Enhanced electron transfer mediated detection of hydrogen peroxide using a silver nanoparticle–reduced graphene oxide–polyaniline fabricated electrochemical sensor

The current study aims at the development of an electrochemical sensor based on a silver nanoparticle–reduced graphene oxide–polyaniline (AgNPs–rGO–PANI) nanocomposite for the sensitive and selective detection of hydrogen peroxide (H₂O₂). The nanocomposite was fabricated by simple in situ synthesis of PANI at the surface of rGO sheet which was followed by stirring with AEC biosynthesized AgNPs to form a nanocomposite. The AgNPs, GO, rGO, PANI, rGO–PANI, and AgNPs–rGO–PANI nanocomposite and their interaction were studied by UV-vis, FTIR, XRD, SEM, EDX and XPS analysis. AgNPs–rGO–PANI nanocomposite was loaded (0.5 mg cm⁻²) on a glassy carbon electrode (GCE) where the active surface area was maintained at 0.2 cm² for investigation of the electrochemical properties. It was found that AgNPs–rGO–PANI–GCE had high sensitivity towards the reduction of H₂O₂ than AgNPs–rGO which occurred at −0.4 V vs. SCE due to the presence of PANI (AgNPs have direct electronic interaction with N atom of the PANI backbone) which enhanced the rate of transfer of electron during the electrochemical reduction of H₂O₂. The calibration plots of H₂O₂ electrochemical detection was established in the range of 0.01 μM to 1000 μM (R² = 0.99) with a detection limit of 50 nM, the response time of about 5 s at a signal-to-noise ratio (S/N = 3). The sensitivity was calculated as 14.7 μA mM⁻¹ cm⁻² which indicated a significant potential as a non-enzymatic H₂O₂ sensor.

The current study aims at the development of an electrochemical sensor based on a silver nanoparticle–reduced graphene oxide–polyaniline (AgNPs–rGO–PANI) nanocomposite for the sensitive and selective detection of hydrogen peroxide (H₂O₂).     

Simultaneous voltammetric detection of dopamine,ascorbic acid and uric acid using a poly(2-(N-morpholine)ethane sulfonic acid)/RGO modified electrode

A poly(2-(N-morpholine) ethane sulfonic acid)/reduced graphene oxide (RGO) modified glassy carbon electrode (GCE) was prepared using an electropolymerization method, and was characterized by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The electrochemical behaviors and simultaneous detection of ascorbic acid (AA), dopamine (DA) and uric acid (UA) at this electrode were studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Tests showed that this electrode exhibited excellent electrocatalytic activity towards the oxidation of AA, DA and UA. The oxidation peak currents of AA, DA and UA were proportional with their concentrations in the ranges 1.0 μM–30 μM (30 μM–100 μM), 0.05 μM–100 μM and 0.1 μM–100 μM, with detection limits of 0.43 μM, 0.0062 μM and 0.056 μM, respectively. In addition, this electrode exhibited an excellent selectivity, reproducibility and stability, and has been successfully used to determine real samples with satisfactory results.

A sensitive electrochemical sensor for simultaneously detecting dopamine, ascorbic acid and uric acid.     

Microporous carbon in the selective electro-oxidation of molecular biomarkers: uric acid,ascorbic acid,and dopamine

Herein, we demonstrate the superior electrocatalytic activities of microporous carbon in the oxidation of three molecular biomarkers, ascorbic acid (AA), dopamine (DA), and uric acid (UA), which are co-present in biological fluids. The voltammetric responses of AA, DA, and UA at the low-cost microporous carbon electrode show significantly better sensitivity and selectivity than other more expensive and commonly used electrode materials such as copper(ii) oxide, copper(i) oxide, and carbon nanotube. Differential pulse voltammetry at the microporous carbon electrode allows the detection of AA, DA, and UA with linear ranges of 100–2000 μM (AA), 10–150 μM (DA), and 10–150 μM (UA), sensitivities of 6.8 ± 0.2 nA μM⁻¹ (AA), 261.4 ± 3.4 nA μM⁻¹ (DA), and 93.5 ± 2.0 nA μM⁻¹ (UA), and detection limits of 23.1 μM (AA), 0.2 μM (DA), and 1.7 μM (UA). The method has been validated with a synthetic urine sample to yield ∼100% recoveries for all three analytes. The developed method has been further applied in the investigation of the peroxide scavenging activity of UA.

