High-performance,synergistically catalytic luminescent nanozyme for the degradation and detection of endocrine-disrupting chemical diethylstilbestrol

A synergistically catalytic luminescent nanozyme was designed and synthesized for the degradation and enzymatic fluorescence detection of diethylstilbestrol, an endocrine-disrupting environmental pollutant. Because of the integration of cocatalytic Cu²⁺ ion and CeO₂ particle, luminescent Tb³⁺ ion, and functional ligand dipicolinic acid through flexible metal-organic framework structure, this nanozyme has not only the dual functions of luminescence and multienzyme such as laccase and horseradish peroxidase but also synergistically catalytic effect via a regeneration of Cu²⁺ oxidized by CeO₂. The synergistically catalytic effect of nanozyme greatly enhances the degradation of diethylstilbestrol. The resultants sensitized the luminescence of Tb³⁺ ions, which was used to sense the pM level of diethylstilbestrol in environmental samples. Such a high-performance catalytic luminescent nanozyme can be used to replace natural enzymes for the enzyme-based degradations and ultrasensitive assays. The strategy of constructing artificial enzymes directly from functional units provides a new way for developing fit-for-purpose multifunctional artificial enzymes.     

Synthesis of ceria nanoparticles for the catalytic activity of cyclohexene epoxidation and selective detection of nitrite

Based on a few noteworthy features, cerium oxide nanoparticles have gained significance in nanotechnology. The effective microwave combustion method (MCM) and the conventional sol–gel (CRSGM) technologies are used in this study to successfully generate the crystalline CeO₂ nanoparticles (NPs). Additionally, using a variety of spectroscopic and analytical methods, the synthesized CeO₂ NPs are examined to assess to understand their structure and morphology. The XRD patterns of CeO₂ NPs show that the structure exhibits a face-centered cubic lattice. Then, with demonstrated good conversion and selectivity, the impact of the epoxidation reaction of cyclohexene was examined. Finally, it can be said that using CeO₂ nanoparticles is an efficient strategy to increase the catalytic activity toward the epoxidation reaction of cyclohexene. In the presence of acetonitrile as a solvent and H₂O₂ as an oxidant, the catalyst samples utilized in the cyclohexene epoxidation reaction were examined. In this study, the CeO₂ catalyst outperformed all other catalysts in terms of cyclohexene maximal conversion and selectivity. After six prolonged cycles, the conversion of cyclohexene oxidation using CeO₂ NPs shows reasonable recyclability and conversion efficiency, making it the best catalyst for an industrial production application.Additionally, the upgraded CeO₂ nanoparticle electrode for nitrite detection has a linear concentration range (0.02–1200 M), a low detection limit (0.22 M), and a higher sensitivity (1.735 A M⁻¹ cm⁻²). CeO₂ NPs, on the other hand, have a quick response time, excellent sensitivity, and high selectivity. Additionally, the manufactured electrode is used to find nitrite in various water samples. Finally, it can be said that using CeO₂ NPs is an efficient strategy to increase the catalytic activity toward cyclohexene oxidation and nitrite.     

Performance improvement in chemical oxygen demand determination using carbon fiber felt/CeO<Subscript>2</Subscript>-β-PbO<Subscript>2</Subscript> electrode deposited by cyclic voltammetry method

A three-dimensional (3D) structured electrode in which a compact CeO₂-β-PbO₂ particle layer on each carbon fiber in the felt (denoted as CF/CeO₂-β-PbO₂) was fabricated using cyclic voltammetry (CV) method in the presence of CeO₂ nanoparticles in the electrolyte and supposed to be used as a sensor for in situ chemical oxygen demand (COD) detection. It was found that CeO₂ was codeposited with PbO₂ onto the anode, and the deposited crystals were tiny and compacted with each other. The electrochemical behaviors demonstrate that the fabricated CF/CeO₂-β-PbO₂ electrode possesses larger effective surface area, higher electrochemically catalytic activity, and better mechanical stability as compared with the anode without CeO₂ deposited by CV method or constant potential (CP) method. The results of COD determination by the fabricated CF/CeO₂-β-PbO₂ electrode show a sensitivity of (3.0 ± 0.02) × 10^?3 mA cm^?2/mg L^?1, a detection limit of 3.6 mg L^?1 (S/N = 3) and a linear range of 30–8500 mg L^?1 with correlation coefficient (R) of 0.9985 and RSD within 5 %.

