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Promoting safer and more cost‐effective lithium‐ion battery manufacturing practices, while also advancing recycling initiatives, is intrinsically tied to reducing reliance on fluorinated polymers like polyvinylidene difluoride (PVDF) as binders and minimizing the use of hazardous and expensive solvents such as N‐methyl pyrrolidone (NMP). In pursuit of this objective, olefin‐ and rubber‐based polymers have been investigated as promising alternatives for binder materials in high‐energy Ni‐rich LiNixCoyMnzO2 (NCM, x≥0.8) cathodes for lithium‐ion batteries (LIBs). Alternative binders such as polyisobutylene (PIB), poly(styrene‐butadiene‐styrene) (SBS), nitrile butadiene rubber (NBR), and its hydrogenated version (HNBR) offer versatile solutions. These polymers can be dissolved in industrial solvents, such as toluene, and have been further processed into homogeneous cathode slurries, thus facilitating the manufacturing of high‐energy Ni‐rich NCM cathodes for lithium‐ion batteries. The evaluation of NCM811 cathodes obtained from PIB, SBS, NBR, and HNBR has involved a thorough assessment of their physical and chemical properties, electrochemical performance, and production expenses, compared with NCM811 cathodes based on PVDF. Notably, cathodes employing PIB and HNBR have exhibited outstanding qualities, showcasing high specific capacity and remarkable electrochemical stability akin to PVDF‐based counterparts. Furthermore, the alternative binders′ superior adhesion, elasticity, and thermal stability have facilitated obtaining uniform and mechanically stable cathode films. Furthermore, using toluene, with its low vapor pressure, has significantly reduced energy costs associated with drying processes, thereby enhancing the overall cost‐effectiveness of the NCM811 cathodes. [ABSTRACT FROM AUTHOR]

This study focuses on formulating a low-surface-energy, water-resistant, and anti-condensation coating utilizing a fluorocarbon and acrylic resins composite (FAC), enhanced by six functional additives: antistatic agents, water-repellent agents, nanofillers, anti-mold and anti-algae agent, leveling agents, and wetting and dispersing agents. An orthogonal experimental design was implemented to systematically investigate the effects of varying concentrations of these additives on the surface tension of the coating. The results show that the optimized combination of fluorocarbon and acrylic resins composite (OFAC)with functional additives significantly reduces the surface tension, thereby improving both water resistance and anti-condensation properties. This research advances the development of more efficient surface treatment technologies, particularly for applications requiring enhanced water resistance and anti-condensation performance. [ABSTRACT FROM AUTHOR]

Solid polymer electrolyte membranes are considered as the nub of many electrochemical devices. Given the climate crisis and related concerns, the evolution of new membrane materials to support the sustainable systems is inevitable. Building on recent advances with the radiation technique and polymer chemistry, herein, anion exchange membranes (AEMs), ETFE‐g‐1VIm/4VP, were fabricated through graft copolymerization of vinyl heterocyclic monomer binary mixture, such as 1‐vinylimidazole (1‐VIm) and 4‐vinylpyridine (4‐VP) onto ethylene tetrafluoroethylene (ETFE), a main polymer backbone without aryl ether bonds. The grafting reaction was achieved at 60°C and then followed by quaternization as a subsequent step. The effects of various reaction grafting conditions were investigated. The ETFE‐g‐1VIm/4VP AEM were characterized w.r.t the morphological and structural features. The dense surface of the grafted membranes is proved by field emission‐scanning electron microscopy (FE‐SEM) images, which also show that the vinyl entities are clearly distributed in the prepolymer, which may lead to a continuous ion transport channel. AEMs processed from the highest graft yield showed good hydroxide conductivity at 90°C, reaching 16.9 mS/cm due to the presence of more transport sites. The same membrane has a relatively good alkaline stability, which is studied through weight percentage method and FT‐IR. Hence, we assume that the introduction of multi‐cationic moieties, pyridinium and imidazolium, contributes to the performance of anion exchange membranes and makes a perfect balance, especially the hydrophilicity and hydrophobicity. These data highlight the potential of the copolymer as an anion exchange membrane for wide spectra of electrochemical applications. Highlights: AEMs based on ETFE‐g‐1VIm/4VP are developed via radiation grafting.The membrane exhibits remarkable alkaline stability.FT‐IR, SEM, and weight percentage methods were used to prove the alkaline stability.The membrane has the potential to be used for different electrochemical applications. [ABSTRACT FROM AUTHOR]

In this study, inorganic-organic coatings composed of titanium dioxide (TiO 2) as the ceramic component and poly(vinylidene fluoride- co -hexafluoropropylene) (PVDF-HFP) as the polymer matrix, hybridized with nano-TiO 2 particles, were developed for protecting mild steel (MS) from corrosion. Prior to TiO 2 coating deposition, the MS substrates were pretreated with a bioinspired sub-layer of polydopamine to improve the surface coating adhesion, followed by uniform co-deposition of PVDF-HFP with varying concentrations of embedded nano-TiO 2. The inclusion of nano-TiO 2 further reinforces and densifies PVDF-HFP, providing added corrosion protection. The fabricated coatings were characterized by microscopy, spectroscopy, and diffraction technique, while the corrosion protection properties were evaluated by impedance, potentiodynamic polarization, salt spray, and cyclic corrosion tests. Results showed that both the PVDF-HFP matrix and TiO 2 contents had substantial effects on the coatings' thermal stability, hydrophobicity, and surface mechanical properties. The coatings also exhibited satisfactory corrosion resistance, with increased impedance modulus to roughly sixteen orders of magnitude for the TiO 2 -PVDF-HFP coating containing 0.5 g/L TiO 2 , relative to the untreated MS substrate. This result can be attributed to the low surface energy of PVDF-HFP, coupled with the dense structure and added physical barrier of nano-TiO 2. Overall, these hybrid polymer/ceramic coatings are poised to help design other highly resilient and hydrophobic surface coatings with durable protection against corrosion. [ABSTRACT FROM AUTHOR]

ESKAPE pathogens are a panel of most recalcitrant bacteria that could "escape" the treatment of antibiotics and exhibit high incidence of drug resistance. The emergence of multidrug-resistant (MDR) ESKAPE pathogens (particularly Gram-negative bacteria) accounts for high risk of mortality and increased resource utilization in health care. Worse still, there has been no new class of antibiotics approved for exterminating the Gram-negative bacteria for more than 50 years. Therefore, it is urgent to develop novel antibacterial agents with low resistance and potent killing efficacy against Gram-negative ESKAPE pathogens. Herein, we present a class of fluoropolymers by mimicking the amphiphilicity of cationic antimicrobial peptides. Our optimal fluoroamphiphilic polymer (PD45HF5) displayed selective antimicrobial ability for all MDR Gram-negative ESAKPE pathogens, low resistance, high in vitro cell selectivity, and in vivo curative efficacy. These findings implied great potential of fluoroamphiphilic cationic polymers as promising antibacterial agents against MDR Gram-negative ESKAPE bacteria and alleviating antibiotic resistance. [ABSTRACT FROM AUTHOR]

Raising the charging voltage and employing high‐capacity cathodes like lithium cobalt oxide (LCO) are efficient strategies to expand battery capacity. High voltage, however, will reveal major issues such as the electrolyte's low interface stability and weak electrochemical stability. Designing high‐performance solid electrolytes from the standpoint of substance genetic engineering design is consequently vital. In this instance, stable SEI and CEI interface layers are constructed, and a 4.7 V high‐voltage solid copolymer electrolyte (PAFP) with a fluoro‐cyanogen group is generated by polymer molecular engineering. As a result, PAFP has an exceptionally broad electrochemical window (5.5 V), a high Li+ transference number (0.71), and an ultrahigh ionic conductivity (1.2 mS cm−2) at 25 °C. Furthermore, the Li||Li symmetric cell possesses excellent interface stability and 2000 stable cycles at 1 mA cm−2. The LCO|PAFP|Li batteries have a 73.7% retention capacity after 1200 cycles. Moreover, it still has excellent cycling stability at a high charging voltage of 4.7 V. These characteristics above also allow PAFP to run stably at high loading, showing excellent electrochemical stability. Furthermore, the proposed PAFP provides new insights into high‐voltage resistant solid polymer electrolytes. [ABSTRACT FROM AUTHOR]

With the gradual miniaturization of electronic devices and the increasing interest in wearable devices, flexible microelectronics is being actively studied. Owing to the limitations of existing battery systems corresponding to miniaturization, there is a need for flexible alternative power sources. Accordingly, energy harvesting from surrounding environmental systems using fluorinated polymers with piezoelectric properties has received significant attention. Among them, polyvinylidene fluoride (PVDF) and PVDF co-polymers have been researched as representative organo-piezoelectric materials because of their excellent piezoelectric properties, mechanical flexibility, thermal stability, and light weight. Electrospinning is an effective method for fabricating nanofibrous meshes with superior surface-to-volume ratios from polymer solutions. During electrospinning, the polymer solution is subjected to mechanical stretching and in situ poling, corresponding to an external strong electric field. Consequently, the fraction of the piezoelectric β-phase in PVDF can be improved by the electrospinning process, and enhanced harvesting output can be realized. An overview of electrospun piezoelectric fibrous meshes composed of PVDF or PVDF co-polymers to be utilized is presented, and the recent progress in enhancement methods for harvesting output, such as fiber alignment, doping with various nanofillers, and coaxial fibers, is discussed. Additionally, other applications of these meshes as sensors are reviewed. [ABSTRACT FROM AUTHOR]

The practical application of new single molecule protein sequencing (SMPS) technologies requires accurate estimates of their associated sequencing error rates. Here, we describe the development and application of two distinct parameter estimation methods for analyzing SMPS reads produced by fluorosequencing. A Hidden Markov Model (HMM) based approach, extends whatprot, where we previously used HMMs for SMPS peptide-read matching. This extension offers a principled approach for estimating key parameters for fluorosequencing experiments, including missed amino acid cleavages, dye loss, and peptide detachment. Specifically, we adapted the Baum-Welch algorithm, a standard technique to estimate transition probabilities for an HMM using expectation maximization, but modified here to estimate a small number of parameter values directly rather than estimating every transition probability independently. We demonstrate a high degree of accuracy on simulated data, but on experimental datasets, we observed that the model needed to be augmented with an additional error type, N-terminal blocking. This, in combination with data pre-processing, results in reasonable parameterizations of experimental datasets that agree with controlled experimental perturbations. A second independent implementation using a hybrid of DIRECT and Powell's method to reduce the root mean squared error (RMSE) between simulations and the real dataset was also developed. We compare these methods on both simulated and real data, finding that our Baum-Welch based approach outperforms DIRECT and Powell's method by most, but not all, criteria. Although some discrepancies between the results exist, we also find that both approaches provide similar error rate estimates from experimental single molecule fluorosequencing datasets. Author summary: Diverse new technologies are being developed for single-molecule protein sequencing, capable of identifying and quantifying mixtures of proteins at the level of individual molecules. There are many biochemical challenges intrinsic to high-throughput studies of proteins at such high sensitivity arising from their heterogeneous chemistries, sizes, and abundances. Beyond these challenges, the technologies themselves involve complex multi-step analytical processes. Thus, in developing and optimizing these technologies, it is important to consider the accuracy of each step and to have reliable approaches for estimating these accuracies. We focus on one particular single-molecule sequencing technology known as flourosequencing. We report and validate two methods for simultaneously determining the error-rates of each of the various steps of the fluorosequencing process. These new error estimation techniques will help researchers to better interpret the effects of changes to the chemistry and sample preparation used in fluorosequencing so that these steps can be improved. Further, more accurate determination of error rates will aid in the creation of better tools for the interpretation of this data. [ABSTRACT FROM AUTHOR]

Polytetrafluoroethylene (PTFE) and, by extension, fluoropolymers are ubiquitous in science, life, and the environment as perfluoroalkyl pollutants (PFAS). In all cases, it is difficult to transform these materials due to their chemical inertness. Herein, we report a direct amination process of PTFE and some fluoropolymers such as polyvinylidene fluoride (PVDF) and Nafion by lithium alkylamide salts. Synthesizing these reactants extemporaneously between lithium metal and an aliphatic primary di- or triamine that also serves as a solvent leads to the rapid nucleophilic substitution of fluoride by an alkylamide moiety when in contact with the fluoropolymer. Moreover, lithium alkylamides dissolved in suitable solvents other than amines can react with fluoropolymers. This highly efficient one-pot process opens the way for further surface or bulk modification if needed, providing an easy, inexpensive, and fast experiment protocol on large scales. [ABSTRACT FROM AUTHOR]

The Mississippi River System is of great ecological and economic importance, making it crucial to monitor contaminants within it. While nutrient pollution is well studied, there are little data on microplastics (MPs) in the Mississippi River System (MSRS), especially during drought conditions. Herein, we characterize MP pollution from seven sites across the MSRS during both flash drought and non-drought periods using FTIR microspectroscopy (µ-FTIR). Additionally, we evaluate the impact of multiple water level conditions on MP polymer composition across five time points at a single sampling site. Of all MPs identified, polyethylene terephthalate (PET, 22%), resin (17%), and polyethylene (PE, 10%) were the most abundant polymers. Average concentrations ranged from 16 to 381 MPs/L across seven sites, with no significant difference in concentration between conditions. Irregular particles were the most common morphology, with most MPs falling in the lowest size range measured (30–100 μm). Drought condition had a significant (p < 0.001) impact on polymer composition, and polymers most strongly correlated with flash drought were mostly fluoropolymers. For the single sampling site, concentrations differed, but not significantly, across the five timepoints. These results demonstrate the complex relationship between MP concentration and drought condition, and also highlight the importance of fully characterizing MPs in environmental studies. [ABSTRACT FROM AUTHOR]

The application of fluoropolymers in energetic materials has attracted increasing attention. The effect of poly(vinylidene difluoride) (PVDF) content on thermal reaction and combustion performance of MnO2-Al nanothermite was reported. Nanothermite samples were prepared by electrospray with the content of PVDF from 0 wt.% to 30 wt.%. Thermal reaction processes influenced by PVDF content were tested by simultaneous thermal analysis (TG-DSC). Finally, ignition threshold tests were designed, and combustion processes were recorded. The results showed that the components of nanothermite materials were evenly distributed and stable. The content of PVDF had a significant influence on thermal reaction process, which is divided into four stages. Ignition threshold was represented by value of instantaneous ignition current. With the increase of PVDF content, ignition threshold decreased first and then tended to a stable value. Besides, PVDF content had important effects on the combustion speed of the samples. This work has practical significance for designing thermite-based ignition propellant. [ABSTRACT FROM AUTHOR]

In the cosmetics industry, the extract from Raphanus sativus L. is fermented using specific starter cultures. These cosmetic ingredients act as preservatives and skin conditioners. Kombucha is traditionally made by fermenting sweetened tea using symbiotic cultures of bacteria and yeast and is used in cosmetic products. The aim of this study was to evaluate the cosmetic properties of radish leaf and root extract fermented with the SCOBY. Both unfermented water extracts and extracts after 7, 14, and 21 days of fermentation were evaluated. The analysis of secondary plant metabolites by UPLC-MS showed higher values for ferments than for extracts. A similar relationship was noted when examining the antioxidant properties using DPPH and ABTS radicals and the protective effect against H2O2-induced oxidative stress in fibroblasts and keratinocytes using the fluorogenic dye H2DCFDA. The results also showed no cytotoxicity to skin cells using Alamar Blue and Neutral Red tests. The ability of the samples to inhibit IL-1β and COX-2 activity in LPS-treated fibroblasts was also demonstrated using ELISA assays. The influence of extracts and ferments on bacterial strains involved in inflammatory processes of skin diseases was also assessed. Additionally, application tests were carried out, which showed a positive effect of extracts and ferments on TEWL and skin hydration using a TEWAmeter and corneometer probe. The results obtained depended on the concentration used and the fermentation time. [ABSTRACT FROM AUTHOR]

