Solution-based printing approaches permit digital designs to be converted into physical objects by depositing materials in a layer-by-layer additive fashion from microscale to nanoscale resolution. The extraordinary adaptability of this technology to different inks and substrates has received substantial interest in the recent literature. In such a context, this review specifically focuses on the realization of inks for the deposition of ZnO, a well-known wide bandgap semiconductor inorganic material showing an impressive number of applications in electronic, optoelectronic, and piezoelectric devices. Herein, we present an updated review of the latest advancements on the ink formulations and printing techniques for ZnO-based nanocrystalline inks, as well as of the major applications which have been demonstrated. The most relevant ink-processing conditions so far explored will be correlated with the resulting film morphologies, showing the possibility to tune the ZnO ink composition to achieve facile, versatile, and scalable fabrication of devices of different natures.
Layered Double Hydroxides (LDHs) are a relevant class of inorganic lamellar nanomaterials that have attracted significant interest in life science-related applications, due to their highly controllable synthesis and high biocompatibility. Under a general point of view, this class of materials might have played an important role for the origin of life on planet Earth, given their ability to adsorb and concentrate life-relevant molecules in sea environments. It has been speculated that the organic–mineral interactions could have permitted to organize the adsorbed molecules, leading to an increase in their local concentration and finally to the emergence of life. Inspired by nature, material scientists, engineers and chemists have started to leverage the ability of LDHs to absorb and concentrate molecules and biomolecules within life-like compartments, allowing to realize highly-efficient bioinspired platforms, usable for bioanalysis, therapeutics, sensors and bioremediation. This review aims at summarizing the latest evolution of LDHs in this research field under an unprecedented perspective, finally providing possible challenges and directions for future research.
A new catalase amperometric biosensor for hydroperoxides detection has been built as part of research aimed at the development of biosensors based on layered double hydroxides (LDH) used as support for enzyme immobilization. The fabricated device differs from those developed so far, usually based on an LDH enzyme nanocomposite adsorbed on a glassy carbon (GC) electrode and cross-linked by glutaraldehyde, since it is based on an amperometric gas diffusion electrode (Clark type) instead of a GC electrode. The new biosensor, which still uses LDH synthesized by us and catalase enzyme, is robust and compact, shows a lower LOD (limit of detection) value and a linearity range shifted at lower concentrations than direct amperometric GC biosensor, but above all, it is not affected by turbidity or emulsions, or by the presence of possible soluble species, which are reduced to the cathode at the same redox potential. This made it possible to carry out accurate and efficient determination of H2O2 even in complex or cloudy real matrices, also containing very low concentrations of hydrogen peroxide, such as milk and cosmetic products, i.e., matrices that would have been impossible to analyze otherwise, using conventional biosensors based on a GC–LDH enzyme. An inaccuracy ≤ 7.7% for cosmetic samples and ≤8.0% for milk samples and a precision between 0.7 and 1.5 (as RSD%), according to cosmetic or milk samples analyzed, were achieved.
The intercalations of anionic molecules and drugs in layered double hydroxides (LDHs) have been intensively investigated in recent years. Due to their properties, such as versatility in chemical composition, good biocompatibility, high density and protection of loaded drugs, LDHs seem very promising nanosized systems for drug delivery. In this work, we report the intercalation of S-allyl-mercapto-cysteine (SAMC), which is a component of garlic that is well-known for its anti-tumor properties, inside ZnAl-LDH (hereafter LDH) nanostructured crystals. In order to investigate the efficacy of the intercalation and drug delivery of SAMC, the intercalated compounds were characterized using X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The increase in the interlayer distance of LDH from 8.9 Å, typical of the nitrate phase, to 13.9 Å indicated the intercalation of SAMC, which was also confirmed using FT-IR spectra. Indeed, compared to that of the pristine LDH precursor, the spectrum of LDH-SAMC was richly structured in the fingerprint region below 1300 cm−1, whose peaks corresponded to those of the functional groups in the SAMC molecular anion. The LDH-SAMC empirical formula, obtained from UV-Vis spectrophotometry and thermogravimetric analysis, was [Zn0.67Al0.33(OH)2]SAMC0.15(NO3)0.18·0.6H2O. The morphology of the sample was investigated using SEM: LDH-SAMC exhibited a more irregular size and shape of the flake-like crystals in comparison with the pristine LDH, with a reduction in the average crystallite size from 3 µm to about 2 µm. In vitro drug release studies were performed in a phosphate buffer solution at pH 7.2 and 37 °C and were analyzed using UV-Vis spectrophotometry. The SAMC release from LDH-SAMC was initially characterized by a burst effect in the first four hours, during which, 32% of the SAMC is released. Subsequently, the release percentage increased at a slower rate until 42% after 48 h; then it stabilized at 43% and remained constant for the remaining period of the investigation. The LDH-SAMC complex that was developed in this study showed the improved efficacy of the action of SAMC in reducing the invasive capacity of a human hepatoma cell line.
Direct catalytic methanol fuel cells (DCMFCs) have been studied for several years for energy conversion. Less extensive is the investigation of their analytical properties. In this paper, we demonstrate that the behavior of both the discharge and charger curves of DCMFCs depends on the chemical composition of the solution injected in the fuel cell. Their discharge and charge curves, analyzed using a chemometric data fusion method named ComDim, enable the identification of various types of aliphatic alcohols diluted in water. The results also show that the identification of alcohols can be obtained from the first portion of the discharge and charge curves. To this end, the curves have been described by a set of features related to the slope and intercept of the initial portion of the curves. The ComDim analysis of this set of features shows that the identification of alcohols can be obtained in a time that is about thirty times shorter than the time taken to achieve steady-state voltage.