Gold Nanorod-Loaded Nano-Contrast Agent with Composite Shell-Core Structure for Ultrasonic/Photothermal Imaging-Guided Therapy in Ischemic Muscle Disorders.

Purpose: This study aims to broaden the application of nano-contrast agents (NCAs) within the realm of the musculoskeletal system. It aims to introduce novel methods, strategies, and insights for the clinical management of ischemic muscle disorders, encompassing diagnosis, monitoring, evaluation, and therapeutic intervention. Methods: We developed a composite encapsulation technique employing O-carboxymethyl chitosan (OCMC) and liposome to encapsulate NCA-containing gold nanorods (GNRs) and perfluoropentane (PFP). This nanoscale contrast agent was thoroughly characterized for its basic physicochemical properties and performance. Its capabilities for in vivo and in vitro ultrasound imaging and photothermal imaging were authenticated, alongside a comprehensive biocompatibility assessment to ascertain its effects on microcirculatory perfusion in skeletal muscle using a murine model of hindlimb ischemia, and its potential to augment blood flow and facilitate recovery. Results: The engineered GNR@OCMC-liposome/PFP nanostructure exhibited an average size of 203.18±1.49 nm, characterized by size uniformity, regular morphology, and a good biocompatibility profile. In vitro assessments revealed NCA's potent photothermal response and its transformation into microbubbles (MBs) under near-infrared (NIR) irradiation, thereby enhancing ultrasonographic visibility. Animal studies demonstrated the nanostructure's efficacy in photothermal imaging at ischemic loci in mouse hindlimbs, where NIR irradiation induced rapid temperature increases and significantly increased blood circulation. Conclusion: The dual-modal ultrasound/photothermal NCA, encapsulating GNR and PFP within a composite shell-core architecture, was synthesized successfully. It demonstrated exceptional stability, biocompatibility, and phase transition efficiency. Importantly, it facilitates the encapsulation of PFP, enabling both enhanced ultrasound imaging and photothermal imaging following NIR light exposure. This advancement provides a critical step towards the integrated diagnosis and treatment of ischemic muscle diseases, signifying a pivotal development in nanomedicine for musculoskeletal therapeutics.

Adsorption of per- and poly-fluoroalkyl substances (PFAS) on Ni: A DFT investigation.

Electrocatalytic destruction of per- and polyfluoroalkyl substances (PFAS) is an emerging approach for treatment of PFAS-contaminated water. In this study, a systematic ab initio investigation of PFAS adsorption on Ni, a widely used electrocatalyst, was conducted by means of dispersion-corrected Density Functional Theory (DFT) calculations. The objective of this investigation was to elucidate the adsorption characteristics and charge transfer mechanisms of different PFAS molecules on Ni surfaces. PFAS adsorption on three of the most thermodynamically favorable Ni surface facets, namely (001), (110), and (111), was investigated. Additionally, the role of PFAS chain length and functional group was studied by comparing the adsorption characteristics of different PFAS compounds, namely perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorobutanesulfonic acid (PFBS), and perfluorobutanoic acid (PFBA). For each PFAS molecule-Ni surface facet pair, different adsorption configurations were considered. Further calculations were carried out to reveal the effect of solvation, pre-adsorbed atomic hydrogen (H), and surface defects on the adsorption energy. Overall, the results revealed that the adsorption of PFAS on Ni surfaces is energetically favorable, and that the adsorption is primarily driven by the functional groups. The presence of preadsorbed H and the inclusion of solvation produced less exothermic adsorption energies, while surface vacancy defects showed mixed effects on PFAS adsorption. Taken together, the results of this study suggest that Ni is a promising electrocatalyst for PFAS adsorption and destruction, and that proper control for the exposed facets and surface defects could enhance the adsorption stability.

Effect of ligand interactions within modified granular activated carbon (GAC) on mixed perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) adsorption.

A new adsorbent based on commercial granular activated carbon (GAC) and loaded with Cu(II) (GAC-Cu) was prepared to enhance the adsorption capacity of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). The surface area (SA) and pore volume of GAC-Cu decreased by ∼15% compared to those of pristine GAC. The scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) and leaching test results indicated that, compared with GAC, the Cu atomic ratio and Cu amount in GAC-Cu increased by 2.91 and 2.43 times, respectively. The point of zero charge (PZC) measured using a salt addition method obtained a pH of 6.0 (GAC) and 5.0 (GAC-Cu). According to the isotherm models obtaining highest coefficient of determination (R2), GAC-Cu exhibited a 20.4% and 35.2% increase for PFOA and PFOS in maximum uptake (qm), respectively, compared to those of GAC. In addition, the adsorption affinity (b) for GAC-Cu increased by 1045% and 175% for PFOA and PFOS, respectively. The pH effect on the adsorption capacity of GAC-Cu was investigated. The uptake of PFOA and PFOS decreased with an increase in pH for both GAC and GAC-Cu. GAC-Cu exhibited higher uptake than GAC at pH 6 and 7, but no enhanced uptake was observed at pH 4.0, 5.0, and 8.5. Therefore, ligand interaction was effective at weak acid or neutral pH.

Tumor-Targeted Perfluorinated Micelles as Efficient Theranostic Agents Combining Positron Emission Tomography and Radiosensitization.

We report the synthesis of biocompatible perfluorinated micelles designed to improve radiotherapeutic efficacy in a radioresistant tumor environment. In vitro and in vivo behaviors of perfluorinated micelles were assessed at both cellular and tissular levels. The micellar platform offers key advantages as theranostic tool: (i) small size, allowing deep tissue penetration; (ii) oxygen transport to hypoxic tissues; (iii) negligible toxicity in the absence of ionizing radiation; (iv) internalization into cancer cells; (v) potent radiosensitizing effect; and (vi) excellent tumor-targeting properties, as monitored by positron emission tomography. We have demonstrated strong in vitro radiosensitizing effects of the micelle and in vivo tumor targeting, making this nanometric carrier a promising tool for the potentiation of focused radiotherapy.

Kinetics and mechanism analysis of advanced oxidation degradation of PFOA/PFOS by UV/Fe3+ and persulfate: A DFT study.

UV/Fe3+ and persulfate are two promising advanced oxidative degradation systems for in situ remediation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), yet a lack of comprehensive understanding of the degradation mechanisms. For the first time, we used density functional theory (DFT) to calculate the entire reaction pathways of the degradation of PFOA/PFOS in water by UV/Fe3+ and persulfate. In addition, we have deeply explored the different attack pathways driven by •OH and SO4-•, and found that SO4-• determines PFOA/PFOS to obtain PFOA/PFOS free radicals through single electron transfer to initiate the degradation reaction, while •OH determines the speed of PFOA/PFOS degradation reaction. Both degradation reactions were thermodynamically advantageous and kinetically feasible under calculated conditions. Based on the thermodynamic data, persulfate was found to be more favorable for the advanced oxidative degradation of Perfluorinated compounds (PFCs). Moreover, for SO4-• and •OH co-existing in the persulfate system, pH will affect the presence and concentration of these two types of free radicals, and low pH is not necessary for the degradation of PFOA/PFOS in the persulfate system. These results can considerably advance our understanding of the PFOA/PFOS degradation process in advanced oxidation processes (AOPs), which is driven by •OH and SO4-•. This study provides a DFT calculation process for the mechanism calculation of advanced oxidation degradation of other types of PFCs pollutants, hoping to elucidate the future development of PFCs removal. Further research should focus on determining the advanced oxidation degradation pathways of other types of PFCs, to support the development of computational studies on the advanced oxidation degradation of PFCs.

Double-layer hollow mesoporous silica nanoparticles for ultrasound-guided photodynamic treatment.

Cervical carcinoma persists as a major global public health burden. While conventional therapeutic modalities inevitably cause ablation of adjacent non-tumorous tissues, photodynamic therapy (PDT) offers a targeted cytotoxic strategy through a photosensitizing agent (PS). However, the hydrophobicity and lack of selective accumulation of promising PS compounds such as zinc(II) phthalocyanine (ZnPc) impedes their clinical translation as standalone agents. The present study sought to incorporate ZnPc within double-layer hollow mesoporous silica nanoparticles (DHMSN) as nanocarriers to enhance aqueous dispersibility and tumor specificity. Owing to their compartmentalized design, the hollow mesoporous silica nanoparticles (HMSN) demonstrated enhanced ultrasonic imaging contrast. Combined with the vaporization of the perfluorocarbon perfluoropentane (PFP), the HMSN-encapsulated ZnPc enabled real-time ultrasound monitoring of PDT treatment.In vivo, the innate thermal energy induced vaporization of the DHMSN-carried PFP to significantly amplify ultrasound signals from the tumor site. Results demonstrated biocompatibility, efficient PFP microbubble generation, and robust photocatalytic activity. Collectively, this investigation establishes ultrasound-guided PDT utilizing multi-layer HMSN as a targeted therapeutic strategy for cervical malignancies with mitigated toxicity.

Fluorine-functionalized magnetic amino microporous organic network for enrichment of perfluoroalkyl substances.

Perfluoroalkyl substances (PFAS) are persistent organic pollutants that pose significant risks to human health and the environment. Efficient and selective enrichment of these compounds was crucial for their accurate detection and quantification in complex matrices. Herein, we report a novel magnetic solid-phase extraction (MSPE) method using fluorine-functionalized magnetic amino-microporous organic network (Fe3O4@MONNH2@F7) adsorbent for the efficient enrichment of PFAS from aqueous samples. The core-shell Fe3O4@MONNH2@F7 nanosphere was synthesized, featuring magnetic Fe3O4 nanoparticles as the core and a porous amino-functionalized MONs coating as the shell, which was further modified by fluorination. The synthesized adsorbent material exhibited high specific surface area, hydrophobicity, and abundant fluorine groups, facilitating efficient and selective adsorption of PFAS via electrostatic attraction, hydrophobic-hydrophobic interactions, fluorine-fluorine interactions, π-CF interactions and hydrogen bonding. Furthermore, the MSPE method coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) allowed for the rapid, sensitive, and accurate determination of ultra-trace PFAS in real water samples, human serum, and human follicular fluid. Under optimal conditions, the established MSPE method demonstrated a linear range (2 to 2000 ng L-1), with a correlation coefficient exceeding 0.9977, low limits of detection ranging from 0.54 to 1.47 ng L-1, with a relative standard deviation (RSD) < 9.1%. Additionally, the method showed excellent performance in complex real samples (recovery ratio of 81.7 to 121.6 %). The adsorption mechanism was investigated through kinetic, isotherm, and molecular simulation studies, revealing that the introduction of fluorine groups enhanced the hydrophobic interaction and fluorine-fluorine attraction between the adsorbent and PFAS. This work provides a proof-of-concept strategy for designing adsorbent materials with high efficiency and selectivity by post-modification, which has great potential for the detection and analysis of PFAS in complex samples.

Carbon-chain length determines the binding affinity and inhibitory strength of per- and polyfluoroalkyl substances on human and rat steroid 5α-reductase 1 activity.

Per- and polyfluoroalkyl substances (PFAS) are widely used synthetic chemicals that persist in the environment and bioaccumulate in animals and humans. There is growing evidence that PFAS exposure adversely impacts neurodevelopment and neurological health. Steroid 5α-reductase 1 (SRD5A1) plays a key role in neurosteroidogenesis by catalyzing the conversion of testosterone or pregnenolone to neuroactive steroids, which influence neural development, cognition, mood, and behavior. This study investigated the inhibitory strength and binding interactions of 18 PFAS on human and rat SRD5A1 activity using enzyme assays, molecular docking, and structure-activity relationship analysis. Results revealed that C9-C14 PFAS carboxylic acid at 100 µM significantly inhibited human SRD5A1, with IC50 values ranged from 10.99 µM (C11) to 105.01 µM (C14), and only one PFAS sulfonic acid (C8S) significantly inhibited human SRD5A1 activity, with IC50 value of 8.15 µM. For rat SRD5A1, C9-C14 PFAS inhibited rat SRD5A1, showing the similar trend, depending on carbon number of the carbon chain. PFAS inhibit human and rat SRD5A1 in a carbon chain length-dependent manner, with optimal inhibition around C11. Kinetic studies indicated PFAS acted through mixed inhibition. Molecular docking revealed PFAS bind to the domain between NADPH and testosterone binding site of both SRD5A1 enzymes. Inhibitory potency correlated with physicochemical properties like carbon number of the carbon chain. These findings suggest PFAS may disrupt neurosteroid synthesis and provide insight into structure-based inhibition of SRD5A1.

Defluorination of PFAS by Acidimicrobium sp. strain A6 and potential applications for remediation.

Acidimicrobium sp. strain A6 is a recently discovered autotrophic bacterium that is capable of oxidizing ammonium while reducing ferric iron and is relatively common in acidic iron-rich soils. The genome of Acidimicrobium sp. strain A6 contains sequences for several reductive dehalogenases, including a gene for a previously unreported reductive dehalogenase, rdhA. Incubations of Acidimicrobium sp. strain A6 in the presence of perfluorinated substances, such as PFOA (perfluorooctanoic acid, C8HF15O2) or PFOS (perfluorooctane sulfonic acid, C8HF17O3S), have shown that fluoride, as well as shorter carbon chain PFAAs (perfluoroalkyl acids), are being produced, and the rdhA gene is expressed during these incubations. Results from initial gene knockout experiments indicate that the enzyme associated with the rdhA gene plays a key role in the PFAS defluorination by Acidimicrobium sp. strain A6. Experiments focusing on the defluorination kinetics by Acidimicrobium sp. strain A6 show that the defluorination kinetics are proportional to the amount of ammonium oxidized. To explore potential applications for PFAS bioremediation, PFAS-contaminated biosolids were augmented with Fe(III) and Acidimicrobium sp. strain A6, resulting in PFAS degradation. Since the high demand of Fe(III) makes growing Acidimicrobium sp. strain A6 in conventional rectors challenging, and since Acidimicrobium sp. strain A6 was shown to be electrogenic, it was grown in the absence of Fe(III) in microbial electrolysis cells, where it did oxidize ammonium and degraded PFAS.

Hydrophobic Sorption Properties of an Extended Series of Anionic Per- and Polyfluoroalkyl Substances Characterized by C18 Chromatographic Retention Measurement.

Partitioning from water to nonaqueous phases is an important process that controls the behavior of contaminants in the environment and biota. However, for ionic chemicals including many perfluoroalkyl and polyfluoroalkyl substances (PFAS), environmentally relevant partition coefficients cannot be predicted using the octanol/water partition coefficient, which is commonly used as a hydrophobicity indicator for neutral compounds. As an alternative, this study measured C18 liquid chromatography retention times of 39 anionic PFAS and 20 nonfluorinated surfactants using isocratic methanol/water eluent systems. By measuring a series of PFAS with different perfluoroalkyl chain lengths, retention factors at 100% water (k0) were successfully extrapolated even for long-chain PFAS. Molecular size was the most important factor determining the k0 of PFAS and non-PFAS, suggesting that the cavity formation process is the key driver for retention. Log k0 showed a high correlation with the log of partition coefficients from water to the phospholipid membrane, air/water interface, and soil organic carbon. The results indicate the potential of C18 retention factors as predictive descriptors for anionic PFAS partition coefficients and the possibility of developing a more comprehensive multiparameter model for the partitioning of anionic substances in general.

Free Radicals Generated in Perfluorocarbon-Water (Liquid-Liquid) Interfacial Contact Electrification and Their Application in Cancer Therapy.

Electron transfer during solid-liquid contact electrification has been demonstrated to produce reactive oxygen species (ROS) such as hydroxyl radicals (•OH) and superoxide anion radicals (•O2-). Here, we show that such a process also occurs in liquid-liquid contact electrification. By preparing perfluorocarbon nanoemulsions to construct a perfluorocarbon-water "liquid-liquid" interface, we confirmed that electrons were transferred from water to perfluorocarbon in ultrasonication-induced high-frequency liquid-liquid contact to produce •OH and •O2-. The produced ROS could be applied to ablate tumors by triggering large-scale immunogenic cell death in tumor cells, promoting dendritic cell maturation and macrophage polarization, ultimately activating T cell-mediated antitumor immune response. Importantly, the raw material for producing •OH is water, so the tumor therapy is not limited by the endogenous substances (O2, H2O2, etc.) in the tumor microenvironment. This work provides new perspectives for elucidating the mechanism of generation of free radicals in liquid-liquid contact and provides an excellent tumor therapeutic modality.

Per- and poly-fluoroalkyl substances in agricultural contexts and mitigation of their impacts using biochar: A review.

Growing concern over the presence of per- and polyfluoroalkyl substances (PFAS) in agricultural compartments (e.g., soil, water, plants, soil fauna) has led to an increased interest in scalable and economically feasible remediation technologies. Biochar is the product of pyrolyzing organic materials (crop waste, wood waste, manures, grasses) and has been used as a low-cost adsorbent to remove contaminants including PFAS. This review frames biochar as a strategy for mitigating the detrimental impacts of PFAS in agricultural systems and discusses the benefits of this strategy within the framework of the needs and challenges of contaminant remediation in agriculture. To gauge the optimal physicochemical characteristics of biochar in terms of PFAS adsorption, principal component analysis using >100 data points from the available literature was performed. The main biochar-based PFAS treatment strategies (water filtration, soil application, mixing with biosolids) were also reviewed to highlight the benefits and complications of each. Life cycle analyses on the use of biochar for contaminant removal were summarized, and data from selected studies were used to calculate (for the first time) the global warming potential and net energy demand of various agriculturally important biochar classes (crop wastes, wood wastes, manures) in relation to their PFAS adsorption performance. This review serves to identify key gaps in our knowledge of (i) PFAS adsorption by biochars in agricultural remediation applications and (ii) environmental costs/benefits of biochars in relation to their adsorptive properties toward PFAS. The concepts introduced in this review may assist in developing large-scale biochar-based PFAS remediation strategies to help protect the agricultural food production environment.

Chloroperfluoropolyether carboxylate compounds: A review.

Several new per- and polyfluoroalkyl substances (PFASs) have been synthesized to replace traditional (legacy) PFASs frequently without clear information on their structure, use and potential toxicity. Among them, chloroperfluoropolyether carboxylates (ClPFPECAs) are an emerging group used as processing aids in the production of fluoropolymers to replace the ammonium salt of perfluorononanoic acid (PFNA). The Solvay Company has produced ClPFPECAs as a mixture of six congeners (oligomers) since the mid-1990s, but other possible manufacturers and annual quantities synthesized and used worldwide are unknown. Initial studies to monitor their presence were conducted because of public authority concerns about suspect environmental contamination near fluoropolymer plants. As of 2015, these chemicals have been found in soil, water, vegetative tissues and wildlife, as well as in biological fluids of exposed workers and people, in research carried out mainly in the United States (New Jersey) and Italy. Analysis of wildlife collected even in non-industrialized areas demonstrated widespread occurrence of ClPFPECAs. From the analytical point of view, the (presumptive) evidence of their presence was obtained through the application of non-targeted approaches performed by liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS). Available toxicological data show that ClPFPECAs have similar adverse effects than the compounds which they have replaced, whereas their carcinogenic potential and reproductive damage are currently unknown. All these observations once again cast doubt on whether many alternatives to traditional PFAS are actually safer for the environment and health.

Treatment of aqueous per- and poly-fluoroalkyl substances: A review of biochar adsorbent preparation methods.

Per- and poly-fluoroalkyl substances (PFAS) are synthetic chemicals widely used in everyday products, causing elevated concentrations in drinking water and posing a global challenge. While adsorption methods are commonly employed for PFAS removal, the substantial cost and environmental footprint of commercial adsorbents highlight the need for more cost-effective alternatives. Additionally, existing adsorbents exhibit limited effectiveness, particularly against diverse PFAS types, such as short-chain PFAS, necessitating modifications to enhance adsorption capacity. Biochar can be considered a cost-effective and eco-friendly alternative to conventional adsorbents. With abundant feedstocks and favorable physicochemical properties, biochar shows significant potential to be applied as an adsorbent for removing contaminants from water. Despite its effectiveness in adsorbing different inorganic and organic contaminants from water environments, some factors restrict its effective application for PFAS adsorption. These factors are related to the biochar properties, and characteristics of PFAS, as well as water chemistry. Therefore, some modifications have been introduced to overcome these limitations and improve biochar's adsorption capacity. This review explores the preparation conditions, including the pyrolysis process, activation, and modification techniques applied to biochar to enhance its adsorption capacity for different types of PFAS. It addresses critical questions about the adsorption performance of biochar and its composites, mechanisms governing PFAS adsorption, challenges, and future perspectives in this field. The surge in research on biochar for PFAS adsorption indicates a growing interest, making this timely review a valuable resource for future research and an in-depth exploration of biochar's potential in PFAS remediation.

Lanthanide metal-organic framework-based surface molecularly imprinted polymers ratiometric fluorescence probe for visual detection of perfluorooctanoic acid with a smartphone-assisted portable device.

Perfluorooctanoic acid (PFOA) poses a threat to the environment and human health due to its persistence, bioaccumulation, and reproductive toxicity. Herein, a lanthanide metal-organic framework (Ln-MOF)-based surface molecularly imprinted polymers (SMIPs) ratiometric fluorescence probe (Eu/Tb-MOF@MIPs) and a smartphone-assisted portable device were developed for the detection of PFOA with high selectivity in real water samples. The integration of Eu/Tb MOFs as carriers not only had highly stable multiple emission signals but also prevented deformation of the imprinting cavity of MIPs. Meanwhile, the MIPs layer preserved the fluorescence of Ln-MOF and provided selective cavities for improved specificity. Molecular dynamics (MD) was employed to simulate the polymerization process of MIPs, revealing that the formation of multiple recognition sites was attributed to the establishment of hydrogen bonds between functional monomers and templates. The probe showed a good linear relationship with PFOA concentration in the range of 0.02-2.8 µM, by giving the limit of detection (LOD) of 0.98 nM. Additionally, The red-green-blue (RGB) values analysis based on the smartphone-assisted portable device demonstrated a linear relationship of 0.1-2.8 µM PFOA with the LOD of 3.26 nM. The developed probe and portable device sensing platform exhibit substantial potential for on-site detecting PFOA in practical applications and provide a reliable strategy for the intelligent identification of important targets in water environmental samples.

An Atomic and Molecular Insight into How PFOA Reduces α-Helicity, Compromises Substrate Binding, and Creates Binding Pockets in a Model Globular Protein.

Per- and polyfluoroalkyl substances (PFAS) pose significant health risks due to their widespread presence in various environmental and biological matrices. However, the molecular-level mechanisms underlying the interactions between PFAS and biological constituents, including proteins, carbohydrates, lipids, and DNA, remain poorly understood. Here, we investigate the interactions between a legacy PFAS, viz. perfluorooctanoic acid (PFOA), and the milk protein ß-lactoglobulin (BLG) obtained using a combination of experimental and computational techniques. Circular dichroism studies reveal that PFOA perturbs the secondary structure of BLG, by driving a dose-dependent loss of α-helicity and alterations in its ß-sheet content. Furthermore, exposure of the protein to PFOA attenuates the on-rate constant for the binding of the hydrophobic probe 8-anilino-1-naphthalene sulfonic acid (ANS), suggesting potential functional impairment of BLG by PFOA. Steered molecular dynamics and umbrella sampling calculations reveal that PFOA binding leads to the formation of an energetically favorable novel binding pocket within the protein, when residues 129-142 are steered to unfold from their initial α-helical structure, wherein a host of intermolecular interactions between PFOA and BLG's residues serve to insert the PFOA into the region between the unfolded helix and beta-sheets. Together, the data provide a novel understanding of the atomic and molecular mechanism(s) by which PFAS modulates structure and function in a globular protein, leading to a beginning of our understanding of altered biological outcomes.

Adsorption and leaching of fluorotelomer compounds and perfluoroalkyl acids in aqueous media by activated carbon prepared from municipal biosolids.

Perfluoroalkyl acids (PFAAs) are ubiquitous in nature and pose serious health risks to humans and animals. Limiting PFAA exposure requires novel technology for their effective removal from water. We investigated the efficacy of biosolid-based activated carbon (Bio-SBAC) in removing frequently detected PFAAs and their precursor fluorotelomer compounds at environmentally relevant concentrations (∼50 µg/L). Batch experiments were performed to investigate adsorption kinetics, isotherms, and leachability. Bio-SBAC achieved >95% removal of fluorotelomeric compounds, indicating that the need for PFAA removal from the environment could be minimised if the precursors were targeted. Kinetic data modelling suggested that chemisorption is the dominant PFAA adsorption mechanism. As evidenced by the isotherm modelling results, Freundlich adsorption intensity, n-1, values of <1 (0.707-0.938) indicate chemisorption. Bio-SBAC showed maximum capacities for the adsorption of perfluorooctanoic acid (1429 µg/g) and perfluorononanoic acid (1111 µg/g). Batch desorption tests with 100 mg/L humic acid and 10 g/L NaCl showed that Bio-SBAC effectively retained the adsorbed PFAA with little or no leaching, except perfluorobutanoic acid. Overall, this study revealed that Bio-SBAC is a value-added material with promising characteristics for PFAA adsorption and no leachability. Additionally, it can be incorporated into biofilters to remove PFAAs from stormwater, presenting a sustainable approach to minimise biosolid disposal and improve the quality of wastewater before discharge into receiving waters.

Prediction of critical micelle concentration for per- and polyfluoroalkyl substances.

In this study, we focus on the development of Quantitative Structure-Property Relationship (QSPR) models to predict the critical micelle concentration (CMC) for per- and polyfluoroalkyl substances (PFASs). Experimental CMC values for both fluorinated and non-fluorinated compounds were meticulously compiled from existing literature sources. Our approach involved constructing two distinct types of models based on Support Vector Machine (SVM) algorithms applied to the dataset. Type (I) models were trained exclusively on CMC values for fluorinated compounds, while Type (II) models were developed utilizing the entire dataset, incorporating both fluorinated and non-fluorinated compounds. Comparative analyses were conducted against reference data, as well as between the two model types. Encouragingly, both types of models exhibited robust predictive capabilities and demonstrated high reliability. Subsequently, the model having the broadest applicability domain was selected to complement the existing experimental data, thereby enhancing our understanding of PFAS behaviour.

Hemostatic and Ultrasound-Controlled Bactericidal Silk Fibroin Hydrogel via Integrating a Perfluorocarbon Nanoemulsion.

Excessive blood loss and infections are the prominent risks accounting for mortality and disability associated with acute wounds. Consequently, wound dressings should encompass adequate adhesive, hemostatic, and bactericidal attributes, yet their development remains challenging. This investigation presented the benefits of incorporating a perfluorocarbon nanoemulsion (PPP NE) into a silk-fibroin (SF)-based hydrogel. By stimulating the ß-sheet conformation of the SF chains, PPP NEs drastically shortened the gelation time while augmenting the elasticity, mechanical stability, and viscosity of the hydrogel. Furthermore, the integration of PPP NEs improved hemostatic competence by boosting the affinity between cells and biomacromolecules. It also endowed the hydrogel with ultrasound-controlled bactericidal ability through the inducement of inner cavitation by perfluorocarbon and reactive oxygen species (ROS) generated by the sonosensitizer protoporphyrin. Ultimately, we employed a laparotomy bleeding model and a Staphylococcus aureus-infected trauma wound to demonstrate the first-aid efficacy. Thus, our research suggested an emulsion-incorporating strategy for managing emergency wounds.

Efficient removal of per/polyfluoroalkyl substances from water using recyclable chitosan-coated covalent organic frameworks: Experimental and theoretical methods.

Covalent organic frameworks (COFs) demonstrate remarkable potential for adsorbing per/polyfluoroalkyl substances (PFAS). Nevertheless, the challenge of recycling powdered COFs hampers their practical application in water treatment. In this research, a quaternary amine COF with inherent positive surface charge was synthesised to adsorb perfluorooctanoic acid (PFOA) via electrostatic interactions. The COF was then combined with chitosan (CS) through a simple dissolution-evaporation process, resulting in a composite gel material termed COF@CS. The findings indicated that the adsorption capacity of COF@CS significantly surpassed that of the original COF and CS. According to the Langmuir model, COF@CS achieved a maximum PFOA capacity of 2.8 mmol g-1 at pH 5. Furthermore, the adsorption rate increased significantly to 6.2 mmol g-1 h-1, compared to 5.9 mmol g-1 h-1 for COF and 3.4 mmol g-1 h-1 for CS. Notably, COF@CS exhibited excellent removal efficacy for ten other types of PFAS. Moreover, COF@CS could be successfully regenerated using a mixture of 70% ethanol and 1 wt% NaCl, and it exhibited stable reusability for up to five cycles. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) characterisation, and theoretical calculations revealed that the quaternary amine functional group in COF served as the primary adsorption site in the composite gel material, while the protonated amino group on CS enhanced PFOA adsorption through electrostatic interaction. This study highlights the significant practical potential of COF@CS in the removal of PFAS from aqueous solution and environmental remediation.