The FDA has approved several drugs based on the fluorinated nucleoside pharmacophore, and numerous drugs are currently in clinical trials. Fluorine-containing nucleos(t)ides offer significant antiviral and anticancer activity. The insertion of a fluorine atom, either in the base or sugar of nucleos(t)ides, alters its electronic and steric parameters and transforms the lipophilicity, pharmacodynamic, and pharmacokinetic properties of these moieties. The fluorine atom restricts the oxidative metabolism of drugs and provides enzymatic metabolic stability towards the glycosidic bond of the nucleos(t)ide. The incorporation of fluorine also demonstrates additional hydrogen bonding interactions in receptors with enhanced biological profiles. The present article discusses the synthetic methodology and antiviral activities of FDA-approved drugs and ongoing fluoro-containing nucleos(t)ide drug candidates in clinical trials. [ABSTRACT FROM AUTHOR]

Fluorinated amino acids serve as an entry point for establishing new-to-Nature chemistries in biological systems, and novel methods are needed for the selective synthesis of these building blocks. In this study, we focused on the enzymatic synthesis of fluorinated alanine enantiomers to expand fluorine biocatalysis. The alanine dehydrogenase from Vibrio proteolyticus and the diaminopimelate dehydrogenase from Symbiobacterium thermophilum were selected for in vitro production of (R)-3-fluoroalanine and (S)-3-fluoroalanine, respectively, using 3-fluoropyruvate as the substrate. Additionally, we discovered that an alanine racemase from Streptomyces lavendulae, originally selected for setting an alternative enzymatic cascade leading to the production of these non-canonical amino acids, had an unprecedented catalytic efficiency in β-elimination of fluorine from the monosubstituted fluoroalanine. The in vitro enzymatic cascade based on the dehydrogenases of V. proteolyticus and S. thermophilum included a cofactor recycling system, whereby a formate dehydrogenase from Pseudomonas sp. 101 (either native or engineered) coupled formate oxidation to NAD(P)H formation. Under these conditions, the reaction yields for (R)-3-fluoroalanine and (S)-3-fluoroalanine reached >85% on the fluorinated substrate and proceeded with complete enantiomeric excess. The selected dehydrogenases also catalyzed the conversion of trifluoropyruvate into trifluorinated alanine as a first-case example of fluorine biocatalysis with amino acids carrying a trifluoromethyl group. Establishing biotechnological alternatives to chemical syntheses requires the rational design of biosynthetic pathways and degradation routes either as enzymatic cascades in vitro or as part of living organisms. Here, the authors use alanine dehydrogenase from Vibrio proteolyticus and the diaminopimelate dehydrogenase from Symbiobacterium thermophilum for the in vitro production of (R) and (S)-3-fluoroalanine, reaching >85% yield with complete enantiomeric excess. [ABSTRACT FROM AUTHOR]

This work investigated material extrusion additive manufacturing (MatEx AM) of specialized fluoroelastomer (FKM) compounds for applications in rubber seals and gaskets. The influence of a commercially available perfluoropolyether (PFPE) plasticizer on the printability of a control FKM rubber compound was studied using a custom-designed ram material extruder, Additive Ram Material Extruder (ARME), for printing fully compounded thermoset elastomers. The plasticizer's effectiveness was assessed based on its ability to address challenges such as high compound viscosity and post-print shrinkage, as well as its impact on interlayer adhesion. The addition of the PFPE plasticizer significantly reduced the FKM compound's viscosity (by 70%) and post-print shrinkage (by 65%). While the addition of the plasticizer decreased the tensile strength of the control compound, specimens printed with the plasticized FKM retained 34% of the tensile strength of compression-molded samples, compared to only 23% for the unplasticized compound. Finally, the feasibility of seals and gaskets manufacturing using both conventional and unconventional additive manufacturing (AM) approaches was explored. A hybrid method combining AM and soft tooling for compression molding emerged as the optimal method for seal and gasket fabrication. [ABSTRACT FROM AUTHOR]

Amphiphilic fluorocarbon substances are a trending topic of research due to their wide range of applications accompanied by an alarming environmental and health impact. In order to predict their fate in the environment, use them more economically, develop new water treatment methods, etc., a better understanding of their physicochemical behavior is required. Their hydrophobicity in water/oil systems is particularly sensitive to one key thermodynamic parameter: the free energy of transfer of a perfluoromethylene group from oil to water. However, for the –CF2– moiety, the transfer energy values reported in the literature vary by more than ±25%. Due to the exponential relationship between this energy and the adsorption constants or the partition coefficients, such an uncertainty can lead to orders of magnitude error in the predicted distribution of fluorinated species. We address this problem by presenting an experimental determination of the hydrophobic effect of a –CF2– moiety with a greater certainty than currently available. The transfer energy is determined by measuring the interfacial tension of water|hexane for aqueous solutions of short-chained fluorotelomer alcohols. The obtained results for the free energy of transfer of a –CF2– moiety from oil to water are 1.68 ± 0.02 × R T 0 , 1.75 ± 0.02 × R T 0 , and 1.88 ± 0.02 × R T 0 at 288.15 K, 293.15 K, and 303.15 K, respectively. [ABSTRACT FROM AUTHOR]

The activities of the phospholipase C gamma (PLCγ) 1 and 2 enzymes are essential for numerous cellular processes. Unsurprisingly, dysregulation of PLCγ1 or PLCγ2 activity is associated with multiple maladies including immune disorders, cancers, and neurodegenerative diseases. Therefore, the modulation of either of these two enzymes has been suggested as a therapeutic strategy to combat these diseases. To aid in the discovery of PLCγ family enzyme modulators that could be developed into therapeutic agents, we have synthesized a high-throughput screening-amenable micellular fluorogenic substrate called C16CF3-coumarin. Herein, the ability of PLCγ1 and PLCγ2 to enzymatically process C16CF3-coumarin was confirmed, the micellular assay conditions were optimized, and the kinetics of the reaction were determined. A proof-of-principle pilot screen of the Library of Pharmacologically Active Compounds 1280 (LOPAC1280) was performed. This new substrate allows for an additional screening methodology to identify modulators of the PLCγ family of enzymes. [ABSTRACT FROM AUTHOR]

Fluorinated polymers are important materials in everyday life; however, most monomers of widely used fluoropolymers are gaseous, and their polymerization is difficult in an ordinary laboratory. Therefore, partially fluorinated polymers have recently been reported. As an easy-to-handle fluorine-containing monomer, α-trifluoromethylstyrene (TFMST) can be used to produce partially fluorinated polymers with trifluoromethyl groups in the main chain; however, TFMST does not homopolymerize, and there are limited reports on its copolymerization with styrene (ST). In this study, we applied the controlled radical polymerization method, which is effective for the polymerization of ST, to the copolymerization of TFMST and ST. We also showed that nitroxide-mediated polymerization is effective. The content ratio of TFMST in the TFMST–ST copolymer can be controlled between 10% and 40% by changing its monomer ratio. Additionally, the polymerization of TFMST and ST with substituents was performed to increase structural variations. The thermal stability as well as water and oil repellency of the synthesized polymers with different composition ratios and substituents were also evaluated. [ABSTRACT FROM AUTHOR]

The formation of products of incomplete destruction (PIDs) from fluoropolymer incineration is poorly understood and it is imperative to environmental impact studies. The lack of analytical standards limits the experimental approaches targeting product analysis. To navigate this challenge, computational modeling of the thermal degradation of fluoropolymers provides simulated product distributions. However, it is essential to benchmark reactive forcefields to accurately simulate fluoropolymer pyrolysis. The present work describes a protocol to perform accurate simulations of the thermal degradation of fluoropolymers to probe the PIDs. The ReaxFF force field was applied to reproduce the experimental bulk density and glass transition temperature of polytetrafluoroethylene (PTFE). The benchmarked methodology developed has been extended to provide simulated product distributions and mechanistic insights which are in excellent agreement with primary literature. On the basis of our simulated data, we observe a degradation mechanism that proceeds through three primary steps: 1) initiation of random backbone cleavage, 2) C2F4 unzipping through β–scission (as opposed to CF2 unzipping), and 3) secondary product formation. An extension of the developed protocol has the potential to simulate the thermal degradation of non-polymeric per- and polyfluoroalkyl substances (PFASs) in addition to long-chain fluoropolymers.