Herein, we demonstrate the superior electrocatalytic activities of microporous carbon in the oxidation of three molecular biomarkers, ascorbic acid (AA), dopamine (DA), and uric acid (UA), which are co-present in biological fluids.     

MoS2/polyaniline/functionalized carbon cloth electrode materials for excellent supercapacitor performance

In this study, molybdenum disulfide (MoS₂), polyaniline (PANI) and their composite (MoS₂/PANI) were facilely prepared via a liquid-phase method and in situ polymerization. An MoS₂/PANI/functionalized carbon cloth (MoS₂/PANI/FCC) was facilely constructed by a drop-casting method. MoS₂/PANI-10/FCC displays remarkable electrochemical performances, and its specific capacitances varied from 452.25 to 355.5 F g⁻¹ at current densities ranging from 0.2 to 4 A g⁻¹, which were higher than those of MoS₂/CC (from 56.525 to 7.5 F g⁻¹) and pure PANI/CC (319.5 to 248.5 F g⁻¹), respectively. More importantly, the MoS₂-10/PANI/FCC electrode has a long cycling life, and a capacity retention of 87% was obtained after 1000 cycles at a large current density of 10 A g⁻¹. Moreover, the MoS₂/PANI-10/FCC-based symmetric supercapacitor also exhibits excellent rate performance and good cycling stability. The specific capacitance based on the total mass of the two electrodes is 72.8 F g⁻¹ at a current density of 0.2 A g⁻¹ and the capacitance retention of 85% is obtained after 1000 cycles.

A MoS₂/PANI/functionalized carbon cloth (MoS₂/PANI/FCC) was constructed by a drop-casting method. Its specific capacitances were higher than those of MoS₂/CC and pure PANI/CC.     

Construction of a Au@MoS2 composite nanosheet biosensor for the ultrasensitive detection of a neurotransmitter and understanding of its mechanism based on DFT calculations

MoS₂ nanosheets can be applied as electrochemical biosensors to selectively and sensitively respond to the surrounding environment and detect various biomolecules due to their large specific surface area and unique physicochemical properties. In this paper, single-layer or few-layer MoS₂ nanosheets were prepared by an improved liquid phase stripping method, and then combining the unique material characteristics of MoS₂ and the metallic property of Au nanoparticles (AuNPs), Au@MoS₂ composite nanosheets were synthesized based on MoS₂ nanosheets. Then, the structure and properties of MoS₂ nanosheets and Au@MoS₂ composite nanosheets were comprehensively characterized. The results proved that AuNPs were successfully loaded on MoS₂ nanosheets. At the same time, on the basis of the successful preparation of Au@MoS₂ composite nanosheets, an electrochemical biosensor targeting dopamine was successfully constructed by cyclic voltammetry. The linear detection range was 0.5–350 μM, and the detection limit was 0.2 μM. The high-sensitive electrochemical detection of dopamine has been achieved, which provides a new idea for the application of MoS₂-based nanomaterials in the biosensing of neurotransmitters. In addition, density functional theory (DFT) was used to explore the electrochemical performance of Au@MoS₂ composite nanosheets. The results show that the adsorption of Au atoms on the MoS₂ 2D structure improves the conductivity of MoS₂ nanosheets, which theoretically supports the possibilities of its application as a platform for the ultrasensitive detection of neurotransmitters or other biomolecules in the field of disease diagnosis.

An electrochemical biosensor based on Au@MoS₂ composite nanosheets was successfully prepared for the high-sensitivity detection of dopamine.     

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.     

A facile one-pot green synthesis of gold nanoparticle-graphene-PEDOT:PSS nanocomposite for selective electrochemical detection of dopamine

A facile one-pot and green method was developed to prepare a nanocomposite of gold nanoparticle (AuNP), graphene (GP) and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). Graphene was first electro-exfoliated in a polystyrene sulfonate solution, followed by a one-step simultaneous in situ formation of gold nanoparticle and PEDOT. The as-synthesized aqueous dispersion of AuNP-GP-PEDOT:PSS was thereafter used to modify the glassy carbon electrode (GCE). For the first time, the quaternary composite between AuNP, GP, PEDOT and PSS was used for selective determination of dopamine (DA) and uric acid (UA) in the presence of ascorbic acid (AA). In comparison to a bare GCE, the nanocomposite electrode shows considerably higher electrocatalytic activities toward the oxidation of DA and UA due to a synergistic effect between AuNP, GP, PEDOT and PSS. Using differential pulse voltammetry (DPV), selective determination of DA and UA in the presence of AA could be achieved with a peak potential separation of 110 mV between DA and UA. The sensor exhibits wide linear responses for DA and UA in the ranges of 1 nM to 300 μM and 10 μM to 1 mM with detection limits (S/N = 3) of 100 pM and 10 μM, respectively. Furthermore, the proposed sensor was also successfully used to determine DA in a real pharmaceutical injection sample as well as DA and UA in human serum with satisfactory recovery results.

