Mn3O4 microspheres as an oxidase mimic for rapid detection of glutathione

Exploiting a rapid and sensitive method for biomarker detection has important implications in the early diagnosis of diseases. Here, we synthesized Mn₃O₄ microspheres which worked as a nanozyme to exhibit outstanding oxidase-like activity for rapid colorimetric determination of glutathione (GSH). The Mn₃O₄ microspheres of about 800 nm in size could be prepared through a hydrothermal method, and we found that the as-prepared Mn₃O₄ microspheres could quickly oxidize 3,3′,5,5′-tetramethylbenzidine (TMB) to its oxidized form (TMBox) in the absence of H₂O₂. After adding glutathione (GSH), TMBox was able to be changed into to its original form and resulted in the corresponding decrease in absorbance value at 652 nm. The Mn₃O₄-TMB system had good linearity with GSH concatenation in the range of 5–60 μM, and the limit of detection was 0.889 μM. Furthermore, this assay possessed high selectivity specificity, which made it possible to detect GSH in human serum samples. Thus, the obtained assay based on the oxidase mimic of Mn₃O₄ would enlarge and exploit the application fields of nanozymes in bio-analysis.

The oxidase-like activity of Mn₃O₄ was used to detect the GSH level directly and rapidly in the absence of H₂O₂.     

Colorimetric determination of ascorbic acid based on carbon quantum dots as peroxidase mimetic enzyme

Carbon quantum dots (CQDs) were synthesized from litchi peel, exhibiting a peroxidase-like activity and enabling the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in association with H₂O₂ to generate blue oxidized TMB (ox-TMB) with a strong absorption peak at 652 nm. Interestingly, the ox-TMB could be further reduced by ascorbic acid (AA) leading to fading of the blue color and an absorbance decrease. Thus, a convenient and sensitive colorimetric method for detection of AA using CQDs as peroxidase mimics was established. Several factors, such as acidity, temperature, incubating time, and TMB concentration, which might influence the response of the analysis signal, were optimized. The results showed that the decrease of absorbance (ΔA) was in good linear agreement with AA concentration in the range of 1.0–105 μM, with a low detection limit of 0.14 μM. The feasibility of this method was also investigated in commercial beverages with the 94.3–110.0% recovery.

Carbon quantum dots (CQDs) were synthesized from litchi peel, exhibiting a peroxidase-like activity and enabling the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in association with H₂O₂ to generate blue oxidized TMB (ox-TMB) with a strong absorption peak at 652 nm.     

Simultaneous determination of methadone and morphine at a modified electrode with 3D β-MnO2 nanoflowers: application for pharmaceutical sample analysis

The present research synthesized manganese dioxide nano-flowers (β-MnO₂-NF) via a simplified technique for electro-catalytic utilization. Moreover, morphological characteristics and X-ray analyses showed Mn in the oxide form with β-type crystallographic structure. In addition, the research proposed a new efficient electro-chemical sensor to detect methadone at the modified glassy carbon electrode (β-MnO₂-NF/GCE). It has been found that oxidizing methadone is irreversible and shows a diffusion controlled procedure at the β-MnO₂-NF/GCE. Moreover, β-MnO₂-NF/GCE was considerably enhanced in the anodic peak current of methadone related to the separation of morphine and methadone overlapping voltammetric responses with probable difference of 510 mV. In addition, a linear increase has been observed between the catalytic peak currents gained by the differential pulse voltammetry (DPV) of morphine and methadone and their concentrations in the range between 0.1–200.0 μM and 0.1–250.0 μM, respectively. Furthermore, the limits of detection (LOD) for methadone and morphine were found to be 5.6 nM and 8.3 nM, respectively. It has been found that our electrode could have a successful application for detecting methadone and morphine in the drug dose form, urine, and saliva samples. Thus, this condition demonstrated that β-MnO₂-NF/GCE displays good analytical performances for the detection of methadone.

Electrochemical sensor based on β-MnO₂ nanoflower-modified glassy carbon electrode for the simultaneous detection of methadone and morphine was fabricated.     

Sweetsop-like α-Fe2O3@CoNi catalyst with superior peroxidase-like activity for sensitive and selective detection of hydroquinone

Hydroquinone (HQ) is poorly degradable in the ecological environment and is highly toxic to human health even at a low concentration. The colorimetric method has the advantages of low cost and fast analysis, which provides the possibility for simple and rapid detection of HQ. In this work, a new colorimetric method has been developed for HQ detection based on a peroxidase-like catalyst, α-Fe₂O₃@CoNi. This sweetsop-like α-Fe₂O₃@CoNi catalyst enables H₂O₂ to produce hydroxyl (˙OH), leading to the oxidization of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) to blue oxTMB. In the presence of HQ, the blue oxTMB is reduced to colorless, which allows for colorimetric detection of HQ in water samples. This method has been validated by detecting HQ in water samples with high selectivity, rapid response, broad detection range (0.50 to 30 μM), and low detection limit (0.16 μM).

A sweetsop-like α-Fe₂O₃@CoNi catalyst with superior peroxidase-like activity was synthesized and successfully applied to the detection of hydroquinone (HQ) based on the colorimetric principle.     

Molecular imprinting on PtPd nanoflowers for selective recognition and determination of hydrogen peroxide and glucose

PtPd nanoflowers (PtPd NFs) exhibit intrinsic peroxidase-like activity as nanozymes, but the nanozymes lack substrate specificity and have low catalytic activity. Herein, a molecularly imprinted nanogel on PtPd NFs was prepared by using 3,3′,5,5′-tetramethylbenzidine (TMB) as the template through the aqueous precipitation polymerization method. After the TMB was washed out, many substrate binding pockets were retained in the PtPd NFs. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) were employed to characterize the molecularly imprinted polymer (MIP) PtPd nanoflowers (T-MIP-PtPd NFs). The obtained T-MIP-PtPd NFs exhibited enhanced catalytic activity and specific recognition for TMB. Compared with PtPd NFs, T-MIP-PtPd NFs showed a linear range from 0.01–5000 μM and a detection limit of 0.005 μM toward the detection of H₂O₂. Glucose can also be sensitively detected through cascade reaction by the T-MIP-PtPd NFs and glucose oxidase. Therefore, molecular imprinting on nanozymes technology shows promising application in biocatalysis and sensing fields.

PtPd nanoflowers (PtPd NFs) exhibit intrinsic peroxidase-like activity as nanozymes, but the nanozymes lack substrate specificity and have low catalytic activity.     

Convenient and sensitive colorimetric detection of melamine in dairy products based on Cu(ii)-H2O2-3,3′,5,5′-tetramethylbenzidine system

The illegal adulteration of melamine in dairy products for false protein content increase is a strong hazard to human health. Herein, a simple and sensitive colorimetric method was developed for the quantification of melamine in dairy products based on a Cu²⁺-hydrogen peroxide (H₂O₂)-3,3′,5,5′-tetramethylbenzidine (TMB) system. In this strategy, Cu²⁺ exhibits peroxidase-like activity and can catalyze the oxidation of TMB to oxidized TMB (oxTMB) in the presence of H₂O₂ with a blue colour change of the solution. However, the presence of melamine quickly interacts with H₂O₂ leading to the consumption of H₂O₂ and thus strongly hinders the oxidation of TMB. Under the optimal conditions, the absorbance change of oxTMB has a linear response to the concentration of melamine from 1 to 100 μM with a detection limit of 0.5 μM for melamine. The proposed method has many merits including more simplicity, good selectivity, and more cost-effectiveness without using any nanomaterials. The method was further successfully applied to detect melamine in dairy products including milk and infant formula powder.

Convenient and sensitive colorimetric detection of melamine in dairy products based on a Cu(ii)-H₂O₂-3,3′,5,5′-tetramethylbenzidine system was reported.     

Structural modification of olibergin A,an isoflavonoid,from Dalbergia stipulacea Roxb. and its cytotoxicity