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Graphical abstract A 3D CF/CeO₂-β-PbO₂ electrode with CeO₂-β-PbO₂ particle layer on each carbon fiber in the felt was supposed to be used as a sensor for in situ chemical oxygen demand (COD) detection. It was fabricated by cyclic voltammetry (CV) method in the presence of CeO₂ nanoparticles in the electrolyte containing Pb²⁺. It was found that CeO₂ was codeposited with PbO₂ onto the anode and the deposited particles became tinier and more compact. The addition of CeO₂ enhances the electrochemical catalytic activity. Tinier and more compact crystals enlarge the effective electrode area and improve the mechanical strength, which makes the CF/CeO₂-β-PbO₂ electrode possess higher detection sensitivity, wider linearity range, and longer service life in COD detection as compared with the anodes without CeO₂ fabricated by CV method or constant potential (CP) method.

     

Electrocatalysis of Puerarin on a Nano-CeO2/MWCNTs Composite Modified Electrode and Its Determination in Pharmaceutical Preparations

A good route for the fabrication of CeO₂ nanoparticles (nano‐CeO₂)/multi‐walled carbon nanotubes (MWCNTs) modified glassy carbon electrodes (GCE) was proposed. MWCNTs are used to immobilize nano‐CeO₂. What′s more, with the addition of the MWCNTs, the agglomeration level of CeO₂ nanoparticles can be reduced, the extremely large surface area can be obtained and the electron transfer rate can be increased. The morphological characterization of nano‐CeO₂/MWCNTs was examined by scanning electron microscopy (SEM). The performances of the nano‐CeO₂/MWCNTs/GCE were characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and typical amperometric response (i‐t). The potential utility of the constructed electrodes was demonstrated by applying them to the analytical determination of puerarin concentration. The catalytic oxidation of puerarin has a better result on nano‐CeO₂/MWCNTs/GCE because of the synergistic effect of nano‐CeO₂ and MWCNTs. An optimized limit of detection of 8.0×10^?9 mol/L was obtained at a signal‐to‐noise ratio of 3 and with a fast response time (within 3 s). Additionally, the nano‐CeO₂/MWCNTs/GCE exhibited a wide linear range from 0.04 to 6.0 μmol/L and high sensitivity.     

Understanding the electrochemical differences of Pt doped and Pt supported over CeO2

Pt supported over CeO₂ (Pt on CeO₂) and Pt doped CeO₂ (Pt in CeO₂) are synthesized using chemical reduction and solution combustion method. In chemical reduction two different reducing agents are used namely; hydrazine hydrate and formaldehyde giving Pt supported over CeO₂. Solution combustion method is used to prepare Pt doped CeO₂. Detailed characterization using X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area measurement and transmission electron microscopy (TEM) is carried out to distinguish the Pt supported and doped compounds. XRD and TEM results have clearly shown the differences in the structure and morphology, however, BET results do not show significant differences. Further, electrochemical measurements are performed in neutral medium to differentiate the electrochemical activity. Cyclic voltammetry (CV) indeed shows noticeable differences between Pt supported over CeO₂ and Pt doped CeO₂. CeO₂ alone has also shown different electrochemical behavior compared to the Pt containing CeO₂. Considering oxygen evolution reaction (OER) as a model reaction, Tafel slope measurements are performed for CeO₂, Pt supported over CeO₂ and Pt doped CeO₂ to observe the differences. It was noted that CeO₂ and Pt doped CeO₂ showed similar Tafel slope indicating the same mechanism, while Pt supported over CeO₂ showed different Tafel slopes, hence the different mechanism.     

Electrochemical Detection of As (III) on a Manganese Oxide‐Ceria (Mn2O3/CeO2) Nanocube Modified Au Electrode

Ceria cubes decorated with manganese oxide nanoparticles (Mn₂O₃/CeO₂ nanocubes) were synthesized and used to modify a Au electrode for analysis of As(III) in aqueous solution. This modified electrode displayed improved sensitivity than either oxide on their own, indicating a synergistic effect due to the effect of Mn₂O₃ on the properties of CeO₂. The improved sensitivity could be ascribed to the enhanced As (III) adsorption ability of Mn₂O₃/CeO₂ nanocube during electrochemical pre‐concentration, combined with the well known As(III) sensing qualities of the gold substrate. The Mn₂O₃/CeO₂ nanocube modified gold electrode behaved as a promising sensor with stable, repeatable square wave anodic stripping voltammetry (SWASV) peaks, separated from common interfering ions in natural water including Cu (II) under practical conditions. Repeatability and stability studies revealed the As (III) sensor to be robust and reliable, with a sensitivity of 0.0414 μA/ppb and a limit of detection (LoD) of 3.35 ppb under optimized conditions, indicating a possible general use of this class of heteronanostructures in electroanalytical chemistry for studies that rely upon adsorption of deposition of the analyte prior to stripping analysis.     

Alkaline Phosphatase-based Electrochemical Analysis for Point-of-Care Testing

Point-of-care testing (POCT) devices have evolved to provide beneficial information about an individual's health whenever needed. Enzyme-based analytical devices have facilitated the highly selective detection of numerous biological molecules and ions. Enzymes are commonly used as the tags of recognition components, such as antibodies, to generate and amplify detection signals. Particularly, alkaline phosphatase (ALP) is one of the most widely used enzymes because of its high turnover number and low cost. Rapid response time and the incorporation of many sensors fabricated by micro/nano processing technologies are the advantages in using electrochemical devices as analytical tools. Therefore, ALP-based electrochemical devices have potential applications for more practical POCT platforms. This review summarizes recent research progress of ALP-based electrochemical devices for POCT. In addition to ALP substrates, the application of ALP-based immunosensors, aptasensors, and DNAzyme sensors are discussed.     

CeO<Subscript>2</Subscript> nanoparticle-modified electrode as a novel electrochemical interface in the quantification of Zn<Superscript>2+ </Superscript>ions at trace level: application to real sample analysis

A simple strategy has been proposed to quantify Zn²⁺ ions using CeO₂ nanoparticle-modified glassy carbon electrode. The CeO₂ nanoparticles were prepared by sucrose-nitrate decomposition method, and it was characterized by X-ray diffraction (XRD), FT-IR, TEM, and surface area analyzer. The synthesized CeO₂ nanoparticles were used as modifier molecules as a thin film on glassy carbon electrode (GCE) in the trace level quantification of Zn²⁺ by using cyclic voltammetry (CV) and differential pulse anodic stripping voltammetry (DPASV) techniques. The fabricated sensor exhibited a good analytical response towards Zn²⁺ ions. The modified electrode showed a wide linearity in the concentration range 20–380 μg L^?1 with a limit of detection 0.36 μg L^?1. The proposed electrochemical sensor was successfully applied to trace level Zn²⁺ quantification from real sample matrices.     

Mechanical,thermal, and ultraviolet resistance properties of polycarbonate/cerium oxide composites

The composites containing polycarbonate (PC) and cerium oxide (CeO₂) nanoparticles as well as nanoparticles modified with stearic acid (mCeO₂) have been prepared using a melt blending method. The composites are studied by using FTIR spectroscopy, differential scanning calorimetry, thermal gravimetric analysis and scanning electron microscopy, and their tensile strength and ultraviolet (UV) resistance are examined. The results indicate that the introduction of CeO₂ nanoparticles at 1 wt% can improve the mechanical properties of PC, while a weight ratio that is over 1 wt% can lead to a reduction in the tensile strength. Compared with the PC/CeO₂ composites, the PC/mCeO₂ composites provide better mechanical properties. Besides, the introduction of CeO₂ nanoparticles gives PC promising UV resistance. However, different amounts of CeO₂ nanoparticles used provide similar thermal and UV resistance in PC. In a comparison of the PC/CeO₂ and PC/mCeO₂ composites, there are no apparent differences observed between CeO₂ and mCeO₂ on improving the UV resistance of PC.     

