Additional Fluorine Research Articles

Bio-inspired magnetically induced self-assembling Janus solar evaporator with antifouling and antiscaling properties

Engineering solar evaporators with Janus structures is crucial for facilitating water transition and heat localization to enhance water evaporation efficiency. However, the fragile discontinuous bilayer structures and unavoidable surface fouling significantly hinder their application. Herein, inspired by the Janus structure of Black Amanita mushrooms, we designed a robust solar evaporator with an integrated wood-like and Janus structure using directional freeze-casting and magnetically induced self-assembly of polypyrrole-coated Fe3O4 particles as a build-in photothermal top layer within a hydrophilic matrix, followed by covering it with an additional hydrophobic fluorine layer to simultaneously regulate surface wettability and antifouling properties. Incorporating the hydrophobic fluorine layer onto the solar evaporator not only enhances its water evaporation efficiency via thermal localization effects, but also prevents fouling, salt, and dust scaling accumulation on its surface, facilitating water transportation, thus achieving a groundbreaking performance with the evaporation rate of 2.13 kg m−2 h−1 under one sun irradiation. Moreover, the mechanical performance of the as-prepared solar evaporator can be further optimized by precisely modulating supramolecular interactions within its structure, achieving Young’s modulus over 4 MPa and maintaining structural integrity after the peel-off tests. The fabricated solar evaporator enables highly efficient water purification from artificial seawater, oil-in-water emulsions, and industrial wastewater, providing a rational strategy for designing high-yield solar evaporation systems for wastewater containing complex contaminants.

Low-temperature etching of silicon oxide and silicon nitride with hydrogen fluoride

Etching of high aspect ratio features into alternating SiO2 and SiN layers is an enabling technology for the manufacturing of 3D NAND flash memories. In this paper, we study a low-temperature or cryo plasma etch process, which utilizes HF gas together with other gas additives. Compared with a low-temperature process that uses separate fluorine and hydrogen gases, the etching rate of the SiO2/SiN stack doubles. Both materials etch faster with this so-called second generation cryo etch process. Pure HF plasma enhances the SiN etching rate, while SiO2 requires an additional fluorine source such as PF3 to etch meaningfully. The insertion of H2O plasma steps into the second generation cryo etch process boosts the SiN etching rate by a factor of 2.4, while SiO2 etches only 1.3 times faster. We observe a rate enhancing effect of H2O coadsorption in thermal etching experiments of SiN with HF. Ammonium fluorosilicate (AFS) plays a salient role in etching of SiN with HF with and without plasma. AFS appears weakened in the presence of H2O. Density functional theory calculations confirm the reduction of the bonding energy when NH4F in AFS is replaced by H2O.

Identification of Plant Peroxidases Catalyzing the Degradation of Fluorinated Aromatics Using a Peroxidase Library Approach.

In this work, the degradation of mono- and polyfluorinated phenolic compounds was demonstrated by a series of crude plant peroxidases, including horseradish root (HRP) and six members of the Cucurbita genus. Highly active samples were identified using a library screening approach in which more than 50 crude plant samples were initially evaluated for defluorination activity toward 4-fluorophenol. The highest concentrations were observed in the HRP, pumpkin skin (PKS), and butternut squash skin (BNS), which consistently gave the highest intrinsic rates of decomposition for all the substrates tested. Although HRP exhibited a significant decrease in activity with increased fluorination of the phenolic substrate, PKS showed only minor reductions. Furthermore, in silico studies indicated that the active site of HRP poorly accommodates the steric bulk of additional fluorines, causing the substrate to dock farther from the catalytic heme and thus slowing the catalysis rate. We propose that the PKS active site might be larger, allowing closer access to the perfluorinated substrate, and therefore maintaining higher activity compared to the HRP enzyme. However, detailed kinetic characterization studies of the peroxidases are recommended. Conclusively, the high catalytic activity of PKS and its high yield per gram of tissue make it an excellent candidate for developing environmentally friendly biocatalytic methods for degrading fluorinated aromatics. Finally, the success of the library approach in identifying highly active samples for polyfluorinated aromatic compound (PFAC) degradation suggests the method may find utility in the quest for other advanced catalysts for PFAS degradation.