Fifteen derivatives were synthesized from olibergin A, a major isoflavonoid isolated from the stems of Dalbergia stipulacea Roxb. All compounds were evaluated for cytotoxicity against HCT-116, HT-29, MCF-7 and vero cell lines using MTT assay. Cytotoxicity results showed 5-hydroxy-7,2′,4′,5′-tetramethoxyisoflavone (5) was the most active with IC₅₀ values of 19.03 ± 0.70, 10.83 ± 1.65, 12.53 ± 0.70 and 13.53 ± 0.84 μM against HCT-116, HT-29, MCF-7 and vero cell lines, respectively. It should be noted that 5-hydroxy-7,2′,4′,5′-tetramethoxyisoflavone (5) showed two times less toxicity against vero cells than the cisplatin standard (IC₅₀ = 6.55 ± 0.81 μM) while 5 and cisplatin exhibited nearly equal cytotoxicity against the MCF-7 cell line. 5,7,2′,4′,5′-Pentamethoxyisoflavanone (10) showed an IC₅₀ value of 30.34 ± 1.15 μM against the HCT-116 cell line and exhibited weak cytotoxicity against normal cells, the vero cell line. In addition, 5,7,4′-trihydroxy-2′,5′-dimethoxyisoflavan oxime (13) demonstrated cytotoxicity against HT-29 cells with an IC₅₀ value of 31.41 ± 1.38 μM and displayed weak activity toward the vero cell line. The information revealed that these compounds were suitable for development to anticancer agents against HCT-116, HT-29 and MCF-7 cell lines.

Fifteen derivatives were synthesized from olibergin A, a major isoflavonoid isolated from the stems of Dalbergia stipulacea Roxb.     

Cu@Au(Ag)/Pt nanocomposite as peroxidase mimic and application of Cu@Au/Pt in colorimetric detection of glucose and l-cysteine

Nanomaterial-based artificial peroxidase has attracted extensive interests due to their distinct advantages over natural counterpart. Cu@Au/Pt and Cu@Ag/Pt nanocomposite with rambutan-like structure were prepared and discovered to function like peroxidase, which was illustrated by catalyzing the oxidation reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) accompanied with a blue color change. Steady-state investigation indicates that the catalytic kinetics of Cu@Au/Pt and Cu@Ag/Pt all followed typical Michaelis–Menten behaviors and Cu@Au/Pt showed a strong affinity for H₂O₂, while Cu@Ag/Pt showed strong affinity for TMB. The color change and absorbance intensity strongly depend on the concentration of H₂O₂, thus the direct determination of H₂O₂ and indirect detection of glucose were demonstrated using Cu@Au/Pt with a detection limit of 1.5 μM and 6 μM, respectively. What is more important, the method was applied for detection of glucose in 50% fetal bovine serum with a detection limit of 80 μM, which is much lower than the lowest glucose content in blood for diabetes (7 mM). Moreover, the Cu@Au/Pt nanocomposite were also successfully applied for sensing l-cysteine because of the inhibition effect. Considering the good peroxidase-like activity and novel structure, Cu@Au(Ag)/Pt is expected to have a wide range of applications in bioassays and biocatalysis.

Cu@Au(Ag)/Pt nanocomposite possess good peroxidase-like activity and can be used for detection of glucose and l-cysteine.     

Colorimetric detection of hydrogen peroxide and glucose by exploiting the peroxidase-like activity of papain

Papain, a natural plant protease that exists in the latex of Carica papaya, catalyzes the hydrolysis of peptide, ester and amide bonds. In this work, we found that papain displayed peroxidase-like activity and catalyzed the oxidation of 3,3′,5′,5′-tetramethylbenzidine (TMB) in the presence of H₂O₂. This results in the formation of a blue colored product with an absorption maximum at 652 nm. The effects of experimental parameters including pH and reaction temperature on catalytic activity of papain were investigated. The increase of absorbance induced by the catalytic effect of papain offers accurate detection of H₂O₂ in the range of 5.00–90.0 μM, along with a detection limit of 2.10 μM. A facile colorimetric method for glucose detection was also proposed by combining the glucose oxidase (GOx)-catalyzed glucose oxidation and papain-catalyzed TMB oxidation, which exhibited a linear response in the range of 0.05–0.50 mM with a detection limit of 0.025 mM. The method proposed here displayed excellent selectivity, indicating that common coexisting substances (urea, uric acid, ascorbic acid, maltose, lactose and fructose) in urine did not interfere with detection of glucose. More importantly, the suggested method was successfully used to precisely detect the glucose concentration in human urine samples with recoveries over 96.0%.

We reported a simple colorimetric method for the detection of glucose based on GOx-catalyzed glucose oxidation and papain-catalyzed TMB oxidation.     