Polymerization degree plays a vital role in material properties. Previous methodologies of molecular weight control generally cannot suppress or alleviate batch-to-batch variations in device performance, especially in polymer solar cells. Herein, we develop an in-situ photoluminescence system in tandem with a set of analysis and processing procedures to track and estimate the polymerization degree of organic photovoltaic materials. To support the development of this protocol, we introduce polymer acceptor PYT constructed by near-infrared Y-series small molecule acceptors via Stille polymerization, and shed light on the correlations between molecular weight, spectral parameters, and device efficiencies that enable the design of the optical setup and confirm its feasibility. The universality is verified in PYT derivatives with stereoregularity and fluoro-substitution as well as benzo[1,2-b:4,5-b']dithiophene-based polymers. Overall, our result provides a tool to tailor suitable conjugated oligomers applied to polymer solar cells and other organic electronics for industrial scalability and desired cost reduction. Polymerization degree plays a vital role in controlling material properties and batch-to-batch variations in device performance of polymer solar cells. Here, authors develop in-situ photoluminescence system in tandem to track and estimate the polymerization degree of organic photovoltaic materials. [ABSTRACT FROM AUTHOR]

This work is devoted to studying the stability of polymer coatings formed from reactive copolymers of glycidyl methacrylate and fluoroalkyl methacrylates and applied onto textured aluminum and cotton textile surfaces. The stability is determined with respect to the action of aggressive media and mechanical stress. The resulting coatings provide the achievement of long-term stable heterogeneous wetting with initial contact angles as large as 170°, thus preventing the penetration of corrosive agents into the hierarchical structure. The study has shown the influence of the composition of the reactive copolymers containing 3–7 fluorine atoms in a monomer unit on the stability of the polymer coatings with respect to the prolonged exposure to media with different acidities, as well as to cavitation, and abrasive wear. [ABSTRACT FROM AUTHOR]

This article discusses a study that aimed to demonstrate the feasibility of using non-invasive imaging to monitor the expression of prostate-specific membrane antigen (PSMA) in vivo. The study used flow cytometry and PET-CT imaging to analyze PSMA expression in different clones of TRAMP-C2 cells before and after induction with doxycycline. The results showed a significant increase in radiotracer uptake after PSMA induction, confirming the potential of PSMA as a reporter gene for monitoring gene expression in vivo. The study suggests that this approach could be useful for improving the design of gene transfer methods and protocols in clinical research studies. [Extracted from the article]

Long-term monitoring of environmental warfare agengts is a challenge for chemical gas sensors. To address this issue, we developed a 433 MHz passive wireless surface acoustic wave (WSAW) gas sensor for dimethyl methylphosphonate (DMMP) detection. This WSAW gas sensor includes a YZ lithium niobate (LiNbO3) substrate with metallic interdigital transducers (IDTs) etched on it, and an antenna was placed near the IDT. A DMMP-sensitive viscoelastic polymer fluoroalcoholpolysiloxane (SXFA) film was prepared on a LiNbO3 substrate, and mode modeling coupling was used to optimize the design parameters. The sensor can function properly in an environments between −30 °C and 100 °C with humidity less than 60% RH. When the wireless transmission distance was within the range of 0–90 cm, the sensor noise increased with distance, and the stability was less than 32°/h. While optimizing the film thickness of SXFA, a relationship was observed between sensor sensitivity and film thickness. When the film thickness of SXFA reached 450 nm, the optimal value was reached. At a distance of 20 cm between the transmitting and receiving antennas, DMMP was detected at different concentrations with the developed WSAW gas sensor. The lower detection limit of DMMP was 0.48 mg/m3, the sensitivity of the sensor was 4.63°/(mg/m3), and repeatable performance of the sensor was confirmed. [ABSTRACT FROM AUTHOR]

BACKGROUND: Per- and polyfluoroalkyl substances (PFAS) are a large class of synthetic (man-made) chemicals widely used in consumer products and industrial processes. Thousands of distinct PFAS exist in commerce. The 2019 U.S. Environmental Protection Agency (U.S. EPA) Per- and Polyfluoroalkyl Substances (PFAS) Action Plan outlines a multiprogram national research plan to address the challenge of PFAS. One component of this strategy involves the use of systematic evidence map (SEM) approaches to characterize the evidence base for hundreds of PFAS. OBJECTIVE: SEM methods were used to summarize available epidemiological and animal bioassay evidence for a set of ~150 PFAS that were prioritized in 2019 by the U.S. EPA’s Center for Computational Toxicology and Exposure (CCTE) for in vitro toxicity and toxicokinetic assay testing. METHODS: Systematic review methods were used to identify and screen literature using manual review and machine-learning software. The Populations, Exposures, Comparators, and Outcomes (PECO) criteria were kept broad to identify mammalian animal bioassay and epidemiological studies that could inform human hazard identification. A variety of supplemental content was also tracked, including information on in vitro model systems; exposure measurement-only studies in humans; and absorption, distribution, metabolism, and excretion (ADME). Animal bioassay and epidemiology studies meeting PECO criteria were summarized with respect to study design, and health system(s) were assessed. Because animal bioassay studies with ≥21-d exposure duration (or reproductive/developmental study design) were most useful to CCTE analyses, these studies underwent study evaluation and detailed data extraction. All data extraction is publicly available online as interactive visuals with downloadable metadata. RESULTS: More than 40,000 studies were identified from scientific databases. Screening processes identified 44 animal and 148 epidemiology studies from the peer-reviewed literature and 95 animal and 50 epidemiology studies from gray literature that met PECO criteria. Epidemiological evidence (available for 15 PFAS) mostly assessed the reproductive, endocrine, developmental, metabolic, cardiovascular, and immune systems. Animal evidence (available for 40 PFAS) commonly assessed effects in the reproductive, developmental, urinary, immunological, and hepatic systems. Overall, 45 PFAS had evidence across animal and epidemiology data streams. DISCUSSION: Many of the ~150 PFAS were data poor. Epidemiological and animal evidence were lacking for most of the PFAS included in our search. By disseminating this information, we hope to facilitate additional assessment work by providing the initial scoping literature survey and identifying key research needs. Future research on data-poor PFAS will help support a more complete understanding of the potential health effects from PFAS exposures. [ABSTRACT FROM AUTHOR]

Polymer‐based composites containing functional organic fillers with polyvinylidene fluoride (PVDF) as a matrix were prepared using a simple and short melt‐compounding method, and their mechanical properties were evaluated. Polyrotaxane and nanocellulose were used as functional organic fillers. A PVDF/organic filler composite with improved mechanical hardness was prepared, even when using a fluoropolymer that tends to separate phases from other components. The optimum conditions for improving in Young's modulus were estimated from the composites prepared by varying the organic filler content. As a result, the Young's modulus increased to 1548 MPa, maximum stress approached 50 MPa, and strain elongation was 20% at contents of polyrotaxane:nanocellulose = 0.6 wt%:0.3 wt%. Furthermore, the miscibility of both components was evaluated based on the change in the crystallization temperature of the composite, the PVDF matrix, and each organic filler. The partial miscibility and dispersion of the organic fillers in the fluoropolymer matrix are suggested to be responsible for improving the mechanical properties. Highlights: Unique composites containing nanocellulose and polyrotaxane were prepared.Organic fillers were introduced into a phase‐separable fluoropolymer matrix.Mechanical properties were improved by introduction of organic fillers.Nanocellulose seems to adsorb to the polymer chain ends of fluoropolymer.Polyrotaxane showed partial miscibility with fluoropolymer matrix. [ABSTRACT FROM AUTHOR]

A block copolymer (BCP) with specific monomer structures of fluoroacrylate polymers was designed by exploiting the inorganic superhydrophobicity and low glass transition temperature of polydimethylsiloxane (PDMS). With the use of a fluorine-containing block providing a surface tension as low as that of PDMS (19.9 < γ < 21.5 mN/m), PDMS-b-poly(2,2,3,3,3-pentafluoropropyl acrylate) (PDMS-b-PPeFPA) copolymer was synthesized to create a volume-symmetric lamellar structure. The compositional randomness of the BCP chains adsorbed onto the substrates provided well-balanced interfacial interactions toward the overlaid PDMS-b-PPeFPA (γ PDMS-ads ≈ γ PPeFPA-ads). Under this symmetric confinement with simultaneous dual neutral interfaces, lamellar microdomains with a sub-10 nm half-pitch feature size were successfully oriented perpendicular to the interfaces at room temperature. We showed the response of the BCP films to a lateral electric field, demonstrating that the perpendicular lamellae were adaptively aligned along the electric vector within a short treatment period. Furthermore, the PDMS-b-PPeFPA system exhibited a remarkable etch contrast for O2 reactive ion etching, yielding unidirectionally aligned air–inorganic nanoarrays emanating from the perpendicular lamellae between the electrodes. This study reports a system engineering approach for conceiving highly immiscible, silicon- and fluorine-containing BCP whose components exhibit identical surface tensions (γ PDMS ≈ γ PPeFPA) and for generating perpendicularly oriented lamellar microdomains due to substrate neutrality. With the use of a fluorine-containing block providing a surface tension as low as that of PDMS (19.9 < γ < 21.5 mN/m), the PDMS-b-PPeFPA copolymer is synthesized to create a volume-symmetric lamellar structure. Under the symmetric confinement with simultaneous dual neutral interfaces, lamellar microdomains with a sub-10 nm half-pitch feature size are successfully oriented perpendicular to the interfaces at room temperature (RT). Together with unidirectionally aligned perpendicular lamellae along the electric vector in a short period (0.5 h) at RT, we demonstrate a unidirectional alignment of the perpendicular air–inorganic (oxidized PDMS) lamellae between the electrodes. [ABSTRACT FROM AUTHOR]

In a longitudinal design, four arterial segments in mice were followed by positron emission tomography/computed tomography (PET/CT) imaging. We aimed to determine how the tracers reflected the development of atherosclerosis via the uptake of 2-deoxy-2-[18F]fluoro-D-glucose ([18F]FDG) for imaging inflammation and [18F]-sodium fluoride (Na[18F]F) for imaging active microcalcification in a murine model of atherosclerosis. Apolipoprotein E knock-out (ApoE) mice and C57 BL/6NtaC (B6) mice were divided into four groups. They received either normal chow (N = 7, ApoE mice and N = 6, B6 mice) for 32 weeks or a high-fat diet (N = 6, ApoEHFD mice and N = 9, B6HFD mice) for 32 weeks. The mice were scanned with [18F]FDG and Na[18F]F using a dedicated small animal PET/CT scanner at three timepoints. The tracer uptakes in four aortic segments (abdominal aorta, aortic arch, ascending aorta, and thoracic aorta) were measured and reported as SUVmax values. The uptake of [18F]FDG (SUVmax: 5.7 ± 0.5 vs 1.9 ± 0.2, 230.3%, p = < 0.0001) and Na[18F]F (SUVmax: 9.6 ± 1.8 vs 4.0 ± 0.3, 175%, p = 0.007) was significantly increased in the abdominal aorta of ApoEHFD mice at Week 32 compared to baseline abdominal aorta values of ApoEHFD mice. [18F]FDG uptake in the aortic arch, ascending aorta and the thoracic aorta of B6HFD mice at Week 32 showed a robust resemblance to the abdominal aorta uptake whereas the Na[18F]F uptake only resembled in the thoracic aorta of B6HFD mice at Week 32 compared to the abdominal aorta. The uptake of both [18F]FDG and Na[18F]F increased as the disease progressed over time, and the abdominal aorta provided a robust measure across mouse strain and diet. Therefore, it seems to be the preferred region for image readout. For [18F]FDG-PET, both B6 and ApoE mice provide valuable information and either mouse strain may be used in preclinical cardiovascular studies, whereas for Na[18F]F -PET, ApoE mice should be preferred. [ABSTRACT FROM AUTHOR]

Malignant transformation is characterised by aberrant phospholipid metabolism of cancers, associated with the upregulation of choline kinase alpha (CHKα). Due to the metabolic instability of choline radiotracers and the increasing use of late-imaging protocols, we developed a more stable choline radiotracer, [18F]fluoromethyl-[1,2-2H4]choline ([18F]D4-FCH). [18F]D4-FCH has improved protection against choline oxidase, the key choline catabolic enzyme, via a 1H/2D isotope effect, together with fluorine substitution. Due to the promising mechanistic and safety profiles of [18F]D4-FCH in vitro and preclinically, the radiotracer has transitioned to clinical development. [18F]D4-FCH is a safe positron emission tomography (PET) tracer, with a favourable radiation dosimetry profile for clinical imaging. [18F]D4-FCH PET/CT in lung and prostate cancers has shown highly heterogeneous intratumoral distribution and large lesion variability. Treatment with abiraterone or enzalutamide in metastatic castrate-resistant prostate cancer patients elicited mixed responses on PET at 12–16 weeks despite predominantly stable radiological appearances. The sum of the weighted tumour-to-background ratios (TBRs-wsum) was associated with the duration of survival. [ABSTRACT FROM AUTHOR]

The fast, affordable, and standardized detection of microplastics (MP) remains one of the biggest challenges in MP research. Comparable data are essential for appropriate risk assessments and the implementation of laws and limit values. The fluorescent staining of MP in environmental samples is a possible solution to this problem. This study investigates the optimization of a sample preparation process (hydrogen peroxide digestion) and the staining process (temperature, concentration, time, surfactants as staining aids) for using a specifically developed fluorescent dye for MP detection. The optimization is performed by comparing the sample preparation process and staining of MP from different polymers and natural particles. Further, the suitability of the optimized process for the detection of fluoropolymers and tire abrasion was tested. The results show that the optimized method (increased temperature and optimized stain concentration) can detect microplastics reliably with a total sample preparation and measurement time of 2.5–3 h per sample, reaching recovery rates of 93.3% (polypropylene) to 101.7% (polyester). Moreover, two of the three tested fluoropolymers could be detected reliably. Tire abrasion could not be detected with the here presented method, as the black color leads to strong quenching. A long-term study measuring the MP pollution in the effluent of a municipal wastewater treatment plant compared the optimized and original processes and confirmed the stability of the improved method for routine measurements and contamination control. [ABSTRACT FROM AUTHOR]

Fluorosilicone rubber, essential in automotive and aerospace owing to its excellent chemical resistance, plays a pivotal role in sealing technology, addressing the industry's evolving demands. This study explores the preparation and properties of fibrillated cellulose-reinforced fluorosilicone rubber composites to enhance their stiffness and oil resistance. Fibrillated cellulose sourced as a wet cake and subjected to processing and modification is incorporated into a fluorosilicone rubber matrix. The resulting composites are analysed by tensile and compression tests, along with compressive stress-relaxation testing in air and in an oil-immersed environment. The findings demonstrate significant improvements in the mechanical properties, including an increased Young's modulus and elongation at break, whereas the tensile strength remained uncompromised throughout the testing procedures. Morphological analysis of the fracture surfaces revealed a remarkable interfacial affinity between the fibrillated cellulose and rubber matrix, which was attributed in part to the modified fatty acids and inorganic nanoparticles. The presence of fibrillated cellulose enhanced the stress-relaxation characteristics under oil-immersion conditions. These results contribute to the domain of advanced elastomer materials, with potential for applications requiring enhanced mechanical properties and superior oil resistance. [ABSTRACT FROM AUTHOR]

In this study, a novel highly sensitive and selective fluorescent optode membrane aimed at the determination of Pb(II) ion is proposed by incorporating N-(3-(1,4-dioxa-7,13-dithia-10-azacyclopentadecan-10-yl)propyl)-5-(dimethylamino)naphthalene-1-sulfonamide (L) as fluoroionophore in polyvinyl chloride (PVC) containing 2-nitrophenyl octylether (NPOE) as a plasticizer. In addition to high stability and reproducibility, the proposed optosensor showed a unique selectivity toward Pb(II) ion, with a wide linear range of molar concentrations (1.0 × 10−9–1.0 × 10−3 M) and a low detection limit of 7.5 × 10−10 M in solution at pH 5.0. The formation constants of the Pb(II) complexes with the fluoroionophore were evaluated by fitting the fluorescence data with a nonlinear least-squares curve-fitting program, and further information about the structures of the complexes were evaluated based on hybrid-DFT calculations. The optosensor exhibited a fast response time of less than three min, being easily regenerated by exposure to a solution of dithiothreitol. The sensor was applied to the determination of Pb(II) in real samples (canned tuna fish), and it provided satisfactory results comparable to those obtained via atomic absorption spectrometry (AAS). [ABSTRACT FROM AUTHOR]

Polytetrafluoroethylene (PTFE) and, by extension, fluoropolymers are ubiquitous in science, life, and the environment as perfluoroalkyl pollutants (PFAS). In all cases, it is difficult to transform these materials due to their chemical inertness. Herein, we report a direct amination process of PTFE and some fluoropolymers such as polyvinylidene fluoride (PVDF) and Nafion by lithium alkylamide salts. Synthesizing these reactants extemporaneously between lithium metal and an aliphatic primary di- or triamine that also serves as a solvent leads to the rapid nucleophilic substitution of fluoride by an alkylamide moiety when in contact with the fluoropolymer. Moreover, lithium alkylamides dissolved in suitable solvents other than amines can react with fluoropolymers. This highly efficient one-pot process opens the way for further surface or bulk modification if needed, providing an easy, inexpensive, and fast experiment protocol on large scales.

In a high-moisture environment where dust and coastal saltwater are prevalent, the stability of power equipment can be adversely affected. This issue can result in equipment downtime, particularly for transformers, severely disrupting the continuous operation of DC transmission systems. To address this challenge, a superhydrophobic modified fluorosilicone coating was developed, incorporating anti-stain properties. To tackle this issue comprehensively, an orthogonal experiment was conducted, involving six factors and three levels. The study focused particularly on assessing the impact of water-repellent recovery agents, nanofillers, antistatic agents, anti-mold agents, leveling agents, as well as wetting and dispersing agents on the coating's surface tension. The results demonstrate that selecting an appropriate base resin and incorporating well-matched functional additives played a central role in effectively reducing the surface tension of the coating. Consequently, optimized coatings exhibited exceptional resistance to stains and displayed strong corrosion resistance. [ABSTRACT FROM AUTHOR]

In contrast to some low-molar-mass per- and polyfluoroalkyl substances (PFASs), which are well established to be toxic, persistent, bioaccumulative, and mobile, fluoropolymers (FPs) are water-insoluble, safe, bioinert, and durable. These niche high-performance polymers fulfil the 13 polymer-of-low-concern (PLC) criteria in their recommended conditions of use. In addition, more recent innovations (e.g., the use of non-fluorinated surfactants in aqueous radical (co)polymerization of fluoroalkenes) from industrial manufacturers of FPs are highlighted. This review also aims to show how these specialty polymers endowed with outstanding properties are essential (even irreplaceable, since hydrocarbon polymer alternatives used in similar conditions fail) for our daily life (electronics, energy, optics, internet of things, transportation, etc.) and constitute a special family separate from other "conventional" C1–C10 PFASs found everywhere on Earth and its oceans. Furthermore, some information reports on their recycling (e.g., the unzipping depolymerization of polytetrafluoroethylene, PTFE, into TFE), end-of-life FPs, and their risk assessment, circular economy, and regulations. Various studies are devoted to environments involving FPs, though they present a niche volume (with a yearly production of 330,300 t) compared to all plastics (with 460 million t). Complementary to other reviews on PFASs, which lack of such above data, this review presents both fundamental and applied strategies as evidenced by major FP producers. [ABSTRACT FROM AUTHOR]

Traditionally, in the oil and gas industry, accelerometers are mounted externally on motors for condition monitoring of vertically suspended, closed suction hydrocarbon pumps due to their inability to withstand harsh downhole environments, preventing the detection of impeller failures. This study addresses the need for encapsulation solutions for accelerometers submerged in hydrocarbon fluid environments. It evaluates the feasibility of epoxy and fluoroelastomer as encapsulation materials for long-term immersion in high-temperature hydrocarbon fluid and determines their impact on the accelerometer's performance. Extensive testing involved submersion in high-temperature hydrocarbon fluid at 150 °C for over 10,000 h and six months in brine. Material characterization, including mass variation, microscopic imaging, and FTIR spectroscopy, revealed negligible degradation. Encapsulated accelerometers effectively detected vibrations with an acceptable alteration in amplitude. In comparison with commercial alternatives, our encapsulation outperformed them. While oil traces became evident within just 24 h in the alternatives, our solution exhibited no signs of leakage. This research pioneers a novel packaging solution employing epoxy and fluoroelastomer for side-exit commercial sensors tailored for high-temperature hydrocarbon fluid applications, addressing a critical gap in the industry. Our work enhances reliability and safety for vertical oil pump condition monitoring in downhole applications, benefiting the oil and gas sector. [ABSTRACT FROM AUTHOR]

The potential of microRNA regulation in oncotherapy is limited by the lack of delivery vehicles. Herein, it is shown that fluoropolymer coated DNA nanoclews (FNCs) provide outstanding ability to deliver oligonucleotide through circulation and realize near infrared (NIR) light activated angiogenesis suppression to abrogate tumors. Oligonucleotides are loaded in DNA nanoclews through sequence specific bindings and then a fluorinated zwitterionic polymer is coated onto the surface of nanoclews. Further incorporating quantum dots in the polymer coating endows the vectors with NIR‐IIb (1500–1700 nm) fluorescence and NIR light triggered release ability. The FNC vector can deliver oligonucleotides to cancer cells systemically and realize on‐demand cytosolic release of the cargo with high transfection efficiency. Taking advantage of the NIR‐IIb emission, the whole delivery process of FNCs is visualized volumetrically in vivo with a NIR light sheet microscope. Loaded by FNCs, an oligonucleotide can effectively silence the target miRNA when activated with NIR light, and inhibit angiogenesis inside tumor, leading to complete ablation of cancer. These findings suggest FNCs can be used as an efficient oligonucleotide delivery platform to modulate the expression of endogenous microRNA in gene therapy of cancer. [ABSTRACT FROM AUTHOR]

Cathepsin D is a protease that is an effector in the immune response of macrophages, yet to date, only a limited number of probes have been developed for its detection. Herein, we report a water soluble, highly sensitive, pH insensitive fluorescent probe for the detection of Cathepsin D activity that provides a strong OFF/ON signal upon activation and with bright emission at 515 nm. The probe was synthesised using a combination of solid and solution-phase chemistries, with probe optimisation to increase its water solubility and activation kinetics by addition of a long PEG chain (5 kDa) at the C-terminus. A BODIPY fluorophore allowed detection of Cathepsin D across a wide pH range, important as the protease is active both at the low pH found in lysosomes and also in higher pH phagolysosomes, and in the cytosol. The probe was successfully used to detect Cathepsin D activity in macrophages challenged by exposure to bacteria. Cathepsin D (CatD) is an aspartic acid protease involved in the immune response of macrophages to bacterial infection, and the development of pH insensitive CatD probes is vital in order to detect its activity across multiple cellular components. Here, the authors develop a water soluble and pH insensitive FRET-based fluorescent probe for the sensitive detection of CatD. [ABSTRACT FROM AUTHOR]

Fluorine forms the strongest single bond to carbon with the highest bond dissociation energy among natural products. However, fluoroacetate dehalogenases (FADs) have been shown to hydrolyze this bond in fluoroacetate under mild reaction conditions. Furthermore, two recent studies demonstrated that the FAD RPA1163 from Rhodopseudomonas palustris can also accept bulkier substrates. In this study, we explored the substrate promiscuity of microbial FADs and their ability to defluorinate polyfluorinated organic acids. Enzymatic screening of eight purified dehalogenases with reported fluoroacetate defluorination activity revealed significant hydrolytic activity against difluoroacetate in three proteins. Product analysis using liquid chromatography‐mass spectrometry identified glyoxylic acid as the final product of enzymatic DFA defluorination. The crystal structures of DAR3835 from Dechloromonas aromatica and NOS0089 from Nostoc sp. were determined in the apo‐state along with the DAR3835 H274N glycolyl intermediate. Structure‐based site‐directed mutagenesis of DAR3835 demonstrated a key role for the catalytic triad and other active site residues in the defluorination of both fluoroacetate and difluoroacetate. Computational analysis of the dimer structures of DAR3835, NOS0089, and RPA1163 indicated the presence of one substrate access tunnel in each protomer. Moreover, protein‐ligand docking simulations suggested similar catalytic mechanisms for the defluorination of both fluoroacetate and difluoroacetate, with difluoroacetate being defluorinated via two consecutive defluorination reactions producing glyoxylate as the final product. Thus, our findings provide molecular insights into substrate promiscuity and catalytic mechanism of FADs, which are promising biocatalysts for applications in synthetic chemistry and bioremediation of fluorochemicals. [ABSTRACT FROM AUTHOR]

This study reports on the synthesis and characterization of novel perfluorinated organic polymers with azo- and azomethine-based linkers using nucleophilic aromatic substitution. The polymers were synthesized via the incorporation of decafluorobiphenyl and hexafluorobenzene linkers with diphenols in the basic medium. The variation in the linkers allowed the synthesis of polymers with different fluorine and nitrogen contents. The rich fluorine polymers were slightly soluble in THF and have shown molecular weights ranging from 4886 to 11,948 g/mol. All polymers exhibit thermal stability in the range of 350–500 °C, which can be attributed to their structural geometry, elemental contents, branching, and cross-linking. For instance, the cross-linked polymers with high nitrogen content, DAB-Z-1h and DAB-Z-1O, are more stable than azomethine-based polymers. The cross-linking was characterized by porosity measurements. The azo-based polymer exhibited the highest surface area of 770 m2/g with a pore volume of 0.35 cm3/g, while the open-chain azomethine-based polymer revealed the lowest surface area of 285 m2/g with a pore volume of 0.0872 cm3/g. Porous structures with varied hydrophobicities were investigated as adsorbents for separating water-benzene and water-phenol mixtures and selectively binding methane/carbon dioxide gases from the air. The most hydrophobic polymers containing the decafluorbiphenyl linker were suitable for benzene separation, while the best methane uptake values were 6.14 and 3.46 mg/g for DAB-Z-1O and DAB-A-1O, respectively. On the other hand, DAB-Z-1h, with the highest surface area and being rich in nitrogen sites, has recorded the highest CO2 uptake at 298 K (17.25 mg/g). [ABSTRACT FROM AUTHOR]

This article reports on the synthesis of materials containing both a fluoroalkyl group and a diazonaphthoquinone (DNQ) moiety as well as the fabrication of negative- and positive-tone stencil patterns. Additionally, the photoreaction mechanism that contributes to the pattern formation process is discussed, and the application of these materials is explored in the pixel-formation process in organic light-emitting diode (OLED) displays. Fluoroalkylated diazonaphthoquinone (RF2D1) was synthesized using chemically binding a DNQ unit, which can be converted into carboxylic acid derivatives having stronger polarity, with two fluorinated alkyl chains. The purified compound is found to be soluble in a nonpolar fluorous solvent and can be uniformly coated as a thin film. When the thin film of RF2D1 is exposed to 365 nm UV light, its solubility in a fluorous solvent decreases due to the Wolff rearrangement and subsequent hydrolysis of a ketene moiety. In contrast, when a mixture of RF2D1 and a hydrophobic, fluorinated copolymer is tested for the patterning process, the copolymer delays the conversion of the ketene intermediate to carboxylic acid, resulting in the dissolution of the exposed areas in the fluorous solvent. Finally, the applicability of these materials in micropatterning is demonstrated by adopting them in the orthogonal photolithography process to create pixels of OLEDs. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cyano-modified graphitic carbon nitride (g-NCNCN x) was developed for photocatalytic perfluoroalkylation reactions.. • Photocatalytic addition or coupling reaction can be achieved selectively and effectively with a broad substrate scope. • g-NCNCN x exhibits excellent photocatalytic activity for at least five catalytic cycles. • More photoelectrons of g-NCNCN x generated after light irradiation, improving the photocatalytic performance, comparing to pristine g-CN x. Photocatalytic radical fluoroalkylation has become an important approach to prepare valuable organofluorine compounds under mild conditions. Compared to the homogenous photocatalytic fluoroalkylation reactions based on the precious metal complexes or organic dyes, heterogeneous photocatalysis using metal-free carbon nitride catalyst shows cost-effective, easier separation and excellent recyclability. In this work, we report the visible-light-induced photocatalytic perfluoroalkylation of alkynes with perfluoroalkyl iodides (R f I) using heterogeneous cyano-modified graphitic carbon nitride (g-NCNCNx) as the photocatalyst. The mechanism proposed by the experimental and computational studies reveals that the long-lived triplet excited states in photoinduced g-NCNCNx are involved in the initial bimolecular electron transfer process, resulting in the effective activation of R f I and the improvement of sequential photocatalytic reactions. Moreover, the stronger interaction between the substate and surface of catalyst g-NCNCNx can further improve the photocatalytic activity, comparing to the pristine carbon nitride (g-CNx). Through simple variation of the reaction conditions, the photocatalytic addition or coupling reaction can be achieved effectively and selectively. Importantly, the heterogeneous g-NCNCNx photocatalyst can not only show high performance with a wide reaction scope, but also be readily recovered and reused for at least five catalytic cycles with high photocatalytic activity. This work provides a sustainable alternative to the conventional metal-based photocatalysts for organofluorine synthesis. [ABSTRACT FROM AUTHOR]

The plasma electrolytic oxidation (PEO) coatings with the color of black or white have good prospects in thermal control application. However, it still remains a challenge for obtaining the PEO coatings on Al alloys to achieve high whiteness that in turn could give adequate low absorption thermal control characteristic. Herein, a bright white oxide coating mainly composed of ZrO 2 was successfully prepared on 6061 aluminium alloy by PEO process from a fluorozirconate electrolytic solution. The microstructure and composition of the coating were studied by SEM, EDS, XRD and XPS. The thermal control properties were measured by UV-VIS-NIR spectrophotometer and infrared emissivity spectrometer, respectively. The stability of thermal control properties of the coating was also evaluated by simulated space environmental tests. The corrosion protection performances of the coating were investigated by potentiodynamic polarization and salt spray tests. Results show that the oxide coating is composed of t -ZrO 2 as well as a little of m -ZrO 2 and γ -Al 2 O 3 with a porous microstructure. The coating exhibits low solar absorptance (α s) of 0.205 and high emissivity (ε) of 0.84, which is comparable for the typical space white paints. In addition, the coating owns excellent stability in thermal control properties under simulated space environments. The coating has a good durability in corrosive environment though it provides only slight improvement in corrosion resistance of 6061 aluminium alloy due to the presence of many larger micropores in the coating. [ABSTRACT FROM AUTHOR]

Precious metals such as palladium (Pd) have many applications, ranging from automotive catalysts to fine chemistry. Platinum group metals are, thus, in massive demand for industrial applications, even though they are relatively rare and belong to the list of critical materials for many countries. The result is an explosion of their price. The recovery of Pd from spent catalysts and, more generally, the development of a circular economy process around Pd, becomes essential for both economic and environmental reasons. To this aim, we propose a sustainable process based on the use of supercritical CO2 (i.e., a green solvent) operated in mild conditions of pressure and temperature (p = 25 MPa, T = 313 K). Note that the range of CO2 pressures commonly used for extraction is going from 15 to 100 MPa, while temperatures typically vary from 308 to 423 K. A pressure of 25 MPa and a temperature of 313 K can, therefore, be viewed as mild conditions. CO2-soluble copolymers bearing complexing groups, such as pyridine, triphenylphosphine, or acetylacetate, were added to the supercritical fluid to extract the Pd from the catalyst. Two supported catalysts were tested: a pristine aluminosilicate-supported catalyst (Cat D) and a spent alumina supported-catalyst (Cat A). An extraction conversion of up to more than 70% was achieved in the presence of the pyridine-containing copolymer. The recovery of the Pd from the polymer was possible after extraction, and the technological and economical assessment of the process was considered. [ABSTRACT FROM AUTHOR]

This study aims to investigate the effect of organically modified zirconium dioxide nanoparticles (m‐ZrO2 NPs) on the mechanical properties, morphology, and weather stability of fluoroethylene/vinyl ether copolymer (FEVE). To modify the surface of ZrO2 NPs, a 3‐(trimethoxysilyl)propyl methacrylate silane (TMSPM) organic coupling agent was utilized. The ZrO2 NPs were treated with 3 wt.% of TMSPM using a solution method with ultrasonication assistance at 50°C. Various amounts of m‐ZrO2 NPs (1, 2, and 4 wt.% of FEVE weight) were dispersed in a xylene solvent and mixed with FEVE resin. The mixture was then cured with polyisocyanate. The mechanical properties of the FEVE nanocomposite coatings, including impact resistance, adhesion, and abrasion resistance were measured. The morphology of the coatings was analyzed using scanning electron microscopy (SEM). To evaluate the weather stability of the coatings, an accelerated weathering test was conducted in a QUV/SPRAY chamber. This test could potentially affect the chemical structure, weight/thickness, and surface characteristics of the coatings. The carbonyl index, weight loss, and changes in mechanical properties of the coatings were monitored and discussed at different intervals during the accelerated weathering test. In addition, the morphology of the coatings after undergoing 42 cycles of accelerated weathering testing was analyzed. The results indicated that m‐ZrO2 NPs had a positive impact on the weather durability of FEVE resin, particularly in significantly enhancing the weather resistance of the FEVE‐based coatings. Therefore, these coatings exhibit potential for outdoor applications. Highlights: Silane modified ZrO2 nanoparticles improve the mechanical properties of FEVE resin.The weather stability of FEVE resin increases as using modified ZrO2 nanoparticles.The suitable content of modified ZrO2 nanoparticles for FEVE resin is 2 wt.%.Mechanical properties of the nanocomposite reduce slightly after 42 cycle testing.Propose the mechanism for weather resistance of the nanocomposite coating. [ABSTRACT FROM AUTHOR]

A novel combined method for the formation of composite coatings on the Mg-Mn-Ce alloy is developed. Ceramic like matrix was formed on the Mg alloy surface by the plasma electrolytic oxidation. Then the samples were subsequently processed by dip-coating in an alcohol suspension of superdispersed polytetrafluoroethylene and spraying with the tetrafluoroethylene telomers solution. SEM, OSP, and SPM was used to study structure of formed surfaces. It was established by measurements of CA and CAH, as well as surface free energy calculations that formed coatings demonstrate superhydrophobic properties due to the presence of an irregular hierarchical surface structure and low surface free energy of fluoropolymers. The coating preserves its hydrophobic properties after exposure to high and low temperatures, for a long time as well as being in corrosive environments. EDS and XRD data analysis confirmed the presence of organofluorine compounds in the composite layers, including in the form of crystalline polytetrafluoroethylene. Using potentiodynamic polarization test and EIS, it was found that the resulting coatings significantly increase the corrosion resistance of Mg material. These data are also confirmed by salt spray tests for 40 days. Incorporation of fluoropolymers additionally decrease coatings coefficient of friction.

To select the appropriate polymer thin films for liquid oxygen composite hoses, the liquid oxygen compatibility and the cryogenic mechanical properties of four fluoropolymer films (PCTFE, ETFE, FEP and PFA) and two non-fluoropolymer films (PET and PI) before and after immersion in liquid oxygen for an extended time were investigated. The results indicated that the four fluoropolymers were compatible with liquid oxygen before and after immersion for 60 days, and the two non-fluoropolymers were not compatible with liquid oxygen. In addition, the cryogenic mechanical properties of these polymer films underwent changes with the immersion time, and the changes in the non-fluoropolymer films were more pronounced. The cryogenic mechanical properties of the two non-fluoropolymer films were always superior to those of the four fluoropolymer films during the immersion. Further analysis indicated that the fundamental reason for these changes in the cryogenic mechanical properties was the variation in the crystalline phase structure caused by the ultra-low temperature, which was not related to the strong oxidizing properties of the liquid oxygen. Analytical results can provide useful guidance on how to select the appropriate material combination to obtain a reasonable liquid oxygen composite hose structure. [ABSTRACT FROM AUTHOR]

Precise detection of early osteolytic metastases is crucial for their treatment but remains challenging in the clinic because of the limited sensitivity and specificity of traditional imaging techniques. Although fluorescence imaging offers attractive features for the diagnosis of osteolytic metastases, it is hampered by limited penetration depth. To address this issue, a fluoro‐photoacoustic dual‐modality imaging probe comprising a near‐infrared dye caged by a cathepsin K (CTSK)‐cleavable peptide sequence on one side and functionalized with osteophilic alendronate through a polyethylene glycol linker on the other side is reported. Through systematic in vitro and in vivo experiments, it is demonstrated that in response to CTSK, the probe generated both near‐infrared fluorescent and photoacoustic signals from bone metastatic regions, thus offering a potential strategy for detecting deep‐seated early osteolytic metastases. [ABSTRACT FROM AUTHOR]

Microfluidic technology is applied across various research areas including organ-on-chip (OOC) systems. The main material used for microfluidics is polydimethylsiloxane (PDMS), a silicone elastomer material that is biocompatible, transparent, and easy to use for OOC systems with well-defined microstructures. However, PDMS-based OOC systems can absorb hydrophobic and small molecules, making it difficult and erroneous to make quantitative analytical assessments for such compounds. In this paper, we explore the use of a synthetic fluoropolymer, poly(4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole-co-tetrafluoroethylene) (Teflon™ AF 2400), with excellent "non-stick" properties to functionalize OOC systems. Cannabinoids, including cannabidiol (CBD), are classes of hydrophobic compounds with a great potential for the treatment of anxiety, depression, pain, and cancer. By using CBD as a testing compound, we examined and systematically quantified CBD absorption into PDMS by means of an LC-MS/MS analysis. In comparison to the unmodified PDMS microchannels, an increase of approximately 30× in the CBD signal was detected with the fluoropolymer surface modification after 3 h of static incubation. Under perfusion conditions, we observed an increase of nearly 15× in the CBD signals from the surface-modified microchannels than from the unmodified microchannels. Furthermore, we also demonstrated that fluoropolymer-modified microchannels are compatible for culturing hCMEC/D3 endothelial cells and for CBD perfusion experiments. [ABSTRACT FROM AUTHOR]

In this work, we discuss the effects of component ratios on plasma characteristics, chemistry of active species, and silicon etching kinetics in CF4 + O2, CHF3 + O2, and C4F8 + O2 gas mixtures. It was shown that the addition of O2 changes electrons- and ions-related plasma parameters rapidly suppresses densities of CFx radicals and influences F atoms kinetics through their formation rate and/or loss frequency. The dominant Si etching mechanism in all three cases is the chemical interaction with F atoms featured by the nonconstant reaction probability. The latter reflects both the remaining amount of fluorocarbon polymer and oxidation of silicon surface. [ABSTRACT FROM AUTHOR]

A new process is reported for the incorporation of a fluoropolymer into a solid perovskite film. Poly(trifluoroethyl methacrylate) [CH2C(CH3)(CO2CH2CF3)]n was delivered to methylammonium lead iodide (CH3NH3PbI3) perovskite films by crystallizing the film in supercritical carbon dioxide/ethanol containing the dissolved fluoropolymer. The surface was characterized before and after fluoropolymer exposure using scanning electron microscopy, Raman spectroscopy, and contact angle measurements. The results indicate that the fluoropolymer was incorporated into the perovskite film during the supercritical fluid crystallization process. The incorporation of a hydrophobic fluoropolymer into perovskite has the potential to improve resistance to environmental degradation. [ABSTRACT FROM AUTHOR]