Electrochemical Characterization of Diffusion in Polymeric vs. Monomeric Solvents.

Polymer electrolyte was used as a medium for testing the performance of microband electrodes under conditions of linear diffusion. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments were performed in a highly viscous medium, where diffusion rates are much slower than in fluid solutions. The log i vs. log v (CV) or log i vs. log t (CA) relationships with the current equation confirmed the existence of such conditions, yielding slope values that were lower than the expected 0.5. This could indicate an impure linear diffusion profile, i.e., some contribution from radial diffusion (edge effects). However, the desired value of 0.5 was obtained when performing these tests in monomeric solvents of similar viscosities, such as glycerol or propylene glycol. These results led to the conclusion that the current equations, which are based on Fick's laws, may not be applicable for polymer electrolytes, where various obstructions to free diffusion result in a more complicated process than for monomeric solvents.

Sonochemistry of molten metals.

Ultrasonic irradiation of molten metals in liquid media causes dispersion of the metals into suspensions of micro- and nanoparticles that can be separated. This is applicable mainly to low-mp elemental metals or alloys, but higher mp elemental metals or alloys were also reported. Among metals, mercury and gallium exhibit especially-low melting points and are thus considered as liquid metals (LMs). Sonication of mercury in aqueous solutions of certain metal ions can cause simultaneous reduction of the ions and reactions between the metals. Gallium can be melted and sonicated in warm water, as well as in aqueous solutions of various solutes such as metal ions and organic compounds, which opened a wide window of interactions between the gallium particles and the solutes. Sonication of molten metals in organic liquids, such as polyethylene glycol (PEG) 400, forms carbon dots (C-dots) doped with nanoparticles of these metals. This review article summarizes the various interactions and reactions that occur upon sonication of metals in liquid media.

Sonochemistry of molten gallium.

This review article summarizes the comprehensive work that was done in our laboratory in recent years, as-well-as other reports, on the various aspects of sonochemistry of molten gallium. The low mp (29.8 °C) of gallium enables its melting in warm water, aqueous solutions and organic liquids. This opened a new research direction that focused on the chemical and physical properties of gallium particles that were formed in such media. It includes their interactions with water and with organic and inorganic solutes in aqueous solutions and with carbon nanoparticles. Formation of nanoparticles of liquid gallium alloys was also reported.

Synthesis of Doped/Hybrid Carbon Dots and Their Biomedical Application.

Carbon dots (CDs) are a novel type of carbon-based nanomaterial that has gained considerable attention for their unique optical properties, including tunable fluorescence, stability against photobleaching and photoblinking, and strong fluorescence, which is attributed to a large number of organic functional groups (amino groups, hydroxyl, ketonic, ester, and carboxyl groups, etc.). In addition, they also demonstrate high stability and electron mobility. This article reviews the topic of doped CDs with organic and inorganic atoms and molecules. Such doping leads to their functionalization to obtain desired physical and chemical properties for biomedical applications. We have mainly highlighted modification techniques, including doping, polymer capping, surface functionalization, nanocomposite and core-shell structures, which are aimed at their applications to the biomedical field, such as bioimaging, bio-sensor applications, neuron tissue engineering, drug delivery and cancer therapy. Finally, we discuss the key challenges to be addressed, the future directions of research, and the possibilities of a complete hybrid format of CD-based materials.

Designing Natural Polymer-Based Capsules and Spheres for Biomedical Applications-A Review.

Natural polymers, such as polysaccharides and polypeptides, are potential candidates to serve as carriers of biomedical cargo. Natural polymer-based carriers, having a core-shell structural configuration, offer ample scope for introducing multifunctional capabilities and enable the simultaneous encapsulation of cargo materials of different physical and chemical properties for their targeted delivery and sustained and stimuli-responsive release. On the other hand, carriers with a porous matrix structure offer larger surface area and lower density, in order to serve as potential platforms for cell culture and tissue regeneration. This review explores the designing of micro- and nano-metric core-shell capsules and porous spheres, based on various functions. Synthesis approaches, mechanisms of formation, general- and function-specific characteristics, challenges, and future perspectives are discussed. Recent advances in protein-based carriers with a porous matrix structure and different core-shell configurations are also presented in detail.

Sonochemically Prepared BSA Microspheres as Adsorbents for the Removal of Organic Pollutants from Water.

This work investigates, for the first time, the application of sonochemically prepared bovine serum albumin (BSA) microspheres (BSAMS) as adsorbents of industrial organic pollutant dyes, such as rhodamine B (RhB), rhodamine 6G (Rh6G), and methylene blue (MB). These dyes also serve as model compounds for other organic pollutants such as bisphenol A and 2-nitrophenol. Adsorption kinetics of the dyes by the BSAMS was studied using pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models. It was found that RhB follows PFO, with an adsorption capacity, qe,cal, of 7.9 mg/g, which was closer to the experimental adsorption capacity of qe,exp. of 7.6 mg/g. However, MB and Rh6G were controlled by PSO kinetics, with a qe,cal of 5.6 mg/g for MB and 6.6 mg/g for Rh6G, closer to the experimental adsorption capacity of 5.7 and 6.4 mg/g, respectively. The intraparticle diffusion (ID) model applied to the three dyes indicated multi-linearity with ID as the rate-limiting step in the adsorption process. Furthermore, the adsorption equilibria for each of the organic pollutants were studied through various isotherm models such as Langmuir, Freundlich, Temkin, and Halsey, which indicated physical interaction between the BSAMS and the dye pollutants, thus suggesting the applicability of the BSAMS as pollutant adsorbent materials. It was found that the BSAMS can effectively remove RhB, MB, and Rh6G from wastewater with efficiencies of 95.5, 83.3, and 97.9%, respectively.

Exploring the Effect of Iron Metal-Organic Framework Particles in Polylactic Acid Membranes for the Azeotropic Separation of Organic/Organic Mixtures by Pervaporation.

A microporous carboxylate metal-organic framework MIL-100 Fe was prepared as submicron particles by microwave-assisted hydrothermal synthesis (Fe-MOF-MW). This product was explored, for the first time, for the preparation of polylactic acid (PLA) mixed matrix membranes. The produced MOF was characterised by powder X-ray diffraction (PXRD), environmental scanning electron microscopy (ESEM) as well as by thermogravimetric analysis (TGA) and nitrogen adsorption/desorption. The effect of different Fe-MOF-MW concentrations (0.1 and 0.5 wt%) on the membrane properties and performance were evaluated. These membranes were used in the pervaporation process for the separation of methanol/methyl tert-butyl-ether mixtures at the azeotropic point. The influence of the feed temperature and vacuum pressure on the membrane performance was evaluated and the results were compared with PLA pristine membranes. Moreover, the produced membranes have been characterised in terms of morphology, MOF dispersion in the polymeric membrane matrix, wettability, thickness, mechanical resistance and swelling propensity. The presence of Fe-MOF-MW was found to have a beneficial effect in improving the selectivity of mixed matrix membranes towards methanol at both concentrations. The highest selectivity was obtained for the PLA membranes embedded with 0.5 wt% of Fe-MOF-MW and tested at the temperature of 25 °C and vacuum pressure of 0.09 mbar.

Entrapment and release kinetics study of dyes from BSA microspheres forming a matrix and a reservoir system.

Two kinds of Bovine Serum Albumin (BSA)-loaded microspheres were prepared in water-organic bilayer systems using ultrasonic irradiation. The first method included an aqueous solution of BSA and water-soluble dye together, mixed with dodecane, that upon sonication formed a matrix system where the dye is concentrated in the protein shell. The other system included an aqueous solution of BSA mixed with octanol-soluble dye that, upon sonication, formed a reservoir system in which the dye filled the inner volume of the microspheres. Each of these microspheres was prepared with two different dyes and their leaching profiles into pure solvents were studied using UV-vis spectrometry. Fast leaching was observed at the beginning for both systems, which levelled-off after a certain time. For the matrix system, an equilibrium state was obtained after 100-200 hours, whereas for the reservoir system, leaching occurred much faster, within 1-3 hours. Such systems can serve as models for drug delivery agents.

Measuring the water content in freshly-deposited fingermarks.

The literature view regarding the composition of deposited fingermarks has long been that the average water content is in the range of 98-99wt.%. This value has recently been challenged by Kent, claiming that it should be 20wt.% at most. Herein we have measured the weight percentage of water content in freshly-deposited fingermarks, with and without hand pre-washing. Two complementary techniques were utilized for the measurements, namely quartz crystal microbalance (QCM) for determining the relative mass-loss and its rate at ca. 37°C, and temperature-programmed desorption-mass spectrometry (TPD-MS) for establishing that the mass loss arises solely from the complete evaporation of all the water content in the fingermarks (done with hand pre-washing only). Unlike the traditional narrow-range values of 98-99% and the limiting value of 20wt.% suggested by Kent, our measurements indicate the occurrence of a broad 20-70% water content. Higher contents of water in fingermarks were found post hand pre-washing, most probably due to removal of the sebum from the fingertips, but none of the results exceeded 90%.

Ultrafine Highly Magnetic Fluorescent γ-Fe2O3/NCD Nanocomposites for Neuronal Manipulations.

In this work, we describe a low-cost, two-step synthesis of composites of nitrogen-doped carbon quantum dots (NCDs) with γ-Fe2O3 (NCDs/γ-Fe2O3), which is based on a hydrothermal cum co-precipitation method. The product is a fine powder of particles having an average diameter of 9 ± 3 nm. The physical and chemical properties of NCDs/γ-Fe2O3 were studied, as well as the superconducting quantum interference device and Mossbauer analysis of the magnetic properties of these nanocomposites. The interaction of NCDs/γ-Fe2O3 nanocomposites with neuron-like cells was examined, showing efficient uptake and low toxicity. Our research demonstrates the use of the nanocomposites for imaging and for controlling the cellular motility. The NCDs/γ-Fe2O3 nanocomposites are promising because of their biocompatibility, photostability, and potential selective affinity, paving the way for multifunctional biomedical applications.

Formation of metallic silver and copper in non-aqueous media by ultrasonic radiation.

Concentrated suspensions of silver and copper salts in silicone oil were heated to 200 °C and irradiated with ultrasonic energy for different time durations. Characterization of the products was done using X-ray powder diffraction. In most cases, metallic Ag or Cu were obtained, together with their oxide forms Ag2O and Cu2O. The salts, used as precursors, do not dissolve in silicone oil but rather form a heterogeneous system, and we assume that local heating, caused by the acoustic cavitation, enhanced their thermal decomposition and the formation of metallic particles. It was found that the presence of silver particles enhances the formation of metallic copper. This phenomenon was observed in the experiment with the acetate salts mixture.

Ga@C-dots as an antibacterial agent for the eradication of Pseudomonas aeruginosa.

The opportunistic pathogen Pseudomonas aeruginosa causes infections that are difficult to treat by antibiotic therapy. This research article reports on the synthesis of gallium (Ga) doped in carbon (C)-dots (Ga@C-dots) and their antimicrobial activity against free-living P. aeruginosa bacteria. The synthesis of Ga@C-dots was carried out by sonicating molten Ga (for 2.5 h) in polyethylene glycol-400, which acts as both a medium and carbon source. The resultant Ga@C-dots, having an average diameter of 9±2 nm, showed remarkably enhanced antibacterial activity compared with undoped C-dots. This was reflected by the much lower concentration of Ga doped within Ga@C-dots which was required for full inhibition of the bacterial growth. These results highlight the possibility of using Ga@C-dots as potential antimicrobial agents.

Sonochemically-fabricated Ga@C-dots@Ga nanoparticle-aided neural growth.

In this paper, we report the fabrication of an antibacterial material, Ga-doped C-dots on Ga nanoparticles (Ga@C-dots@Ga NPs), which is deposited on a glass substrate for neural growth. A one-step sonochemical process is applied for the simultaneous fabrication and coating of Ga@C-dots@Ga NPs using PEG 400 and molten gallium. The physical and chemical characteristics of the synthesized materials were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), fluorescence analysis, dynamic light scattering (DLS) and other techniques. SH-SY5Y cells were plated on the substrates. The effect of the Ga@C-dots@Ga NPs on the development of neurites during the initiation and elongation growth phases was studied and compared with C-dots, Ga@C-dots and Ga NPs. Our research focuses on the influence of the physical and chemical properties of composites on neurite growth. We observed that cells grown on a Ga@C-dots@Ga-coated substrate exhibit a 97% increase in the number of branches originating from the soma. We found that surface modification and particle morphology play a significant role in the neural growth.

Sonochemical synthesis of CH3NH3PbI3 perovskite ultrafine nanocrystal sensitizers for solar energy applications.

The organic-inorganic hybrid perovskite CH3NH3PbI3 is becoming an interesting material in the field of energy harvesting. This material is one of the cleanest and cheapest components in solar cells which is available in ample amounts. However, most of the previous research work was done on thin film of this material. In the present work we describe the preparation of a powder containing nanoparticles of CH3NH3PbI3 using a sonochemical method. Characterization of the product was done by various methods, such as HRTEM, FTIR, PL, DLS and XRD. The particles were found to be highly crystalline (tetragonal crystal structure), polygonal in shape and having diameters of 10-40nm.

