Catalytic reduction in 4‐nitrophenol using Actinodaphne madraspatana Bedd leaves‐mediated palladium nanoparticles

There is a growing demand for the development of non‐toxic, cost‐effective, and environmentally benign green synthetic strategy for the production of metal nanoparticles. Herein, the authors have reported Actinodaphne madraspatana Bedd (AMB) leaves as the bioreducing agent for the synthesis of palladium nanoparticles (PdNPs) and its catalytic activity was evaluated for the reduction of 4‐nitrophenol (4‐NP) to 4‐aminophenol with undisruptive effect on human health and environment. The broad and continuous absorbance spectrum obtained in the UV–visible region indicated the formation of PdNPs. The synthesized PdNPs were found to be crystalline, spherical, and quasi‐spherical in shape with an average particle size of 13 nm was confirmed by X‐ray diffractometer and transmission electron microscope. Fourier transform infrared spectra revealed the active photo constituents present in the aqueous extract of AMB involved in the bioreduction of palladium ions to PdNPs. The catalytic activity of biosynthesized PdNPs was demonstrated for the reduction of 4‐NP via electron‐relay process. Also, the influential parameters such as catalyst dosage, concentration of 4‐NP, and sodium borohydride were studied in detail. From the present study, PdNPs were found to be a potential nanocatalyst for nitro compound reduction and also for environmental remediation of wastewater effluents from industries.Inspec keywords: palladium, nanoparticles, particle size, nanofabrication, catalysis, catalysts, reduction (chemical), organic compounds, ultraviolet spectra, visible spectra, X‐ray diffraction, transmission electron microscopy, Fourier transform infrared spectraOther keywords: nitro compound reduction, environmental remediation, wastewater effluents, Pd, nanocatalyst, sodium borohydride, 4‐NP concentration, catalyst dosage, electron‐relay process, bioreduction, aqueous extract, Fourier transform infrared spectra, transmission electron microscopy, X‐ray diffractometry, particle size, quasispherical shape, spherical shape, crystalline shape, UV‐visible abosprtion spectra, human environment, human health, 4‐aminophenol, catalytic activity, bioreducing agent, metal nanoparticles, Actinodaphne madraspatana Bedd leaves‐mediated palladium nanoparticles, 4‐nitrophenol, catalytic reduction     

Performance enhancement of paper-based SERS chips by shell-isolated nanoparticle-enhanced Raman spectroscopy

Paper-based flexible surface-enhanced Raman scattering (SERS) chips have been demonstrated to have great potential for future practical applications in point-of-care testing (POCT) due to the potentials of massive fabrication, low cost, efficient sample collection and short signal acquisition time. In this work, common filter paper and Ag@SiO₂core-shell nanoparticles (NP) have been utilized to fabricate SERS chips based on shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS). The SERS performance of the chips for POCT applications was systematically investigated. We used crystal violet as the model molecule to study the influence of the size of the Ag core and the thickness of the SiO₂coating layer on the SERS activity and then the morphology optimized Ag@SiO₂core-shell NPs was employed to detect thiram. By utilizing the smartphone as a miniaturized Raman spectral analyzer, high SERS sensitivity of thiram with a detection limit of 10⁻⁹M was obtained. The study on the stability of the SERS chips shows that a SiO₂shell of 3 nm can effectively protect the as-prepared SERS chips against oxidation in ambient atmosphere without seriously weakening the SERS sensitivity. Our results indicated that the SERS chips by SHINERS had great potential of practical application, such as pesticide residues detection in POCT.     

Nanostructured surfaces and assemblies as SERS media

Metallic nanostructures attract much interest as an efficient media for surface-enhanced Raman scattering (SERS). Significant progress has been made on the synthesis of metal nanoparticles with various shapes, composition, and controlled plasmonic properties, all critical for an efficient SERS response. For practical applications, efficient strategies of assembling metal nanoparticles into organized nanostructures are paramount for the fabrication of reproducible, stable, and highly active SERS substrates. Recent progress in the synthesis of novel plasmonic nanoparticles, fabrication of highly ordered one-, two-, and three-dimensional SERS substrates, and some applications of corresponding SERS effects are discussed.     

