Nanoarchitectonics of Bimetallic MOF@Lab-Grade Flexible Filter Papers: An Approach Towards Real-Time Water Decontamination and Circular Economy.

This study presents a novel approach to decontaminate ferrocyanide-contaminated wastewater. The work effectively demonstrates the use of bimetallic Mo/Zr-UiO-66 as a super-adsorbent for rapid sequestration of Prussian blue, a frequently found iron complex in cyanide-contaminated soils/groundwater. The exceptional performance of Mo/Zr-UiO-66 is attributed to the insertion of secondary metallic sites, which deliver synergistic effects, benefiting the inherent qualities of the framework. Moreover, to extend the industrial applications of metal-organic frameworks (MOFs) in real-world scenarios, an approach is delivered to structure the nanocrystalline powders into MOF-based macrostructures. The work demonstrates an interfacial process to develop continuous MOF nanostructures on ordinary laboratory-grade filter papers. The novelty of the work lies in the development of robust free-standing filtration materials to purify PB dye-contaminated water. Additionally, the work embraces a circular economy concept to address problems related to resource scarcity, excessive waste production, and maintenance of economic benefits. Consequently, the PB dye-loaded adsorbent waste is re-employed for the adsorption of heavy metals (Pb2+ and Cd2+ ). Simultaneously, the study aims to address the problems related to the real-time handling of powdered adsorbents, and the generation of ecologically harmful secondary waste, thereby, progressing toward a more sustainable system.

Rhodamine 6G derivative for the selective copper detection and remediation using nanoporous diatomaceous earth-engineered functional receptor.

A rhodamine-derived receptor was synthesized and comprehensively characterized for structural confirmation. The receptor was able to distinguish the copper ions (Cu2+) from other competing cations. The yellow color of the receptor changed to pink upon adding Cu2+ ions, however, other competing cations ions were impotent towards any color variation. The UV-visible titration studies revealed the binding stoichiometry of a 1:1 ratio with a detection limit of 9.663 × 10-8 M. Additionally, a novel idea of the work resides in the use of diatom for the practical application, where the receptor has been tethered on nanoporous diatomaceous earth microparticles (P2D) to remove Cu2+ ions. The results confirmed that 50 mg receptor functionalized DE could adsorb 10 mL of 1 ppm Cu2+ ions from water. Furthermore, a proof-of-concept device that is inexpensive, simple to operate, and continuously removes Cu2+ ions from water has been developed. The efficiency of the device in Cu2+ ion removal could be realized through the naked eye by observing the color change of P2D particles, which has excellent potential for application in remote locations where water contamination is a significant issue.

Ratiometric colorimetric detection of fluoride ions using a schiff base sensor: enhancing selectivity and sensitivity for naked-eye analysis.

A Schiff base receptor with an active -NH group was designed and synthesized for the selective and sensitive colorimetric detection of inorganic fluoride (F-) ions in an aqueous medium. The sensitivity of the receptor for F- ions was enhanced by the influence of two electron-withdrawing -NO2 groups at ortho and para positions which result in a vivid color change. The receptor underwent a remarkable color change from light yellow to violet, enabling naked-eye detection of F- ions without the need for spectroscopic equipment. To ensure the structural integrity of the synthesized receptors, prominent spectroscopic techniques such as 1H NMR, FTIR, and GCMS analysis were used for characterization. With a limit of detection (LoD) of 0.0996 ppm, a 1 : 2 stoichiometric binding ratio was observed for receptor and F- ions. The binding mechanism confirmed the deprotonation of the -NH group followed by the formation of -HF2, resulting in an intramolecular charge transfer (ICT) transition, which correlates with UV-vis and 1H NMR titration results. In addition, the proposed binding mechanism of F- ion interaction with the receptor was theoretically validated using DFT and TDDFT calculations. Furthermore, as a real-life implementation of the receptor, quantification of the F- ions present in a commercially available mouthwash was demonstrated. To assess the sensitivity performance, a paper-based dip sensor and a solid substrate sensor by functionalizing the receptor on diatomaceous earth were demonstrated. Finally, sensors were built into smartphones that could recognize the red, green, and blue percentages (RGB%) where each parameter defines the intensity of the color, which could also be used as a supplement to the colorimetric investigations.