A facile one-pot green synthesis of gold nanoparticle-graphene-PEDOT:PSS nanocomposite was successfully demonstrated.     

One-pot self-assembly preparation of thiol-functionalized poly(3,4-ethylenedioxythiophene) hollow nanosphere/Au composites,and their electrocatalytic properties

In this work, we developed a thiol-functionalized poly(3,4-ethylenedioxythiophene) hollow sphere (poly(EDOT-MeSH)/Au) polymer through a simple one-pot self-assembly method using polyvinylpyrrolidone (PVP) as a soft template. The monomer was used as both a reductant and a stabilizer to decorate gold nanoparticles (Au NPs). FTIR, XRD, EDX, SEM and TEM analyses were used to characterize the composite hollow spheres. The chemical bond between S and Au was confirmed by XPS. The electrochemical performance of the composite hollow spheres was determined by cyclic voltammetry (CV) and an ampere response timing current test. The results revealed that the poly(EDOT-MeSH)/Au hollow-sphere-based electrochemical sensor possesses excellent conductivity and high redox reversibility with detection limits (S/N = 3) of 0.2, 0.02, 0.08 and 0.05 μM in the linear ranges of 0.1–650 μM, 0.05–100 μM and 0.1–600 μM for the determination of ascorbic acid (AA), dopamine (DA), uric acid (UA) and nitrate ions (NO₂⁻), respectively. The preparation method for these composites will further the development of this type of conducting polymer/gold nano-composite material modified electrochemical sensor for biological species.

In this work, we developed a thiol-functionalized poly(3,4-ethylenedioxythiophene) hollow sphere (poly(EDOT-MeSH)/Au) polymer through a simple one-pot self-assembly method using polyvinylpyrrolidone (PVP) as a soft template.     

MOF-derived (MoS2, γ-Fe2O3)/graphene Z-scheme photocatalysts with excellent activity for oxygen evolution under visible light irradiation

Constructing Z-scheme heterojunctions is considered as an effective strategy to obtain catalysts of high efficiency in electron–hole separation in photocatalysis. Unfortunately, suitable heterojunctions are difficult to fabricate because the direct interaction between two semiconductors may lead to unpredictable negative effects such as electron scattering or electron trapping due to the existence of defects which causes the formation of new substances. Furthermore, the van der Waals contact between two semiconductors also results in bad electron diffusion. In this work, a MOF-derived carbon material as a Z-scheme photocatalyst was synthesized via one-step thermal treatment of MoS₂ dots @Fe-MOF (MIL-101). Under visible light irradiation, the well-constructed Z-scheme (MoS₂, γ-Fe₂O₃)/graphene photocatalyst shows 2-fold photocatalytic oxygen evolution activity (4400 μmol g⁻¹ h⁻¹) compared to that of γ-Fe₂O₃/graphene (2053 μmol g⁻¹ h⁻¹). Based on ultraviolet photoelectron spectrometry (UPS), Mott–Schottky plot, photocurrent and photoluminescence spectroscopy (PL) results, the photo-induced electrons from the conduction band of γ-Fe₂O₃ could transport quickly to the valence band of MoS₂via highly conductive graphene as an electron transport channel, which could significantly enhance the electron–hole separation efficiency as well as photocatalytic performance.

The heterojunction between MoS₂ and γ-Fe₂O₃ was constructed via linking by in situ formed graphene, which resulted in a good photocatalyst for the oxygen evolution reaction, showing O₂ evolution activity of 4400 μmol g⁻¹ h⁻¹.     