Silver nanoparticles deposited on anodic aluminum oxide template using magnetron sputtering for surface-enhanced Raman scattering substrate

Low-cost and highly sensitive surface-enhanced Raman scattering (SERS) substrates have been fabricated by a simple anodizing process and a magnetron sputtering deposition. The substrates, which consist of silver nanoparticles embedded on anodic aluminum oxide (AAO) templates, are investigated by a scanning electron microscope and a confocal Raman spectroscopy. The SERS activities are demonstrated by Raman scattering from adsorbed solutions of methylene blue and pyridine on the SERS substrate surface. The most optimized SERS substrate contains the silver nanoparticles, with a size distribution of 10-30 nm, deposited on the AAO template. From a calculation, the SERS enhancement factor is as high as 8.5 × 10⁷, which suggests strong potentials for direct applications in the chemical detection and analyses.     

Structural and Optical Properties and Emerging Applications of Metal Nanomaterials

Nanomaterials possess intriguing optical properties that depend sensitively on size, shape, and material content of the structures. Controlling such structural characteristics of the nanostructures allows the tailoring of their physical and chemical properties, e.g. optical, electronic, and catalytic, to achieve what is desired lot specific applications of interest. This review will cover the development of various shapes for silver and gold nanomaterials with emphasis on their relation to optical properties. Examples of various modern synthetic methods and characterization techniques are highlighted. The influence of the metal nanomaterial＇s shape and optical absorption on surface enhanced Raman scattering （SERS） and a final note on new emerging applications of metal nanostructures are also discussed.     

Performance improvement of fuel cells using platinum-functionalised aligned carbon nanotubes

The focus of this research was towards the improvement of the performance of proton exchange membrane fuel cells. The overarching goals were: (1) providing guidelines for design of new catalysts; (2) promoting nanocatalyst applications towards alternative energy applications; and (3) integrating advanced instrumentation into nanocharacterisation and fuel cell (FC) electrochemical behaviour. In tandem with these goals, the cathode catalysts were extensively refined to improve FC performance and minimise noble metal usage. In this study, the major accomplishment was producing aligned carbon nanotubes (ACNT), which were then modified by platinum (Pt) nanoparticles via a post-synthesis colloidal chemistry approach. The Pt-ACNTs demonstrated improved cathodic catalytic activity, as a result of incorporation of the nanotubes with the additional advantage of decreased Pt loading. It was also determined that surface mechanical properties, such as elastic modulus and hardness were increased. Collectively, these enhancements provided an improved FC performance.     

Simple,green approach for the synthesis of solid support‐embedded PdNPs for ligand exchange

Green approaches have the potential to significantly reduce the costs and environmental impact of chemical syntheses. Here, the authors used green tea (GT) leaf extract to synthesise and anchor palladium nanoparticles (PdNPs) to silica. The synthesised PdNPs in GT extract were characterised by ultraviolet–visible spectroscopy, Fourier‐transform infrared spectroscopy, X‐ray diffraction, and transmission electron microscopy. PdNPs primarily formed as capped NPs dispersed in GT extract before reduction completed after 24 h. This capped phytochemical solution was employed as a green precursor solution to synthesise PdNP‐embedded solid supports. The morphology of PdNPs anchored to silica differed to that of PdNPs in solution. Silica‐embedded PdNPs was employed as a new ligand exchanger to isolate trace polycyclic aromatic sulphur heterocycles from a hydrocarbon matrix. The isolation efficiency of the new, greener ligand exchanger was the same as an efficient chemical ligand exchanger and may, therefore, hold promise for future applications.Inspec keywords: nanofabrication, palladium, visible spectra, transmission electron microscopy, nanoparticles, reduction (chemical), ultraviolet spectra, X‐ray diffraction, Fourier transform infrared spectra, surface morphologyOther keywords: ultraviolet–visible spectroscopy, Fourier‐transform infrared spectroscopy, transmission electron microscopy, phytochemical solution, green precursor solution, PdNP‐embedded solid supports, solid support‐embedded PdNPs, green tea leaf extract, chemical ligand exchanger, anchor palladium nanoparticles, X‐ray diffraction, isolate trace polycyclic aromatic sulphur heterocycles, hydrocarbon matrix, green synthesis, time 24.0 hour, Pd     

