Mohamed A. Shenashen

Optical mesosensors for monitoring and removal of ultra-trace concentration of Zn(II) and Cu(II) ions from water

Optical captor design is necessary for the controlled development of a technique for detecting and removing heavy and toxic metals from drinking water with high flexibility and low capital cost. We designed chemical mesocaptors for optical separation/extraction and monitoring/detection of Cu(II) and Zn(II) ions from water even at trace concentration levels without a preconcentration process. The mesoporous aluminosilica carriers with three-dimensional (3D) structures, high aluminum content, natural surfaces, and active acid sites strongly induced H-bonding and dispersive interactions with organic moieties, thereby leading to the formation of stable captors without chromophore leaching during the removal assays of Cu(II) and Zn(II) ions. Using such a tailored mesocaptor design, the direct immobilization of these hydrophobic ligands (4,5-diamino-6-hydroxy-2-mercaptopyrimidine and diphenylthiocarbazone) into ordered pore-based aluminasilica monoliths enabled the easy generation and transduction of optical colour signals as a response to metal-to-ligand binding events, even at ultra-trace concentrations (~10(-9) mol dm(-3)) of Cu(II) and Zn(II) ions in drinking water, without the need for sophisticated instruments. Theoretical models have been developed to provide insights into the effect of active site surfaces on the enhancement of the optical removal process in terms of long-term stability, reversibility, and selectivity, hence allowing us to understand the role of mesoscopic geometry and nanoscale pore orientation of mesocaptors better. Generally, this ion-capture model enables the development of a simple and effective technique for effective wastewater treatment and management.

Architecture of optical sensor for recognition of multiple toxic metal ions from water.

Here, we designed novel optical sensor based on the wormhole hexagonal mesoporous core/multi-shell silica nanoparticles that enabled the selective recognition and removal of these extremely toxic metals from drinking water. The surface-coating process of a mesoporous core/double-shell silica platforms by several consequence decorations using a cationic surfactant with double alkyl tails (CS-DAT) and then a synthesized dicarboxylate 1,5-diphenyl-3-thiocarbazone (III) signaling probe enabled us to create a unique hierarchical multi-shell sensor. In this design, the high loading capacity and wrapping of the CS-DAT and III organic moieties could be achieved, leading to the formation of silica core with multi-shells that formed from double-silica, CS-DAT, and III dressing layers. In this sensing system, notable changes in color and reflectance intensity of the multi-shelled sensor for Cu(2+), Co(2+), Cd(2+), and Hg(2+) ions, were observed at pH 2, 8, 9.5 and 11.5, respectively. The multi-shelled sensor is added to enable accessibility for continuous monitoring of several different toxic metal ions and efficient multi-ion sensing and removal capabilities with respect to reversibility, selectivity, and signal stability.

Tailor‐Made Micro‐Object Optical Sensor Based on Mesoporous Pellets for Visual Monitoring and Removal of Toxic Metal Ions from Aqueous Media

Methods for the continuous monitoring and removal of ultra-trace levels of toxic inorganic species (e.g., mercury, copper, and cadmium ions) from aqueous media such as drinking water and biological fluids are essential. In this paper, the design and engineering of a simple, pH-dependent, micro-object optical sensor is described based on mesoporous aluminosilica pellets with an adsorbed dressing receptor (a porphyrinic chelating ligand). This tailor-made optical sensor permits ultra-fast (≤ 60 s), specific, pH-dependent visualization and removal of Cu(2+) , Cd(2+) , and Hg(2+) at sub-picomolar concentrations (∼10(-11) mol dm(-3) ) from aqueous media, including drinking water and a suspension of red blood cells. The acidic active acid sites of the pellets consist of heteroatoms arranged around uniformly shaped pores in 3D nanoscale gyroidal mesostructures densely coated with the chelating ligand. The sensor can be used in batch mode, as well as in a flow-through system in which sampling, target ion recognition and removal, and analysis are integrated in a highly automated and efficient manner. Because the pellets exhibit long-term stability, reproducibility, and versatility over a number of analysis/regeneration cycles, they can be expected to be useful for the fabrication of inexpensive sensor devices for naked-eye detection of toxic pollutants.

A multi-pH-dependent, single optical mesosensor/captor design for toxic metals

The fabrication of low-cost, simple nanodesigns with sensing/capture functionality has been called into question by the toxicity and non-degradability of toxic metals, as well as the persistent threat they pose to human lives. In this study, a single, pH-dependent, mesocaptor/sensor was developed for the optical and selective removal of toxic ions from drinking water and physiological systems such as blood.

Optical detection/collection of toxic Cd(II) ions using cubic Ia3d aluminosilica mesocage sensors

Optical sensors for selective removal and detection of extremely toxic ions such as cadmium (Cd(II)) in aquatic samples were successfully fabricated via simple strategy. Aluminosilica-based network platforms are used as selective mesopore shape and size carriers in order to fabricate optical sensors through the direct functionalization of α, β, γ, and δ-tetrakis(1-methylpyridinium-4-yl)porphine ρ-toluenesulfonate (TMPyP) moieties without any prior surface modification using silane or thiol agents. In turn, the key advantage of a heretical three-dimensional (3D) cubic Ia3d mesocage is the facile access of target ions such as ion transports and the high affinity responses of TMPyP receptor-Cd(II) analyte binding events, which result in the easy generation and transduction of optical signals even at the trace level of the Cd(II) ion. The optical sensor design-based aluminosilica cages enable the sensitive detection and selective removal of Cd(II) ions even at ultra-trace concentrations of 10(-10)mol/dm(3) with rapid response time (in minutes). This rational strategy is crucial to the development of optical mesocollectors (i.e., probe surface-mounted naked-eye ion-sensor strips) with highly selective Cd(II) ion removal from aqueous water. These new classes of optical mesocollectors exhibit long-term stability and reusability of deleterious Cd(II) ions, which makes them efficient for various analytical applications.