Strongly bound anions featuring bismuth fluoride building blocks

The stability of polynuclear superhalogen anions composed of BiF5 building blocks was investigated using ab initio electronic structure methods and flexible basis sets. A comprehensive exploration of the ground state potential energy surfaces of (Bi2F11)−, (Bi3F16)− and (Bi4F21)− anions, which can be viewed as comprising BiF5 fragments and an additional fluorine atom, led to the identification of their isomeric structures. It was found that the most stable isomers, predicted to dominate at room temperature, correspond to chain-like extended structures containing BiF6 subunits, with fluorine ligands arranged octahedrally around Bi atoms, sharing F atoms to form Bi–F–Bi bridging linkages. The vertical electron detachment energies of the (BinF5n+1)− anions (n = 1–4) were found to be very high (ranging from 10.91 to 13.36 eV) and increased with the number of bismuth atoms (n) and thus the BiF5 building blocks involved in the structure. Thermodynamic stability of the (BinF5n+1)− anions (i.e., their susceptibility to fragmentation) was also verified and discussed.

Screening of Functional Small Molecules via Modified Machine Learning Strategy toward Efficient All-Inorganic Perovskite Solar Cells.

Organic small molecules are proven to be capable of passivating the bulk/interfacial defects in inorganic perovskite solar cells. Considering the burdensome situation to screen the functional small molecules, we employ a modified machine learning (ML) strategy to guide screening suitable small molecules toward efficient solar cells through three modified ML algorithms to construct the prediction model: (i) random forest algorithm (RF), (ii) support vector machine algorithm (SVR), and (iii) XGBoost. Among them, the XGBoost algorithm displays a better overall predictive performance, whereby the R2 index reaches 0.939. Accordingly, eight small molecules are selected to modify the interface of perovskite films, and both the theoretical and experimental results certify that the difluorobenzylamine with additional fluorine atoms has a better interface modification effect among the small molecules containing functional groups, e.g., the benzene ring and amino group. The high accuracy of the modified machine learning model enables us to simplify the small-molecule screening process and form an important step for ongoing developments in perovskite solar cells and other optoelectronic devices.

Synthesis and herbicidal activities of 2-((3-pyridinyl-2-oxo-2,3-dihydrobenzo[d]thiazol-6-yl)oxy)propionates.

The discovery of lead compounds is fundamental to herbicide innovation, yet the limited availability of valuable lead compounds has impeded their progress in recent years. The study presents a novel molecular scaffold that exhibits remarkably potent herbicidal activity. Through a scaffold-hopping strategy, a highly potent lead compound for herbicides, namely 3-(2-pyridinyl)-benzothiazol-2-one, was unexpectedly discovered during attempts to structurally modify haloxyfop, a commercial aryl-oxy-phenoxy-propionate herbicide. To investigate the structure-activity relationship (SAR) of the newly discovered herbicidal chemicals, a series of 2-(2-oxo-3-(pyridin-2-yl)-2,3-dihydrobenzo[d]thiazol-6-yloxy)propanoic acid derivatives, I-01 ~ I-27, were designed and synthesized. SAR analysis revealed that trifluoromethyl at the 5-position of pyridine is crucial for herbicidal activity, whereas additional fluorine or Cl atom at the 3-position of pyridine significantly enhances activity. Carboxylic ester derivatives exhibit superior herbicidal activity compared with amide derivatives. Moreover, the activity of carboxylic ester derivatives decreases with C chain extension, but the introduction of O atoms in the side chain benefits activity enhancement. Pot experiments conducted in a glasshouse demonstrated that I-01 and I-09 exhibited potent postemergence herbicidal activity against broadleaf weeds, and completely inhibited growth of Amaranthus retroflex, Abutilon theophrasti and Portulaca oleracea at a dosage of 75 g ha-1. Despite the initial goal of scaffold-hopping not being achieved, we have successfully identified a novel molecular scaffold exhibiting exceptional herbicidal activity, thereby presenting innovative prospects for herbicide development. © 2024 Society of Chemical Industry.

Strongly Bound Polynuclear Anions Comprising Scandium Fluoride Building Blocks.

The stability of polynuclear anions composed of ScF3 building blocks was studied by using ab initio and density functional theory electronic structure methods and flexible basis sets. Thorough exploration of ground state potential energy surfaces of (Sc2F7)-, (Sc3F10)-, and (Sc4F13)- anions which may be viewed as comprising ScF3 fragments and the additional fluorine atom led to determining the isomeric structures thereof. It was found that the most stable isomers which are predicted to dominate at room temperature correspond to the compact structures enabling the formation of a large number of Sc-F-Sc bridging linkages rather than to the chain-like structures. The vertical electron detachment energies of the (ScnF3n+1)- anions were found to be very large (spanning the 10.85-12.29 eV range) and increasing with the increasing number of scandium atoms (n) and thus the ScF3 building blocks involved in the structure. Thermodynamic stability of (ScnF3n+1)- anions (i.e., their susceptibility to fragmentation) was also verified and discussed.

One-step synthesis of perfluorinated polyphenylenes using modified Ullmann coupling conditions

Fluorinated compounds have attracted attention in both the pharmaceutical industry and materials science due to the small size and strong electron-withdrawing property of the fluorine atom. In materials science, perfluorinated polyphenylenes play an important role as electron transport layers in organic electronics. While various strategies for the preparation of fluorinated arenes have been reported, the number of synthetic methods available for perfluorinated arenes remains limited, mainly due to the change in reactivity of reagents and substrates at the reaction site upon the introduction of additional fluorine atoms. Given the important applications of perfluorinated polyphenyl-based compounds, this article describes the one-step synthesis of the dendrimer perfluoro-3,3’5,5’-tetrakisphenyldiphenyl-1,1’, which to date no example of a targeted synthesis has been reported in literature, and the synthetic methodology for the direct preparation of linear perfluorinated para-sexiphenyl. Both strategies use starting materials that are either commercially available or can be easily accessed using standard literature methods.

Modification of structure and properties of fluoro-sulfo-sodium alumino-phosphate glass through additional fluorine and sulfur agents

Laser glass has been widely used in laser ignition devices, fundamental physical research, and material processing. In addition to the exploration of the glass composition, the optimization of preparation conditions is also of crucial importance to the performance of laser glass. Herein, the modification effect of additional fluorine and sulfur agents on Nd3+-doped fluoro-sulfo-phosphate glasses (FSP) has been investigated in detail. The contents of F and S were increased by up to 42% and 40% after agent addition. Fluorine and sulfur agents also decrease the non-linear effect and increase the chemical durability of FSP glasses, respectively. Moreover, the local environment around Nd3+ ions is examined by electron paramagnetic resonance (EPR)., The direct connection between Nd-F and the possible connection between Nd3+ and [SO4]2− have been detected with agent addition, which facilitate the promotion of radiation parameters. The emission cross-section and quantum efficiency of FSP glass increase by up to 56% and 54% after agent addition. This study aims to demonstrate the structure and property variations brought by additional agents, providing insight into the optimization of the melting procedure of high-performance FSP laser glasses.

Efficient dialkyl‐difluoro‐substituted quinoxaline‐based medium bandgap polymeric donor for high‐energy‐converting organic solar cells

AbstractA new medium bandgap polymer incorporating electron‐rich 4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b']dithiophene (BDTT) and electron‐deficient 2,3‐didodecyl‐6,7‐difluoro‐5,8‐di(thiophen‐2‐yl)quinoxaline (2TffQ) units in an alternate manner, namely P(BDTT‐2TffQ), was prepared for organic solar cell (OSC) applications. The optical and electrochemical properties of P(BDTT‐2TffQ) were found to be suitable to use it as an electron donor in OSCs. The absorption band covers the region from 300 to 600 nm with an optical bandgap (Eg) of 1.84 eV, and it highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) were found to be positioned at −5.36 and − 3.52 eV. The OSCs prepared by using P(BDTT‐2TffQ):[6,6]‐Phenyl‐C71‐butyric acid methyl ester (PC70BM) and P(BDTT‐2TffQ):2,2′‐((2Z,2'Z)‐((12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile (Y6) blends provided a maximum power conversion efficiency (PCE) of 5.50% and 11.65%, respectively. The differences in the photovoltaic performances of OSCs are mainly attributed to their dissimilar short‐circuit current (Jsc), which depends on their absorption spectrum. Herein, we also compared the properties of P(BDTT‐2TffQ) with a structurally similar polymer, namely P(BDTT‐2TfQ), made up of BDTT and 2,3‐didodecyl‐6‐fluoro‐5,8‐di(thiophen‐2‐yl)quinoxaline (2TfQ) units, for better understanding the effects of the incorporation of additional fluorine atom on the backbone of quinoxaline‐based polymers.