Biofunctional hollow γ-MnO2 microspheres by a one-pot collagen-templated biomineralization route and their applications in lithium batteries

γ-MnO₂ nanomaterials play an essential role in the development of advanced electrochemical energy storage and conversion devices with versatile industrial applications. Herein, novel dandelion-like hollow microspheres of γ-MnO₂ mesocrystals have been fabricated for the first time by a one-pot biomineralization route. Recombinant collagen with unique rod-like structure has been demonstrated as a robust template to tune the morphologies of γ-MnO₂ mesocrystals, and a very low concentration of collagen can alter the nanostructures of γ-MnO₂ from nanorods to microspheres. The as-prepared γ-MnO₂ mesocrystals formed well-ordered hollow microspheres composed of delicate nanoneedle-like units. Among all the reported γ-MnO₂ with various nanostructures, the γ-MnO₂ microspheres showed the most prowess to maintain high discharge capacities after 100+ cycles. The superior electrochemical performance of γ-MnO₂ likely results from its unique hierarchical micro-nano structure. Notably, the γ-MnO₂ mesocrystals display high biocompatibility and cellular activity. Collagen plays a key dual role in mediating the morphology as well as endowing the biofunction of the γ-MnO₂ mesocrystals. This environmentally friendly biomineralization approach using rod-like collagen as the template, provides unprecedented opportunity for the production of novel nanostructured metal oxides with superior biocompatibility and electrochemical performance, which have great potential in advanced implantable and wearable health-care electronic devices.

Recombinant collagen with unique rod-like structure has been demonstrated as a robust template to create novel dandelion-like hollow microspheres of γ-MnO₂ mesocrystals, which display superior biocompatibility and electrochemical performance.     

A nano-sized Cu-MOF with high peroxidase-like activity and its potential application in colorimetric detection of H2O2 and glucose

Peroxidase widely exists in nature and can be applied for the diagnosis and detection of H₂O₂, glucose, ascorbic acid and other aspects. However, the natural peroxidase has low stability and its catalytic efficiency is easily affected by external conditions. In this work, a copper-based metal–organic framework (Cu-MOF) was prepared by hydrothermal method, and characterized by means of XRD, SEM, FT-IR and EDS. The synthesized Cu-MOF material showed high peroxidase-like activity and could be utilized to catalyze the oxidation of o-phenylenediamine (OPDA) and 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H₂O₂. The steady-state kinetics experiments of the oxidation of OPDA and TMB catalyzed by Cu-MOF were performed, and the kinetic parameters were obtained by linear least-squares fitting to Lineweaver–Burk plot. The results indicated that the affinity of Cu-MOF towards TMB and OPDA was close to that of the natural horseradish peroxidase (HRP). The as-prepared Cu-MOF can be applied for colorimetric detection of H₂O₂ and glucose with wide linear ranges of 5 to 300 μM and 50 to 500 μM for H₂O₂ and glucose, respectively. Furthermore, the specificity of detection of glucose was compared with other sugar species interference such as sucrose, lactose and maltose. In addition, the detection of ascorbic acid and sodium thiosulfate was also performed upon the inhibition of TMB oxidation. Based on the high catalytic activity, affinity and wide linear range, the as-prepared Cu-MOF may be used for artificial enzyme mimics in the fields of catalysis, biosensors, medicines and food industry.

A Cu-MOF with high peroxidase-like activity was prepared and could be used for colorimetric detection of H₂O₂ and glucose with high selectivity and good linear range (50–500 μM).     

Co nanoparticles decorated with N-doped carbon nanotubes as high-efficiency catalysts with intrinsic oxidase-like property for colorimetric sensing

Artificial nanozymes are designed for pursuing the functions of splendid catalytic efficiency and prominent selectivity of natural enzymes, meanwhile obtaining higher stability than that of natural enzymes. This emerging technology shows widespread application in the crossing field between nanotechnology and biomedicine. In this work, we employed a universal approach to fabricate a Co@N-CNTs hybrid nanocomposite as an oxidase mimic, in which fine Co nanoparticles were wrapped in N-doped carbon nanotubes, stacking on a hollow dodecahedron carbon skeleton. The synergistic effects of nanostructure engineering, N-doping and carbon coating, as well as the derived interfacial effect contribute to the glorious oxidase-like activity, stability and reusability. It can catalytically oxidize the colorless substrate 3,3′,5,5′-tetramethylbenzidine (TMB) to a blue oxidation product (ox-TMB). As a result, a colorimetric technique with excellent selectivity and sensitivity for detecting ascorbic acid (AA) with naked eyes was established, in view of specific inhibitory effects towards oxidation of TMB. Under optimal detection conditions, this method exhibits a good linearity ranging from 0.1 to 160 μM with a low limit of detection (LOD) of 0.076 μM. For practical applications, Co@N-CNTs hybrid catalyst as a mimic oxidase was used for the determination of AA in human serum, which yielded satisfactory results. This work may serve as a new research thought to guide the design of high-performance nanozymes and establish a sensing platform for the detection of AA.