Facile synthesis of a zeolitic imidazolate framework-8 with reduced graphene oxide hybrid material as an efficient electrocatalyst for nonenzymatic H2O2 sensing

A zeolitic imidazolate framework-8 (ZIF-8)/reduced graphene oxide (rGO) nanocomposite was formed by using an efficient synthetic method. The morphology and structure of the ZIF-8/rGO nanocomposite were characterized by scanning electron spectroscopy (SEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA) mapping. The ZIF-8/rGO nanocomposites were immobilized on a carbon paste electrode (CPE) to construct a high-performance nonenzymatic electrochemical H₂O₂ sensor. A cyclic voltammetry (CV) study showed that the ZIF-8/rGO nanocomposites displayed better electrocatalytic activity toward H₂O₂ reduction compared to that of ZIF-8. An amperometric study indicated that the H₂O₂ sensor displayed high performance, which offered a low detection limit (0.05 μM) (S/N = 3), a high sensitivity (4.01 μA mM⁻¹ cm⁻²), and a wide linear range (from 1.0 to 625 μM). An electrochemical reaction mechanism was proposed for H₂O₂ reduction on the ZIF-8/rGO/CPE. Importantly, the as-fabricated H₂O₂ sensor exhibited good reproducibility and excellent selectivity. Furthermore, the constructed high-performance sensor was utilized to monitor the H₂O₂ levels in real samples, and satisfactory results were obtained. These results demonstrated that the ZIF-8/rGO nanocomposite can be used as a good electrochemical sensor material in practical applications.

A zeolitic imidazolate framework-8 (ZIF-8)/reduced graphene oxide (rGO) nanocomposite was formed by using an efficient synthetic method.     

Deposition of an ultra-thin polyaniline coating on a TiO2 surface by vapor phase polymerization for electrochemical glucose sensing and photocatalytic degradation

Here, we have synthesized an ultra-thin coating of polyaniline on a TiO₂ nanoparticle surface (PANI–TiO₂) using a simple vapor phase polymerization method. By this method, an ultra-thin layer of PANI is obtained selectively on the TiO₂ surface. This ultra-thin coating exhibits the properties of both the parent materials due to the composite surface causing an effective synergistic effect. SEM, TEM, and EDX studies and elemental mapping confirmed the formation of ultra-thin films on the TiO₂ surface. TGA, UV/Vis and XRD studies were also done for further characterization. The composite has been used as a biosensor for glucose detection by immobilization of the enzyme glucose oxidase (GOx). Cyclic voltammetry, electrochemical impedance spectroscopy and amperometry studies were performed for glucose sensing. The linear range was observed from 20 to 140 μM glucose concentration from the amperometric analysis. The LOD of the biosensor was found to be 5.33 μM. The composite has also been used for photocatalytic degradation of the cationic dye Rhodamine B (RB). The order of degradation efficiency of RB is found to be PANI < TiO₂ < PANI–TiO₂. The synergetic effect of PANI and TiO₂ is the reason for the enhanced degradation efficiency of the composite PANI–TiO₂.

Here, we have synthesized an ultra-thin coating of polyaniline on a TiO₂ nanoparticle surface (PANI–TiO₂) using a simple vapor phase polymerization method.     

Uncovering the origin of enhanced field emission properties of rGO–MnO2 heterostructures: a synergistic experimental and computational investigation

The unique structural merits of heterostructured nanomaterials including the electronic interaction, interfacial bonding and synergistic effects make them attractive for fabricating highly efficient optoelectronic devices. Herein, we report the synthesis of MnO₂ nanorods and a rGO/MnO₂ nano-heterostructure using low-cost hydrothermal and modified Hummers'' methods, respectively. Detailed characterization and confirmation of the structural and morphological properties are done via X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Compared to the isolated MnO₂ nanorods, the rGO/MnO₂ nano-heterostructure exhibits impressive field emission (FE) performance in terms of the low turn-on field of 1.4 V μm⁻¹ for an emission current density of 10 μA cm⁻² and a high current density of 600 μA cm⁻² at a relatively very low applied electric field of 3.1 V μm⁻¹. The isolated MnO₂ nanorods display a high turn-on field of 7.1 for an emission current density of 10 μA cm⁻² and a low current density of 221 μA cm⁻² at an applied field of 8.1 V μm⁻¹. Besides the superior FE characteristics of the rGO/MnO₂ nano-heterostructure, the emission current remains quite stable over the continuous 2 h period of measurement. The improvement of the FE characteristics of the rGO/MnO₂ nano-heterostructure can be ascribed to the nanometric features and the lower work function (6.01 and 6.12 eV for the rGO with 8% and 16% oxygen content) compared to the isolated α-MnO₂(100) surface (Φ = 7.22 eV) as predicted from complementary first-principles electronic structure calculations based on density functional theory (DFT) methods. These results suggest that an appropriate coupling of rGO with MnO₂ nanorods would have a synergistic effect of lowering the electronic work function, resulting in a beneficial tuning of the FE characteristics.