Synthesis and application in surface-enhanced Raman scattering property of fist-like platinum microparticles

Platinum microparticles with fist-like shape were synthesized through the reduction of chloroplatinic acid (H₂PtCl₆) with absolute ethanol under hydrothermal atmosphere, whose diameters and lengths can be effectively controlled by varying H₂PtCl₆ concentration. Unlike previous methods for only synthesizing platinum nanoparticles of about 10 nm or even smaller, the use of the hydrothermal and surfactant-free system provides a shortcut strategy to prepare micron-sized platinum particles. Surface-enhanced Raman scattering (SERS) investigation demonstrated that the microfists have SERS activity and similar SERS enhancement to an electrochemically roughened Pt electrode. We believe that the Pt microfists should be not only an ideal model to understand and calculate the SERS enhancement mechanism of electrochemically roughened transitional metal but also may find practical applications for electronics, photonics, and microdevices.     

GGA+U method from first principles: application to reduction–oxidation properties in ceria-based oxides

We implement DFT calculations by a Hubbard-like correction for localized strongly correlated electrons, coupled with a generalized gradient approximation to the exchange-correlation functional to elucidate the role of the ceria based catalytically active supports for the chemical reactions involving reduction–oxidation processes. These catalytic processes are relevant for many industrial applications, such as catalytic converters in automotive applications, solid oxide fuel cells, and hydrogen production from biomass. The Hubbard-like correction U is computed from first principles as physical property of the system. We find that the high performance of ceria-based oxides as an active support for noble metals in catalysis relies on an efficient supply of lattice oxygen at reaction sites governed by oxygen vacancy formation.     

Spectroscopic ultra-trace detection of nitroaromatic gas vapor on rationally designed two-dimensional nanoparticle cluster arrays

Nanoparticle cluster arrays (NCAs) are engineered two-dimensional plasmonic arrays that provide high signal enhancements for critical sensing applications using surface enhanced Raman spectroscopy (SERS). In this work we demonstrate that rationally designed NCAs are capable of detecting ultra-traces of 2,4-dinitrotoluene (DNT) vapor. NCAs functionalized with a thin film of an aqueous NaOH solution facilitated the detection of DNT vapor at a concentration of at least 10 ppt, even in the presence of an excess of potential interferents, including Diesel fuel, fertilizers, and pesticides. Both in the presence and in the absence of this complex background the SERS signal intensity of the NO(2) stretching mode showed a continuous, concentration dependent response over the entire monitored concentration range (10 ppt-100 ppb). The small size, superb sensitivity, and selectivity, as well as the fast response time of <5 min, make NCAs a valuable photonic sensor platform for ultra-trace nitroaromatic gas vapor detection with potential applications in landmine removal and homeland security.     

Transparent and catalytic carbon nanotube films

We report on the synthesis of thin, transparent, and highly catalytic carbon nanotube films. Nanotubes catalyze the reduction of triiodide, a reaction that is important for the dye-sensitized solar cell, with a charge-transfer resistance as measured by electrochemical impedance spectroscopy that decreases with increasing film thickness. Moreover, the catalytic activity can be significantly enhanced by exposing the nanotubes to ozone in order to introduce defects. Ozone-treated, defective nanotube films could serve as catalytic, transparent, and conducting electrodes for the dye-sensitized solar cell. Other possible applications include batteries, fuel cells, and electroanalytical devices.     

Shape-dependent catalytic activity of CuO/MgO nanocatalysts

CuO/MgO catalysts with various shapes have been obtained by using morphology-controlled synthesis technology. It is demonstrated that there is a remarkable difference in catalytic activity for CO oxidation among these samples. However, when all these catalysts react with water before calcination, their shapes become irregular and similar, consequently, the difference of their catalytic activities disappears.     

Ultrathin Molybdenum Dioxide Nanosheets as Uniform and Reusable Surface‐Enhanced Raman Spectroscopy Substrates with High Sensitivity

Metal oxides have advantages over the traditional noble metals to be used as substrate materials for surface‐enhanced Raman spectroscopy (SERS) with low cost, versatility, and biocompatibility, but their enhancement factors are generally quite low with a poor limit of detection. Here, ultrathin molybdenum dioxide (MoO₂) nanosheets synthesized by chemical vapor deposition demonstrated in large area are used as SERS substrates with superior signal uniformity in the whole area with a limit of detectable concentration down to 4 × 10^?8m and enhancement factor up to 2.1 × 10⁵, exceeding that of 2D materials and comparable to that of noble metal films. More practically important, the planar MoO₂ substrate is more robust than noble metals and shows excellent reusability and uniformity, which is usually prohibited for nanostructured or nanoparticle‐based metal oxide substrates. The enhancement is mainly attributed to the surface plasmon resonance effect as evidenced by the first principle calculations and UV–vis absorption spectroscopy characterization, which can be further increased by decreasing the thickness of the MoO₂ nanosheets. The overall superior performance makes the MoO₂ nanosheets an ideal substrate for practical SERS applications.     

Biological applications of localised surface plasmonic phenomenae

Researchers and industrialists have taken advantage of the unusual optical, magnetic, electronic, catalytic, and mechanical properties of nanomaterials. Nanoparticles and nanoscale materials have proven to be useful for biological uses. Nanoscale materials hold a particular interest to those in the biological sciences because they are on the same size scale as biological macromolecules, proteins and nucleic acids. The interactions between biomolecules and nanomaterials have formed the basis for a number of applications including detection, biosensing, cellular and in situ hybridisation labelling, cell tagging and sorting, point-of-care diagnostics, kinetic and binding studies, imaging enhancers, and even as potential therapeutic agents. Noble metal nanoparticles are especially interesting because of their unusual optical properties which arise from their ability to support surface plasmons. In this review the authors focus on biological applications and technologies that utilise two types of related plasmonic phenomonae: localised surface plasmon resonance (LSPR) spectroscopy and surface-enhanced Raman spectroscopy (SERS). The background necessary to understand the application of LSPR and SERS to biological problems is presented and illustrative examples of resonant Rayleigh scattering, refractive index sensing, and SERS-based detection and labelling are discussed.     

Ultralow loading Pt nanocatalysts prepared by atomic layer deposition on carbon aerogels

Using atomic layer deposition (ALD), we show that Pt nanoparticles can be deposited on the inner surfaces of carbon aerogels (CA). The resultant Pt-loaded materials exhibit high catalytic activity for the oxidation of CO even at loading levels as low as approximately 0.05 mg Pt/cm2. We observe a conversion efficiency of nearly 100% in the 150-250 degrees C temperatures range, and the total conversion rate seems to be limited only by the thermal stability of the CA support in ambient oxygen. The ALD approach described here is universal in nature, and can be applied to the design of new catalytic materials for a variety of applications, including fuel cells, hydrogen storage, pollution control, green chemistry, and liquid fuel production.     

Complex line shapes in surface-enhanced coherent Raman spectroscopy

Peaks, dips, and intermediate line shapes have been observed in surface-enhanced coherent Raman spectroscopy. Here, we report an experimental observation of a peculiar line shape revealing both a peak and a dip as two vibrational transitions of pyridazine in the presence of aggregated gold nanoparticles. We propose a simple model based on plasmonic phase effects and quantum chemistry calculations, and compare the simulated coherent (SECARS) and incoherent (SERS) Raman signals from several complexes. Complex SECARS line shapes provide additional information compared to SERS and can be used as a tool in nanoscale sensing and spectroscopy.     