A comprehensive review on water remediation using UiO-66 MOFs and their derivatives.

Metal-organic frameworks (MOFs) are a versatile class of porous materials offering unprecedented scope for chemical and structural tunability. On account of their synthetic versatility, tunable and exceptional host-guest chemistry they are widely utilized in many prominent water remediation techniques. However, some of the MOFs present low structural stabilities specifically in aqueous and harsh chemical conditions which impedes their potential application in the field. Among the currently explored MOFs, UiO-66 exhibits structural robustness and has gained immense scientific popularity. Built with a zirconium-terephthalate framework, the strong Zr-O bond coordination contributes to its stability in aqueous, chemical, and thermal conditions. Moreover, other exceptional features such as high surface area and uniform pore size add to the grand arena of porous nanomaterials. As a result of its stable nature, UiO-66 offers relaxed admittance towards various functionalization, including synthetic and post-synthetic modifications. Consequently, the adsorptive properties of these highly stable frameworks have been modulated by the addition of various functionalities. Moreover, due to the presence of catalytically active sites, the use of UiO-66 has also been extended towards the degradation of pollutants. Furthermore, to solve the practical handling issues of the crystalline powdered forms, UiO-66 has been incorporated into various membrane supports. The incorporation of UiO-66 in various matrices has enhanced the rejection, permeate flux, and anti-fouling properties of membranes. The combination of such exceptional characteristics of UiO-66 MOF has expanded its scope in targeted purification techniques. Subsequently, this review highlights the role of UiO-66 in major water purification techniques such as adsorption, photocatalytic degradation, and membrane separation. This comprehensive review is expected to shed light on the existing developments and guide the inexhaustible futuristic scope of UiO-66 MOF.

Insights into the mechanically resilient, well-balanced polymeric membranes by incorporating Rhizophora mucronata derived activated carbon for sustainable wastewater decontamination.

In this study, hydrophilic activated carbon has been prepared and used to synthesize innovative activated carbon/polysulfone mixed matrix membranes (MMMs). These membranes were investigated in terms of membrane morphology, hydrophilicity, antifouling ability, and metal ions rejection. The activated carbon (AC) was prepared from a simple chemical activation method using Rhizophora mucronata propagules, which are rich in aerenchyma cells and possess a high surface area. The hydrophilicity of the MMMs is enhanced by the incorporation of activated carbon, which is confirmed by the measurement of equilibrium water contact angle, water uptake and pure water flux. The optimized concentration of 0.625 wt% activated carbon (A2) incorporated mixed matrix membrane exhibits better rejection efficiencies of 98 ± 0.5%, 99 ± 0.5%, 92 ± 2%, and 44 ± 1% for Pb+2, Cd+2, Hg+2, and F- with the permeate flux of 28.27, 31.88, 33.21, 43.82 L/m2/h, respectively. The fabricated mixed matrix membranes demonstrated an excellent flux recovery ratio and reversible fouling, when filtrating a mixed feed solution containing 200 ppm BSA, 10 ppm Pb+2 and 10 ppm Cd+2. The optimized A2 membrane showed excellent long-term stability up to 120 h without compromising in permeate flux and rejection efficiency. Finally, a numerical investigation using a usual transport model has shown that dielectric exclusion was the most probable mechanism that can physically explain experimental trends.

Recent Advances in Microfluidic Platform for Physical and Immunological Detection and Capture of Circulating Tumor Cells.

