Synthesis and characterization of MoSe2 nanoscrolls via pulsed laser ablation in deep eutectic solvents.

There is ongoing interest in the rapid, reproducible production of 2-dimensional (2-D) transition metal dichalcogenides (TMD), such as molybdenum-based TMD (MoX2), where X is a chalcogen atom such as sulphur (S), selenium (Se) or tellurium (Te), driven by their unique optical and electronic properties. Once fabricated into an atomically thin layer structure, these materials have a direct-indirect bandgap transition, strong spin-orbit coupling, and favourable electronic and mechanical strain-dependent properties which are attractive for electronics. Pulsed laser ablation in liquid (PLAL) is an economic, green alternative for synthesis of TMD. It has been shown that in the case of MoX2, the chemical processes during the plasma phase of the ablation can yield the formation of multispecies, including MoOx quantum dots when oxygen-containing solvents are used. Here, we introduce the formation of MoSe2 nanoscrolls with low oxygen content synthesized via pulsed laser ablation in deep eutectic solvents (PLADES). Our results suggest that the synthesis produces a stable colloidal solution of large 2-D structures with tuneable surface charge by replacing the deep eutectic solvent (DES) with DI water. Nuclear Magnetic Resonance (NMR) results suggest that irradiating the solvent at near infrared NIR energy does not affect its chemical composition. NMR also proves that serial washing can completely remove solvent from the nanostructures. Raman shifts suggest the formation of large, thin MoSe2 nanosheets aided by the solvent confinement resulting from van der Waal forces and hydrogen bonds interactions between MoSe2 and urea. Binding energies measured by X-ray photoelectron spectroscopy (XPS) confirm MoSe2-DES preference to form 1T-MoSe2versus molybdenum oxides and 2H MoSe2 in DI-water. Raman and XPS findings were validated by transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Results of this work validate the use of PLADES for the synthesis of stable, crystalline, low-surface-oxygen-content colloidal MoSe2 nanoscrolls in scalable quantities.

Green synthesized Cu-doped CeO2nanoparticles for Congo red dye adsorption and antibacterial action.

The removal of pollutants from water bodies is crucial for the well-being of humanity and is a topic of global research. Researchers have turned their attention to green synthesized nanoparticles for wastewater treatment due to their eco-friendly nature, biocompatibility, and cost-effectiveness. This work demonstrates the efficient removal of organic dye and both gram-positive and gram-negative bacteria from water bodies using copper-doped cerium oxide nanoparticles synthesized withMurraya Koenigiiextract. Characterized via various methods, the 15% copper doped cerium oxide nanoparticles (Cu 15% NPs) exhibited maximum Congo red dye adsorption (98% degradation in 35 min). Kinetic analysis favoured a pseudo-second-order model, indicating the chemical nature of adsorption. Equilibrium adsorption isotherms aligned with the Langmuir model, indicating homogenous monolayer dye adsorption on the doped adsorbent. The maximum uptake of adsorbate,Qmobtained from Langmuir model for Cu 15% NPs was 193 mg g-1. The study also showed enhanced antibacterial activity againstBacillus subtilis, Staphylococcus aureus, Escherichia coliandPseudomonas aeruginosafor Cu-doped ceria, attributed to generation of reactive oxygen species (ROS) induced by the redox cycling between Ce3+and Ce4+. This substantiated that the green synthesized copper doped cerium oxide nanoparticles are potential candidates for adsorptive removal of Congo red dye and as antibacterial agents.

Lead-Free Piezoelectric Energy Harvester Based on 2D Bismuth Titanate.

The use of two-dimensional (2D) layered materials with a noncentrosymmetric structure dramatically increases the potential of nanoscale electromechanical systems and electronic devices. In this work, liquid-phase exfoliation of bulk bismuth titanate was employed to synthesize atomically thin 2D sheets and fabricate a high-performance piezoelectric energy harvester. The structural and morphological properties of the 2D sheets were analyzed, confirming their phase purity and layer formation. Piezoelectric properties of the 2D sheets were evaluated using Piezoresponse Force Microscopy (PFM), demonstrating a high d33 piezoelectric coefficient of 40 pm/V in a few-layer bismuth titanate nanosheet. A prototype energy harvesting device was fabricated with 2D bismuth titanate as the active material. The piezoelectric response of the fabricated device was recorded at different frequencies and forces, which yielded a maximum d33 of 57.8 pC/N at 1 Hz. Such a solid electromechanical performance at a relatively infinitesimal input response indicates that 2D bismuth titanate can be useful for piezoelectric energy harvesting applications.

