a scan rate of 20 mVs^?1 with a sensitivity of 23.58 μA/mM was observed with the modified electrode using cyclic voltammetry. The synergetic effect of PB film with AuNPs has resulted in a linear range of 0.05 to 7,800 μM with a detection limit of 0.015 μM for H₂O₂ detection with the present electrode. Chronoamperometric studies recorded for the successive additions of H₂O₂ with the modified electrode showed an excellent linearity (R ²?=?0.9932) in the range of 4.8?×?10^?8 to 7.4?×?10^?8 M with a limit of detection of 1.4?×?10^?8 M. Selective determination of H₂O₂ in presence of various interferents was successfully demonstrated. Human urine samples and stain remover solutions were also investigated for H₂O₂ content.     

Prussian Blue‐Modified Titanate Nanotubes: A Novel Nanostructured Catalyst for Electrochemical Reduction of Hydrogen Peroxide

Prussian blue (PB) modified titanate nanotubes (PB‐TiNT) have been synthesized by the reaction of Fe²⁺‐modified TiNT with hexacyanoferrate(III) ions. The rate constant for heterogeneous catalytic reaction between PB‐TiNT and H₂O₂ was found to be k=2×10⁴ dm³ mol^?1 s^?1, which is an order of magnitude higher than the values of k reported for conventionally prepared, electrochemically deposited PB films. On the PB‐TiNT modified electrode with subnanomolar surface concentration of PB (Γ(PB)=2.8×10^?11 mol/cm²), a stable, reproducible and linear response towards H₂O₂ was obtained in the concentration range 0.02–4 mM, with the sensitivity of 0.10 AM^?1 cm^?2 at ?150 mV.     

Redox Dyshomeostasis Strategy for Hypoxic Tumor Therapy Based on DNAzyme-Loaded Electrophilic ZIFs

Redox homeostasis is one of the main reasons for reactive oxygen species (ROS) tolerance in hypoxic tumors, limiting ROS-mediated tumor therapy. Proposed herein is a redox dyshomeostasis (RDH) strategy based on a nanoplatform, FeCysPW@ZIF-82@CAT Dz, to disrupt redox homeostasis, and its application to improve ROS-mediated hypoxic tumor therapy. Once endocytosed by tumor cells, the catalase DNAzyme (CAT Dz) loaded zeolitic imidazole framework-82 (ZIF-82@CAT Dz) shell can be degraded into Zn²⁺ as cofactors for CAT Dz mediated CAT silencing and electrophilic ligands for glutathione (GSH) depletion under hypoxia, both of which lead to intracellular RDH and H₂O₂ accumulation. These “disordered” cells show reduced resistance to ROS and are effectively killed by ferrous cysteine-phosphotungstate (FeCysPW) induced chemodynamic therapy (CDT). In vitro and in vivo data demonstrate that the pH/hypoxia/H₂O₂ triple stimuli responsive nanocomposite can efficiently kill hypoxic tumors. Overall, the RDH strategy provides a new way of thinking about ROS-mediated treatment of hypoxic tumors.     

Cytoprotective effect of selenium polysaccharide from Pleurotus ostreatus against H2O2-induced oxidative stress and apoptosis in PC12 cells

One main fraction of Selenium-enriched Pleurotus ostreatus (P. ostreatus) polysaccharide (Se-POP-1) was extracted and purified by DEAE-52 and sephadex G-100. Se-POP-1 was an approximate homogenous polysaccharide with an average molecular weight of 1.62 × 10⁴ Da, and mainly composed of glucose, mannose and galactose, with molar ratio of 5.30:1.55:2.14. The absorption peaks at 941 cm^?1 and 1048 cm^?1 in FT-IR analysis were ascribed as C-O-Se and Se=O bonds. Pr-treatment of Se-POP-1 (400 μg/mL) increased the cell survival of H₂O₂-stimulated PC12 cells and inhibited intrinsic apoptosis and oxidative stress in H₂O₂-stimulated PC12 cells via limiting DNA degradation and decreasing the reactive oxygen species (ROS) generation. In addition, up-regulation of anti-apoptotic protein Bcl-2, down- regulation of pro-apoptotic protein Bax, cleaved caspase 3, and cytochrome c were also observed. Se-POP-1 presented an obvious effect to alleviate oxidative damage and apoptosis in PC12 cells induced by H₂O₂. Therefore, Se-POP-1 possessed potent antioxidant and biological activities with the ability to prevent oxidation via scavenging ROS and free radicals in cells. It could be developed as organic selenium dietary supplement and functional food.     

Functionalization of Single‐Walled Carbon Nanotubes with Cubic Prussian Blue and Its Application for Amperometric Sensing

In this work, we synthesized electroactive cubic Prussian blue (PB) modified single‐walled carbon nanotubes (SWNTs) nanocomposites using the mixture solution of ferric‐(III) chloride and potassium ferricyanide under ambient conditions. The successful fabrication of the PB‐SWNTs nanocomposites was confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV‐vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and cyclic voltammetry (CV). PB nanocrystallites are observed to be finely attached on the SWNTs sidewalls in which the SWNTs not only act as a carrier of PB nanocrystallites but also as Fe(III)‐reducer. The electrochemical properties of PB‐SWNTs nanocomposites were also investigated. Using the electrodeposition technique, a thin film of PB‐SWNTs/chitosan nanocomposites was prepared onto glassy carbon electrode (GCE) for the construction of a H₂O₂ sensor. PB‐SWNTs/chitosan nanocomposites film shows enhanced electrocatalytic activity towards the reduction of H₂O₂ and the amperometric responses show a linear dependence on the concentration of H₂O₂ in a range of 0.5–27.5 mM and a low detection limit of 10 nM at the signal‐to‐noise ratio of 3. The time required to reach the 95% steady state response was less than 2 s. CV studies demonstrate that the modified electrode has outstanding stability. In addition, a glucose biosensor is further developed through the simple one‐step electrodeposition method. The observed wide concentration range, high stability and high reproducibility of the PB‐SWNTs/chitosan nanocomposites film make them promising for the reliable and durable detection of H₂O₂ and glucose.     

Electrochemical detection of benzo(a)pyrene and related DNA damage using DNA/hemin/nafion–graphene biosensor

A novel electrochemical biosensor, DNA/hemin/nafion–graphene/GCE, was constructed for the analysis of the benzo(a)pyrene PAH, which can produce DNA damage induced by a benzo(a)pyrene (BaP) enzyme-catalytic product. This biosensor was assembled layer-by-layer, and was characterized with the use of cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and atomic force microscopy. Ultimately, it was demonstrated that the hemin/nafion–graphene/GCE was a viable platform for the immobilization of DNA. This DNA biosensor was treated separately in benzo(a)pyrene, hydrogen peroxide (H₂O₂) and in their mixture, respectively, and differential pulse voltammetry (DPV) analysis showed that an oxidation peak was apparent after the electrode was immersed in H₂O₂. Such experiments indicated that in the presence of H₂O₂, hemin could mimic cytochrome P450 to metabolize benzo(a)pyrene, and a voltammogram of its metabolite was recorded. The DNA damage induced by this metabolite was also detected by electrochemical impedance and ultraviolet spectroscopy. Finally, a novel, indirect DPV analytical method for BaP in aqueous solution was developed based on the linear metabolite versus BaP concentration plot; this method provided a new, indirect, quantitative estimate of DNA damage.     

Self‐Assembled Prussian Blue Nanoparticles Based Electrochemical Sensor for High Sensitive Determination of H2O2 in Acidic Media

In this paper, self‐assembled Prussian blue nanoparticles (PBNPs) on carbon ceramic electrode (CCE) were developed as a high sensitive hydrogen peroxide (H₂O₂) electrochemical sensor. The PBNPs film was prepared by a simple dipping method. The morphology of the PBNPs‐modified CCE was characterized by scanning electron microscopy (SEM). The self‐assembled PB film exhibited sufficient mechanical, electrochemical stability and high sensitivity in compare with other PB based H₂O₂ sensors. The sensor showed a good linear response for H₂O₂ over the concentration range 1 μM–0.26 mM with a detection limit of ca. 0.7 μM (S/N=3), and sensitivity of 754.6 mA M^?1 cm^?2. This work demonstrates the feasibility of self‐assembled PBNPs‐modified CCE for practical sensing applications.     