In this work, we designed a Co@N-CNTs hybrid nanocomposite as an oxidase mimic for the colorimetric detection of ascorbic acid with the naked eye.     

CNT modified layered α-MnO2 hybrid flame retardants: preparation and their performance in the flame retardancy of epoxy resins

In this paper, CNT modified layered α-MnO₂ hybrid flame retardants (α-MnO₂–CNTs) were synthesized through one-pot preparation. The structure and composition of the α-MnO₂–CNTs hybrid flame retardants were investigated by X-ray diffraction, TEM and SEM. Subsequently, the α-MnO₂–CNTs hybrids were then incorporated into epoxy resin (EP) to improve the fire safety properties. Compared with pure EP and the composites with CNTs or α-MnO₂, EP/α-MnO₂–CNTs composites exhibited improved flame retardancy and smoke suppression properties. With the incorporation of only 2.0 wt% of α-MnO₂–CNTs hybrid flame retardants, the peak heat release rate and total heat release of the composites showed 34% and 10.7% reduction respectively. In addition, the volatile gases such as CO and CO₂ were reduced and the smoke generation was also effectively inhibited. The improved fire safety of the composites is generally due to the network structures and the synergistic effect of α-MnO₂ and CNTs, the catalyzing charring effect, smoke suppression and the physical barrier effect of α-MnO₂ nanosheets.

In this paper, CNT modified layered α-MnO₂ hybrid flame retardants (α-MnO₂–CNTs) were synthesized through one-pot preparation.     

Removal of manganous dithionate (MnS2O6) with MnO2 from the desulfurization manganese slurry

Manganese desulfurization has been increasingly explored, but the generated manganous dithionate (MD) by-product affects the valuable use of the desulfurized slurry. In this study, α-MnO₂, β-MnO₂, γ-MnO₂, and δ-MnO₂ were prepared for MD removal in desulfurization manganese slurry. Results showed that δ-MnO₂ had the best activity among the four because of its porosity and favorable surface properties. The operation conditions showed that 12.00 g L⁻¹ MD can be removed by more than 80.00% under the conditions of 1.4 mol L⁻¹ sulfuric acid, 100 g L⁻¹ δ-MnO₂ dosage, and reaction at 90 °C for 3 h. The MD removal with MnO₂ followed the decomposition–oxidation pass and direct oxidation–reduction reaction and consequently induced structure destruction and crystalline transfer. MD removal with natural MnO₂ ore was also examined, and natural MnO₂ ore in the δ type was found to have prominent activity. Thus, this type of natural MnO₂ may serve as a good alternative to pure MnO₂ for decreasing the cost of MD removal from desulfurization manganese slurry.

The manganous dithionate by-product of the desulfurized slurry could be oxidized with MnO₂ without any impurity. σ-MnO₂ showed the best activity due to its high surface area and expose much more surface-active oxygen.     

Synthesis,cytotoxicity evaluation and molecular docking studies on 2′,4′-dihydroxy-6′-methoxy-3′,5′-dimethylchalcone derivatives

