Polyfluoroalkylation of 2-Aminothiazoles： Unexpected sp3 C CI Substitution under Mild Conditions

An efficient, highly selective method for polyfluoroalkylation of 2-aminothiazole derivatives was described. Specifically, a di-polyfluoroalkylated derivative was produced when 2-amino-4-chloromethylthiazole was reacted with perfluoroalkyl iodides under very mild conditions.

PFAS及含氟气体管控下环保绝缘气体研究与电力装备应用展望

全球气候变化背景下,SF6的使用将受到更严格的限制。以C_(4)F_(7)N和C_(5)F_(10)O等为代表的低全球变暖潜在值(global warming potential,GWP)、高绝缘强度气体得到了广泛关注,相关高压电气装备已在多个国家推广应用。然而随着2019年《斯德哥尔摩公约》的签署,世界多国逐步出台了针对全氟烷基和多氟烷基物质(polyfluoroalkylsubstances,PFAS)以及含氟气体限制使用的法规和标准,以美国和欧盟为代表的激进PFAS政策也间接导致3M公司计划于2025年底累计停产包括C_(4)F_(7)N、C_(5)F_(10)O在内的58种含氟物质。为此,该文深入剖析PFAS及含氟气体管控背景下环保绝缘气体与装备发展面临的挑战,阐述相关政策对我国气体绝缘装备低碳发展的影响,指出氟碳类环保绝缘气体的全生命周期管控标准的制定及应用监管规范化是目前的重要工作,并对新型绝缘气体分子设计方法、绝缘与放电理论、工程应用技术及产品研发等方面的未来发展进行展望,以期为我国环保电力装备研发及相关政策的制定提供参考。

PFAS: Ecological Implications, Remedial Actions and Ethical Considerations

The C-F bond is one of the strongest in organic chemistry. It is responsible for the great stability of perfluoroalkyl and polyfluoroalkyl substances, commonly referred to as “PFAS”, a group of man-made chemicals that include perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). Thermal stability, surface activity, dielectric characteristics, chemical resistance, and inertness are just a few of the technical advantages that this group has over hydrocarbons, and since the 1950s, these chemicals have been largely utilized in a variety of domestic and industrial endeavors. The hydrophilic and lipophilic nature of this class of chemicals accounts for its uniqueness. Up until today, the chemistry and ecotoxicology of these chemicals continue to emerge. Issues concerning the destructive power of ignorance expedited by an ineffective regulatory institution continue to show that manufacturing chemicals are insufficient without giving serious thought to issues of openness and humanity’s awareness of its own safety. When discussing the nature of humanity and how it can be defined or redefined, it is important to allude to the significance of integrating business with ethics in its various forms. This paper highlights the importance of holding polluters accountable for PFAS contamination cleanup costs while emphasizing the need for chemical manufacturers to test and disclose the health and environmental effects of PFAS compounds. In addition, the sources, types, properties, applications, distribution, toxicological implications, regulations, and analytical methods associated with PFAS (per- and polyfluoroalkyl substances) are explored. The effectiveness of the remedial methods described in this paper needs to be progressively tested while exploring other sustainable approaches.

PFAS: Ecological Implications, Remedial Actions and Ethical Considerations

The C-F bond is one of the strongest in organic chemistry. It is responsible for the great stability of perfluoroalkyl and polyfluoroalkyl substances, commonly referred to as “PFAS”, a group of man-made chemicals that include perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). Thermal stability, surface activity, dielectric characteristics, chemical resistance, and inertness are just a few of the technical advantages that this group has over hydrocarbons, and since the 1950s, these chemicals have been largely utilized in a variety of domestic and industrial endeavors. The hydrophilic and lipophilic nature of this class of chemicals accounts for its uniqueness. Up until today, the chemistry and ecotoxicology of these chemicals continue to emerge. Issues concerning the destructive power of ignorance expedited by an ineffective regulatory institution continue to show that manufacturing chemicals are insufficient without giving serious thought to issues of openness and humanity’s awareness of its own safety. When discussing the nature of humanity and how it can be defined or redefined, it is important to allude to the significance of integrating business with ethics in its various forms. This paper highlights the importance of holding polluters accountable for PFAS contamination cleanup costs while emphasizing the need for chemical manufacturers to test and disclose the health and environmental effects of PFAS compounds. In addition, the sources, types, properties, applications, distribution, toxicological implications, regulations, and analytical methods associated with PFAS (per- and polyfluoroalkyl substances) are explored. The effectiveness of the remedial methods described in this paper needs to be progressively tested while exploring other sustainable approaches.

