Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in ...

National Institute for Materials Science, Japan

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.

Encapsulation of proteins into tunable and giant mesocage alumina.

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.

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

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.

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

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.

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

High exposure to metals, such as cobalt (Co), copper (Cu) and cadmium (Cd), potentially has adverse effects, and can cause severe health problems, leading to a number of specific diseases. This study primarily aims to monitor, detect, separate, and remove the trace concentrations of Co(II), Cu(II), and Cd(II) ions in water, without a preconcentration process, using aluminosilica optical sensor (ASOS) monoliths. These monolithic scaffolds with advantageous physical features (i.e., large surface area-to-volume ratios of the scaffolds, active acid sites and uniform mesocage cubic pores) can strongly induce H-bonding and dispersive interactions with organic chelating agent, resulting in the formation of stable ASOS. In this engineering process, ASOS offers a simple and one-step sensing/capture procedure for the quantification and visual detection of the target elements from water, without requiring sophisticated instrumentation. The key result in this study is the ion selectivity exhibited by the designed ASOS toward the targets, Co(II), Cu(II), and Cd(II) ions, in environmental and waste disposal samples, as well as its reproducibility over a number of analysis/regeneration cycles. These findings can be useful in the fabrication of ASOS can be tailored to suit various applications.

Monolithic scaffolds for highly selective ion sensing/removal of Co(II), Cu(II), and Cd(II) ions in water.

Nanomembrane canister-like architectures were fabricated by using hexagonal mesocylinder-shaped aluminosilica nanotubes (MNTs)-porous anodic alumina (PAA) hybrid nanochannels. The engineering pattern of the MNTs inside a 60 μm-long membrane channel enabled the creation of unique canister-like channel necks and cavities. The open-tubular canister architecture design provides controllable, reproducible, and one-step processing patterns of visual detection and rejection/permeation of oxyanion toxins such as selenite (SeO3 (2-) ) in aquatic environments (i.e., in ground and river water sources) in the Ibaraki Prefecture of Japan. The decoration of organic ligand moieties such as omega chrome black blue (OCG) into inorganic Al2 O3 @tubular SiO2 /Al2 O3 canister membrane channel cavities led to the fabrication of an optical nanomembrane sensor (ONS). The OCG ligand was not leached from the canister as observed in washing, sensing, and recovery assays of selenite anions in solution, which enabled its multiple reuse. The ONS makes a variety of alternate processing analyses of selective quantification, visual detection, rejection/permeation, and recovery of toxic selenite quick and simple without using complex instrumentation. Under optimal conditions, the ONS canister exhibited a high selectivity toward selenite anions relative to other ions and a low-level detection limit of 0.0093 μm. Real analytical data showed that approximately 96 % of SeO3 (2-) anions can be recovered from aquatic and wastewater samples. The ONS canister holds potential for field recovery applications of toxic selenite anions from water.

Nanomembrane Canister Architectures for the Visualization and Filtration of Oxyanion Toxins with One-Step Processing.

Architecture of nanoscale electrochemical sensors for ultra-trace detection of glucose in blood is important in real-life sampling and analysis. To broaden the application of electrochemical sensing of glucose, we fabricated, for the first time, a glucose sensor electrode based on radially oriented NiO nanostrands (NSTs) onto 3D porous Ni foam substrate for monitoring, as well as selective and sensitive sensing of glucose in mammalian blood. The simple, scalable one-pot fabrication of this NST-Ni sensor design enabled control of the pattern of radially oriented NSTs onto 3D porous Ni foam substrate. The radial orientation of NST-Ni electrode onto the interior of the 3D porous substrate with controlled crystal structure size and atomic arrangement along the axis of the strands, intrinsic surface defects, and superior surface properties, such as hydrophilicity, high surface energy, and high density led to highly exposed catalytic active sites. The hierarchical NST-Ni electrode was used to develop a sensitive and selective sensor over a wide range of glucose concentrations among actively competitive ions, chemical species and molecular agents, and multi-cyclic sensing assays. The NST-Ni electrode shows significant glucose sensing performance in terms of unimpeded diffusion pathways, a wide range of concentration detection, and lower limit of detection (0.186µM) than NiO nanosheet (NS)-Ni foam electrode pattern, indicating the effectiveness of the shape-dependent structural architecture of NST-Ni electrode. In this study, the NST-Ni electrode is fabricated to develop a simple, selective method for detecting glucose in physiological fluids (e.g., mammalian blood).

Mohamed A. Shenashen

National Institute for Materials Science, Japan

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores