Metal-organic framework/Nb4C3Tx MXene composites for ultrasensitive detection of dopamine.

An easy, in situ growth approach led to the formation of several composites of metal-organic framewoks and Nb4C3Tx MXenes mixed intimately at the submicron scale. The high affinity of MXene surface for dopamine, enhanced by a nanostructuration induced by MOFs, resulted in superior sensing performances. The system exhibited good linearity over the 1-100 nM range, with an excellent limit of detection of 0.2 nM.

Hexagonal Boron Nitride Quantum Dots Embedded on Layer-by-Layer Films for Peroxidase-Assisted Colorimetric Detection of ß-Galactosidase Producing Pathogens.

Pathogen detection has become a major research area all over the world for water quality surveillance and microbial risk assessment. Therefore, designing simple and sensitive detection kits plays a key role in envisaging and evaluating the risk of disease outbreaks and providing quality healthcare settings. Herein, we have designed a facile and low-cost colorimetric sensing strategy for the selective and sensitive determination of ß-galactosidase producing pathogens. The hexagonal boron nitride quantum dots (h-BN QDs) were established as a nanozyme that showed prominent peroxidase-like activity, which catalyzes 3,3',5,5'-tetramethylbenzidine (TMB) oxidation by H2O2. The h-BN QDs were embedded on a layer-by-layer assembled agarose biopolymer. The ß-galactosidase enzyme partially degrades ß-1,4 glycosidic bonds of agarose polymer, resulting in accessibility of h-BN QDs on the solid surface. This assay can be conveniently conducted and analyzed by monitoring the blue color formation due to TMB oxidation within 30 min. The nanocomposite was stable for more than 90 days and was showing TMB oxidation after incubating it with Escherichia coli (E. coli). The limit of detection was calculated to be 1.8 × 106 and 1.5 × 106 CFU/mL for E. coli and Klebsiella pneumonia (K. pneumonia), respectively. Furthermore, this novel sensing approach is an attractive platform that was successfully applied to detect E. coli in spiked water samples and other food products with good accuracy, indicating its practical applicability for the detection of pathogens in real samples.

Water-Soluble Ionic Metal-Organic Polyhedra as a Versatile Platform for Enzyme Bio-immobilization.

Metal-organic polyhedra (MOPs) can act as elementary structural units for the design of modular porous materials; however, their association with biological systems remains greatly restricted by their typically low stabilities and solubilities in water. Herein, we describe the preparation of novel MOPs bearing either anionic or cationic groups and exhibiting a high affinity for proteins. Simple mixing of the protein bovine serum albumin (BSA) and ionic MOP aqueous solutions resulted in the spontaneous formation of MOP-protein assemblies, in a colloidal state or as solid precipitates depending on the initial mixing ratio. The versatility of the method was further illustrated using two enzymes, catalase and cytochrome c, with different sizes and isoelectric points (pI's) below and above 7. This mode of assembly led to the high retention of catalytic activity and enabled recyclability. Furthermore, the co-immobilization of cytochrome c with highly charged MOPs resulted in a substantial 44-fold increase of its catalytic activity.

Correction: Highly sensitive and selective colorimetric detection of dual metal ions (Hg2+ and Sn2+) in water: an eco-friendly approach.

[This corrects the article DOI: 10.1039/D0RA09926K.].

Correction: A novel method for the rapid sensing of H2O2 using a colorimetric AuNP probe and its DFT study.

Correction for 'A novel method for the rapid sensing of H2O2 using a colorimetric AuNP probe and its DFT study' by Nirangkush Borah et al., Anal. Methods, 2021, 13, 2055-2065, DOI: 10.1039/D1AY00355K.

A novel method for the rapid sensing of H2O2 using a colorimetric AuNP probe and its DFT study.

Hydrogen peroxide (H2O2) has tremendous applications in industry, medicine and in our day-to-day lives. It is toxic to human health upon exposure at a high concentration. Therefore, a green and cost-effective sensing technique is greatly needed for the sensitive naked eye detection of peroxide. This study is mainly focused on the synthesis of Au nanoparticles (AuNPs) using an aqueous extract of Elsholtzia blanda, a flower that is widely available in the North Eastern part of India, the characterization of which was carried out using different analytical techniques. The bioactive molecule (epigallocatechin gallate) present in the aqueous extract was identified, isolated and confirmed through high-performance liquid chromatography-photodiode array, high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy analysis which could be responsible for the reduction of Au3+ ions. By approaching this greener route, the synthesized nanomaterial was further used as a colorimetric probe for the detection of H2O2 and the degradation of AuNPs was observed. The limit of detection was found to be 0.7435 µM in the present work. The degradation of the AuNPs was found to be linearly dependent on peroxide concentration. Along with these results, kinetic studies were carried out by considering different effects to monitor the sensing speed of the AuNPs. The plausible mechanism of the work was supported by density functional theory study.