Enhanced photovoltaic performance of D-π-A organic sensitizers by simple fluorination of acceptor unit

A simple and facile molecular modification method is presented to enhance the photovoltaic and photoelectrochemical properties of D- π -A organic sensitizers. This modification is obtained by incorporating fluorine as an additional acceptor unit. By the electron-withdrawing ability of fluorine, the electron transfer to the anchoring group is promoted, which ultimately leads to a decrease in the HOMO-LUMO energy gap. In addition, the incorporated fluorine also induces prominent J -aggregation, resulting in an increase in the dye loading amount on the photoanode. Because of these positive effects, the additional fluorine acceptor enhances both the photocurrent and photovoltage of dye-sensitized solar cells (DSSCs). In particular, electrochemical impedance study reveals that the electron lifetime in the dye-sensitized photoanode also increases by the incorporation of fluorine in the dye molecules, mostly because of enhanced dye loading. • Simple fluorination leads to enhanced photovoltaic property of organic sensitizer. • Electron-withdrawing ability of fluorine extends light absorption range. • Fluorine also induces prominent J -aggregation, resulting in an increased dye loading. • Fluorine greatly enhances the conversion efficiency of DSSCs by about 29%.

Spray pyrolyzed fluorinated inorganic-organic passivation for solution-processed a-InZnO thin-film transistors

Reliability is largely considered an important device requirement for commercial electronic devices. In this work, the reliability of solution-processed amorphous indium zinc oxide (a-IZO) thin-film transistors (TFTs) were evaluated through incorporation of inorganic-organic fluorinated polysilsesquioxane (PSQ:F) passivation deposited through spray pyrolysis (SP) and spin coating (SC) techniques. The barrier property of SP and SC PSQ:F passivation layers were examined under positive and negative bias stress tests and both devices revealed superior stability with smaller threshold voltage shift of 0.9 V/−0.4 V and 1.0 V/−0.2 V respectively, after 10000 s. In addition, both PSQ:F films were confirmed to have an excellent hydrophobic property compared to a-IZO film hindering moisture adsorption. Futheremore, XRR data demonstrates that through SP deposition technique, higher density PSQ:F passivation layer was achieved which inhibits the interaction between the ambient atmosphere and the exposed back-channel region efficiently. Enhancement in the reliability and electrical performance of a-IZO TFTs were achieved through combination of additional fluorine additives from PSQ:F with spray pyrolysis deposition technique.

Electrochemical Reduction and Oxidation of Ruddlesden–Popper-Type La2NiO3F2 within Fluoride-Ion Batteries

Within this article, it is shown that an electrochemical defluorination and additional fluorination of Ruddlesden–Popper-type La2NiO3F2 is possible within all-solid-state fluoride-ion batteries. St...

Mechanistic Study of Potent Fluorinated EGFR Kinase Inhibitors with a Quinazoline Scaffold against L858R/T790M/C797S Resistance Mutation: Unveiling the Fluorine Substituent Cooperativity Effect on the Inhibitory Activity.

Fluorination has considerable potential with regard to the design of kinase inhibitors for anticarcinoma therapy. It was recently reported that fluorination increases the potency of inhibitors of the epidermal growth factor receptor (EGFR), mutations of which have been linked specifically to nonsmall-cell lung cancer. For the L858R/T790M/C797S triplet mutant (EGFRTM), a difluorinated inhibitor, 25g, was found to have 4.23 times greater potency against the EGFRTM than an unfluorinated inhibitor, 25a. This discovery necessitates a rational explanation for the underlying inhibitory mechanisms. Here, we apply multiple computational approaches to explore, validate, and differentiate the binding modes of 25a and 25g in the EGFRTM and investigate the cooperativity effect of fluorine substituents on the inhibitory activity. Our results showed that the EGFRTM in the presence of 25g undergoes a series of conformational changes that favor inhibitor binding to both the active and allosteric sites. Further, the cooperativity effect of fluorine substituents is positive: the complex stability is increased by each additional fluorine substituent. Estimated binding free energies show good correlation with the experimental biological activity. Subsequently, the decomposition energy analysis revealed that the van der Waals interaction is the principal force contributing to variations in the binding affinities of 25a and 25g to the EGFRTM. Per-residue energy-based hierarchical clustering analysis suggests that three hot-spot residues, L718, K745, and D855, are the key in achieving optimal binding modes for 25g with higher affinity in the EGFRTM compared to 25a. This study provides a rationale for the superior EGFRTM-inhibitory potency exhibited by 25g over 25a, which is expected to be useful for the future rational structure-based design of novel EGFRTM inhibitors with improved potency and selectivity.

Effects of Plasma Treatment on the Composition and Phase Changes of Sputter-Deposited SnOx Thin Films.

This study examined the effects of the plasma treatment of CF₄ or SF6 on the properties of tin oxide (SnOx) thin films prepared at room temperature using a radio frequency sputtering technique. The properties of the samples were characterized by dynamic-secondary ion mass spectrometry, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Hall Effect measurements. All untreated samples showed Sn4+ and Sn2+ XPS peak area percentages of 57.6 and 34.6%, respectively, indicating a larger amount of SnO₂ phase in the samples than SnO. The samples treated with CF₄ plasma exhibited the maximum and minimum Sn4+ and Sn2+ peak areas, respectively, at a treatment time of 35 s. This was attributed to the maximum oxygen atomic percentage at 35 s and the injection of additional carbon and fluorine into the sample with increasing treatment time. On the other hand, in the case of samples treated with SF6 plasma, the Sn4+ peak area increased with increasing treatment time while the Sn2+ peak area decreased. This suggests that SnO₂ is a stronger phase for samples treated with SF6 plasma for a longer duration. Furthermore, the changes in the Sn4+ and Sn2+ peak areas of the samples treated with CF₄ plasma were much larger than those of the samples treated with SF6 plasma, which indicates that CF₄ plasma has a larger impact on the properties of the samples. This difference in impact showed a correlation with the sharper decrease in the number of oxygen vacancies for CF₄ plasma-treated samples. These results were attributed to the introduction of additional fluorine and carbon into CF₄ plasma-treated samples compared to the SF6 plasma-treated ones. In addition, XRD showed that the plasma treatment did not affect the amorphous phase in the samples.

A computational study of anisotropic charge transport in air-stable fluorinated benzobisbenzothiophene (FBBBT) derivatives.

A computational study of anisotropical charge transport properties of fluorinated benzobisbenzothiohphene derivatives (FBBBT) is presented. The values of IPadia of all FBBBTs are found in the range of 6.00-6.20 eV inferring the fact that the investigated compounds have ambient air-stability. In addition, the energy levels of FBBBT s are found to be lower than those of benzobisbenzothiophene (BBBT) compound indicating higher charge carrier stability in the former. Hirshfield surface analyses showed that, in all the studied compounds, the principal identifiable interaction were mostly due to F⋯H and H⋯H intermolecular couplings with no contribution from S⋯S bondings. The calculated maximum μhole(μelec) value of the compounds FBBBT-a and FBBBT-b was found to be 0.483 (0.794) cm2V- 1s- 1 and 0.688 (0.542) cm2V- 1s- 1 respectively in the direction of transistor channel (Φ = 93.39 ∘(273.30∘) for FBBBT-a and Φ = 92.24 ∘/272.72 ∘ for FBBBT-b). For FBBBT-c, the maximum μelec(μhole) value of 0.933 (0.233) cm2V- 1s- 1 appeared for Φ = 0 ∘/179.90 ∘. In addition, the compounds FBBBT-a and FBBBT-b possess two additional fluorine atoms attached at the X positions in the backbone, which result in an increment in μelec values (1.4 times and 0.78 times higher than μhole) in these two compounds at a particular crystal direction.

The role of charge transfer at reduced graphene oxide/organic semiconductor interface on the charge transport properties

The effect of 1-pyrenesulfonicacid sodium salt (1-PSA), tetracyanoethylene (TCNE) and tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) on charge transport properties of reduced graphene oxide (RGO) is examined by measuring the transfer characteristics of field-effect transistors and co-planar time-of-flight photocurrent technique. Evidence of p-type doping and a reduction of mobility of electrons in RGO upon deposition of these materials is observed. Time-resolved photocurrent measurements show a reduction in electron mobility even at submonolayer coverage of these materials. The variation of transit time with different coverages reveals that electron mobility decreases with increasing the surface coverage of 1-PSA, TCNE and F4-TCNQ to a certain extent, while at higher coverage the electron mobility is slightly recovered. All three molecules show the same trend in charge carrier mobility variation with coverage, but with different magnitude. Among all three molecules, 1-PSA acts as weak electron acceptor compared to TCNE and F4-TCNQ. The additional fluorine moieties in F4-TCNQ provides excellent electron withdrawing capability compared to TCNE. The experimental results are consistent with the density functional theory calculations. • RGO FETs, exhibit a positive shift of the charge-neutrality point due to deposition of organic semiconductor layer. • The amount of shift varies with the molecule electron affinity. • The electron mobility is quenched by the presence of F4-TCNQ and TCNE, while 1-PSA don’t affect the electron mobility. • With increasing the coverage of 1-PSA, the electron mobility drops and then slightly recovers at higher coverages. • The change in the electron mobility is due to effect of teh RGO/organic-layer interface dipole field.

β-Fluorofentanyls Are pH-Sensitive Mu Opioid Receptor Agonists.

The concept recently postulated by Stein and co-workers (Science 2017, 355, 966) that mu opioid receptor (MOR) agonists possessing amines with attenuated basicity show pH-dependent activity and can selectively act at damaged, low pH tissues has been additionally supported by in vitro studies reported here. We synthesized and tested analogs of fentanyl possessing one or two fluorine atoms at the beta position of the phenethylamine side chain, with additional fluorines optionally added to the benzene ring of the side chain. These compounds were synthesized in 1 to 3 steps from commercial building blocks. The novel bis-fluorinated analog RR-49 showed superior pH sensitivity, with full efficacy relative to DAMGO, but with 19-fold higher potency (IC50) in a MOR cAMP assay at pH 6.5 versus 7.4. Such compounds hold significant promise as analgesics for inflammatory pain with reduced abuse potential.

The Geochemistry of Phosphorite and Associated Rocks of Akashat Formation (Middle Paleocene) in Akashat Mine, Iraqi Western Desert. Part I: Major Oxides

The phosphatic compounds in the phosphorites of Akashat Formation (Middle Paleocene) are mainly composed of francolite. The associated rocks (phosphatic limestone) consist of calcite and francolite. As well as, there are little amounts of dolomite, palygorskite, quartz and iron oxides. Francolite is composed of Ca, P, F and O, the tetrahedron SO4 and planar CO3 as CO3+F substitute PO4. Some of Na and Mg are substituted in both sites Ca(I) and Ca(II). F occupied its sites in the channel. Some F subsititute O in CO3 to form the pseudo-tetrahedron of CO3+F. The elements Si, Al, Mg, Fe and K represent the clay minerals; montmorillonite, palygorskite and sepiolite, as well as, quartz and iron oxides. The geochemistry of phosphorite reflects the primary neoformation conditions of marine apatite (francolite) from calcium, phosphate and fluorine, in addition to the substitution of positive mono- and di- valance cations for calcium in Ca(I) in submarine mud of the oceanic floor. The phosphate deposits were exposed to winnowing and transporting by upwelling currents to the continental shelf area. This led the phosphatic deposits to be affected by early and late chemical and biochemical diagenetic processes, causing activities in substitution of cations for calcium in Ca(II) and carbonate, also, additional fluorine and sulfates for phosphate. The flow of continental water to near-shore area, whose content is magnesium leading to remineralization of clay minerals, (e.g. palygorskite and sepiolite from montmorillonite) by depleting magnesium from sea water, as well as the activity of microorganism, all that is provided by suitable growth conditions for phosphatic compounds in continental shelf area.

Additional fluorine abundance determinations in evolved stars

We present new fluorine abundance measurements for a sample of carbon-rich asymptotic giant branch (AGB) stars and two other metal-poor evolved stars of Ba/CH types. The abundances are derived from IR, K-band, high-resolution spectra obtained using GEMINI-S/Phoenix and TNG/Giano-b. Our sample includes an extragalactic AGB carbon star belonging to the Sagittarius dSph galaxy. The metallicity of our stars ranges from [Fe/H] = 0.0 down to − 1.4 dex. The new measurements, together with those previously derived in similar stars, show that normal (N-type) and SC-type AGB carbon stars of near solar metallicity present similar F enhancements, discarding previous hints that suggested that SC-type stars have larger enhancements. These mild F enhancements are compatible with current chemical-evolution models pointing out that AGB stars, although relevant, are not the main sources of this element in the solar neighbourhood. Larger [F/Fe] ratios are found for lower-metallicity stars. This is confirmed by theory. We highlight a tight relation between the [F/⟨s⟩] ratio and the average s-element enhancement [⟨s⟩/Fe] for stars with [Fe/H] > −0.5, which can be explained by the current state-of-the-art low-mass AGB models assuming an extended 13C pocket. For stars with [Fe/H] < −0.5, discrepancies between observations and model predictions still exist. We conclude that the mechanism of F production in AGB stars needs further scrutiny and that simultaneous F and s-element measurements in a larger number of metal-poor AGB stars are needed to better constrain the models.