Fluoride Research Articles

Influence of Qingzhuan Tea Polysaccharides on F- Adsorption: Molecular Structure, Binding Behavior, and In Vitro and In Vivo Digestion and Metabolism.

The high level of fluoride in Qingzhuan tea (QZT) poses a potential health risk to consumers. This study aims to explore the binding behavior of purified Qingzhuan tea polysaccharides (pTPS) and fluoride ions (F-), as well as their regulatory role in the digestion and metabolism of fluoride. The sugar content of pTPS was 94.64 ± 3.01%, with a molecular weight of 7.373 × 104 Da and high homogeneity. The effects of different proportions and environmental conditions on the adsorption of F- by pTPS were investigated. The influence of the complexation of pTPS and F- on the digestion and metabolism of fluoride was explored using an in vitro gastrointestinal digestion model and C57BL/6 mice. The structural alterations of pTPS were observed during simulated gastrointestinal digestion. Furthermore, pTPS were found to reduce serum fluoride levels and inhibit accumulation in major organs and tissues, especially the heart, liver, kidneys, muscles, and femur. This study investigated the binding pattern between fluorine and pTPS and its influence on the digestion and absorption of fluorine, providing a promising potential for pTPS as a bioadsorbent of fluorine to alleviate the toxicity of fluorine in QZT, which laid a theoretical foundation for the safety of consumption of QZT.

Comparative assessment of enamel surface remineralisation with three different dentifrices: An energy dispersion x-ray spectroscopy analysis

Comparative assessment of remineralisation of enamel surface when treated with three different dentifrices. Sixty-six extracted upper right first premolars were demineralized to form artificial white spot lesions. The samples were divided into 3 groups: Group 1-Biomin F, Group 2- Clinpro ToothCreme, Group 3- Amflor. They were treated with three different dentifrices (22/ group) for 14 days in simulated oral conditions. Energy dispersion X-Ray Spectroscopy was done pre and post remineralistaion. The primary evaluation parameter for this study was the Ca/P ratio. As per the results, the maximum increase in Ca/P ratio was seen in Group1, followed by Group 3 and 2 respectively. The results were found to be statistically significant. (p=0.045 i.e. p<0.05) The secondary evaluation parameter for this study was the change in Fluoride content. As per the results, the maximum increase in Fluoride content was seen in Group 2 which was followed by Group 3 which is equivalent to Group 1. However, the results were found to be statistically non-significant. (p=0.219 i.e. p>0.05) Biomin F has the highest remineralisation efficiency when compared to the other 2 dentifrices. Biomin F contains an optimum combination of fluoride (600 ppm), phosphate and calcium ions, incorporated within the structure of the glass itself. The glass gradually dissolves over up to 12 hours neutralizing acids in the mouth and deposit fluorapatite. Thus, it can be used in patients undergoing orthodontic treatment to prevent or reduce the formation of white spot lesions.

Pyrene Based Schiff Base for Cascade Fluorescent "On-Off" Detection of Aluminium(III) and Fluoride Ions and its Applications in Live Cells Imaging.

An easy-to-prepare pyrene-based Schiff base PNZ was synthesized by condensing equimolar amount of 1-pyrenebutyric hydrazide with 2-hydroxy-naphthaldehyde, and employed as a fluorescent chemosensor for in-situ cascade detection of aluminium (Al3+) and fluoride (F-) ions. In DMSO:H2O (1 : 1, v/v), the weakly emissive PNZ showed a significant fluorescence enhancement at 455 nm selectively upon the addition of Al3+ due to the complexation-induced formation of a pyrene excimer. Schiff base PNZ and Al3+ formed a complex in 2 : 1 binding ratio with the estimated binding constants of K1:1=9826.01 M-1 and K2:1=3188.49 M-1. The sensing mechanism was explored by performing quantum mechanical calculations and 1H-NMR titration of PNZ with Al3+. The in-situ formed PNZ-Al3+ complex species enabled the fluorescent turn-off detection of F-. Using PNZ and PNZ-Al3+, the concentrations of Al3+ and F- ions can be detected down to 2.89×10-7 M and 1.88×10-7 M, respectively. The cytotoxicity of the PNZ and its ability to bioimage Al3+ and F- ions was examined in the human cervical cancer cell line. Finally, the receptor PNZ was applied for the quantification of Al3+ and F- ions in various real samples, such as tap water, river water, rainwater, mouthwash, and toothpaste.