A Convenient Method of Polyfluoroalkyl-lactonization

A novel synthesis of polyfluoroalkyl substituted -butyrolactones from the reaction of polyfluoroalkyl iodides with 4-pentenoic acid initiated with sodium dithionite was realized in good yields.

STUDIES ON POLYHALOALKANES Ⅳ. THE REACTION OF POLYFLUOROALKYL IODIDES WITH SILVER(I) SALTS

The conversion of polyfluoroalkyl iodides into the corresponding carboxylic acids by the reaction with silver (I) salts is described.

Distribution of per-and polyfluoroalkyl substances in blood,serum,and urine of patients with liver cancer and associations with liver function biomarkers

Studies have shown that per-and polyfluoroalkyl substances(PFASs)may be hepatotoxic in animals or humans.However,data on clinical epidemiology are very limited.In this study,21PFASs were determined in patients with liver diseases,with the highest median concentrations detected in the serum sample(26.7 ng/mL),followed by blood(10.7 ng/mL)and urine(5.02 ng/mL).Higher total PFAS concentrations were found in hepatocellular carcinoma(HCC)patients compared to non-HCC patients,with significant discrepancies in serum and blood samples.Besides,significant correlations were also found among PFAS concentrations and age,gender,body mass index(BMI),and liver function biomarkers levels.For example,PFAS concentrations are significantly higher in males than in females;Several serum PFASs concentrations increase with age and BMI,while the serum perfluorohexane sulfonic acid(PFHxS)concentrations are negatively correlated with age.In addition,multiple regression models adjusted for age,gender and BMI found that increased serum perfluorobutane sulfonic acid(PFBS),perfluoroheptane sulfonic acid(PFHpS)and perfluorohexylphosphonic acid(PFHxPA)conentrations are correlated with elevated alkaline phosphatase(ALP),aspartate aminotransferase(AST),and alpha-fetoprotein(AFP)(p<0.05).Our results provide epidemiological support for the future study on the potential clinical hepatotoxicity of PFAS.

Occurrence,Spatial Distribution,Sources and Risk Assessment of Per-and Polyfluoroalkyl Substances in Surface Sediments of the Yellow River Delta Wetland

Per-and polyfluoroalkyl substances(PFASs)are emerging persistent organic pollutants(POPs).In this study,47 surface sediment samples were collected from the Yellow River Delta wetland(YRDW)to investigate the occurrence,spatial distribution,potential sources,and ecological risks of PFASs.Twenty-three out of 26 targeted PFASs were detected in surface sediment samples from the YRDW,with totalΣ23PFASs concentrations ranging from 0.23 to 16.30 ng g^(-1) dw and a median value of 2.27 ng g^(-1) dw.Perfluorooctanoic acid(PFOA),perfluorobutanoic acid(PFBA)and perfluorooctanesulfonic acid(PFOS)were the main contaminants.The detection frequency and concentration of perfluoroalkyl carboxylic acids(PFCAs)were higher than those of perfluoroal-kanesulfonic acids(PFSAs),while those of long-chain PFASs were higher than those of short-chain PFASs.The emerging PFASs substitutes were dominated by 6:2 chlorinated polyfluoroalkyl ether sulfonic acid(6:2 Cl-PFESA).The distribution of PFASs is significantly influenced by the total organic carbon content in the sediments.The concentration of PFASs seems to be related to human activities,with high concentration levels of PFASs near locations such as beaches and villages.By using a positive matrix factorization model,the potential sources of PFASs in the region were identified as metal plating mist inhibitor and fluoropolymer manufacturing sources,metal plating industry and firefighting foam and textile treatment sources,and food packaging material sources.The risk assessment indicated that PFASs in YRDW sediments do not pose a significant ecological risk to benthic organisms in the region overall,but PFOA and PFOS exert a low to moderate risk at individual stations.

Non-conventional sorption materials for the removal of legacy and emerging PFAS from water:A review

Per-and polyfluoroalkyl substances(PFAS)are a class of ubiquitous,persistent,and hazardous pollutants that raise concerns for human health and the environment.Typically,PFAS removal from water relies on adsorption techniques using conventional sorption materials like activated carbons(ACs)and ion exchange resins(IERs).However,there is a continuous search for more efficient and performing adsorbent materials to better address the wide range of chemical structures of PFAS in the environment,to increase their selectivity,and to achieve an overall high adsorption capacity and faster uptake kinetics.In this context,results from the application of non-conventional sorption materials(i.e.,readily available biological-based materials like proteins and advanced materials like nanocomposites and cyclodextrins)are reported and discussed in consideration of the following criteria:i)removal efficiency and kinetics of legacy PFAS(e.g.,PFOA,PFBA)as well as newly-introduced and emerging PFAS(e.g.,GenX),ii)representativity of environmental conditions in the experimental setup(e.g.,use of environmentally relevant experimental concentrations),iii)regenerability,reusability and applicability of the materials,and iv)role of the material modifications on PFAS adsorption.From this review,it emerged that organic frameworks,nano(ligno)cellulosic-based materials,and layered double hydroxides are among the most promising materials herein investigated for PFAS adsorption,and it was also observed that the presence of fluorine-and amine-moieties in the material structure improve both the selectivity and PFAS uptake.However,the lack of data on their applicability in real environments and the costs involved means that this research is still in its infancy and need further investigation.

Emergency of per-and polyfluoroalkyl substances in drinking water:Status,regulation,and mitigation strategies in developing countries

The detection of per-and polyfluoroalkyl substances(PFAS)in water presents a significant challenge for developing countries,requiring urgent attention.This review focuses on understanding the emergence of PFAS in drinking water,health concerns,and removal strategies for PFAS in water systems in developing countries.This review indicates the need for more studies to be conducted in many developing nations due to limited information on the environmental status and fate of PFAS.The health consequences of PFAS in water are enormous and cannot be overemphasized.Efforts are ongoing to legislate a national standard for PFAS in drinking water.Currently,there are few known mitigation efforts from African countries,in contrast to several developing nations in Asia.Therefore,there is an urgent need to develop economically viable techniques that could be integrated into largescale operations to remove PFAS from water systems in the region.However,despite the success achieved with removing long-chain PFAS from water,more studies are required on strategies for eliminating short-chain moieties in water.

Influence of microplastics on the photodegradation of perfluorooctane sulfonamide (FOSA)

PFAS(per-and polyfluoroalkyl substances)are omnipresent in the environment and their transportation and transformation have attracted increased attention.Microplastics are another potential risk substances that can serve as a carrier for ubiquitous pollutants,thus affecting the presence of PFAS in the environment.In this study,the adsorption of perfluorooctane sulfonamide(FOSA)and perfluorooctanoic acid(PFOA)on four microplastics(PE,PVC,PS,and PTFE)and their effect on the photodegradation of FOSA were studied.The adsorption capacity of FOSA by PS was the highest,in similar,PS displayed the highest adsorption capacity in the presence of PFOA.Different effects of pH and salinity on the adsorption of FOSA and PFOA were observed among different microplastics indicating inconsistent interaction mechanisms.Furthermore,FOSA could be photodegraded,with PFOA as the main product,while the presence of microplastics had a negligible effect on the degradation of this contaminant.The results indicated that microplastics could act as PFAS concentrators.Moreover,their photochemical inertiasmake the pollutants enriched onmicroplastics more resistant to degradation.

Recent Advances in the Analytical Techniques for PFASs and Corresponding Intermediates During Their Chemical Decomposition

Per-and polyfluoroalkyl substances(PFASs)have been restricted from production and consumption in many countries due to their persistence and biological toxicity.With the development of removal technologies,the requirement on the detection of different kinds of PFASs and their derivates is increasing.A suitable analytical method is the prerequisite and basis for the study of the degradation of PFASs.As various analytical methods have been reported,questions about which one is more suitable have arisen.It is a right time to summarize the past and suggest the future.In this paper,we summarized and discussed the analytical methods applied in the chemical degradation of PFASs.We also proposed the current problems and discussed the future directions in this field.

Distribution characteristics of poly-and perfluoroalkyl substances in the Yangtze River Delta

In this work, a method was developed and optimized for the analysis of polyfluoroalkyl and/or perfluoroalkyl substances（PFASs） content in surface water and sediment samples with high instrumental response and good separation. Surface water and sediment samples were collected from the Yangtze River Delta（YRD） to analyze the distribution characteristics of perfluoroalkyl carboxylic acids（PFCAs）, perfluoroalkane sulfonic acids（PFSAs）, perfluoroalkyl phosphonic acids（PFPAs）, perfluoroalkyl phosphinic acids（PFPiAs）, and polyfluoroalkyl phosphoric acid diesters（di PAPs）. The results showed that the total concentrations of PFCAs and PFSAs in YRD varied from 31 to 902 ng/L. PFCAs（≥ 11 carbons） and PFSAs（≥ 10 carbons atoms） were not detected in any surface water samples. The mean concentrations of all PFCAs and PFSAs in surface water from the sampling areas decreased in the following order：Yangtze river（191 ng/L） ≈ Taihu lake（189 ng/L） 〉 Huangpu river（122 ng/L） ≈ Qiantang river（120 ng/L） 〉 Jiaxing urban river（100 ng/L）. Strong significant（p 〈 0.05） correlations between the concentrations of many of the compounds were found in the sampling areas, suggesting a common source for these compounds. Only perfluorooctanoic acid（PFOA） was observed in all sediment samples, at concentrations varying from 0.02 to 1.35 ng/g. Finally, detection rates of two di PAPs were only 8% and 10%, respectively and the concentration of di PAPs was two to three times lower compared to PFCAs and PFSAs.

Determination of polyfluoroalkyl compounds in water and suspended particulate matter in the river Elbe and North Sea,Germany

The distribution of polyfluoroalkyl compounds(PFCs)in the dissolved and particulate phase and their discharge from the river Elbe into the North Sea were studied.The PFCs quantified included C_(4)-C_(8) perfluorinated sulfonates(PFSAs),6∶2 fluorotelomer sulfonate(6∶2 FTS),C_(6) and C_(8) perfluorinated sulfinates(PFSiAs),C_(4)-C_(12) perfluorinated carboxylic acids(PFCAs),perfluoro-3,7-dimethyl-octanoic acid(3,7m_(2)-PFOA),perfluorooctane sulfonamide(FOSA),and n-ethyl perfluroctane sulfonamidoethanol(EtFOSE).PFCs were mostly distributed in the dissolved phase,where perfluorooctanoic acid(PFOA)dominated with 2.9–12.5 ng/L.In the suspended particulate matter FOSA and perfluorooctane sulfonate(PFOS)showed the highest concentrations(4.0 ng/L and 2.3 ng/L,respectively).The total flux ofΣPFCs from the river Elbe was estimated to be 802 kg/year for the dissolved phase and 152 kg/year for the particulate phase.This indicates that the river Elbe acts as a source of PFCs into the North Sea.However,the concentrations of perfluorobutane sulfonate(PFBS)and perfluorobutanoic acid(PFBA)in the North Sea were higher than that in the river Elbe,thus an alternative source must exist for these compounds.

Maternal exposure to specific perfluoroalkyl substances is associated with increasing blood glucose in pregnant women

Imagine if a group of toxic substances that increase oxidative stress and disrupt glucose and lipid metabolism have been broadly used worldwide for applications such as repellent,food packaging,and non-stick frying pan coatings.Now imagine if some of these substances have half-lives as long as 3-8 years.

The occurrence of per-and polyfluoroalkyl substances(PFASs) in fluoropolymer raw materials and products made in China

Perfluorooctanoic acid(PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019.In this study, the occurrence of residues of PFOA and other per-and polyfluoroalkyl substances(PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time.The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10^(6) ng/g, and <MDL(method detection limit) to 5.3 × 10^(3) ng/g,respectively.Generally, the levels of PFOA in raw materials were higher than in products,implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps.By tracking a company’s polytetrafluoroethylene(PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10^(6) to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued.High concentrations of HFPO-TrA(2.7 × 10^(5) to 8.2 × 10^(5) ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.

Interaction and combined toxicity of microplastics and per-and polyfluoroalkyl substances in aquatic environment

Microplastics(MPs)are recognized as vectors for the transport of organic contaminants in aquatic environments in addition to their own adverse effects on aquatic organisms.Per-and polyfluoroalkyl substances(PFASs)are widely present in aquatic environments due to their widespread applications,and thus coexist with MPs.Therefore,we focus on the interaction of MPs and PFASs and related combined toxicity in aquatic environments in this work The adsorption of PFASs on MPs is critically reviewed,and new mechanisms such as halogen bonding,π-πinteraction,cation-πinteractions,and micelle formation are proposed.Moreover,the effect of MPs on the transport and transformation of PFASs in aquatic environments is discussed.Based on four typical aquatic organisms(shellfish,Daphnia,algae,and fish),the toxicity of MPs and/or PFASs at the organismal or molecular levels is also evaluated and summarized.Finally,challenges and research perspectives are proposed,and the roles of the shapes and aging process of MPs on PFAS biogeochemical processes and toxicity,especially on PFAS substitutes,are recommended for further investigation.This review provides a better understanding of the interactions and toxic effects of coexisting MPs and PFASs in aquatic environments.

Design,synthesis and insecticidal activities of novel anthranilic diamides containing polyfluoroalkyl pyrazole moiety

In order to discover new molecules with good insecticidal activities, a series of anthranilic diamides containing polyfluoroalkyl pyrazole were designed and synthesized, and their structures were characterized by1 H NMR and HRMS. Bioassays demonstrated that some of the title compound exhibited excellent insecticidal activities. The larvicidal activities of compound 8a, 8c, 8g, 8k and 8l against Mythimna separata Walker were 100% at 0.8 mg/L. The insecticidal activities of compound 8a, 8c,8e, 8g, 8k and 8l against Plutella xylostella Linnaeus were 100% at 0.4 mg/L. Surprisingly compounds 8a and 8c still showed 100% larvicidal activities against Plutella xylostella Linnaeus at 0.08 mg/L comparable to the commercialized Chlorantraniliprole. The LC_（50） of compound 8a and 8c against M. separata is 0.048 and 0.043 mg/L respectively.

Temporal trends of per-and polyfluoroalkyl substances(PFAS)in the influent of two of the largest wastewater treatment plants in Australia

Per-and polyfluoroalkyl substances(PFAS)are found ubiquitously in wastewater treatment plants(WWTPs)due to their multiple sources in industry and consumer products.In Australia,limited spatial data are available on PFAS levels inWWTPs influent,while no temporal data have been reported.The aim of this study was to investigate the occurrence and temporal trend of PFAS in the influent of two large WWTPs in Australia(WWTP A and B)over a four-year period.Daily influent samples were collected over one week at different seasons from 2014 to 2017.Eleven perfluoroalkyl acids(PFAA)(i.e.seven perfluoroalkyl carboxylic acids(PFCAs)and four perfluoroalkyl sulfonic acids(PFSA))were detected with mean S11PFAA concentrations of 57±3.3e94±17 ng/L at WWTP A,and 31±6.1e142±73 ng/L at WWTP B.The highest mean concentrations were observed for perfluorohexanoate(PFHxA)(20±2 ng/L)in WWTP A,and perfluorooctane sulfonate(PFOS)(17±13 ng/L)in WWTP B.The precursor 6:2 fluorotelomer sulfonate was detected over five sampling periods from Aug 2016 to Oct 2017,with mean concentrations of 37±18e138±51 ng/L for WWTP A and 8.8±4.5e29±5.1 ng/L for WWTP B.Higher concentration of 6:2 FTS(1.8e11 folds)than those of PFOA and PFOS in WWTP A indicate a likely substitution of C8 PFAA by fluorotelomer-based PFAS in this catchment.Temporal trends(annual and seasonal)in per-capita mass load were observed for some PFAA,increasing for PFPeA,PFHxA,PFHpA,PFNA,and PFHxS,while decreasing for PFBS and PFOS in either WWTPs.Notably,elevated levels of PFOS in October 2017 were observed at both WWTPs with the highest per capita mass load of up to 67 mg/day/inhabitant.For some PFAS release trends,longer sampling periods would be required to achieve acceptable statistical power.

A two-step approach to 2-polyfluoroalkyl quinolines from N-aryl polyfluoroalkyl imidoyl iodides

2-Polyfluoroalkyl quinoline derivatives were synthesized from the enaminones which were obtained from the reaction of FT-aryl polyfluoroalkyl imidoyl iodides with methyl ketones.