CTCs (circulating tumor cells) are well-known for their use in clinical trials for tumor diagnosis. Capturing and isolating these CTCs from whole blood samples has enormous benefits in cancer diagnosis and treatment. In general, various approaches are being used to separate malignant cells, including immunomagnets, macroscale filters, centrifuges, dielectrophoresis, and immunological approaches. These procedures, on the other hand, are time-consuming and necessitate multiple high-level operational protocols. In addition, considering their low efficiency and throughput, the processes of capturing and isolating CTCs face tremendous challenges. Meanwhile, recent advances in microfluidic devices promise unprecedented advantages for capturing and isolating CTCs with greater efficiency, sensitivity, selectivity and accuracy. In this regard, this review article focuses primarily on the various fabrication methodologies involved in microfluidic devices and techniques specifically used to capture and isolate CTCs using various physical and biological methods as well as their conceptual ideas, advantages and disadvantages.

MOF based engineered materials in water remediation: Recent trends.

The significant upsurge in the demand for freshwater has prompted various developments towards water sustainability. In this context, several materials have gained remarkable interest for the removal of emerging contaminants from various freshwater sources. Among the currently investigated materials for water treatment, metal organic frameworks (MOFs), a developing class of porous materials, have provided excellent platforms for the separation of several pollutants from water. The structural modularity and the striking chemical/physical properties of MOFs have provided more room for target-specific environmental applications. However, MOFs limit their practical applications in water treatment due to poor processability issues of the intrinsically fragile and powdered crystalline forms. Nevertheless, growing efforts are recognized to impart macroscopic shapability to render easy handling shapes for real-time industrial applications. Furthermore, efforts have been devoted to improve the stabilities of MOFs that are subjected to fragile collapse in aqueous environments expanding their use in water treatment. Advances made in MOF based material design have headed towards the use of MOF based aerogels/hydrogels, MOF derived carbons (MDCs), hydrophobic MOFs and magnetic framework composites (MFCs) to remediate water from contaminants and for the separation of oils from water. This review is intended to highlight some of the recent trends followed in MOF based material engineering towards effective water regeneration.

New optofluidic based lab-on-a-chip device for the real-time fluoride analysis.

A PDMS (Polydimethylsiloxane) microfluidic channel coupled with UV-vis fibre-optic spectrometer and new synthesized colorimetric probe was integrated into an optofluidic based Lab-on-a-chip device for highly sensitive and real-time quantitative measurements of fluoride ions (F¯). An 'S' shaped microchannel in a microfluidic device was designed to act as microreactor to facilitate the continuous reaction between synthetized colorimetric probe (sensor) and F¯ ions. Following this reaction, the UV-vis optical probe in the downstream detection zone of the microfluidic device was used to capture their spectrum and present as F¯ concentration in real-time conditions. An initial study of the developed colorimetric probe with multi-colour change with several binding and chromophore groups such as -OH, -NH and -NO2 groups confirmed its high sensitivity and selectivity for F¯ ions with a detection limit of 0.79 ppm. The performance of the developed optofluidic device was evaluated for the selective, sensitive detection of F¯ ions including real samples out-performing conventional methods. The technology has advantages such as low sample consumption, rapid analysis, high sensitivity and portability. Presented new Lab-on-a-chip device provides many competitive advantages for the real-time analysis of F¯ ions needed across broad sectors.

Cerium based UiO-66 MOF as a multipollutant adsorbent for universal water purification.