2′,4′-Dihydroxy-6′-methoxy-3′,5′-dimethylchalcone (DMC, 1) was isolated from seeds of Syzygium nervosum A.Cunn. ex DC. exhibiting intriguing biological activities. Herein, thirty three DMC derivatives including 4′-O-monosubstituted-DMC (2), 7-O-acylated-4-hydroxycoumarin derivatives (3), stilbene–coumarin derivatives (4), 2′,4′-disubstituted-DMC (5), and flavanone derivatives (6), were synthesised through acylation, alkylations, and sulfonylation. These semi-synthetic DMC derivatives were evaluated for in vitro cytotoxicity against six carcinoma cell lines. It was found that most derivatives exhibited higher cytotoxicity than DMC. In particular, 4′-O-caproylated-DMC (2b) and 4′-O-methylated-DMC (2g) displayed the strongest cytotoxicity against SH-SY5Y with IC₅₀ values of 5.20 and 7.52 μM, respectively. Additionally, 4′-O-benzylated-DMC (2h) demonstrated the strongest cytotoxicity against A-549 and FaDu with IC₅₀ values of 9.99 and 13.98 μM, respectively. Our structure–activity relationship (SAR) highlights the importance of 2′-OH and the derivatisation pattern of 4′-OH. Furthermore, molecular docking simulation studies shed further light on how these bioactive compounds interact with cyclin-dependent kinase 2 (CDK2).

Semi-synthetic DMC derivatives were synthesised and displayed biological potency against various cancer cell lines.      

Ultrasensitive detection of uric acid in serum of patients with gout by a new assay based on Pt@Ag nanoflowers

A ultrasensitive assay for the determination of uric acid (UA) based on Pt@Ag nanoflowers (Pt@Ag NFs) was constructed. H₂O₂ was formed by the reaction of uricase and UA and produced the hydroxyl radical (˙OH). The system was catalyzed by Pt@Ag NFs to change the color of 3,3′,5,5′-tetramethylbenzidine (TMB) from colorless to blue, and the morphology and chemical properties of Pt@Ag NFs were characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. Under the optimized conditions, a linear relationship between the absorbance and UA concentration was in the range of 0.5–150 μM (R² = 0.995) with a limit of detection of 0.3 μM (S/N = 3). The method can be applied to detection of UA in actual samples with satisfactory results. The proposed assay was successfully applied to the detection of UA in human serum with recoveries over 96.8%. Thus, these results imply that the UA assay provides an effective tool in fast clinical analysis of gout.

A ultrasensitive assay for the determination of uric acid (UA) based on Pt@Ag nanoflowers (Pt@Ag NFs) was constructed.     

Highly efficient redox reaction between potassium permanganate and 3,3′,5,5′-tetramethylbenzidine for application in hydrogen peroxide based colorimetric assays

Potassium permanganate (KMnO₄) is one of the most important oxidants, which plays important roles in many fields. Here, we found that KMnO₄ could directly induce the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to generate an oxidized product with a color change. This redox reaction is highly efficient, and 1 μM KMnO₄ is enough to cause detectable changes in the absorbance signal. Meanwhile, this reaction is very fast and the generated blue product can stabilize for a relatively long period, which has great advantages in practical applications. Since hydrogen peroxide (H₂O₂) is able to react with KMnO₄ under acidic conditions, the KMnO₄-TMB system can be used for the detection of H₂O₂; the absorbance signal induced by 5 μM H₂O₂ can be easily detected in this method. Meanwhile, the KMnO₄-TMB system can also be used for the detection of glucose by monitoring the generation of H₂O₂, which is the main product of glucose oxidation; this method permits detection of concentrations as low as 10 μM glucose, and the sensitivity is comparable to or higher than most peroxidase mimetic based methods, but avoiding the preparation and storage of the nanomaterials. Furthermore, the KMnO₄-TMB system can even be used for analyzing glucose in serum samples, which can also be expected to be used in immunoassays.

The redox reaction between potassium permanganate and 3,3′,5,5′-tetramethylbenzidine is fast and highly efficient, which can be used for different biosensing.     

Fabrication of novel electrochemical sensors based on modification with different polymorphs of MnO2 nanoparticles. Application to furosemide analysis in pharmaceutical and urine samples