An electrochemical sensor for nanomolar detection of caffeine based on nicotinic acid hydrazide anchored on graphene oxide (NAHGO).

A simple modified sensor was developed with nicotinic acid hydrazide anchored on graphene oxide (NAHGO), by ultrasonic-assisted chemical route, using hydroxy benzotriazole as a mediator. Structural and morphologies of NAHGO samples were investigated in detail by Fourier-Transform Infrared spectroscopy (FT-IR), Powder X-ray diffraction (P-XRD), Raman spectroscopy, Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Thermogravimetric analysis (TGA). The detailed morphological examination and electrochemical studies revealed the delaminated sheet with the tube-like structure of NAHGO provided the route for more electroactive surface which influenced the electrooxidation of caffeine with increased current. The electrochemical behaviour of NAHGO on a glassy carbon electrode (GCE) for caffeine detection was demonstrated by employing voltammetric techniques. The influence of scan rate, pH, and concentration on caffeine's peak current was also studied. The NAHGO sensor was employed for the determination of caffeine in imol plus and energy drinks. The detection limit determined was 8.7 × 10-9 M, and the best value was reported so far. The results show that NAHGO modified electrodes are one of the best preferences to establish new, efficient, and reliable analytical tools for the detection of caffeine.

LED control of gene expression in a nanobiosystem composed of metallic nanoparticles and a genetically modified E. coli strain.

BACKGROUND: Within the last decade, genetic engineering and synthetic biology have revolutionized society´s ability to mass-produce complex biological products within genetically-modified microorganisms containing elegantly designed genetic circuitry. However, many challenges still exist in developing bioproduction processes involving genetically modified microorganisms with complex or multiple gene circuits. These challenges include the development of external gene expression regulation methods with the following characteristics: spatial-temporal control and scalability, while inducing minimal permanent or irreversible system-wide conditions. Different stimuli have been used to control gene expression and mitigate these challenges, and they can be characterized by the effect they produce in the culture media conditions. Invasive stimuli that cause permanent, irreversible changes (pH and chemical inducers), non-invasive stimuli that cause partially reversible changes (temperature), and non-invasive stimuli that cause reversible changes in the media conditions (ultrasound, magnetic fields, and light). METHODS: Opto-control of gene expression is a non-invasive external trigger that complies with most of the desired characteristics of an external control system. However, the disadvantage relies on the design of the biological photoreceptors and the necessity to design them to respond to a different wavelength for every bioprocess needed to be controlled or regulated in the microorganism. Therefore, this work proposes using biocompatible metallic nanoparticles as external controllers of gene expression, based on their ability to convert light into heat and the capacity of nanotechnology to easily design a wide array of nanostructures capable of absorbing light at different wavelengths and inducing plasmonic photothermal heating. RESULTS: Here, we designed a nanobiosystem that can be opto-thermally triggered using LED light. The nanobiosystem is composed of biocompatible gold nanoparticles and a genetically modified E. coli with a plasmid that allows mCherry fluorescent protein production at 37 °C in response to an RNA thermometer. CONCLUSIONS: The LED-triggered photothermal protein production system here designed offers a new, cheaper, scalable switchable method, non-destructive for living organisms, and contribute toward the evolution of bioprocess production systems.

A simple synthesis of ZnO:Co2O3 nanocomposites by pulsed laser irradiation in liquid.

Nanocomposite materials are emerging in popularity due to their enhanced performance over the constituent materials. In this work, we report the fabrication of zinc oxide: cobalt oxide nanocomposites in a simple, fast and room temperature synthesis with good productivity. The nanocomposites synthesized were characterized by SEM, XPS and UV-Visible spectroscopy to analyze their morphology, composition, chemical states, optical absorption, band gap etc. The nanocolloids of the composite were drop casted to form thin films for photocatalytic studies. In SEM analysis, the morphological transformation of the material is observed where it transformed from agglomerated spherical particles to petals shaped and then to partially spherical forms due to pulsed laser irradiation. XPS analysis showed a gradual change in oxygen high resolution spectra in the samples with respect to the concentration difference of cobalt oxide. The optical studies show an enhanced absorption in visible region for the nanocomposite and the energy band gap reduced to 2.4 eV. All the thin films of nanocomposite showed photocatalytic decay of methylene blue dye under visible light irradiation. The results of this study support the effective use of laser irradiation in liquid to obtain nanocomposites of metal oxides for photocatalytic applications.

Influence of p-n junction mechanism and alumina overlayer on the photocatalytic performance of TiO2 nanotubes.

Modified hybrid structures of TiO2 nanotubes (TONT), p-Al doped TONT/n-TONT with an additional overlayer of alumina, are constructed to achieve 99.57% photodegradation of the stable organic pollutant methylene blue (MB) within 180 min, a degradation rate 17 times higher than pure TONTs. The anodization at three different temperatures 2, 28 and 40 °C followed by impregnation of Al is used for their preparation. The analyses of structure, chemical composition and morphology are completed using x-ray diffraction, x-ray photoelectron spectroscopy (XPS) and high resolution transmission microscopy, respectively, Rutherford back scattering and field emission scanning electron microscopy confirm the formation of the hybrid structure. This structure exhibits the highest photodegradation rate with TONT based catalysts to date for MB blue, by enhancing the electron-hole separation, the absorption of visible photons and the adsorption sites for the pollutant. The optical data coupled with valence band XPS is used for elucidating the energy band structure of the p-n junctions and to gain insight into the effect of the junction mechanism on photoactivity. The rectification ratios of the impregnated p-n junctions, determined by current-voltage measurements, are found to vary from 102 to 106.

Development of a Theoretical Model That Predicts Optothermal Energy Conversion of Gold Metallic Nanoparticles.

Gold nanoparticles (AuNPs) can be found in different shapes and sizes, which determine their chemical and physical characteristics. Physical and chemical properties of metallic NPs can be tuned by changing their shape, size, and surface chemistry; therefore, this has led to their use in a wide variety of applications in many industrial and academic sectors. One of the features of metallic NPs is their ability to act as optothermal energy converters, where they absorb light at a specific wavelength and heat up their local nanosurfaces. This feature has been used in many applications where metallic NPs get coupled with thermally responsive systems to trigger an optical response. In this study, we synthesized AuNPs that are spherical in shape with an average diameter of 20.07 nm. This work assessed simultaneously theoretical and experimental techniques to evaluate the different factors that affect heat generation at the surface of AuNPs when exposed to a specific light wavelength. The results indicated that laser power, concentration of AuNPs, time × laser power interaction, and time illumination, were the most important factors that contributed to the temperature change exhibited in the AuNPs solution. We report a regression model that allows predicting heat generation and temperature changes with residual standard errors of less than 4%. These results are highly relevant in the future design and development of applications where metallic NPs are incorporated into systems to induce a temperature change triggered by light exposure.

Impact of activator incorporation on red emitting rods of ZnGa2O4:Cr3+ phosphor.

Chromium doped zinc gallium oxide (ZnGa2O4:Cr3+) microrods were synthesized by simple solid state reaction method. The transformation on crystal structure and optical properties with molar concentration of Cr3+ were analyzed. The cubic spinel nature of ZnGa2O4:Cr3+phosphor and their crystalline nature were confirmed from x- ray diffractogram. The average grain size of the samples range between 24 and 29 nm, with lattice parameter values greater than that of bulk. Lattice strain produced in the lattice on doping was estimated from the Williamson-Hall plot. It increases on Cr3+ doping up to 3 mol% and then decreases. Rod like nature of zinc gallate was observed from the surface morphological analysis using SEM. X-ray photoelectron spectroscopy was used for the chemical state identification of the constituent elements in the compound. The photoluminescense spectra consists of various emission lines originated from the chromium ion in the spinel lattice. The purity of red emissions were observed from chromaticity diagram with a concentration quenching initiated from the dipole-dipole interaction, with increase in dopant concentration. Band gap of the samples were estimated using Kubelka-Munk equation which exhibited red shift compared to bulk due to band tailing effect.