Novel CeO2–CuO-decorated enzymatic lactate biosensors operating in low oxygen environments

The detection of the lactate level in blood plays a key role in diagnosis of some pathological conditions including cardiogenic or endotoxic shocks, respiratory failure, liver disease, systemic disorders, renal failure, and tissue hypoxia. Here, we described for the first time the use of a novel mixed metal oxide solution system to address the oxygen dependence challenge of first generation amperometric lactate biosensors. The biosensors were constructed using ceria-copper oxide (CeO₂–CuO) mixed metal oxide nanoparticles for lactate oxidase immobilization and as electrode material. The oxygen storage capacity (OSC, 492 μmol-O₂/g) of these metal oxides has the potential to reduce the oxygen dependency, and thus eliminate false results originated from the fluctuations in the oxygen concentration. In an effort to compare the performance of our novel sensor design, ceria nanoparticle decorated lactate sensors were also constructed. The enzymatic activity of the sensors were tested in oxygen-rich and oxygen-lean solutions. Our results showed that the OSC of the electrode material has a big influence on the activity of the biosensors in oxygen-lean environments. While the CeO₂ containing biosensor showed an almost 21% decrease in the sensitivity in a O₂-depleted solution, the CeO₂–CuO containing electrode, with a higher OSC value, experienced no drop in sensitivity when moving from oxygen-rich to oxygen-lean conditions. The CeO₂–CuO decorated sensor showed a high sensitivity (89.3 ± 4 μA mM⁻¹ cm⁻²), a wide linear range up to 0.6 mM, and a low limit of detection of 3.3 μM. The analytical response of the CeO₂–CuO decorated sensors was studied by detecting lactate in human serum with good selectivity and reliability. The results revealed that CeO₂–CuO containing sensors are promising candidates for continuous lactate detection.     

Highly Sensitive Amperometric Sensor for Eugenol Quantification Based on CeO2 Nanoparticles and Surfactants

Amperometric sensor for eugenol based on glassy carbon electrode (GCE) modified with CeO₂ nanoparticles dispersed in surfactant was fabricated. The effect of surfactant nature (sodium dodecylsulfate, cetylpyridinium bromide (CPB) and Brij® 35) on eugenol voltammetric behaviour was tested. In comparison to CeO₂‐H₂O/GCE, CeO₂‐CPB/GCE showed 2.8‐fold increased current and 70 mV cathodic shift of potential in the diffusion‐controlled irreversible electrooxidation. The electrodes were characterized with SEM and EIS. CeO₂‐CPB/GCE showed significantly lower charge transfer resistance (2.6±0.3 kΩ vs. 20±1 kΩ for CeO₂‐H₂O/GCE and 173±9 kΩ for GCE). Under conditions of DPV, the sensor linear dynamic range is 0.075‐75.0 μM of eugenol with the limits of detection (LOD) and quantification (LOQ) of 19.1 and 63.8 nM, respectively. The sensor exhibited high sensitivity, selectivity, good reproducibility and fast response and was applied for the real samples analysis (essential oils and clove spices). The results obtained correspond well to the data of spectrophotometric method.     

Role of step sites on water dissociation on stoichiometric ceria surfaces

The adsorption and dissociation of water on CeO₂(111), CeO₂(221), CeO₂(331), and CeO₂(110) has been studied by means of periodic density functional theory using slab models. The presence of step sites moderately affects the adsorption energy of the water molecule but in some cases as in CeO₂(331) is able to change the sign of the energy reaction from endo- to exothermic which has important consequences for the catalytic activity of this surface. Finally, no stable molecular state has been found for water on CeO₂(110) where the reaction products lead to a very stable hydroxylated surface which will rapidly become inactive.     