Facile one-step sonochemical synthesis of ultrafine and stable fluorescent C-dots.

This work describes a one-step synthesis of carbon dots (C-dots), which is carried out by sonication of polyethylene glycol (PEG-400) for 0.5-3h. The effect of the various experimental parameters, such as sonication time, amplitude and temperature on the size and the fluorescence of the C-dots was studied. It was found that the average diameter of the C-dots is between 2 and 9 nm, depending on the preparation conditions. The highest quantum yield of emission was ∼ 16%. These high fluorescence properties of the C-dots could be used for bioimaging and for solar cell applications.

Dispersion of Polymers in Metallic Gallium.

This work examines the concept of dispersing polymers in metals. Herein, this was mainly studied with molten gallium, in which 5-18 wt % of various short-chain polymers were incorporated and mixed. The nature of the solidified products was examined by using X-ray diffraction, electron microscopy, UV/Vis, differential scanning calorimetry, and thermal gravimetric analyses. It was found that some polymers can be dispersed as small domains within molten metals to form a heterogeneous solid. The ability to dope Ga with large polymers opens a new avenue to electronic materials.

Facile synthesis of gallium oxide hydroxide by ultrasonic irradiation of molten gallium in water.

This work describes the single-step synthesis of GaO(OH) by ultrasonic irradiation of molten gallium in warm water. The ultrasonic energy causes dispersion of the liquid gallium into micrometric spheres, as-well-as decomposition of some of the water into H and OH radicals. The OH radicals and the dissolved oxygen react on the surface of the gallium spheres to form crystallites of GaO(OH). These crystallites prevent the re-coalescence of the gallium spheres, and as the reaction proceeds all the gallium is converted into crystalline GaO(OH).

Green synthesis of gold nanoparticles using plant extracts as reducing agents.

Gold nanoparticles (GNPs) were prepared using four different plant extracts as reducing and stabilizing agents. The extracts were obtained from the following plants: Salvia officinalis, Lippia citriodora, Pelargonium graveolens and Punica granatum. The size distributions of the GNPs were measured using three different methods: dynamic light scattering, nanoparticle-tracking analysis and analysis of scanning electron microscopy images. The three methods yielded similar size distributions. Biocompatibility was examined by correlation of L-cell growth in the presence of different amounts of GNPs. All GNPs showed good biocompatibility and good stability for over 3 weeks. Therefore, they can be used for imaging and drug-delivery applications in the human body. High-resolution transmission electron microscopy was used to view the shapes of the larger GNPs, while infrared spectroscopy was employed to characterize the various functional groups in the organic layer that stabilize the particles. Finally, active ingredients in the plant extract that might be involved in the formation of GNPs are proposed, based on experiments with pure antioxidants that are known to exist in that plant.

Ultrasonic cavitation of molten gallium: formation of micro- and nano-spheres.

Pure gallium has a low melting point (29.8°C) and can be melted in warm water or organic liquids, thus forming two immiscible liquid phases. Irradiation of this system with ultrasonic energy causes cavitation and dispersion of the molten gallium as microscopic spheres. The resultant spheres were found to have radii range of 0.2-5 µm and they do not coalesce upon cessation of irradiation, although the ambient temperature is well above the m.p. of gallium. It was found that the spheres formed in water are covered with crystallites of GaO(OH), whereas those formed in organic liquids (hexane and n-dodecane) are smooth, lacking such crystallites. However, Raman spectroscopy revealed that the spheres formed in organic liquids are coated with a carbon film. The latter may be the factor preventing their coalescence at temperatures above the m.p. of gallium.

Silver nanoparticles deposited on porous silicon as a surface-enhanced Raman scattering (SERS) active substrate.

Silver nanoparticles were deposited spontaneously from their aqueous solution on a porous silicon (PS) layer. The PS acts both as a reducing agent and as the substrate on which the nanoparticles nucleate. At higher silver ion concentrations, layers of nanoparticle aggregates were formed on the PS surface. The morphology of the metallic layers and their SERS activity were influenced by the concentrations of the silver ion solutions used for deposition. Raman measurements of rhodamine 6G (R6G) and crystal violet (CV) adsorbed on these surfaces showed remarkable enhancement of up to about 10 orders of magnitude.