Fabrication of poly(ϵ-caprolactone)/paclitaxel (core)/chitosan/zein/multi-walled carbon nanotubes/doxorubicin (shell) nanofibers against MCF-7 breast cancer

In the present study, paclitaxel (PTX), multi-walled carbon nanotubes (MWCNTs), and doxorubicin (DOX) have been simultaneously doped into the poly(ϵ-caprolactone) (PCL)/chitosan/zein core-shell nanofibers to increase its cytotoxicity for MCF-7 breast cancers killing. The physico-chemical properties of synthesized nanofibers were determined by scanning electron microscope, Fourier-transform infrared spectroscopy, tensile strength, and degradation rate determinations. The in vitro release studies demonstrated the sustained release of drugs from core-shell nanofibrous scaffold. The cytotoxicity and compatibility of core-shell nanofibers were investigated by their treating with MCF-7 breast cancer cells and L929 normal cells, respectively. PCL/PTX/chitosan/zein/MWCNTs/DOX core-shell nanofibers containing 1 wt% MWCNTs, 100 μg ml⁻¹ DOX and 100 μg ml⁻¹ PTX had a high biocompatibility with a 84% MCF-7 cancer cells killing. The in vivo studies revealed the synergic effects of MWCNTs and anticancer drugs on the tumor inhibition. This method could be considered as a new way for developing of MWCNTs loaded-nanofibers for cancer treatment in future.     

Facile synthesis methodology and characterization studies of silica-decorated hybridized anisotropic nanotubes and nanosheets

Carbonaceous nanomaterials and their derivatives have been inspired tremendous enthusiasm in the scientific community. They have been excogitated as the encouraging attributes and the qualified dispersed phase to develop multi-functional composites. Particularly, graphene and carbon nanotube (anisotropic fillers) have gained substantial research interest owing to their promising characteristics. This highlights an innovative technique to synthesize hybridized nanotube and nanosheet. Initially, parent materials have been synthesized: The pristine CNT has been modified by acid mixture solution, and reduced graphene oxide has been prepared by chemical reduction method. Henceforth, the self-assembly in situ sol–gel technique has been endorsed here. The synthesized nanohybrids have been characterized by different spectroscopic techniques: FTIR, Raman, UV, and XPS to confirm the attachment of multifunctionalities; meanwhile, the composition and stability have been investigated from XRD and TGA plots. The magnitude of surface charge and particle size distribution have been evaluated for the parent and hybridized products; further, morphology of all the samples has been authenticated from FESEM and TEM.     

Heterogeneous Hydrogenation with Hydrogen Spillover Enabled by Nitrogen Vacancies on Boron Nitride-Supported Pd Nanoparticles

Heterogeneous hydrogenation with hydrogen spillover has been demonstrated as an effective route to achieve high selectivity towards target products. More effort should be paid to understand the complicated correlation between the nature of supports and hydrogenation involving hydrogen spillover. Herein, we report the development of the hydrogenation system of hexagonal boron nitride (h-BN)-supported Pd nanoparticles for the hydrogenation of aldehydes/ketones to alcohols with hydrogen spillover. Nitrogen vacancies in h-BN determine the feasibility of hydrogen spillover from Pd to h-BN. The hydrogenation of aldehydes/ketones with hydrogen spillover from Pd proceeds on nitrogen vacancies on h-BN. The weak adsorption of alcohols to h-BN inhibits the deep hydrogenation of aldehydes/ketones, thus leading to high catalytic selectivity to alcohols. Moreover, the hydrogen spillover-based hydrogenation mechanism makes the catalyst system exhibit a high tolerance to CO poisoning.     

Activating Bi p-orbitals in Dispersed Clusters of Amorphous BiOx for Electrocatalytic Nitrogen Reduction

Catalytic strategies based on main group metals are significantly less advanced than those of transition metal catalysis, leaving untapped areas of potentially fruitful research. We here demonstrate an effective approach for the modulation of Bi 6p energy levels during the construction of atomically dispersed clusters of amorphous BiO_x. Bi oxidation state is proposed to strongly affects the nitrogen fixation activity, with the half-occupied p_z orbitals of the Bi²⁺ ions being highly efficient toward electron injection into the inert N₂ molecule. With sufficient catalytic sites to adsorb and activate N₂, the bonding between N₂ and catalyst is able to be in situ identified. The catalyst shows an outstanding Faraday efficiency (≈30 %) and high yield (≈113 μg h⁻¹ mg⁻¹_cat) in NH₃ production, outperforming most of the existing catalysts in aqueous solution. These results lay the basis for developing the potential of p-block elements for catalysis of multi-electron reactions.     

Pulsed Electrocatalysis Enabling High Overall Nitrogen Fixation Performance for Atomically Dispersed Fe on TiO2

Atomically dispersed Fe was designed on TiO₂ and explored as a Janus electrocatalyst for both nitrogen oxidation reaction (NOR) and nitrogen reduction reaction (NRR) in a two-electrode system. Pulsed electrochemical catalysis (PE) was firstly involved to inhibit the competitive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Excitingly, an unanticipated yield of 7055.81 μmol h⁻¹ g⁻¹_cat. and 12 868.33 μmol h⁻¹ g⁻¹_cat. were obtained for NOR and NRR at 3.5 V, respectively, 44.94 times and 7.8 times increase in FE than the conventional constant voltage electrocatalytic method. Experiments and density functional theory (DFT) calculations revealed that the single-atom Fe could stabilize the oxygen vacancy, lower the energy barrier for the vital rupture of N≡N, and result in enhanced N₂ fixation performance. More importantly, PE could effectively enhance the N₂ supply by reducing competitive O₂ and H₂ agglomeration, inhibit the electrocatalytic by-product formation for longstanding *OOH and *H intermediates, and promote the non-electrocatalytic process of N₂ activation.     

Electrochemical Affinity Sensors Using Field Effect Transducer Devices for Chemical Analysis

The review presents advances and main challenges of the affinity sensors based on field- effect transistors published during the last five years. The different nanomaterial-based field-effect transistors are classified according to the nature of the nanomaterials, beginning by silicon, the “gold-standard” semiconductor, the gallium nitride semiconductor, the organic semiconductors, the silicon nanowires, the inorganic nanomaterials, the carbon nanotubes and the graphene. Due to its exceptional electrical properties, the main works are devoted to graphene. The obtained analytical performances for the detection of biomarkers, of DNA sequences and of miRNA are listed. The relation between the operational conditions - nature of the nanomaterials, procedure of preparation, choice of the receptor molecule, method of immobilization – and the analytical performance are discussed. The perspective of industrialization of these affinity sensors based on field-effect transistors is discussed.     

Highly Sensitive Enzyme-free Sensor Based on a Carbon Paste Electrode Modified with Binary Zinc Oxide/Polyaniline Nanocomposites for Dopamine,Ascorbic Acid and Uric Acid Sensing

Hybrid composites ZnO/PANI were facily synthesized by a sonication process at room temperature. This procedure is non-expensive, time/energy saving and environmentally safe. The as-prepared ZnO/PANI were characterized by FTIR, UV-vis spectroscopies and SEM in order to investigate the structure and morphology of the studied composites. The samples were used to modify carbon paste electrode (CPE) in order to develop electrochemical biosensors (ZnO/PANI/CPE). The sensing properties of the nanoparticles were evaluated for dopamine, ascorbic acid and uric acid non-enzymatic detection. The effect of percentage of polyaniline in the composites and the effect of calcination on the biosensor's response were also examined in the present study. It was revealed that the existence of PANI in ZnO/PANI/CPE largely enhanced the electroactive surface area and therefore the sensitivity for electrochemical sensing. A good electrochemical behavior was noted for ZnO/40 wt% PANI-cal/CPE modified electrode toward DA, AA and UA oxidation. The electroactive surface area of the previously mentioned modified electrode (0.235 cm²) was two times higher than that of the bare electrode (0.117 cm²). The liner relationships between current intensities and concentrations were found to be 0.01–1.4 mM, 0.1–1.3 mM and 0.01–0.12 mM, with detection limit of 0.029 mM, 0.063 mM and 0.007 mM, for DA, AA and UA respectively. In the mixtures of ascorbic acid (AA), dopamine (DA) uric acid (UA) and glucose (Glu) the sensor showed high selectivity of DA with low interference of ascorbic acid by a current change of 14 %. The as-prepared ZnO/PANI/CPE biosensor displayed a good reproducibility and stability.     