Nanostructured SnS2 Thin Films from Laser Ablated Nanocolloids: Structure, Morphology, Optoelectronic and Electrochemical Properties.

Tin disulfide (SnS2 ) is a binary chalcogenide semiconductor having applications in solar cells, energy storage, and optoelectronics. SnS2 thin films were deposited by spraying the nanocolloids synthesized by pulsed laser ablation in liquid. The structure, morphology, and optoelectronic properties were studied for films obtained from two liquid media (ethanol and isopropanol) and after heat treatments at various temperatures. X-ray diffraction analysis confirmed the hexagonal crystal structure of the films, whereas the 2-H polytype structure was identified by micro-Raman spectroscopy. Oxidation states of Sn (4+) and S (2-) identified from high resolution X-ray photoelectron spectra confirmed the composition and chemical states of the films. The SnS2 thin films exhibited distinct porous surface morphologies as the liquid medium in laser ablation was varied. All as-prepared and annealed films showed photoluminescence with a high intensity peak at 485 nm and a low intensity peak at 545 nm. Thin films annealed at 300 °C showed improved electrochemical properties upon illumination using a blue LED light source. Current-voltage curves recorded in dark and light as well as the photoresponse measurements showed their suitability for utilization in optoelectronic devices. The results of this study may trigger further research towards fabrication of nanostructured thin films in large area for optoelectronic and photoelectrochemical applications in an environment friendly and cost-effective way.

Effects of Liquid Medium and Ablation Wavelength on the Properties of Cadmium Sulfide Nanoparticles Formed by Pulsed-Laser Ablation.

Pulsed-laser ablation in liquid (PLAL) is a green synthesis technique to obtain semiconductor nanomaterials in colloidal form. Herein, cadmium sulfide (CdS) nanoparticles were synthesized by the pulsed-laser ablation of a CdS target in different liquid media by using λ=532 and 1064 nm outputs from a pulsed (10 ns, 10 Hz) Nd:YAG laser at different ablation fluence values. The morphology, structure, crystalline phase, elemental composition, optical, and luminescent properties of CdS nanomaterials were analyzed by using transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV/Vis absorption spectroscopy, and fluorescence spectroscopy. By changing the liquid medium and ablation wavelength, CdS nanoparticles with different morphology and size were formed, as demonstrated by using TEM analysis. The crystallinity and chemical states of the ablation products were confirmed by using XRD and XPS analyses. The optical bandgap of the CdS nanoparticles was dependent on the ablation wavelength and the fluence. These nanocolloids presented different green emissions, which implied the presence of several emission centers. CdS nanocolloids in distilled water catalyzed the photocatalytic decay of methylene blue dye under light irradiation from a solar simulator.

Synthesis and Properties of Tin Sulfide Thin Films from Nanocolloids Prepared by Pulsed Laser Ablation in Liquid.

Tin sulfide (SnS) nanoparticles were synthesized by pulsed laser ablation in liquid (PLAL) technique using an Nd:YAG laser operated at 532 nm. SnS thin films were deposited by spraying the colloidal suspension onto the heated substrates. The influence of different liquid media (dimethyl formamide and isopropyl alcohol) on the thin film properties were studied. Morphology, crystalline structure, and chemical composition of the nanoparticles were identified using transmission electron microscopy with energy dispersive X-ray analysis. The crystalline structure of the thin films was analyzed by using grazing incidence X-ray diffraction, and the chemical states by X-ray photoelectron spectroscopy. Scanning electron microscopy was employed for the morphological analysis of the thin films. Annealing the films at 380 °C improved the crystallinity of the films exhibiting a layered morphology, which may be useful in optoelectronic and sensing applications. Cyclic voltammetry studies showed that the films have good electrochemical properties.