Protective Effect of Resveratrol on Immortalized Duck Intestinal Epithelial Cells Exposed to H2O2

Resveratrol is a polyphenolic compound with anti-oxidation effects. The mechanisms underlying the antioxidant effects of resveratrol in duck intestinal epithelial cells remain unclear. The protective effects of resveratrol against oxidative stress induced by H₂O₂ on immortalized duck intestinal epithelial cells (IDECs) were investigated. IDECs were established by transferring the lentivirus-mediated simian virus 40 large T (SV40T) gene into small intestinal epithelial cells derived from duck embryos. IDECs were morphologically indistinguishable from the primary intestinal epithelial cells. The marker protein cytokeratin 18 (CK18) was also detected in the cultured cells. We found that resveratrol significantly increased the cell viability and activity of catalase and decreased the level of intracellular reactive oxygen species and malondialdehyde, as well as the apoptosis rate induced by H₂O₂ (p < 0.05). Resveratrol up-regulated the expression of NRF2, p-NRF2, p-AKT, and p-P38 proteins and decreased the levels of cleaved caspase-3 and cleaved caspase-9 and the ratio of Bax to Bcl-2 in H₂O₂-induced IDECs (p < 0.05). Our findings revealed that resveratrol might alleviate oxidative stress by the PI3K/AKT and P38 MAPK signal pathways and inhibit apoptosis by altering the levels of cleaved caspase-3, cleaved caspase-9, Bax, and Bcl-2 in IDECs exposed to H₂O₂.     

Prussian blue modified glassy carbon electrodes-study on operational stability and its application as a sucrose biosensor

Stabilisation of electrochemically deposited Prussian blue (PB) films on glassy carbon (GC) electrodes has been investigated and an enhancement in the stability of the PB films is reported if the electrodes are treated with tetrabutylammonium toluene-4-sulfonate (TTS) in the electrochemical activation step following the electrodeposition. A multi-enzyme PB based biosensor for sucrose detection was made in order to demonstrate that PB films can be coupled with an oxidase system. A tri-enzyme system, comprising glucose oxidase, mutarotase and invertase, was crosslinked with glutaraldehyde and bovine albumin serum on the PB modified glassy carbon electrode. The deposited PB operated as an electrocatalyst for electrochemical reduction of hydrogen peroxide, the final product of the enzyme reaction sequence. The electrochemical response was studied using flow injection analysis for the determination of sucrose, glucose and H₂O₂. The optimal concentrations of the immobilisation mixture was standardised as 8 U of glucose oxidase, 8 U of mutarotase, 16 U of invertase, 0.5% glutaraldehyde (0.025 μl) and 0.5% BSA (0.025 mg) in a final volume of 5 μl applied at the electrode surface (0.066 cm²). The biosensor exhibited a linear response for sucrose (4-800 μM), glucose (2-800 μM) and H₂O₂ (1-800 μM) and the detection limit was 4.5, 1.5 and 0.5 μM for sucrose, glucose and H₂O₂, respectively. The sample throughput was ca. 60 samples h⁻¹. An increase in the operational and storage stability of the sucrose biosensor was also noted when the PB modified electrodes were conditioned in phosphate buffer containing 0.05 M TTS during the preparation of the PB films.     

Cytotoxic Mechanism of Sphaerodactylomelol,an Uncommon Bromoditerpene Isolated from Sphaerococcus coronopifolius

Marine natural products have exhibited uncommon chemical structures with relevant antitumor properties highlighting their potential to inspire the development of new anticancer agents. The goal of this work was to study the antitumor activities of the brominated diterpene sphaerodactylomelol, a rare example of the dactylomelane family. Cytotoxicity (10–100 µM; 24 h) was evaluated on tumor cells (A549, CACO-2, HCT-15, MCF-7, NCI-H226, PC-3, SH-SY5Y, SK-ML-28) and the effects estimated by MTT assay. Hydrogen peroxide (H₂O₂) levels and apoptosis biomarkers (membrane translocation of phosphatidylserine, depolarization of mitochondrial membrane potential, Caspase-9 activity, and DNA condensation and/or fragmentation) were studied in the breast adenocarcinoma cellular model (MCF-7) and its genotoxicity on mouse fibroblasts (L929). Sphaerodactylomelol displayed an IC₅₀ range between 33.04 and 89.41 µM without selective activity for a specific tumor tissue. The cells’ viability decrease was accompanied by an increase on H₂O₂ production, a depolarization of mitochondrial membrane potential and an increase of Caspase-9 activity and DNA fragmentation. However, the DNA damage studies in L929 non-malignant cell line suggested that this compound is not genotoxic for normal fibroblasts. Overall, the results suggest that the cytotoxicity of sphaerodactylomelol seems to be mediated by an increase of H₂O₂ levels and downstream apoptosis.     