Highly Sensitive Electrochemical Immunosensor Based on Mesoporous PdPt Nanoparticles Anchored on a Three-dimensional PANI@CNTs Network as Nanozyme Labels

In this study, a novel strategy to amplify electrochemical signals by mesoporous PdPt nanoparticles with core-shell structures anchored on a three-dimensional PANI@CNTs network as nanozyme labels (PdPt/PANI@CNTs) was proposed for the sensitive monitoring of α-fetoprotein (AFP, Ag). First, the mesoporous PdPt nanoparticles prepared by a facile chemical reduction method had excellent biocompatibility with biomolecules, which could capture a large amount of AFP-Ab₂ (Ab₂) and exhibit plentiful pores to entrap more thionine (Thi) into mesoporous PdPt nanoparticles with enhanced loading and abundant active sites. Furthermore, the resulting mesoporous PdPt nanoparticles were abundantly dotted on the surface of a three-dimensional PANI@CNTs network with excellent conductivity and a high specific surface area through the bonding of the amino group to form PdPt/PANI@CNTs nanozyme labels. Most importantly, the as-prepared PdPt/PANI@CNTs nanozyme labels exhibited unexpected enzyme-like activity towards the reduction of hydrogen peroxide owing to the highly indexed facets, enhancing the current response to realize signal amplification. In view of the advantages of nanozyme labels and the involvement of gold nanoparticles (AuNPs, which behave as electrode materials) for the sensitive determination of AFP, the as-developed immunosensor could obtain a dynamic working range of 0.001 ng mL^−1–100.0 ng mL⁻¹ at a detection limit of 0.33 pg mL⁻¹ via DPV (at 3σ). Furthermore, the nanozyme-based electrochemical immunosensor exhibited remarkable analytical performance, which brought about feasible ideas for disease diagnosis in the future.     

Screen-printed electrochemical sensors for label-free potentiometric and impedimetric detection of human serum albumin

Herein, two electrochemical methods based on potentiometric and impedimetric transductions were presented for albumin targeting, employing screen-printed platforms (SPEs) to make easy and cost-effective sensors with good detection merits. The SPEs incorporated ion-to-electron multi-walled carbon nanotubes (MWCNTs) transducer. Sensors were constructed using either tridodecyl methyl-ammonium chloride (TDMACl) (sensor I) or aliquate 336S (sensor II) in plasticized polymeric matrices of carboxylated poly (vinyl chloride) (PVC-COOH). Analytical performances of the sensors were evaluated using the above-mentioned electrochemical techniques. For potentiometric assay, constructed sensors responded to albumin with −81.7 ± 1.7 (r² = 0.9986) and −146.2 ± 2.3 mV/decade (r² = 0.9991) slopes over the linearity range 1.5 μM–1.5 mM with 0.8 and 1.0 μM detection limits for respective TDMAC- and aliquate-based sensors. Interference study showed apparent selectivity for both sensors. Impedimetric assays were performed at pH = 7.5 in 10 mM PBS buffer solution with a 0.02 M [Fe(CN)₆]^−3/−4 redox-active electrolyte. Sensors achieved detection limits of 4.3 × 10⁻⁸ and 1.8 × 10⁻⁷ M over the linear ranges of 5.2×10⁻⁸–1.0×10⁻⁴ M and 1.4×10⁻⁶–1.4×10⁻³ M, with 0.09 ± 0.004 and 0.168 ± 0.009 log Ω/decade slopes for sensors based on TDMAC and aliquate, respectively. These sensors are characterized with simple construction, high sensitivity and selectivity, fast response time, single-use, and cost-effectiveness. The methods were successfully applied to albumin assessment in different biological fluids.     

Amperometric detection of indapamide on glassy carbon electrode

This work describes the development of a fast, precise and reliable voltammetric method for the quantification of indapamide, an orally active diuretic sulfonamide used for hypertensive treatment. This compound acts inhibiting sodium reabsorption and increasing the elimination of water. This characteristic was responsible for its banishment by the International Olympic Committee since 1999. The study begins by finding an adequate potential range (−0.20 to 0.30 V) to avoid poisoning the working glassy carbon electrode (GCE) in phosphate buffer 0.10 mol L⁻¹ (pH=12.0). Utilizing flow injection analysis, linear responses between 2.0 × 10⁻⁶ mol L⁻¹ to 2.5 × 10⁻⁵ mol L⁻¹ of indapamide (R²=0.995), and detection limit (LOD) 3.0 × 10⁻⁷ mol L⁻¹ were obtained. This method was applied for the quantification of indapamide in tablets and in synthetic urine. The same flow system was used for the analysis of commercial drugs and the response obtained corresponded to 98 % of the concentration indicated on the drug label. These tablets were also analyzed by high performance liquid chromatography (HPLC), obtaining a recovery of 103 % and LOD 4.0 × 10⁻⁷ mol L⁻¹. The velocity of analysis using flow methods compares advantageously to the classical chromatographic methods. For synthetic urine, linear responses were obtained in samples spiked in the region from 5.0 × 10⁻⁶ mol L⁻¹ to 30 × 10⁻⁶ mol L⁻¹ (R²=0.991) and LOD 3.0 × 10⁻⁷ mol L⁻¹.