A novel MnO₂ nanoparticles/chitosan-modified pencil graphite electrode (MnO₂ NPs/CS/PGE) was constructed using two different MnO₂ polymorphs (γ-MnO₂ and ε-MnO₂ nanoparticles). X-ray single phases of these two polymorphs were obtained by the comproportionation reaction between MnCl₂ and KMnO₄ (molar ratio of 5 : 1). The temperature of this reaction is the key factor governing the formation of the two polymorphs. Their structures were confirmed by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) and energy dispersive X-ray (EDX) analysis. Scanning electron microscopy (SEM) was employed to investigate the morphological shape of MnO₂ NPs and the surface of the bare and modified electrodes. Moreover, cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used for surface analysis of the modified electrodes. Compared to bare PGE, MnO₂ NPs/CS/PGE shows higher effective surface area and excellent electrocatalytic activity towards the oxidation of the standard K₃[Fe(CN)₆]. The influence of different suspending solvents on the electrocatalytic activity of MnO₂ was studied in detail. It was found that tetrahydrofuran (THF) is the optimum suspending solvent regarding the peak current signal and electrode kinetics. The results reveal that the modified γ-MnO₂/CS/PGE is the most sensitive one compared to the other modified electrodes under investigation. The modified γ-MnO₂/CS/PGE was applied for selective and sensitive determination of FUR. Under the optimized experimental conditions, γ-MnO₂/CS/PGE provides a linear response over the concentration range of 0.05 to 4.20 μmol L⁻¹ FUR with a low limit of detection, which was found to be 4.44 nmol L⁻¹ (1.47 ng mL⁻¹) for the 1^st peak and 3.88 nmol L⁻¹ (1.28 ng mL⁻¹) for the 2^nd one. The fabricated sensor exhibits a good reproducibility and selectivity and was applied successfully for the determination of FUR in its dosage forms and in spiked urine samples with good accuracy and precision.

A novel MnO₂ nanoparticles/chitosan-modified pencil graphite electrode (MnO₂ NPs/CS/PGE) was constructed using two different MnO₂ polymorphs (γ-MnO₂ and ε-MnO₂ nanoparticles).     

Synthesis and bioevaluation of thienopyrimidines bearing a pyrazoline unit as selective PI3Kα inhibitors

A series of thienopyrimidines containing a pyrazoline unit (4a–d, 7a–d and 13a–l) were designed and synthesized. The target compounds were evaluated for antiproliferative activity against A549, HepG2 and MCF-7 cancer cell lines. Among the twenty target compounds, most of them exhibited excellent antiproliferative activity against one or several cancer cell lines. Compound 13f showed the best activity against A549, MCF-7 and HepG2 cancer cell lines, with IC₅₀ values of 2.84 ± 0.09 μM, 2.88 ± 0.43 μM and 2.08 ± 0.36 μM, respectively. Four selected compounds (13c, 13f, 13g and 13h) were further evaluated for their inhibitory activity against the PI3Kα/mTOR protein kinase. Moreover, time-dependent and dose-dependent experiments, AO fluorescence staining, Annexin V-FITC/PI staining and docking studies were carried out in this study. The results indicated that compound 13f may be a potential selective PI3Kα inhibitor.

A series of thienopyrimidines containing a pyrazoline unit (4a–d, 7a–d and 13a–l) were designed and synthesized. The compound 13f showed the best activity with the IC₅₀ of 0.92 μM against PI3Kα.     

Al-doped α-MnO2 coated by lignin for high-performance rechargeable aqueous zinc-ion batteries

Zn/MnO₂ batteries, one of the most widely studied rechargeable aqueous zinc-ion batteries, suffer from poor cyclability because the structure of MnO₂ is labile with cycling. Herein, the structural stability of α-MnO₂ is enhanced by simultaneous Al³⁺ doping and lignin coating during the formation of α-MnO₂ crystals in a hydrothermal process. Al³⁺ enters the [MnO₆] octahedron accompanied by producing oxygen vacancies, and lignin further stabilizes the doped Al³⁺via strong interaction in the prepared material, Al-doped α-MnO₂ coated by lignin (L + Al@α-MnO₂). Meanwhile, the conductivity of L + Al@α-MnO₂ improves due to Al³⁺ doping, and the surface area of L + Al@α-MnO₂ increases because of the production of nanorod structures after Al³⁺ doping and lignin coating. Compared with the reference α-MnO₂ cathode, the L + Al@α-MnO₂ cathode achieves superior performance with durably high reversible capacity (∼180 mA h g⁻¹ at 1.5 A g⁻¹) and good cycle stability. In addition, ex situ X-ray diffraction characterization of the cathode at different voltages in the first cycle is employed to study the related mechanism on improving battery performance. This study may provide ideas of designing advanced cathode materials for other aqueous metal-ion batteries.

Al³⁺ doping combined with lignin coating improves the structural stability and electrochemical performance of the modified α-MnO₂, L + Al@α-MnO₂.