Hierarchical inorganic–organic multi-shell nanospheres for intervention and treatment of lead-contaminated blood

The highly toxic properties, bioavailability, and adverse effects of Pb(2+) species on the environment and living organisms necessitate periodic monitoring and removal whenever possible of Pb(2+) concentrations in the environment. In this study, we designed a novel optical multi-shell nanosphere sensor that enables selective recognition, unrestrained accessibility, continuous monitoring, and efficient removal (on the order of minutes) of Pb(2+) ions from water and human blood, i.e., red blood cells (RBCs). The consequent decoration of the mesoporous core/double-shell silica nanospheres through a chemically responsive azo-chromophore with a long hydrophobic tail enabled us to create a unique hierarchical multi-shell sensor. We examined the efficiency of the multi-shell sensor in removing lead ions from the blood to ascertain the potential use of the sensor in medical applications. The lead-induced hemolysis of RBCs in the sensing/capture assay was inhibited by the ability of the hierarchical sensor to remove lead ions from blood. The results suggest the higher flux and diffusion of Pb(2+) ions into the mesopores of the core/multi-shell sensor than into the RBC membranes. These findings indicate that the sensor could be used in the prevention of health risks associated with elevated blood lead levels such as anemia.

Encapsulation of proteins into tunable and giant mesocage alumina

Protein bioadsorption has rapidly attracted attention partially because of the promising advances in diagnostic assays, sensors, separations, and gene technology. Tunable and giant mesocage alumina cavities (5 nm to 20 nm) show capability in size-selective encapsulation and diffusivity of large proteins into interior pores.

Bioadsorption of proteins on large mesocage-shaped mesoporous alumina monoliths

With the remarkable progress in the field of gene technology, proteins have gained an important function in the field of disease diagnosis and treatment. Protein bioadsorption has drawn increasing attention partly because of the promising advances for diagnostic assays, sensors, separations, and gene technology. Mesocage alumina has a cage-type structure with high surface area and pore volume, exhibiting superior capabilities for protein adsorption. In this study, we report the size-selective adsorption/removal of virtual proteins having different shapes, sizes, functions, and properties, including insulin, HopPmaL domain, lysozyme, galectin-3, β-lactoglobulin, α-1-antitrypsin, α-amylase, and myosin in aqueous water using mesocage alumina. The mesoporous alumina monoliths have unique morphology and physical properties and enhanced protein adsorption characteristics in terms of sample loading capacity and quantity, thereby ensuring a higher concentration of proteins, interior pore diffusivity, and encapsulation in a short period. Thermodynamic analysis shows that protein adsorption on mesocage alumina monoliths is favorable and spontaneous. Theoretical models have been studied to investigate the major driving forces to achieve the most optimal performance of protein adsorption. The development of ultra- or micrometer-scale morphology composed of mesocage-shaped mesoporous monoliths or alumina network clusters can be effectively used to encapsulate the macromolecules into the interior cage cavities, which can greatly assist in other potentials for biomedical applications. Furthermore, the adsorption of a single protein from mixtures based on size- and shape-selective separation can open up new ways to produce micro-objects that suit a given protein encapsulation design.

Effective, Low Cost Recovery of Toxic Arsenate Anions from Water Using Hollow Sphere Trapper Geodes

Because of the devastating impact of arsenic on terrestrial and aquatic organisms, the recovery, removal, disposal, and management of arsenic-contaminated water is a considerable challenge and has become an urgent necessity in the field of water treatment. This study reports the controlled fabrication of a low-cost adsorbent based on microscopic C-,N-doped NiO hollow spheres with geode shells composed of poly-CN nanospherical nodules (100 nm) that were intrinsically stacked and wrapped around the hollow spheres to form a shell with a thickness of 500-700 nm. This C-,N-doped NiO hollow-sphere adsorbent (termed CNN) with multiple diffusion routes through open pores and caves with connected open macro/meso windows over the entire surface and well-dispersed hollow-sphere particles that create vesicle traps for the capture, extraction, and separation of arsenate (AsO43- ) species from aqueous solution. The CNN structures are considered to be a potentially attractive adsorbent for AsO43- species due to 1) superior removal and trapping capacity from water samples and 2) selective trapping of AsO43- from real water samples that mainly contained chloride and nitrate anions and Fe2+ , and Mn2+ , Ca2+ , and Mg2+ cations. The structural stability of the hierarchal geodes was evident after 20 cycles without any significant decrease in the recovery efficiency of AsO43- species. To achieve low-cost adsorbents and toxic-waste management, this superior CNN AsO43- dead-end trapping and recovery system evidently enabled the continuous control of AsO43- disposal in water-scarce environments, presents a low-cost and eco-friendly adsorbent for AsO43- species, and selectively produced water-free arsenate species. These CNN geode traps show potential as excellent adsorbent candidates in environment remediation tools and human healthcare.

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes.