Acid Dimer Research Articles

Synthesis of High-Value Bio-Based Polyamide 12,36 Microcellular Foams with Excellent Dimensional Stability and Shape Recovery Properties.

The search for alternatives to petroleum-based thermoplastic polyamide elastomers (TPAEs) has recently drawn great interest. In this study, a bio-massed TPAE, PA12,36, was synthesized using 1,12-dodecanediamine (DDA) and fatty dimer acid (FDA, PripolTM1009) precursors via catalyst and solvent-free melt polycondensation. The molecular structure and molecular weight of the PA12,36 were characterized by 1H NMR, FTIR, and GPC. PA12,36 displayed a low melting temperature of 85.8 °C, an initial degradation temperature of 425 °C, and a glass-transition temperature of 30.4 °C, whereas it sustained satisfactory tensile strength (10.0 MPa) and superior strain at break (1378%). Furthermore, PA12,36 was foamed by supercritical CO2, and the cell size, cell density, and porosity were determined. The entangled long-chained FDA component generated a physically crosslinked network, which promoted the melt viscosity of PA12,36 against elongations of foam cell growth and increased foamability significantly. As a result, uniform structured cellular foams with a cell diameter of 15-24 µm and high cell density (1011 cells/cm3-1012 cells/cm3) were successfully achieved. The foaming window was widened from 76 to 81 °C, and the expansion ratio was increased from 4.8 to 9.6. Additionally, PA12,36 foam with a physically crosslinked structure presented a better creep shape recovery percentage (92-97.9%) and sturdier dimensional stability. This bio-based PA12,36 foam is a promising candidate to replace petroleum-based thermoplastic elastomer foams for engineering applications, particularly shoe soles.

Structural dependence of PFAS oxidation in a boron doped diamond-electrochemical system

Driven by long-term persistence and adverse health impacts of legacy perfluorooctanoic acid (PFOA), production has shifted towards shorter chain analogs (C4, perfluorobutanoic acid (PFBA)) or fluorinated alternatives such as hexafluoropropylene oxide dimer acid (HFPO-DA, known as GenX) and 6:2 fluorotelomer carboxylic acid (6:2 FTCA). Yet, a thorough understanding of treatment processes for these alternatives is limited. Herein, we conducted a comprehensive study using an electrochemical approach with a boron doped diamond anode in Na2SO4 electrolyte for the remediation of PFOA common alternatives, i.e., PFBA, GenX, and 6:2 FTCA. The degradability, fluorine recovery, transformation pathway, and contributions from electro-synthesized radicals were investigated. The results indicated the significance of chain length and structure, with shorter chains being harder to break down (PFBA (65.6 ± 5.0%) < GenX (84.9 ± 3.3%) < PFOA (97.9 ± 0.1%) < 6:2 FTCA (99.4 ± 0.0%) within 120 min of electrolysis). The same by-products were observed during the oxidation of both low and high concentrations of parent PFAS (2 and 20 mg L−1), indicating that the fundamental mechanism of PFAS degradation remained consistent. Nevertheless, the ratio of these by-products to the parent PFAS concentration varied which primarily arises from the more rapid PFAS decomposition at lower dosages. For all experiments, the main mechanism of PFAS oxidation was initiated by direct electron transfer at the anode surface. Sulfate radical (SO4•−) also contributed to the oxidation of all PFAS, while hydroxyl radical (•OH) only played a role in the decomposition of 6:2 FTCA. Total fluorine recovery of PFBA, GenX, and 6:2 FTCA were 96.5%, 94.0%, and 76.4% within 240 min. The more complex transformation pathway of 6:2 FTCA could explain its lower fluorine recovery. Detailed decomposition pathways for each PFAS were also proposed through identifying the generated intermediates and fluorine recovery. The proposed pathways were also assessed using 19F Nuclear Magnetic Resonance (NMR) spectroscopy.

Transfer learning of hyperparameters for fast construction of anisotropic GPR models: design and application to the machine-learned force field FFLUX.

The polarisable machine-learned force field FFLUX requires pre-trained anisotropic Gaussian process regression (GPR) models of atomic energies and multipole moments to propagate unbiased molecular dynamics simulations. The outcome of FFLUX simulations is highly dependent on the predictive accuracy of the underlying models whose training entails determining the optimal set of model hyperparameters. Unfortunately, traditional direct learning (DL) procedures do not scale well on this task, especially when the hyperparameter search is initiated from a (set of) random guess solution(s). Additionally, the complexity of the hyperparameter space (HS) increases with the number of geometrical input features, at least for anisotropic kernels, making the optimization of hyperparameters even more challenging. In this study, we propose a transfer learning (TL) protocol that accelerates the training process of anisotropic GPR models by facilitating access to promising regions of the HS. The protocol is based on a seeding-relaxation mechanism in which an excellent guess solution is identified by rapidly building one or several small source models over a subset of the target training set before readjusting the previous guess over the entire set. We demonstrate the performance of this protocol by building and assessing the performance of DL and TL models of atomic energies and charges in various conformations of benzene, ethanol, formic acid dimer and the drug fomepizole. Our experiments suggest that TL models can be built one order of magnitude faster while preserving the quality of their DL analogs. Most importantly, when deployed in FFLUX simulations, TL models compete with or even outperform their DL analogs when it comes to performing FFLUX geometry optimization and computing harmonic vibrational modes.

Selective encapsulation of carboxylic acid dimers within a size-regulable resorcinarene-based hemicarcerand.

A cavity within a resorcinarene-based hemicarcerand was contracted and expanded through conformational changes induced by the complexation and decomplexation, allowing self-sorting of homo- and heterodimeric carboxylic acid pairs.

Porphyrin metabolism and carbon fixation response of Skeletonema costatum at different growth phases to mixed emerging PFASs at environmental concentrations.

Per- and polyfluoroalkyl substances (PFASs), especially as emerging compounds, have been widely detected in coastal seawater. However, the awareness of the interaction between PFASs at environmental concentrations and marine diatoms is still limited. In this study, Skeletonema costatum was exposed to three co-existing PFASs, namely hexafluoropropylene oxide dimer acid (HFPO-DA), 6 : 2 chlorinated polyfluorinated ether sulfonate (Cl-PFAES), and perfluoroethylcyclohexane sulfonate (PFECHS) (15-300 ng L-1 in total), for 14 days. In the 300 ng L-1 test group, the significant down-regulation of chlorophyllide a in porphyrin metabolism, light-harvesting capacity and carbon fixation were the main inhibitory mechanisms of photosynthesis by emerging PFASs at the 14th day compared to the 8th day, which indicated that they may have a shading effect on S. costatum. Additionally, mixed PFASs could also activate nicotinamide adenine dinucleotide phosphate (NADPH) oxidase by up-regulating gene gp91 and down-regulating genes CaM4 and NDPK2 to generate excessive ROS. This resulted in a decrease in the algal biomass, which would further weaken the primary productivity of S. costatum. Our findings illustrated that mixed emerging PFASs at environmental concentrations may interfere with the carbon balance of marine diatoms.

Modulation of bacterial infection and inflammation by release of lactide from a silicone elastomer device

The aim of this project is to assess the anti-bacterial and anti-inflammation properties of a matrix-type silicone elastomer device providing sustained release of DL-lactide (a cyclic ester dimer of lactic acid). Lactide-loaded matrices were prepared by injection molding, and the devices were assessed for of in vitro release, anti-bacterial activity, and anti-inflammatory activity. The devices provided sustained release of lactide/lactic acid over five days and were effective against&amp;nbsp;E. coli&amp;nbsp;and&amp;nbsp;S. aureus. Further, the devices reduced inflammation through activation of the GPR81 receptor via the NF-κB and&amp;nbsp;JAK-STAT&amp;nbsp;signalling pathway. These lactide-releasing silicone elastomer devices could improve clinical outcomes with certain short-term medical devices.

Improvement in BHETA yield by aminolysis and its application in hot melt adhesive

Polyethylene terephthalate (PET) recycling has been carried out by various methods, e.g., mechanical recycling, chemical recycling, and energy recovery method. In this study, chemical recycling of PET was carried out by aminolysis using ethanolamine and converted into bis(2-hydroxyethyl) terephthalamide (BHETA). We have studied the effective polymeric catalysis of the aminolytic depolymerization of waste polyethylene terephthalate (PET) using sulfated polyborate producing a broad range of crystalline terephthalamides. The reaction was performed by varying the PET: ethanolamine ratio, reaction time and catalyst. Recycled PET bottles, film, and fibres were used for conversion. A yield of 95 % was obtained for PET: ethanolamine ratio of 1:4 (w/w), with 4 h reaction time, at 160oC with sulfated polyborate as a catalyst. BHETA was characterized with FTIR, 1H,13C NMR, and DSC analysis. BHETA further gets reacted with dimer acid along with Ethylenediamine (EDA) at different molar ratios which produces polyesteramide (PEA) based hot melt adhesive (HMA). Thermal, mechanical, and rheological tests are performed and compared with traditional HMA. The effect on the properties of the hot melt adhesive, such as mechanical properties: tensile strength, shore D hardness, elongation at break; thermal properties: glass transition temperature (Tg), melting temperature (Tm), the heat of crystallization (Hc), crystallization temperature (Tc); adhesion properties: lap shear strength (LSS) and T-peel strength (TPS); rheological properties and degree of crystallinity were investigated. It was observed that the mechanical and thermal properties are increased by optimizing the concentration of BHETA. These HMA materials may have the capacity of being eco-friendly and have high adhesion properties.

Effects of hydrolyzed animal protein application on nitrogen translocation, phenolic and volatile profile of Ocimum basilicum L. under salinity conditions

The application of biostimulants based on hydrolysed animal protein to leaves (foliar) or nutrient solution was studied on hydroponically grown Genovese 'Marian' basil grown under salinity conditions. The effect on N yield and N fertilizer utilization was tested with the stable isotope 15N, which indicated the part of the plant that accumulated the highest amount of N. The use of the biostimulant in the nutrient solution produced the best results regarding N fertilizer utilization and N yield, being about 13 % higher than the foliar application and 24 % higher than the salt control (SC) treatment. In general, basil leaves contained the most N from the fertilizer. The total analysed phenolic content (TAPC) was 270.1 % higher in the nutrient solution-applied biostimulant (NSB) than in the control (C) treatment and 211.9 % higher than in the SC treatment. Foliar application of the biostimulant (FB) showed lower efficacy than NSB regarding phenolic contents. The most abundant individual phenolics in basil were dihydroxyphenyllactic acid dimer, caffeic acid hexoside derivatives, and rosmarinic acid. NSB increased the total sesquiterpene content by 25.2 % and the total alcohol content by 31.8 % compared to SC treatment. In addition, NSB increased the total aldehydes content by 27.0 % compared to SC treatment. The total volatile content was less variable than the individual volatiles. The results of our study show how different application methods of the biostimulant affect nitrogen conversion and utilization in different plant parts of basil and how they influence the internal quality of basil.

GenX Disturbs the Indicators of Hepatic Lipid Metabolism Even at Environmental Concentration in Drinking Water via PPARα Signaling Pathways.

Hexafluoropropylene oxide dimer acid (HFPO-DA; trade name GenX), as a substitute for perfluorooctanoic acid (PFOA), has been attracting increasing attention. However, its impact and corresponding mechanism on hepatic lipid metabolism are less understood. To investigate the possible mechanisms of GenX for hepatotoxicity, a series of in vivo and in vitro experiments were conducted. In in vivo experiment, male mice were exposed to GenX in drinking water at environmental concentrations (0.1 and 10 μg/L) and high concentrations (1 and 100 mg/L) for 14 weeks. In in vitro experiments, human hepatocellular carcinoma cells (HepG2) were exposed to GenX at 10, 160, and 640 μM for 24 and 48 h. GenX exposure via drinking water resulted in liver damage and disruption of lipid metabolism even at environmental concentrations. The results of triglycerides (TG) and total cholesterol (TC) in this study converged with the results of the population study, for which TG increased in the liver but unchanged in the serum, whereas TC increased in both liver and serum concentrations. KEGG and GO analyses revealed that the hepatotoxicity of GenX was associated with fatty acid transport, synthesis, and oxidation pathways and that Peroxisome Proliferator-Activated Receptor (PPARα) contributed significantly to this process. PPARα inhibitors significantly reduced the expression of CD36, CPT1β, PPARα, SLC27A1, ACOX1, lipid droplets, and TC, suggesting that GenX exerts its toxic effects through PPARα signaling pathway. In general, GenX at environmental concentrations in drinking water causes abnormal lipid metabolism via PPARα signaling pathway.

Ruthenium catalysts based on porous aromatic frameworks synthesized by modified impregnation methods for hydrogenation of levulinic acid and its esters

Ruthenium catalysts supported on porous aromatic frameworks (PAFs) were synthesized using different protocols for metal impregnation to achieve high catalytic performance in the hydrogenation of levulinic acid. Significant effect of the support modification with functional groups (amino-, sulfo-) was demonstrated. The main factors affecting the process including substrate concentration, temperature, reaction time and hydrogen pressure were investigated. Ruthenium catalyst Ru-PAF-30-SO3H (COD) based on PAF-30 modified with sulfo groups synthesized with the use of 1,5-COD was able to promote levulinic acid dimerization at high temperatures (200–250 °C).

GenX uptake by wheat and rice in flooded and non-flooded soils: a greenhouse experiment

GenX (hexafluoropropylene oxide dimer acid) belongs to the group of per- and poly-fluoroalkyl substance (PFAS) compounds introduced to replace perfluorooctanoic acid (PFOA), which has been phased out in industrial and consumer product formulations. While GenX has been investigated in lab animals, there is limited information available regarding its uptake and translocation in wheat and rice. This study reports on a greenhouse experiment in which wheat and rice grown under flooded and non-flooded conditions were exposed to two GenX concentrations in the soil (0.4 mg kg−1 and 2 mg kg−1). GenX was analysed in the soil, porewater and shoots using targeted liquid chromatography-tandem mass spectroscopy (LC-MS/MS) analysis. Extractable organic fluorine (EOF) was determined using high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-GFMAS) instrument. Results showed that different species took up different amounts of GenX. The GenX concentration in rice shoots was found to be 2.34 (± 0.45) and 4.11 (± 0.87) μg g−1 under flooded and non-flooded conditions, respectively, at a low exposure level. At high exposure, the GenX concentrations in flooded and non-flooded rice shoots increased threefold to 10.4 (± 0.41) and 13.4 (± 0.72) μg g−1, respectively. Wheat shoots showed similar concentrations and increases between low- and high-level exposure. The translocation factor was significantly higher (P = 0.013) in non-flooded rice compared to flooded rice. The GenX bioaccumulation behaviours under the same culture conditions (e.g. temperature, humidity, light, same GenX concentration in the soil) were significantly different in non-flooded and flooded rice (P < 0.001). Non-flooded rice plants displayed a higher level of GenX bioaccumulation than flooded ones. Following exposure to GenX, flooded rice plants showed a reduction in biomass (25%) compared to the control plants (P < 0.014). Our findings indicate that GenX is a bioaccumulative compound, the presence of which likely inhibits the growth of plants.

4-Aminophenylboronic acid dimer sensitized carbon nanotubes for the construction of portable and disposable sulfide electrochemical sensors

Abnormal sulfide levels in serum can cause kidney failure, Alzheimer's, Parkinson's, stroke, diabetes, and even cancer. Therefore, maintaining proper sulfide balance is crucial for managing and preventing these conditions. Electrochemical approaches have emerged as potential alternatives for sulfide detection. However, the adsorption of elemental sulfur on the working electrode leads to surface fouling and passivation, posing a significant challenge in developing reliable electrochemical methods for sulfide detection. In this study, we present a portable and surface fouling-free electrochemical system that utilizes functionalized multi-walled carbon nanotubes and 4-aminophenylboronic acid dimers for accurate sulfide measurement. The sensor showed excellent electrocatalytic activity to sulfide and antifouling activity to possible interferences. The method had a linear range from 10 µM to 2 mM and a detection limit of 2.3 µM. The effectiveness and applicability of this method were evaluated by analyzing sulfide levels in different serum samples and comparing the results with their glucose levels. As both blood glucose and sulfide levels can serve as indicators of certain health conditions, such as diabetes or sulfur metabolism disorders, this comparison provides valuable insights. Importantly, no complicated sample pretreatment was involved, thus this method can be easily adopted as a point-of-care diagnostic device. Additionally, the study also revealed a higher concentration of sulfide in cancer cells than in normal cells, offering a new development direction for differentiating between cancer cells and normal cells.

Preparation of Cellulose Nanofibrils with the Pretreatments using Inexpensive Protic Ionic Liquids based on Dimeric Oxalic Acid Anions

AbstractPreparation of cellulose nanofibrils (CNFs) with the pretreatments using alkanolamine‐based protic ionic liquids (PILs) with dimeric oxalic acid anions ([(HOA)(H2OA)]−) was fully investigated. The cation type [ethanolamine ([MEA]+), diethanolamine ([DEA]+), triethanolamine ([TEA]+)], and water addition greatly influenced the CNF yields. Under the pretreatment conditions of 110 °C and 3 h, the CNF yields with different PIL‐based systems followed the order: [MEA][(HOA)(H2OA)]&gt;[DEA][(HOA)(H2OA)]&gt;[TEA][(HOA)(H2OA)], similar to their swelling capacities. The highest CNF yield of 85.0 % was obtained after the pretreatment with [MEA][(HOA)(H2OA)]‐water containing 30 wt % PILs. The optimal pH range of PILs‐water was 1.10–1.15. The good recyclability indicated that these inexpensive PILs can be employed as a simple and efficient pretreatment system for preparing CNFs. The physicochemical properties of the prepared CNFs were greatly changed by varying the PILs’ pretreatment systems. The thermal stability of CNFs was intimately connected with the crystalline structures and hydrogen bonding modes.

Legacy and alternative per-and polyfluoroalkyl substances (PFASs) in the Bohai Bay Rim: Occurrence, partitioning behavior, risk assessment, and emission scenario analysis

The use of alternative per- and polyfluoroalkyl substances (PFASs) has been practiced because of the restrictions on legacy PFASs. However, knowledge gaps exist on the ecological risks of alternatives and relationships between restrictions and emissions. This study systematically analyzed the occurrence characteristics, water-sediment partitioning behaviors, ecological risks, and emissions of legacy and alternative PFASs in the Bohai Bay Rim (BBR). The mean concentration of total PFASs was 46.105 ng/L in surface water and 6.125 ng/g dry weight (dw) in sediments. As an alternative for perfluorooctanoic acid (PFOA), hexafluoropropylene oxide dimer acid (GenX) had a concentration second only to PFOA in surface water. In sediments, perfluorobutyric acid (PFBA) and GenX were the two predominant contaminants. In the water-sediment partitioning system, GenX, 9-chlorohexadecafluoro-3-oxanone-1-sulfonic acid (F-53B), and 11-chloroeicosafluoro-3-oxaundecane-1-sulfonic acid (8:2 Cl-PFESA) tended to be enriched towards sediments. The species sensitivity distribution (SSD) models revealed the low ecological risks of PFASs and their alternatives in the BBR. Moreover, predicted no-effected concentrations (PNECs) indicated that short-chain alternatives like PFBA and perfluorobutane sulfonate (PFBS) were safer for aquatic ecosystems, while caution should be exercised when using GenX and F-53B. Due to the incremental replacement of PFOA by GenX, cumulative emissions of 1317.96 kg PFOA and 667.22 kg GenX were estimated during 2004–2022, in which PFOA emissions were reduced by 59.2 % due to restrictions implemented since 2016. If more stringent restrictions are implemented from 2023 to 2030, PFOA emissions will further decrease by 85.0 %, but GenX emissions will increase by an additional 21.3 %. Simultaneously, GenX concentrations in surface water are forecasted to surge by 2.02 to 2.45 times in 2023. This study deepens the understanding of PFAS alternatives and assists authorities in developing policies to administer PFAS alternatives.

Thermal Synthesis of Carbamic Acid and Its Dimer in Interstellar Ices: A Reservoir of Interstellar Amino Acids.

Reactions in interstellar ices are shown to be capable of producing key prebiotic molecules without energetic radiation that are necessary for the origins of life. When present in interstellar ices, carbamic acid (H2NCOOH) can serve as a condensed-phase source of the molecular building blocks for more complex proteinogenic amino acids. Here, Fourier transform infrared spectroscopy during heating of analogue interstellar ices composed of carbon dioxide and ammonia identifies the lower limit for thermal synthesis to be 62 ± 3 K for carbamic acid and 39 ± 4 K for its salt ammonium carbamate ([H2NCOO-][NH4+]). While solvation increases the rates of formation and decomposition of carbamic acid in ice, the absence of solvent effects after sublimation results in a significant barrier to dissociation and a stable gas-phase molecule. Photoionization reflectron time-of-flight mass spectrometry permits an unprecedented degree of sensitivity toward gaseous carbamic acid and demonstrates sublimation of carbamic acid from decomposition of ammonium carbamate and again at higher temperatures from carbamic acid dimers. Since the dimer is observed at temperatures up to 290 K, similar to the environment of a protoplanetary disk, this dimer is a promising reservoir of amino acids during the formation of stars and planets.

Differential Developmental Neurotoxicity and Tissue Uptake of the Per- and Polyfluoroalkyl Substance Alternatives, GenX and PFBS.

Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic chemicals with several applications. Multiple adverse health effects are reported for longer carbon chain (≤C8) PFAS. Shorter carbon chain PFAS, [e.g., hexafluoropropylene oxide dimer acid (HFPO-DA; GenX) and perfluorobutanesulfonic acid (PFBS)] were introduced as alternatives. Past studies indicate that longer-chain PFAS are neurotoxic targeting the dopamine pathway, but it is not known if shorter-chain PFAS act similarly. This study aimed to evaluate developmental neurotoxicity and tissue uptake of GenX and PFBS using the zebrafish (Danio rerio). First, acute toxicity was assessed by measuring LC50 at 120 h postfertilization (hpf). Body burden was determined after embryonic exposure (1-72 hpf) to sublethal concentrations of GenX or PFBS by LC-ESI-MS/MS. Locomotor activity using a visual motor response assay at 120 hpf and dopamine levels at 72 hpf was assessed after embryonic exposure. PFBS was more acutely toxic and bioaccumulative than GenX. GenX and PFBS caused hyperactivity at 120 hpf, but stronger behavioral alterations were observed for PFBS. An increase in whole organism dopamine occurred at 40 ppb of GenX, while a decrease was observed at 400 ppb of PFBS. Differences detected in dopamine for these two PFAS indicate differential mechanisms of developmental neurotoxicity.

Dimeric ferulic acid conjugate as a prodrug for brain targeting after nasal administration of loaded solid lipid microparticles

ABSTRACT Objective Ferulic acid (Fer) displays antioxidant/anti-inflammatory properties useful against neurodegenerative diseases. To increase Fer uptake and its central nervous system residence time, a dimeric prodrug, optimizing the Fer loading on nasally administrable solid lipid microparticles (SLMs), was developed. Methods The prodrug was synthesized as Fer dimeric conjugate methylated on the carboxylic moiety. Prodrug antioxidant/anti-inflammatory properties and ability to release Fer in physiologic environments were evaluated. Tristearin or stearic acid SLMs were obtained by hot emulsion technique. In vivo pharmacokinetics were quantified by HPLC. Results The prodrug was able to release Fer in physiologic environments (whole blood and brain homogenates) and induce in vitro antioxidant/anti-inflammatory effects. Its half-life in rats was 18.0 ± 1.9 min. Stearic acid SLMs, exhibiting the highest prodrug loading and dissolution rate, were selected for nasal administration to rats (1 mg/kg dose), allowing to obtain high prodrug bioavailability and prolonged residence in the cerebrospinal fluid, showing AUC (Area Under Concentration) values (108.5 ± 3.9 μg∙mL−1∙min) up to 30 times over those of Fer free drug, after its intravenous/nasal administration (3.3 ± 0.3/5.16 ± 0.20 μg∙mL−1∙min, respectively) at the same dose. Chitosan presence further improved the prodrug brain uptake. Conclusions Nasal administration of prodrug-loaded SLMs can be proposed as a noninvasive approach for neurodegenerative disease therapy.

Alkylbenzoic and Alkyloxybenzoic Acid Blending for Expanding the Liquid Crystalline State and Improving Its Rheology.

Thermotropic mesogens typically exist as liquid crystals (LCs) in a narrow region of high temperatures, making lowering their melting point with the temperature expansion of the mesophase state an urgent task. Para-substituted benzoic acids can form LCs through noncovalent dimerization into homodimers via hydrogen bonds, whose strength and, consequently, the temperature region of the mesophase state can be potentially altered by creating asymmetric heterodimers from different acids. This work investigates equimolar blends of p-n-alkylbenzoic (kBA, where k is the number of carbon atoms in the alkyl radical) and p-n-alkyloxybenzoic (kOBA) acids by calorimetry and viscometry to establish their phase transitions and regions of mesophase existence. Non-symmetric dimerization of acids leads to the extension of the nematic state region towards low temperatures and the appearance of new monotropic and enantiotropic phase transitions in several cases. Moreover, the crystal-nematic and nematic-isotropic phase changes have a two-step character for some acid blends, suggesting the formation of symmetric and asymmetric associates from heterodimers. The mixing of 6BA and 8OBA most strongly extends the region of the nematic state towards low temperatures (from 95-114 °C and 108-147 °C for initial homodimers, respectively, to 57-133 °C for the resulting heterodimer), whereas the combination of 4OBA and 5OBA gives the most extended high-temperature nematic phase (up to 156 °C) and that of 6BA and 9OBA (or 12OBA) provides the existence of a smectic phase at the lowest temperatures (down to 51 °C).

Kinetics and proposed mechanisms of hexafluoropropylene oxide dimer acid (GenX) degradation via vacuum-UV (VUV) photolysis and VUV/sulfite processes

We investigated the degradation of hexafluoropropylene oxide dimer acid (GenX) in water via VUV photolysis and VUV/sulfite reactions under nitrogen-saturated conditions. Approximately 35% and 90% of GenX were degraded in 3 h in the VUV photolysis and VUV/sulfite reaction. While GenX removal rate was highest at pH 6 in VUV photolysis, it increased under alkaline pHs, especially at pH 10, in VUV/sulfite reaction. Radical scavenging experiments showed that, while both eaq- and •H contributed to VUV photolysis, eaq- played a significant role and •OH had a negative effect during VUV/sulfite reaction. Two transformation products (TPs) (TFA and PFPrA) were identified in VUV photolysis, whereas five TPs (TFA, PFPrA, TP182, TP348, and TP366) were identified in VUV/sulfite reaction by LCMS/MS and LCQTOF/MS. Defluorination of GenX was observed with the defluorination efficiency after 6 h reaching 17% and 67% in the VUV photolysis and VUV/sulfite reactions, respectively. Degradation mechanism for GenX based on the identified TPs and the theoretical calculation confirmed the susceptibility of GenX to nucleophilic attack. The initial reactions for GenX decomposition were C–C and C–O bond cleavage in both reactions, whereas sulfonation followed by decarboxylation was observed only in the VUV/sulfite reaction. ECOSAR ecotoxicity simulation showed that the toxicities of the TPs were not as harmful as those of GenX.

Removal of per- and polyfluoroalkyl substances by activated hydrochar derived from food waste: Sorption performance and desorption hysteresis

Carbonaceous materials, derived from waste biomass, have proven to be a viable and appealing alternative for removing emerging micro-pollutants, such as per- and polyfluoroalkyl substances (PFAS). To assess the feasibility and efficacy of using material derived from food waste to alleviate PFAS pollution, this study prepared activated hydrochar (AHC) for sorbing ten PFAS, including five perfluoroalkyl carboxylic acids (PFCA; C4–C8), three perfluoroalkyl sulfonic acids (PFSA; C4, C6, C8), and two emerging PFAS, namely hexafluoropropylene oxide dimer acid (commercial name GenX, an alternative to perfluorooctanoic acid (PFOA)) and 6:2 fluorotelomer sulfonic acid (6:2 FTS). The results demonstrated that AHC possessed a relatively high specific surface area (207 m2/g) and hydrophobic surface properties. At environmentally relevant concentrations (40 μg/L), the sorption partition coefficients (log Kd) of PFAS on AHC ranged from 2.33 to 6.49 L/kg. Notably, GenX exhibited a lower log Kd value (2.33 L/kg) than PFOA (3.88 L/kg). The AHC showed favorable sorption performance for all tested PFAS, with log Kd values surpassing other reported sorbents (e.g., 0.83 for GenX on pyrochar, and 2.83 for PFOA on commercial biochar). Additionally, desorption hysteresis was observed for all PFAS, except for PFOA, and was particularly pronounced in PFBA, GenX, and 6:2 FTS at high initial concentrations, with Hysteresis Index (HI) values varying from 0.31 to 1.45, 0.68 to 1.88, and 0.51 to 1.85, respectively. Given its robust sorption capacity and desorption hysteresis toward PFAS, AHC is expected to be a favorable candidate for remediating PFAS-contaminated water. This study underscores, for the first time, the potential of food waste-derived hydrochar as an efficient sorbent for alleviating PFAS contamination, and further study is needed to investigate the sorption and desorption behaviors of PFAS on AHC at various environmental conditions.