Polydopamine functionalized graphene sheets decorated with magnetic metal oxide nanoparticles as efficient nanozyme for the detection and degradation of harmful triazine pesticides.

A facile and an eco-friendly reduction and functionalization of reduced graphene oxide (rGO) sheets is carried out using dopamine and decorated with magnetic Fe3O4 nanoparticles with an average size of 12 nm by a simple co-precipitation method which is established as an artificial nanozyme. Here, functionalization of graphene using dopamine has introduced several advantages and insights into this study. The Fe3O4 nanoparticles decorated functionalized rGO sheets (FDGs) nanozymes are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric (TGA) and vibrating sample magnetometer (VSM) analysis. FDGs nanozymes exhibits dual characteristics towards detection and degradation of harmful simazine pesticide. The hydrogen bonding interactions between pesticide molecules and 3,3',5,5'-tetramethylbenzidine (TMB) causes inhibition of the catalytic activity of the FDGs towards oxidation of TMB molecule. Based on that, the presence of simazine pesticide in an aqueous medium can be easily determined and a certain value (2.24 µM) of detection limit was achieved. The photocatalytic degradation of simazine is also executed and excellent photocatalytic activity was observed under irradiation of direct natural sunlight. The FDGs nanozyme is also reusable up to several times with insignificant loss in its catalytic activity towards simazine degradation.

Highly sensitive and selective colorimetric detection of dual metal ions (Hg2+ and Sn2+) in water: an eco-friendly approach.

Application of an alliin-based precursor for the synthesis of silver nanoparticles (Ag NPs) which is an emerging, reliable and rapid sensor of heavy metal ion contaminants in water is reported here. The Ag NPs were characterized by using UV-visible spectroscopy, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy analysis techniques. The Ag NPs simultaneously and selectively detect Hg2+ and Sn2+ ions from aqueous solution. The sensitivity and selectivity of the prepared Ag NPs towards other representative transition-metal ions, alkali metal ions and alkaline earth metal ions were also studied. For more precise evidence, a density functional theory study was carried out to understand the possible mechanism and interaction in the detection of Hg2+ and Sn2+ by Ag NPs. The limits of detection for Hg2+ and Sn2+ ions were found as 15.7 nM and 11.25 nM, respectively. This assay indicates the possible use of garlic extract-synthesized Ag NPs for sensing Hg2+ and Sn2+ in aqueous solution very significantly. So, the simple, green, eco-friendly and easy method to detect the dual metal ions may further lead to a potential sensor of heavy metal ion contaminants in water of industrial importance.

Biocompatible functionalized AuPd bimetallic nanoparticles decorated on reduced graphene oxide sheets for photothermal therapy of targeted cancer cells.

Graphene, which is a unique 2D nanomaterials has received widespread attention for photothermal therapy (PTT) application. Here, we have designed the nanocomposite using polydopamine (PDA) functionalized reduced graphene oxide (rGO) nanosheets and bimetallic AuPd nanoparticles (NPs). The bimetallic AuPd nanoparticles decorated PDA functionalized rGO (AuPd-rGO/PDA) nanocomposite is synthesized by simple chemical reduction technique resulting in an average size of AuPd bimetallic nanostructure of 4.18 nm. The photothermal activity of the AuPd-rGO/PDA nanocomposite is explored under the irradiation of near infrared (NIR) laser sources of wavelength 915 nm. The temperature rises nearly 51 ± 3 °C within 3 min of irradiation NIR laser light resulting in the ablation of MDAMB-231 cancer cells up to concentration of 25 µg mL-1 of AuPd-rGO/PDA nanocomposite. This high performance of the ablation of cancer cells by photothermal therapy technique was facilitated using a low concentration of the nanocomposite by the synergistic effects of the bimetallic AuPd as well as rGO and PDA functionalization. The AuPd-rGO/PDA nanocomposite demonstrated the high biocompatibility towards normal healthy cell lines (L929) and exhibits survival efficiency of more than 85%. We also demonstrated the biocompatibility of the AuPd-rGO/PDA nanocomposite materials on the zebrafish embryos (Danio rerio). This work thus illustrates that the AuPd-rGO/PDA nanocomposite could behave as favourable nanoplatform for tumor therapeutics.

Dual responsive magnetic Fe3O4-TiO2/graphene nanocomposite as an artificial nanozyme for the colorimetric detection and photodegradation of pesticide in an aqueous medium.