Antioxidant Activity of Ruthenium Cyclopentadienyl Complexes Bearing Succinimidato and Phthalimidato Ligands

In these studies, we investigated the antioxidant activity of three ruthenium cyclopentadienyl complexes bearing different imidato ligands: (η⁵-cyclopentadienyl)Ru(CO)₂-N-methoxysuccinimidato (1), (η⁵-cyclopentadienyl)Ru(CO)₂-N-ethoxysuccinimidato (2), and (η⁵-cyclopentadienyl)Ru(CO)₂-N-phthalimidato (3). We studied the effects of ruthenium complexes 1–3 at a low concentration of 50 µM on the viability and the cell cycle of peripheral blood mononuclear cells (PBMCs) and HL-60 leukemic cells exposed to oxidative stress induced by hydrogen peroxide (H₂O₂). Moreover, we examined the influence of these complexes on DNA oxidative damage, the level of reactive oxygen species (ROS), and superoxide dismutase (SOD) activity. We have observed that ruthenium complexes 1–3 increase the viability of both normal and cancer cells decreased by H₂O₂ and also alter the HL-60 cell cycle arrested by H₂O₂ in the sub-G1 phase. In addition, we have shown that ruthenium complexes reduce the levels of ROS and oxidative DNA damage in both cell types. They also restore SOD activity reduced by H₂O₂. Our results indicate that ruthenium complexes 1–3 bearing succinimidato and phthalimidato ligands have antioxidant activity without cytotoxic effect at low concentrations. For this reason, the ruthenium complexes studied by us should be considered interesting molecules with clinical potential that require further detailed research.     

An Electrochemical Nanosensor for Monitoring the Dynamics of Intracellular H2O2 Upon NADH Treatment

Reactive oxygen species (ROS)-based therapeutic strategies play an important role in cancer treatment. However, in situ, real-time and quantitative analysis of intracellular ROS in cancer treatment for drug screening is still a challenge. Herein we report one selective hydrogen peroxide (H₂O₂) electrochemical nanosensor, which is prepared by electrodeposition of Prussian blue (PB) and polyethylenedioxythiophene (PEDOT) onto carbon fiber nanoelectrode. With the nanosensor, we find that the level of intracellular H₂O₂ increases with NADH treatment and that increase is dose-dependent to the concentration of NADH. High-dose of NADH (above 10 mM) can induce cell death and intratumoral injection of NADH is validated for inhibiting tumor growth in mice. This study highlights the potential of electrochemical nanosensor for tracking and understanding the role of H₂O₂ in screening new anticancer drug.     

Improvement of Selectivity and Stability of Amperometric Detection of Hydrogen Peroxide Using Prussian Blue‐PAMAM Supramolecular Complex Membrane as a Catalytic Layer

A novel hydrogen peroxide (H₂O₂) sensor was fabricated by using a submonolayer of 3‐mercaptopropionic acid (3‐MPA) adsorbed on a polycrystalline gold electrode further reacted with poly(amidoamine) (PAMAM) dendrimer (generation 4.0) to obtain a film on which Prussian Blue (PB) was later coordinated to afford a mixed and stable electrocatalytic layer for H₂O₂ reduction. On the basis of the electrochemical behaviors, atomic force microscopy (AFM) and X‐ray photoelectron spectra (XPS), it is suggested that the PB molecules are located within the dendritic structure of the surface attached PAMAM dendrimers. It was found that the PB/PAMAM/3‐MPA/Au modified electrode showed an excellent electrocatalytic activity for H₂O₂ reduction. The effects of applied potential and pH of solution upon the response of the modified electrode were investigated for an optimum analytical performance. Even in the presence of dissolved oxygen, the sensor exhibited highly sensitive and rapid response to H₂O₂. The steady‐state cathodic current responses of the modified electrode obtained at ?0.20 V (vs. SCE) in air‐saturated 0.1 mol L^?1 phosphate buffer solution (PBS, pH 6.50) showed a linear relationship to H₂O₂ concentration ranging from 1.2×10^?6 mol L^?1 to 6.5×10^?4 mol L^?1 with a detection limit of 3.1×10^?7 mol L^?1. Performance of the electrode was evaluated with respected to possible interferences such as ascorbic acid and uric acid etc. The selectivity, stability, and reproducibility of the modified electrode were satisfactory.