The unique structural merits of heterostructured nanomaterials including the electronic interaction, interfacial bonding and synergistic effects make them attractive for fabricating highly efficient optoelectronic devices.     

Thiolated poly(aspartic acid)-functionalized two-dimensional MoS2, chitosan and bismuth film as a sensor platform for cadmium ion detection

In this work, a sensitive electrochemical platform for determination of cadmium ions (Cd²⁺) is obtained using thiolated poly(aspartic acid) (TPA)-functionalized MoS₂ as a sensor platform by differential pulse anodic stripping voltammetry (DPASV). The performance of the TPA–MoS₂-modified sensor is systemically studied. It demonstrates that the TPA–MoS₂ nanocomposite modified sensor exhibits superior analytical performance for Cd²⁺ over a linear range from 0.5 μg L⁻¹ to 50 μg L⁻¹, with a detection limit of 0.17 μg L⁻¹. Chitosan is able to form a continuous coating film on the surface of the GC electrode. The good sensing performance of the TPA–MoS₂-modified sensor may be attributed to the following factors: the large surface area of MoS₂ (603 m² g⁻¹), and the abundant thiol groups of TPA. Thus, the TPA–MoS₂-modified sensor proves to be a reliable and environmentally friendly tool for the effective monitoring of Cd²⁺ existing in aquacultural environments.

In this work, a sensitive electrochemical platform for determination of cadmium ions (Cd²⁺) is obtained using thiolated poly(aspartic acid) (TPA)-functionalized MoS₂ as a sensor platform by differential pulse anodic stripping voltammetry (DPASV).     

A simple electrochemical sensor based on rGO/MoS2/CS modified GCE for highly sensitive detection of Pb(ii) in tobacco leaves

High-performance electrode modification materials play a crucial role in improving the sensitivity of sensor detection in electrochemical determination of heavy metals. In this study, a rGO/MoS₂/CS nanocomposite modified glassy carbon electrode (GCE) was used to construct a sensitive sensor for detecting lead ions in tobacco leaves. The reduced graphene oxide (rGO) was used to increase the conductivity of the sensor, and the nano-flowered MoS₂ could provide a large reaction specific surface area and a certain active site for heavy metal reaction. Chitosan (CS) was used to improve the enrichment ability of heavy metals and increase the electrocatalytic activity of electrode. Thus, an electrochemical sensor with excellent performance in reproducibility, stability and anti-interference ability was established. The stripping behavior of Pb(ii) and the application conditions of the sensor were studied by square wave anodic stripping voltammetry (SWASV). The investigation indicated that the sensor exhibited high detection sensitivity in the range of 0.005–0.05–2.0 μM, and the limit of detection (LOD) was 0.0016 μM. This work can provide a fast and effective method for determination of Pb(ii) in samples with low content, such as tobacco leaves.

High-performance electrode modification materials play a crucial role in improving the sensitivity of sensor detection in electrochemical determination of heavy metals.     

Enhancing the chloramphenicol sensing performance of Cu–MoS2 nanocomposite-based electrochemical nanosensors: roles of phase composition and copper loading amount

The rational design of nanomaterials for electrochemical nanosensors from the perspective of structure–property–performance relationships is a key factor in improving the analytical performance toward residual antibiotics in food. We have investigated the effects of the crystalline phase and copper loading amount on the detection performance of Cu–MoS₂ nanocomposite-based electrochemical sensors for the antibiotic chloramphenicol (CAP). The phase composition and copper loading amount on the MoS₂ nanosheets can be controlled using a facile electrochemical method. Cu and Cu₂O nanoparticle-based electrochemical sensors showed a higher CAP electrochemical sensing performance as compared to CuO nanoparticles due to their higher electrocatalytic activity and conductivity. Moreover, the design of Cu–MoS₂ nanocomposites with appropriate copper loading amounts could significantly improve their electrochemical responses for CAP. Under optimized conditions, Cu–MoS₂ nanocomposite-based electrochemical nanosensor showed a remarkable sensing performance for CAP with an electrochemical sensitivity of 1.74 μA μM⁻¹ cm⁻² and a detection limit of 0.19 μM in the detection range from 0.5–50 μM. These findings provide deeper insight into the effects of nanoelectrode designs on the analytical performance of electrochemical nanosensors.