The Fe3O4-TiO2/reduced graphene oxide (Fe3O4-TiO2/rGO) nanocomposite was successfully prepared by one step hydrothermal method and exhibit intrinsic peroxidase mimic activity and photocatalytic efficiency. The as-prepared nanomaterials were characterized by several analytical tools including XRD, HRTEM, FESEM, XPS, VSM, FT-IR, AFM, TGA and zeta potential analysis. The average particle size of Fe3O4 and TiO2 NPs on the rGO nanosheets are found to be 9 ±â€¯0.2 nm. The synthesized nanocomposite showed dual responsive including highly sensitive colorimetric detection of harmful atrazine pesticide in an aqueous medium as well as photocatalytic degradation of atrazine pesticide. The Fe3O4-TiO2/rGO nanocomposite showed the efficient peroxidase-like catalytic activity throughout the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) as a peroxidase substrate to the blue-colored oxidized product (ox-TMB) in presence of H2O2. Based on this observation, the colorimetric detection technique is applied for the sensing of atrazine as model pesticides using TMB as a peroxidase substrate molecule and 2.98 µg/L of the limit of detection (LOD) was obtained in the linear range of 2-20 µg/L. Thus the proposed colorimetric sensing technique is simple and low cost for the real-time monitoring of the pesticides in an aqueous medium. Further, the Fe3O4-TiO2/rGO nanocomposite was also successfully utilized towards efficient photocatalytic degradation of atrazine molecule (100 %) under irradiation of natural sunlight. Moreover, Fe3O4-TiO2/rGO nanocomposite was successfully recycled for 10 times without a significant loss of its photocatalytic efficiency. This work delivers a new insight for the dual responsive of the Fe3O4-TiO2/rGO nanocomposite as an artificial nanozyme for colorimetric sensing of the water pollutant and also removal of the water pollutant by simple photocatalytic degradation method under natural sunlight irradiation.

Superbending (0-180°) and High-Voltage Operating Metal-Oxide-Based Flexible Supercapacitor.

Among various energy storage devices, flexible supercapacitors having high mechanical stability with extreme bending and foldable features are highly attractive for a large number of emerging portable lightweight consumer devices. Here, we report the fabrication of such a superflexible supercapacitor by using novel octahedron-shaped NiCo2O4 nanoparticles as the electrode material for the first time. A new, low-cost hydrothermal method was used to synthesize 50-60 nm monodispersed perfect octahedron nanoparticles without any structural deformation. An all-solid-state symmetric flexible supercapacitor was fabricated by sandwiching the octahedron nanoparticles and [EMIM][BF4] ionic liquid electrolyte between two sheets of newly developed superflexible current collector substrate. The calculated specific capacity and specific capacitance values are found to be 97.9 mAh g-1 and 117.3 F g-1, respectively, at 0.625 A g-1 current density and 3.0 V applied potential. It also offered a high energy density value of 33.54 Wh kg-1 and 10 000 measured cycling stability. The supercapacitor is so flexible that it can be bent or fold up to 180° without any mechanical deformation, and the measured capacitance and energy and power densities remain almost constant at any angle of twisting. For instance, calculated values of capacitances obtained by bending the cell at angles of 180, 150, 135, 90, and 45° are found to be 62, 63.3, 63.73, 64, and 66 F g-1 respectively, in comparison to 67 F g-1 for a nonbending or flat (0°) cell. A faster ion switching between electrode/electrolyte interface, [EMIM][BF4] electrolyte, and octahedron shape of the nanoparticle electrode material is found to be responsible for the outstanding charge storage behavior.

Effect of Substrates on Catalytic Activity of Biogenic Palladium Nanoparticles in C-C Cross-Coupling Reactions.

This work describes a practical methodology for C-C bond formation reactions with the aid of biogenic palladium nanoparticles, which are synthesized by using phytochemicals extracted from two common plant species. Comparative studies have been done on the activity of two plant species (Ocimum sanctum and Aloe vera) in generation of palladium nanoparticles via ex situ and in situ methods. The structural and morphological characteristics of the nanoparticles are examined by UV/visible spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy analyses. We have observed a significant influence of the substrates on the catalytic activity of the palladium nanoparticles in Sonogashira and Suzuki cross-coupling reactions.

Pt-Decorated Boron Nitride Nanosheets as Artificial Nanozyme for Detection of Dopamine.