Herein, we demonstrate the use of cerium (Ce)-UiO-66 metal organic framework (MOF) for the removal of a variety of potentially toxic pollutants. The Ce-UiO-66 MOF, with similar framework topologies to Zr-UiO-66, has not been explored for its adsorptive properties in water remediation. The replacement of Zr metal center with Ce yields a MOF that can be synthesized in shorter durations with lesser energy consumptions and with excellent multipollutant adsorption properties. Further, the Ce-UiO-66 MOF was also studied for its adsorption abilities in the binary component system. Interestingly, the adsorbent showed higher adsorption capacities in the presence of other pollutants. Removal studies for other potentially toxic anionic and cationic dyes showed that the Ce-UiO-66 MOF has a wide range of contaminant removal abilities. Investigations of individual adsorption capacities revealed that the Ce-UiO-66 MOF has a maximum adsorption capacity of 793.7 mg/g for congo red (CR), 110 mg/g for methylene blue (MB), 66.1 mg/g for fluoride (F-), 30 mg/g for Cr6+ and 485.4 mg/g for the pharmaceutical waste diclofenac sodium (DCF). To imply the practical applications of the Ce-UiO-66 MOF we have also demonstrated an adaptable filter that could separate all the potentially toxic pollutants.

Bio-inspired materials for defluoridation of water: A review.

The polluted water sources pose a serious issue concerning the various health hazards they bring along. Due to various uncontrolled anthropogenic and industrial activities, a great number of pollutants have gained entry into the water systems. Among all the emerging contaminants, anionic species such as fluoride cause a major role in polluting the water bodies because of its high reactivity with other elements. The need for water remediation has led the research community to come up with several physicochemical and electrochemical methods to remove fluoride contamination. Among the existing methods, biosorption using bio and modified biomaterials has been extensively studied for defluoridation, as they are cheap, easily available and effectively recyclable when compared to other methods for defluoridation. Adding on, these materials are non-toxic and are safe to use compared to many other synthetic materials that are toxic and require high-cost design requirements. This review focuses on the recent developments made in the defluoridation techniques by biosorption using bio and modified biomaterials and defines the current perspectives of fluoride removal specifically using biomaterials.

Naturally available diatomite and their surface modification for the removal of hazardous dye and metal ions: A review.

The presence of toxic pollutants such as dyes and metal ions at higher concentrations in water is very harmful to the environment. Removal of these pollutants using diatomaceous earth or diatomite (DE) and surface-modified DE has been extensively explored due to their excellent physio-chemical properties and low cost. Therefore, naturally available DE being inexpensive, their surface modified adsorbents could be one of the potential candidates for the wastewater treatment in the future. In this context, the current review has been summarized for the removal of both pollutants i.e., dyes and metal ions by surface-modified DE using the facile adsorption process. In addition, this review is prominently focused on the various modification process of DE, their cost-effectiveness; the physio-chemical characteristics and their maximum adsorption capacity. Further, real-time scenarios of reported adsorbents were tabulated based on the cost of the process along with the adsorption capacity of these adsorbents.

Ceria decorated porous diatom-xerogel as an effective adsorbent for the efficient removal of Eriochrome Black T.

Diatomaceous earth or diatom (DE) are naturally available and low cost micro particles with distinct porous structure were used as an adsorbent for the removal of a hazardous dye, Eriochrome Black T (EBT). The surface modification of these DE were performed by sol-gel and hydrothermal methods to obtain a series of adsorbents such as diatom-ceria (DC), diatom-silica xerogel (DX), and diatom-silica xerogel-ceria (DXC). A cauliflower like morphology structure of ceria was observed on DE and DX. The adsorption performance of EBT was conducted by varying various parameters such as pH, adsorbent dosage, initial concentration, contact time and ionic strength. The materials DE, DC, DX and DXC showed the EBT removal efficiencies of 52, 77, 20, and 93%, respectively. The maximum adsorption capacity (qm) of DE, DC, DX and DXC was found to be 13.83, 23.64, 0.2 and 47.02 mgg-1 for the adsorption of EBT, respectively. The selectivity of EBT towards DXC was evaluated by treating a mixture of anionic dyes. The dye removal experiments was performed in presence of inorganic salts, however the presence of these salts did not affect the removal efficiency of DXC. Furthermore, the reusability of DXC was studied by recycling it up to 5 times and even at 5th cycle a removal efficiency of ∼66.8% was found. Thus, these studies demonstrate that the DXC material could be a promising candidate for the removal of EBT via adsorption for real time application in water treatment.