In this work, we clarify the roles of phase composition and copper loading amount on the CAP sensing performance of Cu–MoS₂ nanocomposite-based electrochemical nanosensors.     

Comprehensive In Vitro Analysis of Voriconazole Inhibition of Eight Cytochrome P450 (CYP) Enzymes: Major Effect on CYPs 2B6, 2C9, 2C19, and 3A

Voriconazole is an effective antifungal drug, but adverse drug-drug interactions associated with its use are of major clinical concern. To identify the mechanisms of these interactions, we tested the inhibitory potency of voriconazole with eight human cytochrome P450 (CYP) enzymes. Isoform-specific probes were incubated with human liver microsomes (HLMs) (or expressed CYPs) and cofactors in the absence and the presence of voriconazole. Preincubation experiments were performed to test mechanism-based inactivation. In pilot experiments, voriconazole showed inhibition of CYP2B6, CYP2C9, CYP2C19, and CYP3A (half-maximal [50%] inhibitory concentrations, <6 μM); its effect on CYP1A2, CYP2A6, CYP2C8, and CYP2D6 was marginal (<25% inhibition at 100 μM voriconazole). Further detailed experiments with HLMs showed that voriconazole is a potent competitive inhibitor of CYP2B6 (K_i < 0.5), CYP2C9 (K_i = 2.79 μM), and CYP2C19 (K_i = 5.1 μM). The inhibition of CYP3A by voriconazole was explained by noncompetitive (K_i = 2.97 μM) and competitive (K_i = 0.66 μM) modes of inhibition. Prediction of the in vivo interaction of voriconazole from these in vitro data suggests that voriconazole would substantially increase the exposure of drugs metabolized by CYP2B6, CYP2C9, CYP2C19, and CYP3A. Clinicians should be aware of these interactions and monitor patients for adverse effects or failure of therapy.     

A Conserved Hydrogen-Bonding Network of P2 bis-Tetrahydrofuran-Containing HIV-1 Protease Inhibitors (PIs) with a Protease Active-Site Amino Acid Backbone Aids in Their Activity against PI-Resistant HIV

In the present study, GRL008, a novel nonpeptidic human immunodeficiency virus type 1 (HIV-1) protease inhibitor (PI), and darunavir (DRV), both of which contain a P2-bis-tetrahydrofuranyl urethane (bis-THF) moiety, were found to exert potent antiviral activity (50% effective concentrations [EC₅₀s], 0.029 and 0.002 μM, respectively) against a multidrug-resistant clinical isolate of HIV-1 (HIV_A02) compared to ritonavir (RTV; EC₅₀, >1.0 μM) and tipranavir (TPV; EC₅₀, 0.364 μM). Additionally, GRL008 showed potent antiviral activity against an HIV-1 variant selected in the presence of DRV over 20 passages (HIV_DRV^R_P20), with a 2.6-fold increase in its EC₅₀ (0.097 μM) compared to its corresponding EC₅₀ (0.038 μM) against wild-type HIV-1_NL4-3 (HIV_WT). Based on X-ray crystallographic analysis, both GRL008 and DRV showed strong hydrogen bonds (H-bonds) with the backbone-amide nitrogen/carbonyl oxygen atoms of conserved active-site amino acids G27, D29, D30, and D30′ of HIV_A02 protease (PR_A02) and wild-type PR in their corresponding crystal structures, while TPV lacked H-bonds with G27 and D30′ due to an absence of polar groups. The P2′ thiazolyl moiety of RTV showed two conformations in the crystal structure of the PR_A02-RTV complex, one of which showed loss of contacts in the S2′ binding pocket of PR_A02, supporting RTV''s compromised antiviral activity (EC₅₀, >1 μM). Thus, the conserved H-bonding network of P2-bis-THF-containing GRL008 with the backbone of G27, D29, D30, and D30′ most likely contributes to its persistently greater antiviral activity against HIV_WT, HIV_A02, and HIV_DRV^R_P20.     