Over the past decade, nanosized metal oxides, metals, and bimetallic particles have been actively researched as enzyme mimetic nanomaterials. However, the common issues with individual nanoparticles (NPs) are stabilization, reproducibility, and blocking of active sites by surfactants. These problems promote further studies of composite materials, where NPs are spread on supports, such as graphene derivatives or dichalcogenide nanosheets. Another promising type of support for NPs is the few-layered hexagonal boron nitride (hBN). In this study, we develop surfactant-free nanocomposites containing Pt NPs dispersed on chemically modified hydrophilic hBN nanosheets (hBNNSs). Ascorbic acid was used as a reducing agent for the chemical reduction of the Pt salt in the presence of hBNNS aqueous colloid, resulting in Pt/hBNNS nanocomposites, which were thoroughly characterized with X-ray diffraction, transmission electron microscopy, dynamic light scattering, and X-ray photoelectron and infrared spectroscopies. Similar to graphene oxide binding the metal NPs more efficiently than pure graphene, hydrophilic hBNNSs well stabilize Pt NPs, with particle size down to around 8 nm. We further demonstrate for the first time that Pt/hBNNS nanocomposites exhibit peroxidase-like catalytic activity, accelerating the oxidation of the classical colorless peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) to its corresponding blue-colored oxidized product in the presence of H2O2. Kinetic and mechanism studies involving terephthalic acid and isopropanol as a fluorescent probe and an •OH radical scavenger, respectively, proved that Pt/hBNNSs assist H2O2 decomposition to active oxygen species (•OH), which are responsible for TMB oxidation. The Pt/hBNNS nanocomposite-assisted oxidation of TMB provides an effective platform for the colorimetric detection of dopamine, an important biomolecule. The presence of increased amounts of dopamine gradually inhibits the catalytic activity of Pt/hBNNSs for the oxidation of TMB by H2O2, thus enabling selective sensing of dopamine down to 0.76 µM, even in the presence of common interfering molecules and on real blood serum samples. The present investigation on Pt/hBNNSs contributes to the knowledge of hBN-based nanocomposites and discovers their new usage as nanomaterials with good enzyme-mimicking activity and dopamine-sensing properties.

Colorimetric determination of glucose in solution and via the use of a paper strip by exploiting the peroxidase and oxidase mimicking activity of bimetallic Cu-Pd nanoparticles deposited on reduced graphene oxide, graphitic carbon nitride, or MoS2 nanosheets.

This work describes the preparation of bimetallic Cu-Pd nanoparticles (NPs) on supports like reduced graphene oxide (rGO), graphitic carbon nitride (g-C3N4) and MoS2 sheets with a size of <10 nm. rGO is found to be the best support for synthesizing Cu-Pd NPs with controlled shape, size and oxidation state. The Cu-Pd/rGO nanocomposite also demonstrated the best peroxidase and oxidase mimicking activity compared to Cu-Pd/g-C3N4 and Cu-Pd/MoS2 nanocomposites. The peroxidase mimicking activity of Cu-Pd/rGO was investigated in more detail, and a glucose oxidase (GOx) based glucose sensor was constructed that is based on the enzymatic formation of H2O2 and the Cu-Pd NPs-assisted oxidation of tetramethylbenzidine by H2O2 to give a blue-green coloration with absorption maxima at 652 nm. The assay has a 0.29 µM detection limit and a detection range that extends from 0.2 to 50 µM. The method was applied to the determination of glucose in diluted serum samples, and results compared well to those acquired with a clinical analyzer. The method also was applied in a colorimetric paper-based test stripe that can detect glucose within 10 min. Graphical abstract Schematic representation of a sensitive colorimetric glucose assay based on bimetallic Cu-Pd nanoparticles supported on 2D nanosheets, and construction of a paper based device for rapid glucose detection.

Magnetic Fe3O4@V2O5/rGO nanocomposite as a recyclable photocatalyst for dye molecules degradation under direct sunlight irradiation.

Reduced graphene oxide nanosheets decorated with Fe3O4 and V2O5 nanoparticles as a magnetically recoverable nanocomposite (Fe3O4@V2O5/rGO) was synthesized by a simple solution chemistry approach. The synthesized nanocomposite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM), Fourier transform infrared (FTIR), fluorescence, and zeta potential measurements. The narrow band gap and different band gap energies of Fe3O4 and V2O5 proved to be suitable for the absorption of visible light in the solar spectrum. The Fe3O4@V2O5/rGO displayed indeed excellent photocatalytic activity towards the degradation of harmful cationic Bismarck Brown (BB) as well as anionic Acid Orange 7 (AO) dyes under direct sunlight irradiation. The photocatalytic activity of the Fe3O4@V2O5/rGO is influenced by solution pH, catalyst loading, initial dye concentration and the presence of different inorganic ions (NH4+, Na+, Mg2+, Ca2+, SO42-, Br-, NO3-, Cl-, HCO3-). This study provides a new scientific knowledge on the sunlight driven photocatalytic degradation of dye molecules using novel mixed metal oxide/rGO nanocomposite photocatalyst.