A SERS‐Assisted 3D Barcode Chip for High‐Throughput Biosensing

A surface enhanced Raman scattering (SERS)‐assisted 3D barcode chip has been developed for high‐throughput biosensing. The 3D barcode is realized through joint 2D spatial encoding with the Raman spectroscopic encoding, which stores the SERS fingerprint information in the format of a 2D array. Here, the concept of SERS‐assisted 3D barcode is demonstrated through multiplex immunoassay, where simultaneous detection of multiple targets in different samples has been achieved using a microfluidic platform. First, multiple proteins in different samples are spatially separated using a microfluidic patterned antibody barcode substrate, forming a 2D hybridization array. Then the SERS probes are used to identify and quantify the proteins. As different SERS probes are labeled with different Raman reporters, they could be employed as “SERS tags” to incorporate spectroscopic information into the 3D barcode. In this 3D barcode, the 2D spatial information helps to differentiate the samples and targets while the SERS information allows quantitative multiplex detection. It is found that the SERS‐assisted 3D barcode chip can not only accomplish one‐step multiplex detection within 30 min but also achieve an ultrasensitivity down to 10 fg mL^?1 (≈70 aM), which is expected to provide a promising tool for high‐throughput biomedical applications.     

Nanoparticle-functionalized porous polymer monolith detection elements for surface-enhanced Raman scattering

The use of porous polymer monoliths functionalized with silver nanoparticles is introduced in this work for high-sensitivity surface-enhanced Raman scattering (SERS) detection. Preparation of the SERS detection elements is a simple process comprising the synthesis of a discrete polymer monolith section within a silica capillary, followed by physically trapping silver nanoparticle aggregates within the monolith matrix. A SERS detection limit of 220 fmol for Rhodamine 6G is demonstrated, with excellent signal stability over a 24 h period. The capability of the SERS-active monolith for label-free detection of biomolecules was demonstrated by measurements of bradykinin and cytochrome c. The SERS-active monoliths can be readily integrated into miniaturized micrototal-analysis systems for online and label-free detection for a variety of biosensing, bioanalytical, and biomedical applications.     

Fabrication of metal half-shells using colloidal particle monolayer and their application in surface-enhanced Raman scattering

Three types of Au shells, an isolated half-shell, one-dimensional strings of shells, and two-dimensional films, were fabricated by using a monolayer of polystyrene (PS) particles with diameters of 213, 560, and 1360 nm. The three types of Au shells that were removed from the PS particle monolayer and the as-deposited Au shells that adhered to PS particles were modified with 4-mercaptopyridine for use as platforms for surface-enhanced Raman scattering (SERS). We examined the effects of the shapes and sizes of Au shells on their SERS efficiency and found that the Au shells exhibited strong SERS signals and that Au shells prepared by using 560-nm PS particles were the most suitable platform for SERS at both 632.8- and 785-nm excitations. Further, we found that SERS enhancements depended on the shape of Au shells and on whether Au shells adhered to PS particles or not.     

Engineered Functional Surfaces by Laser Microprocessing for Biomedical Applications

Metallic biomaterials are increasingly being used in various medical applications due to their high strength, fracture resistance, good electrical conductivity, and biocompatibility. However, their practical applications have been largely limited due to poor surface performance. Laser microprocessing is an advanced method of enhancing the surface-related properties of biomaterials. This work demonstrates the capability of laser microprocessing for biomedical metallic materials including magnesium and titanium alloys, with potential applications in cell adhesion and liquid biopsy. We investigate laser-material interaction, microstructural evolution, and surface performance, and analyze cell behavior and the surface-enhanced Raman scattering (SERS) effect. Furthermore, we explore a theoretical study on the laser microprocessing of metallic alloys that shows interesting results with potential applications. The results show that cells exhibit good adhesion behavior at the surface of the laser-treated surface, with a preferential direction based on the textured structure. A significant SERS enhancement of 6 × 10³ can be obtained at the laser-textured surface during Raman measurement.