Iron-Based Layered Perovskite Oxyfluoride Electrocatalyst for Oxygen Evolution: Insights from Crystal Facets with Heteroanionic Coordination.

Mixed-anion compounds have recently attracted attention as solid-state materials that exhibit properties unattainable with those of their single-anion counterparts. However, the use of mixed-anion compounds to control the morphology and engineer the crystal facets of electrocatalysts has been limited because their synthesis method is still immature. This study explored the electrocatalytic properties of a Pb-Fe oxyfluoride, Pb3Fe2O5F2, with a layered perovskite structure for oxygen evolution reaction (OER) and compared its properties in detail with those of a bulk-type cubic three-dimensional (3D) perovskite, PbFeO2F. A Pb3Fe2O5F2 electrode prepared with carbon nanotubes and a graphite sheet as a conductive support and a substrate, respectively, demonstrated better OER performance than a PbFeO2F electrode. The role of specific crystal facets of Pb3Fe2O5F2 in enhancing the OER activity was elucidated through electrochemical analysis. Density functional theory calculations indicated that the Pb3Fe2O5F2 (060) facet with Fe sites exhibited a lower theoretical overpotential for the OER, which was attributed to a moderately strong interaction between the active sites and the reaction intermediates; this interaction was reinforced by the strong electron-withdrawing behavior of fluoride ions. This finding offers new insights for developing efficient electrocatalysts based on oxyfluorides, leveraging the high electronegativity of fluorine to optimize the electronic states at active sites for the OER, without relying on precious metals.

Recent Advances in Adsorption Techniques for the Removal of Fluoride Ions from Wastewater: A Review

Recent Advances in Adsorption Techniques for the Removal of Fluoride Ions from Wastewater: A Review

Aryl‐Fluorocyclopropane β‐Lactams with Activity Against Mycobacteroides abscessus and Mycobacterium bovis BCG

AbstractA novel series of aryl‐α‐fluorocyclopropyl 1 and α,β,β‐trifluorocyclopropyl 2 β‐lactams have been prepared and their activity explored across various Mycobacteria and also the ESKAPE panel of pathogens. The most active of these compounds 1 a displayed good activity against clinically challenging Mycobacteria such as M. bovis BCG (MIC 0.39 mg/mL)) and did not show any significant activity against the ESKAPE pathogens indicating selectivity for this otherwise challenging class of pathogen. Compound 1 a was however rapidly metabolised and toxic to a human model cell line (HepG2) limiting its clinical development at this stage. The compounds were designed to exploit a fluoride ion elimination mechanism concomitant with β‐lactam ring opening, as the basis of a mechanism induced trigger to generate a reactive intermediate (suicide inhibition). In model alkoxide reactions a representative from both classes 1 and 2 resulted in β‐lactam ring opening but only the more active mono‐fluoro cyclopropane series 1 triggered fluoride ion elimination after ring opening and this may form the basis of its activity.

Organic–inorganic covalent–ionic network enabled all–in–one multifunctional coating for flexible displays

Touch displays are ubiquitous in modern technologies. However, current protective methods for emerging flexible displays against static, scratches, bending, and smudge rely on multilayer materials that impede progress towards flexible, lightweight, and multifunctional designs. Developing a single coating layer integrating all these functions remains challenging yet highly anticipated. Herein, we introduce an organic–inorganic covalent–ionic hybrid network that leverages the reorganizing interaction between siloxanes (i.e., trifluoropropyl–funtionalized polyhedral oligomeric silsesquioxane and cyclotrisiloxane) and fluoride ions. This nanoscale organic–inorganic covalent–ionic hybridized crosslinked network, combined with a low surface energy trifluoropropyl group, offers a monolithic layer coating with excellent optical, antistatic, anti–smudge properties, flexibility, scratch resistance, and recyclability. Compared with existing protective materials, this all–in–one coating demonstrates comprehensive multifunctionality and closed–loop recyclability, making it ideal for future flexible displays and contributing to ecological sustainability in consumer electronics.

Cr6+ Loaded Lewis Acidic Sn‐Beta Zeolites as Reusable Catalysts for Selective Production of Light Olefins via Polyolefin Cracking

AbstractCatalysts for the selective recovery of light olefins from polyolefins should be developed to save limited fossil resources. It is previously revealed that Brønsted acid‐free Sn‐Beta zeolites selectively produced light olefins from polyolefin cracking. Brønsted acid sites ionize olefins by protonation and the generated carbenium ions are converted into other hydrocarbons via various reactions, thereby the elimination of their effects led to the improvement of light olefin production ability. However, the deactivation of zeolites by coke deposition is a critical problem for industrialization. Inhibition of coking deactivation is previously achieved by doping Cr6+ species connected to silanol groups in zeolites. This work aimed to inhibit coke deposition and realize selective and continuous production of light olefins through repetitive polyolefin catalytic cracking. Sn‐Beta zeolites are prepared with various crystallinity by changing the feed fluoride ions content in their synthesis and found that their activity on low‐density polyethylene (LDPE) cracking strongly depended on the feed F/Si ratios, implying the active sites for polyolefin cracking are Lewis acidic open‐Sn sites. Moreover, Cr6+‐doped Sn‐Beta zeolites showed over 45% light olefin yields even in the third LDPE cracking test, although excess Cr adding led to reduce the catalytic activity of Sn‐Beta zeolites.

Defluoridation of Groundwater Using Low-cost Adsorbents

Excessive fluoride in groundwater poses significant health risks to millions of people worldwide, necessitating effective and accessible defluoridation methods. This study investigates the use of column filtration for removing fluoride from groundwater. The study employs a systematic approach to evaluate the performance of different adsorbent materials in a fixed-bed column setup. Various materials were tested as adsorbents in column, including Brick powder, Neem leaf powder, Lime, Sawdust, and Vetiver. The research examines the effects of key operational parameters such as bed depth, flow rate, and initial fluoride concentration on the overall removal efficiency. Experiments were conducted using groundwater to assess the method's effectiveness. Results indicated that column filtration can effectively reduce fluoride concentrations to below the World Health Organization's recommended limit of 1.5 mg/L. This report contributes to the development of efficient, cost-effective, and sustainable solutions for groundwater defluoridation. All adsorbents used were inexpensive materials, available easily in nature and locally at village or rural level. Some of the adsorbents were very effective in removal of fluoride ion and can be used as defluoridating agents but they impart color and turbidity to the groundwater. Among all the adsorbents used, Vetiver demonstrated higher removal efficiency of 78% followed up by limestone 77% removal but hindered by its precipitation. Sawdust and brick powder were also efficient up to a certain extent of 72% and 69% respectively in adsorbing fluoride ions. Neem leaves powder was found to be least effective in adsorbing showing about 50% removal efficiency.

Study on dissociation mechanism and process of regenerated cryolite

Solid waste produced in the process of aluminum electrolysis is a substantial secondary source of fluorine, the fluoride electrolyte in aluminum electrolysis carbon slag accounts for about 75%. Regenerative cryolite, extracted from anode carbon residue through flotation or calcination, possesses a significant potential for fluorine recovery. The fluoride in regenerated cryolite is mainly insoluble, making its efficient dissociation crucial for utilizing the solid waste from aluminum electrolysis. This study uses regenerative cryolite and sodium carbonate to examine how roasting temperature, time, and the reagent-to-cryolite ratio (R/C) affect cryolite dissociation. Dissociation efficiency is measured using indices like baking loss, leaching loss, fluoride ion concentration in the leachate, and fluoride ion conversion rate. Optimal dissociation is achieved at 780-820°, 2.0-2.5 hours roasting time, and an R/C ratio of 1.0-1.2. Orthogonal experimental results highlight the predominant influence of R/C, with roasting temperature being the secondary factor and roasting time having the least impact. Notably, at 780°, 2.0 hours, and an R/C ratio of 1.2:1, the fluoride ion conversion rate reaches a peak of 94.23%. This allows for recycling and production of high-value fluoride products, benefiting both the environment and the economy.

Polymer Electrolyte Based All‐Solid‐State Rechargeable Fluoride Ion Batteries

Polymer Electrolyte Based All‐Solid‐State Rechargeable Fluoride Ion Batteries

Enhanced removal of fluoride ions using lanthanum-doped coconut shell biochar in PVDF ultrafiltration membranes

Fluoride contamination in surface and ground water poses significant health risks, necessitating a low-energy, cost-effective removal method. Herein, an ultrafiltration (UF) adsorptive membrane doped with lanthanum (La)-based coconut shell biochar was synthesized to effectively remove fluoride ions. Based on the results of adsorption and membrane separation performance, it was found that La-based biochar showed a significantly higher adsorption capacity (126.7 mg F/g) compared to bare biochar (27.41 mg F/g), due to the oxygen-containing functional groups from La2O2CO3 that enhance binding sites and electrostatic attraction for fluoride ions. Furthermore, the addition of La-modified adsorbent to the polyvinylidene fluoride (PVDF) UF membrane markedly altered its structure and surface properties, changing the pore structure to porous, narrowing pore size, increasing active adsorption sites, and improving hydrophilicity. These changes boosted fluoride ion rejection from 9.53 % to 62.07 % with tiny effect on membrane permeability. More important, this UF adsorptive membrane exhibited excellent antifouling ability with the lowest flux decline (J/J0 =0.450) compared to pristine PVDF membrane (J/J0 =0.142), which was owing to the better improved surface properties. In all, this study provides a novel strategy for efficient, economic and selective separation of fluoride ions and further extends the application of UF to the field of ion removal.

Mentioned Magnesium Oxide Nanomaterials for Effective Adsorption of Congo Red Dye and Fluoride Ions From Aqueous Solutions

This study investigates the synthesis of nanostructured magnesium oxide (MgO) using the auto-combustion method with urea (MgO-U), glycine (MgO-G), and citric acid (MgO-C) as fuels, followed by subsequent calcination. The selection of fuel plays a crucial role in determining the morphology of the nanostructures.X-ray diffraction (XRD) analysis confirms that the samples exhibit a well-crystallized structure with the desired phase and are free of impurities. Field emission scanning electron microscopy (FESEM) shows that MgO-U nanoparticles have diameters ranging from 10 to 20nm, MgO-C nanoparticles from 60 to 80nm, and MgO-G nanoparticles from 80 to 100nm. These MgO nanomaterials are specifically engineered for adsorption applications, aimed at removing toxic organic dyes and fluoride ions from aqueous solutions. Results demonstrate that MgO-G nanoparticles exhibit superior adsorption activity compared to MgO-U and MgO-C nanoparticles, with maximum uptake capacities of 1429 and 14mg/g, respectively. The adsorption processes adhere to second-order kinetic model. These findings highlight the potential application of the synthesized MgO nanoparticles for mitigating water pollution by adsorbing pollutants from aqueous media.

From HgGa2(SeO3)4 to Hg2Ga(SeO3)2F: The first HgI-based selenite birefringent crystal triggered by linear groups and fluoride ions

From HgGa2(SeO3)4 to Hg2Ga(SeO3)2F: The first HgI-based selenite birefringent crystal triggered by linear groups and fluoride ions

Synthesis and enhanced adsorption for F− by three novel high entropy LDHs using TEA-assisted hydrothermal technology

Nowadays the design, preparation and application of high entropy LDHs (HE-LDHs) has already become research hotspots. In this paper, three types of high entropy ZnCoCrMgZr-LDHs (HE-LDHs-1, 2 and 3) were successfully prepared for the first time using TEA as alkali source by simple hydrothermal synthesis, and characterized by XRD, TG, SEM, X-ray photoelectron spectroscopy, BET and zeta potential. The effect of triethanolamine (TEA) on the formation of high entropy LDHs and their adsorption behaviour for F− were investigated. Research showed that high content of TEA can maintain and provide more hydroxyl groups required for the formation of LDHs, while the introduction of high valence Zr4+ breaks the regular arrangement of LDHs themselves. Three types of high entropy LDHs have excellent adsorption performance for F− with the maximum adsorption capacities of 113.78 mg/g, 142.12 mg/g and 128.24 mg/g, respectively. They also have strong resistance to anionic interference. The adsorption process is the transition from physical adsorption to chemical adsorption in the F− adsorption process from HE-LDHs-1 to 3. The adsorption isotherm models of LDHs-1 exhibit high R2 values which shown that their F− adsorption behaviour is the result of the combined effect of physical and chemical adsorption. The adsorption behaviour of LDHs-2 and 3 is more in line with the quasi second-order kinetic model and Langmuir model, indicating that the F− adsorption process is a single-layer adsorption based on chemical reaction-controlled kinetics. The lower temperatures are more conducive to the process for all three adsorbents adsorption process generates heat. FLDHs can still re-adsorb the dye CR after four cycles of adsorbing fluoride ions. HE-LDHs exhibit high adsorption, selectivity, and good reuse performance for fluoride ions, making them promising for wastewater treatment applications.

La1−xSrxF3−x: A Solid-State Electrolyte for Fluoride Ion Battery with High Ionic Conductivity and Wide Electrochemical Potential Window

Fluoride ion conductors are developed for use as solid-state electrolytes in fluoride ion batteries which are one of promising candidates for next-generation storage batteries. Ba-doped LaF3 (La0.9Ba0.1F2.9: LBF) is mainly used as a solid-state electrolyte in fluoride ion batteries. However, room temperature conductivity of LBF is considerably low, on the order of 10−6 S cm−1 and it is still unclear the optimal elements to be doped to LaF3. In this study, we have explored La0.9Sr x Ba0.1−x F2.9 system (x = 0, 0.01, 0.025, 0.05, 0.1), in which Ba in LBF is substituted for Sr and investigated the composition dependence of ionic conductivity. We elucidate that the higher concentration of Sr without Ba can significantly improve the ionic conductivity, and the maximum ionic conductivity of La0.9Sr0.1F2.9 is 1.5 × 10−5 S cm−1 at room temperature, which is one order of magnitude larger than that of LBF. The higher ionic conductivity of LSF is due to the larger grain size and higher sintering density of LSF compared to LBF, which results in lower grain boundary resistance. The LSF total ionic conductivity of 10−4 S cm−1 can be achieved at 350 K, which significantly lowers operating temperature of fluoride ion batteries down to 350 K.

Removal of antibiotics from aquaculture wastewater using a continuous flow/EC/PMS coupled system

The electricity activated peroxomonosulfate (ion) coupled system (EC/PMS) has important application value in water pollution treatment. However, the traditional batch system commonly used in this coupled system poses significant challenges in treating large volume and low concentration aquaculture wastewater, such as poor mass transfer, long treatment time, and increased risk of secondary pollution. Therefore, this study proposed to introduce the continuous flow operation mode into the EC/PMS system to form a continuous flow electrocatalytic peroxomonosulfate (ion) (CF/EC/PMS) coupling system, achieving 100 % removal of tetracycline (TC) with an initial concentration of 2 mg/L. Subsequently, through cathodic optimization, an 85 % removal efficiency was achieved for antibiotics with secondary pollution risks, such as norfloxacin and NOR. It is worth noting that the secondary pollutants (such as fluoride ions, F−) generated during the degradation process have also successfully achieved a removal efficiency of 70 %. In this system, singlet oxygen (1O2) was the main active species. This system has advantages such as a processing volume of at least 3L, a wide pH range (3–9), low oxidant dosage (PMS = 2 mM), and low energy consumption (EEO = 0.018 kWh/m3 log). The coupling system effectively removes the main pollutants, and the optimized cathode coupling system achieves safe removal of fluorinated drugs, reducing the risk of secondary pollution. In summary, this study has the characteristics of low cost and engineering applicability, providing a promising method for economically, efficiently, and environmentally friendly treatment of aquaculture wastewater.

Hydrochemical processes and fluoride enrichment patterns in high-fluoride geothermal water in the Weihe Basin, China.

The enrichment of fluoride in the deep geothermal water of the Lantian - Bahe Formation in parts of the Weihe Basin in China is a potential health hazard for the millions of inhabitants of this region. We conducted hydrochemical and hydrogeological analyses of water samples from 31 geothermal wells in the Weihe Basin, with the aims of determining the distribution characteristics, enrichment patterns, hydrochemical processes, and the factors influencing the geochemistry of deep geothermal fluids. We also evaluated the potential health hazards of fluoride ions in these fluids. Our results show that geothermal fluids with high fluoride content are widely distributed in the deep aquifers of the Weihe Basin. The principal hydrochemical types are: HCO3-Na and SO4⋅HCO3⋅Cl-Na. We used hydrodynamic simulation and regression analysis to show that the high proportion of HCO3- in the geothermal water facilitates the precipitation of Ca2+ and the dissolution of fluorine-bearing minerals. The high temperature, alkaline environment, cation exchange reactions, and dissolution and precipitation processes lead to Ca2+ depletion, which facilitates the release of fluoride ions from the surrounding rocks into the geothermal fluids. A human health risk assessment shows that the hazard quotient (HQ) values of geothermal water for adult males, adult females, children, and infants are: 3.96 - 14.41 (median 6.55), 3.32 - 12.08 (median 4.50), 4.63 - 16.84 (median 5.50), and 7.48 - 27.22 (median 9.00), respectively. Infants are the most susceptible to the effects of high fluoride in groundwater due to their physiological characteristics. while the potential health risks of F- for children and adult women/men are relatively low. Therefore, in the process of developing deep geothermal water, it is necessary to prevent it from mixing into shallow drinking water as much as possible. If the fluoride ion content in the shallow water exceeds the standard, it may have an impact on the local environment and residents' health. These findings provide a scientific foundation for the effective management of high fluoride groundwater in the Weihe Basin and analogous regions elsewhere.

Label-Free Electrochemical Sensor Sensitivity Enhancement Using Field Effect Transistors: Fluoride Ions for Fuel Cell Degradation Analysis

In the context of proton exchange membrane fuel cells, precise monitoring of fluoride ions in the effluent water is crucial. Associated with the fluoride ion accumulation, membrane degradation and reduction of fuel cell efficiency arise. This study focuses on developing extended gate field-effect transistors (EGFET) sensors for real-time monitoring of fluoride ion concentrations. High sensitivity and specificity in detecting the concentration of fluoride ions using both N-type (TN0702) and P-type (LP0701) metal-oxide-semiconductor field-effect transistors (MOSFET) were achieved. The transfer characteristics (Id vs Vgs) owere thoroughly examined across a range of fluoride concentrations from parts per million (ppm) to parts per billion (ppb). N-type MOSFET-based sensors showed a distinct decrease in drain current (Id) with increasing fluoride concentration. With fluoride concentrations changed, the P-type MOSFET exhibited a notable shift in the threshold voltage (Vgs). A robust linear relationship was observed on calibration curves with R2 values exceeding 0.90 between the natural logarithm of fluoride concentration (lnC) and gate-source voltage (Vgs). This work demonstrates that MOSFET can significantly enhance the sensitivity of electrochemical sensors without complex labeling processes. The improvement has a future in the miniaturization of cost-effective sensor systems for fuel cell applications, facilitating real-time performance and degradation monitoring.

Fluoride removal using membrane capacitive deionization: The role of pH-dependent dissolved inorganic carbon

Defluorination technology is crucial for ensuring safe and accessible water. The application of capacitive deionization (CDI) technology faces challenges due to competitive adsorption of fluoride ions within complex natural fluoride-rich brackish water matrices, which often contain high levels of dissolved inorganic carbon (DIC) species (mainly HCO3– and CO32–). These DIC species are pH-dependent, playing a significant role in the selective removal of fluoride by the CDI process. Thus, there is a knowledge gap in understanding the effects of membranes in membrane capacitive deionization (MCDI) on fluoride removal. In this study, we examined the key operating parameters in CDI and MCDI, including applied constant voltages and different types of anion-exchange membranes (AEMs), on the desalination performance in F- and dissolved inorganic carbon water matrices. The application of AEMs significantly improved the salt adsorption capacity (SAC) for both F- and DIC species, and reduced energy consumption. However, it simultaneously resulted in a notable decrease in F- selectivity as membranes control mass transfer. Higher applied voltages enhance the SAC performance for F- and DIC species, but also induce more severe Faradaic reactions, leading to increased energy consumption and lower energy efficiency. Additionally, ion species and pH changes during CDI and MCDI processes are interrelated, indicating that stability tests of CDI electrodes in batch mode are not reliable when using the same testing solution repeatedly. The diverse valence states of ions in the solution impact pH variations under different voltages in the CDI/MCDI process. These findings provide valuable insights into the development of water purification and desalination technology, particularly for the application and further advancement of selective fluoride removal by the CDI process.