Opto-electronics on/with paper is fostering a novel generation of flexible and recyclable devices for sunlight harvesting and intelligent optical sensing.
For analytical applications in portable sensors to be used in the point-of-need, low-cost SERS substrates using paper as a base, are an alternative. In this work, SERS substrates were produced on two different types of paper: a high porosity paper (Whatman no. 1); and a low porosity paper (commercially available office paper, Portucel Soporcel). Solutions containing spherical silver nanoparticles (AgNPs) and silver nanostars (AgNSs) were separately drop-casted on hydrophilic wells patterned on the papers. The porosity of the paper was found to play a determinant role on the AgNP and AgNS distribution along the paper fibres, with most of the nanoparticles being retained at the illuminated surface of the office paper substrate. The highest SERS enhancements were obtained for the office paper substrate, with deposited AgNSs. A limit of detection for rhodamine-6G as low as 11.4 ± 0.2 pg could be achieved, with an analytical enhancement factor of ≈107 for this specific analyte. The well patterning technique allowed good signal uniformity (RSD of 1.7%). Besides, these SERS substrates remained stable after 5 weeks of storage (RSD of 7.3%). Paper-induced aggregation of AgNPs was found to be a viable alternative to the classical salt-induced aggregation, to obtain a highly sensitive SERS substrates.
Semiconductor nanowires are mostly processed by complex, expensive, and high temperature methods. In this work, with the intent of developing zinc tin oxide nanowires (ZTO NWs) by low-cost and low-complexity processes, we show a detailed study on the influence of chemical parameters in the hydrothermal synthesis of ZTO nanostructures at temperatures of only 200 °C. Two different zinc precursors, the ratio between zinc and tin precursors, and the concentration of the surfactant agent and of the mineralizer were studied. The type and the crystallinity of the nanostructures were found to be highly dependent on the used precursors and on the concentration of each reagent. Conditions for obtaining different ZTO nanostructures were achieved, namely, Zn 2 SnO 4 nanoparticles and ZnSnO 3 nanowires with length ∼600 nm, with the latter being reported for the first time ever by hydrothermal methods without the use of seed layers. Optical and electrical properties were analyzed, obtaining band gaps of 3.60 and 3.46 eV for ZnSnO 3 and Zn 2 SnO 4 , respectively, and a resistivity of 1.42 kΩ·cm for single ZnSnO 3 nanowires, measured using nanomanipulators after localized deposition of Pt electrodes by e-beam assisted gas decomposition. The low-temperature hydrothermal methods explored here proved to be a low-cost, reproducible, and highly flexible route to obtain multicomponent oxide nanostructures, particularly ZTO NWs. The diversity of the synthesized ZTO structures has potential application in next-generation nanoscale devices such as field effect nanotransistors, nanogenerators, resistive switching memories, gas sensors, and photocatalysis.
The degradation of organic pollutants in wastewaters assisted by oxide semiconductor nanostructures has been the focus of many research groups over the last decades, along with the synthesis of these nanomaterials by simple, eco-friendly, fast, and cost-effective processes. In this work, porous zinc oxide (ZnO) nanostructures were successfully synthesized via a microwave hydrothermal process. A layered zinc hydroxide carbonate (LZHC) precursor was obtained after 15 min of synthesis and submitted to different calcination temperatures to convert it into porous ZnO nanostructures. The influence of the calcination temperature (300, 500, and 700 °C) on the morphological, structural, and optical properties of the ZnO nanostructureswas investigated. All ZnO samples were tested as photocatalysts in the degradation of rhodamine B (RhB) under UV irradiation and natural sunlight. All samples showed enhanced photocatalytic activity under both light sources, with RhB being practically degraded within 60 min in both situations. The porous ZnO obtained at 700 °C showed the greatest photocatalytic activity due to its high crystallinity, with a degradation rate of 0.091 and 0.084 min−1 for UV light and sunlight, respectively. These results are a very important step towards the use of oxide semiconductors in the degradation of water pollutants mediated by natural sunlight.
Due to its properties, paper represents an alternative to perform point-of-care tests for colorimetric determination of glucose levels, providing simple, rapid, and inexpensive means of diagnosis. In this work, we report the development of a novel, rapid, disposable, inexpensive, enzyme-free, and colorimetric paper-based assay for glucose level determination. This sensing strategy is based on the synthesis of gold nanoparticles (AuNPs) by reduction of a gold salt precursor, in which glucose acts simultaneously as reducing and capping agent. This leads to a direct measurement of glucose without any enzymes or depending on the detection of intermediate products as in conventional enzymatic colorimetric methods. Firstly, we modelled the synthesis reaction of AuNPs to determine the optical, morphological, and kinetic properties and their manipulation for glucose sensing, by determining the influence of each of the reaction precursors towards the produced AuNPs, providing a guide for the manipulation of nucleation and growth. The adaptation of this synthesis into the developed paper platform was tested and calibrated using different standard solutions with physiological concentrations of glucose. The response of the colorimetric signals obtained with this paper-based platform showed a linear behavior until 20 mM, required for glycemic control in diabetes, using the Red × Value/Grey feature combination as a calibration metric, to describe the variations in color intensity and hue in the spot test zone. The colorimetric sensor revealed a detection limit of 0.65 mM, depending on calibration metric and sensitivity of 0.013 AU/mM for a linear sensitivity range from 1.25 to 20 mM, with high specificity for the determination of glucose in complex standards with other common reducing interferents and human serum.
Paper substrates, coated with ZnO nanorods (NRs) decorated with Ag nanoparticles (NPs), allowed the production of inexpensive, highly-performing and extremely reproducible three-dimensional (3D) SERS platforms. The ZnO NRs were synthesized by a simple, fast and low-temperature hydrothermal method assisted by microwave radiation and made SERS-active by decorating them with a dense array of silver nanoparticles deposited via a single-step thermal evaporation technique. Using Rhodamine 6G (R6G) as a probe molecule, with an amount down to 10 −9 M, the SERS substrates allowed a Raman signal enhancement of 10 7 . The contribution of the inter-Ag-NPs gaps for 3D geometry, ZnO NRs orientation and the large sensing area allowed by the NR scaffolds, were determinant factors for the significant Raman enhancement observed. The results demonstrate that plasmonic nanorod forests, covered with Ag NPs, are efficient SERS substrates with the advantages of being recyclable, flexible, lightweight, portable, biocompatible and extremely low-cost.
In the present study, zinc oxide (ZnO) nanorods (NRs) with a hexagonal structure have been synthesized via a hydrothermal method assisted by microwave radiation, using specialized cardboard materials as substrates. Cardboard-type substrates are cost-efficient and robust paper-based platforms that can be integrated into several opto-electronic applications for medical diagnostics, analysis and/or quality control devices. This class of substrates also enables highly-sensitive Raman molecular detection, amiable to several different operational environments and target surfaces. The structural characterization of the ZnO NR arrays has been carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical measurements. The effects of the synthesis time (5–30 min) and temperature (70–130 °C) of the ZnO NR arrays decorated with silver nanoparticles (AgNPs) have been investigated in view of their application for surface-enhanced Raman scattering (SERS) molecular detection. The size and density of the ZnO NRs, as well as those of the AgNPs, are shown to play a central role in the final SERS response. A Raman enhancement factor of 7 × 105 was obtained using rhodamine 6 G (R6G) as the test analyte; a ZnO NR array was produced for only 5 min at 70 °C. This condition presents higher ZnO NR and AgNP densities, thereby increasing the total number of plasmonic “hot-spots”, their volume coverage and the number of analyte molecules that are subject to enhanced sensing.
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