Facile preparation of rGO/MFe2O4 (M = Cu,Co, Ni) nanohybrids and its catalytic performance during the thermal decomposition of ammonium perchlorate

Reduced graphene oxide/metal ferrite (rGO/MFe₂O₄, M = Cu, Co, Ni) nanohybrids are successfully prepared through a simple, one-step hydrothermal method. The rGO/MFe₂O₄ nanohybrids are characterized by XRD, TEM, FT-IR, XPS, Raman and BET surface area measurements. The rGO/MFe₂O₄ nanohybrids demonstrate amazing catalytic activities on the thermal decomposition of ammonium perchlorate (AP). DSC results indicate that rGO/MFe₂O₄ nanohybrids (3 wt%), could decrease the decomposition temperature of pure AP from 424.7 °C to 329.1 °C, 338.3 °C, and 364.8 °C, respectively. This enhanced catalytic performance is mainly attributed to the synergistic effect of NPs and rGO. The activation energy (E_a) of AP mixed with nanohybrids is investigated by two isoconversion methods, Flynne–Walle–Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS), on a conversion degree (α) range from 0.05 to 0.95. The values of E_a calculated from the above two methods matched with each other. A strong dependence of E_a on α is observed, indicating a complex decomposition process.

The rGO/MFe₂O₄ (M = Cu, Co, Ni) nanohybrids show amazing catalytic activity in the thermal decomposition process of AP.     

Mesoporous NiO nanosphere: a sensitive strain sensor for determination of hydrogen peroxide

Exploring the sensitive and reliable methods for the determination of hydrogen peroxide (H₂O₂) is a crucial issue for the health and environmental challenges. Herein, we demonstrate a facile, but rational and effective solvothermal approach to the synthesis of hierarchical NiO mesoporous nanospheres (NiO-MNS) as an effective non-enzymatic sensor towards the H₂O₂ detection. Owing to the intercalation and stabilization effect of polyethylene glycol for the Ni(OH)₂ intermediate, the NiO mesoporous nanosphere (NiO-MNS) product is consistent with the low-dimensional nanostructured NiO blocks with large surface area and plentiful mesopores after the calcination treatment. The obtained NiO-MNS sensor presents superior electrochemical performance with a high sensitivity (236.7 μA mM⁻¹ cm⁻²) and low limit of detection (0.62 μM), as well as the good selectivity and reliability for the further application of H₂O₂ detection. In addition, the unraveling mechanism of the mesopores formation derived from the in situ measurements also offers the valuable guidance for the future design of porous materials for electrochemical devices and other applications.

The NiO mesoporous nanosphere constructing from the low-dimensional nanostructured NiO blocks presents the excellent electrochemical activity for H₂O₂ detection.     

Novel derivatives of eugenol as potent anti-inflammatory agents via PPARγ agonism: rational design,synthesis, analysis,PPARγ protein binding assay and computational studies

Eugenol is a natural product abundantly found in clove buds known for its pharmacological activities such as anti-inflammatory, antidiabetic, antioxidant, and anticancer activities. It is well known from the literature that peroxisome proliferator-activated receptors (PPARγ) have been reported to regulate inflammatory responses. In this backdrop, we rationally designed semi-synthetic derivatives of eugenol with the aid of computational studies, and synthesized, purified, and analyzed four eugenol derivatives as PPARγ agonists. Compounds were screened for PPARγ protein binding by time-resolved fluorescence (TR-FRET) assay. The biochemical assay results were favorable for 1C which exhibited significant binding affinity with an IC₅₀ value of 10.65 μM as compared to the standard pioglitazone with an IC₅₀ value of 1.052 μM. In addition to the protein binding studies, as a functional assay, the synthesized eugenol derivatives were screened for in vitro anti-inflammatory activity at concentrations ranging from 6.25 μM to 400 μM. Among the four compounds tested 1C shows reasonably good anti-inflammatory activity with an IC₅₀ value of 133.8 μM compared to a standard diclofenac sodium IC₅₀ value of 54.32 μM. Structure–activity relationships are derived based on computational studies. Additionally, molecular dynamics simulations were performed to examine the stability of the protein–ligand complex, the dynamic behavior, and the binding affinity of newly synthesized molecules. Altogether, we identified novel eugenol derivatives as potential anti-inflammatory agents via PPARγ agonism.

Rational design, synthesis, analysis, PPARγ protein binding assay and computational studies of novel eugenol derivatives.