Fabrication of CeO2 Nanoparticle Modified Glassy Carbon Electrode for Ultrasensitive Determination of Trace Amounts of Uric Acid in Urine

The preparation of a glassy carbon electrode modified by CeO2 nanoparticles was described, which was characterized by cyclic voltammetry and electrochemical impedance spectroscopy. In pH 6.0 buffer, the CeO2 nanoparticle modified electrode （CeO2 NP/GC） gave an excellent electrocatalytic activity for the oxidation of uric acid （UA）. The catalytic current of UA versus its concentration had a good linear relation in the range of 2.0 × 10^-7-5.0 × 10^- 4 mol/L, with the correlation coefficient of 0.9986 and detection limit of 1.0 ×10^-7 mol/L. The modified electrode can be used for the determination of UA in urine, which can tolerate the interference of ascorbic acid up to 1000-fold. The method was simple, quick and sensitive.     

Novel Synthesis of CeO2 Nanoparticles Within Formamide/Tri(ethyleneglycol)monododecyl Ether/n-Octane Nonaqueous Microemulsion Systems

The present study evaluates a new method to prepare Cerium oxide (CeO₂) nanoparticles by formamide/tri(ethyleneglycol)monododecyl ether (C₁₂E₃)/n-octane oil-continuous nonaqueous microemulsion. The effect of the polar phase (formamide/water) on the phase behavior, drop size, and conductivity behavior of the reverse microemulsion were investigated. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the phase and morphology of synthesized CeO₂ nanoparticles. It was found that the CeO₂ powders synthesized within nonaqueous microemulsions and aqueous microemulisons had an average particle size of 30–50 nm and 15–40 nm, respectively. The experimental results indicate the formation mechanism of CeO₂ nanoparticles in formamide nonaqueous microemulsion and aqueous microemulsion is similar, and the formamide nonaqueous microemulsion can be used as nanoreactors for preparation of nanoparticles.     

一维CeO2纳米管载体对Pd纳米粒子团聚的抑制及催化性能的提高

用一维CeO₂纳米管替代非一维结构的商用CeO₂, 用于负载Pd而制得的催化剂在空气气氛下高温煅烧过程中Pd纳米粒子的团聚受到明显抑制, 在选择性有氧氧化苯甲醇生成苯甲醛反应中, 所制CeO₂纳米管负载的Pd催化剂表现出更高的催化活性. 可见, 一维金属氧化物材料有望用作载体以抑制贵金属纳米粒子的团聚, 从而提高其催化性能.     

低于300℃时两种氧化铈材料对稀燃阶段NOx存储性能的影响

研究了低于300 ℃时两种氧化铈对稀燃阶段NO_x存储性能的影响,催化剂由2%（w）Pt/Al₂O₃（PA）与CeO₂-X（X=S,I）机械混合制备. X射线衍射（XRD）,BET表面积和扫描电子显微镜（SEM）用于表征材料的物理结构. X射线光电子能谱（XPS）和H₂程序升温还原（H₂-TPR）用于表面Ce³⁺和活性氧定量. 原位漫反射傅里叶变换红外光谱（in-situ DRIFTS）用于分析表面NO_x吸附物种. 相比于CeO₂-I,CeO₂-S 具有优良的物理化学性能,包括高比表面积、丰富的空隙结构、较高的抗老化能力及表面Ce³⁺浓度. 因而,Pt/Al₂O₃+CeO₂-S 表现出优异的NO_x存储能力. 此外,PA+CeO₂-X（X=S,I）上存在Pt 与CeO₂之间的相互作用,可提高表面氧物种的活性进而促进NO氧化及NO_x存储. PA+CeO₂-S上的这种相互作用要强于PA+CeO₂-I. 研究表明,表面Ce³⁺浓度和活性氧含量对NO_x存储起到重要作用. 然而经过水热处理后,Pt 与老化的氧化铈（ACS,ACI）之间的相互作用降低,并且两种氧化铈NO_x存储性能显著下降. 另外,与PA+ACS（ACI）相比,PA+PACS（PACI）样品NO_x存储能力得到改善,这归因于表面氧物种活性增加能促进硝酸盐的形成.     

A Sensitive Signal-off Electrochemical Aptasensor for Thrombin Detection using PB−Au@MoS2 Nanomaterial as Both Platform and Signal Reporter

Human serum is one of the effective samples for point-of-care testing (POCT). Sensitive and quick determination of thrombin content in human serum samples is important. An electrochemical aptasensor based on Prussian blue and Au nanoparticles loaded MoS₂ nanoflowers (PB−Au@MoS₂) hybrid was constructed. By using PB−Au@MoS₂ as both a substrate and a signal reporter, this aptasensor could demonstrate excellent performance for thrombin detection with a detection linear range from 0.01 pM to 30 nM and detection limit down to 1 fM. This work may provide a strategy to establish effective and sensitive sensing devices for thrombin in clinical diagnosis.     

Direct Electrochemistry of Hemoglobin in Cerium Dioxide/Carbon Nanotubes/Chitosan for Amperometric Detection of Hydrogen Peroxide

Abstract

A novel hemoglobin (Hb) biosensor based on the remarkable synergistic effects of cerium dioxide (CeO₂) and multiwalled carbon nanotubes (MWNTs) for detection of hydrogen peroxide (H₂O₂) is presented. The Hb/CeO₂/MWNTs/CHIT nanocomposite was nanoengineered by selected matched material components and optimized composition ratio to produce a superior H₂O₂ sensor. The preparation method is quite simple and practical. This composite matrix combined the advantages of MWNTs, CeO₂ nanoparticles, and chitosan (CHIT), with good electron-transfer ability, attractive biocompatibility, and fine film-forming ability, which could increase Hb attachment quantity and H₂O₂ detection sensitivity. In the optimum pH 7.0 phosphate buffer, the electrocatalytic response exhibited a linear dependence on H₂O₂ concentration in a wide range from 5.0 × 10^?6 to 4.6 × 10^?4 mol L^?1 with a detection limit of 6.5 × 10^?7 mol/L (3σ).     

Density functional study on electronic and optical properties of C (or N)-doped cubic cerium dioxide

Density functional calculations were performed on electronic and optical properties of C (or N)-doped cubic cerium dioxide (CeO₂). When O is replaced by C (or N) in CeO₂, obvious band-gap (E_g) reduction is observed. Meanwhile, it is interesting to find that the substitutional doping of C (or N) in CeO₂ obviously increases the O 2p–Ce 4f transition intensity and also the refractive index. The increase in the O 2p–Ce 4f transition intensity on going from undoped, N-doped and C-doped CeO₂ was related to the covalent character of the Ce–O bond. Compared with the undoped CeO₂, the C (or N)-doped CeO₂, with steep absorption peaks at lower energy, can be used for visible-light absorption applications.     

Perylene diimide‐modified magnetic γ‐Fe2O3/CeO2 nanoparticles as peroxidase mimics for highly sensitive colorimetric detection of Vitamin C

Perylene diimide‐modified magnetic γ‐Fe₂O₃/CeO₂ nanoparticles (γ‐Fe₂O₃/CeO₂‐PDI) were prepared and exhibited excellent peroxidase‐like activity. The samples were characterized by HR‐TEM, XRD, Raman, N₂ adsorption, magnetic strength and XPS. The obtained γ‐Fe₂O₃/CeO₂‐PDI had size of 10~20 nm with high specific surface area of 77 m²/g, and could be easily separated from the aqueous solution by using a magnet, which are in favor of its practical application. Due to the decoration of PDI, the γ‐Fe₂O₃/CeO₂‐PDI possessed more surface defects (Ce³⁺) and active oxygen species than that of γ‐Fe₂O₃/CeO₂, resulting in the outstanding catalytic performance. And the composite catalyst also showed highly sensitive and selectivity toward VC with a limit of detection of 0.45 μM. Based on the fluorescent results, a possible hydroxyl radical (?OH) catalytic mechanism was proposed. It is believed that the as‐prepared γ‐Fe₂O₃/CeO₂‐PDI nanoparticles are promising biosensors applied for biomedical and food analysis.