Ammonia-modified graphene sheets decorated with magnetic Fe3O4 nanoparticles for the photocatalytic and photo-Fenton degradation of phenolic compounds under sunlight irradiation.

Synthesis of easily separable and eco-friendly efficient catalyst with both photocatalytic and photo-Fenton degradation properties is of great importance for environment remediation application. Herein, ammonia-modified graphene (AG) sheets decorated with Fe3O4 nanoparticles (AG/Fe3O4) as a magnetically recoverable photocatalyst by a simple in situ solution chemistry approach. First, we have functionalized graphene oxide (GO) sheets by amide functional group and then Fe3O4 nanoparticles (NPs) are doped onto the functionalized GO surface. The AG/Fe3O4 nanocomposite showed efficient photocatalytic activity towards degradation of phenol (92.43%), 2-nitrophenol (2-NP) (98%) and 2-chlorophenol (2-CP) (97.15%) within 70-120min. Consequently, in case of photo-Fenton degradation phenomenon, 93.56% phenol, 98.76% 2-NP and 98.06% of 2-CP degradation were achieved within 50-80min using AG/Fe3O4 nanocomposite under sunlight irradiation. The synergistic effect between amide functionalized graphene and Fe3O4 nanoparticles (NPs) enhances the photocatalytic activity by preventing the recombination rate of electron-hole-pair in Fe3O4 NPs. Furthermore, the remarkable reusability of the AG/Fe3O4 nanocomposite was observed up to ten cycles during the photocatalytic degradation of these phenolic compounds.

Magnetically recoverable Fe3O4/graphene nanocomposite towards efficient removal of triazine pesticides from aqueous solution: Investigation of the adsorption phenomenon and specific ion effect.

Spillage of effluents containing high concentration levels of pesticides into water has been considered as one of the serious environmental problems. In this study Fe3O4/reduced graphene oxide (rGO) nanocomposite has been efficiently utilized for the adsorption of five harmful pesticides namely ametryn, prometryn, simazine, simeton and atrazine in an aqueous medium. Electrostatic interaction between the pesticides and Fe3O4/rGO nanocomposite was analyzed by the zeta potential analysis, which is strongly related to the adsorption capacity of the adsorbent. The kinetics parameters of adsorption followed the pseudo second-order linear model. The adsorption isotherm studies show that, the maximum adsorption capacity of 54.8 mg g-1 is achieved at pH 5 and it was enhanced in the presence of different ions (Mg2+, Ca2+, Na+ and SO42) and maximum (63.7 mg g-1) for ametryn adsorption was found in seawater medium. Thermodynamic parameter shows that, the adsorption process is physisorption and spontaneity in nature. The mechanism of the adsorption process was established by the DRIFT spectroscopy analysis. Efficient adsorption (93.61%) of pesticides was observed due to electrostatic, hydrophobic and π-π interactions of composite towards the heterocyclic conjugation of pesticide molecules. Further, Fe3O4/rGO nanocomposite was easily and rapidly separated from an aqueous medium using the external magnet for reuse and 88.66% adsorption efficiency was observed up to seven cycles.

Correction: Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles towards efficient photocatalytic degradation of phenolic compounds in water.

Correction for 'Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles towards efficient photocatalytic degradation of phenolic compounds in water' by Gitashree Darabdhara, et al., Nanoscale, 2016, 8, 8276-8287.

Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles towards efficient photocatalytic degradation of phenolic compounds in water.

Reduced graphene oxide nanosheets decorated with Au-Pd bimetallic alloy nanoparticles are successfully prepared via a chemical approach consisting of reducing the metal precursors using ascorbic acid as reductant at an elevated temperature. The prepared nanocomposite is employed as a photocatalyst for the degradation of organic contaminants such as phenol, 2-chlorophenol (2-CP), and 2-nitrophenol (2-NP). The complete degradation of phenol is achieved after 300 min under natural sunlight irradiation whereas the degradation of 2-CP and 2-NP is completed after 180 min. The activity of the photocatalyst is evaluated considering several parameters such as the initial phenol concentration, the photocatalyst loading, and the pH of the solution. The degradation kinetics of all the compounds is carefully studied and found to follow a linear Langmuir-Hinshelwood model. Furthermore, the reusability of the photocatalyst is successfully achieved up to five cycles and the catalyst exhibits an excellent stability.