Surface Perfluoroalkyl Chains Segregation: A Tool for Reducing Calcium Deposits in Medical Grade Poly(Methyl Methacrylate)

Intraocular lenses can be manufactured from a wide variety of polymers, but due to the lost cost associated with the use of Poly (methyl methacrylate) (PMMA), it is still the preferred material used in the developing countries. However, a major drawback to its use is the build-up of calcium containing deposits that are formed on the intraocular lens over a period of time. In an attempt to hinder this deposition, surface modification of medical grade PMMA has been carried out using perfluoroalkyl chain (1,2,4-trifluoro-3-(C10F21CH2O)-7-(N,N)-dimethylaminoacridine) segregation. The segregation was explored using a 1% 1,2,4-trifluoro-3-(C10F21CH2O)-7-(N,N)-dimethyla-minoacridine in two methods: film casting and spin-coating, a thin film onto preformed PMMA discs. Both methods were compared against control PMMA to determine which method provided the best hindrance against calcium containing deposits when immersed in a simulated aqueous humour solution. Characterisation of the surface using scanning electron microscopy coupled with energy;dispersive x-ray analysis indicated that the surface segregation of perfluoroalkyl chains had hindered calcification in both methods. This pleminary research shows promising results of employing perfluoroalkyl chains in the surface segregation of biomaterials that can be employed in intraocular lenses.

A NEW CONVENIENT METHOD FOR THE SYNTHESIS OF PERFLUOROALKYL 2H-PYRROLE

The reaction between 2,5-Dimethylpyrrole (1) and R_FI (2)(R_F: a, Cl(CF_2)_4; b, Cl(CF_2)_6; c, Cl(CF_2)_8; d, n-C_6F_(13); e, n-C_8F_(17)) in the presence of Na_2S_2O_4-NaHCO_3 in acetonitrile resulted in the formation of 2-perfluoroalkyl-2,5-dimethyl-2H-pyrrole (3) as a major product in good yield.

NEW METHOD FOR GENERATION OF t-BUTYL PERFLUOROALKYL NITROXIDES

Electron transfer reactions between O-benzoyl t-butylhydroxyl- amine,t-BuNHOCOPh(1)and perfluorodiacyl peroxides(RfCO_2)_2(2)may serve as a novel method for generating useful t-hutyl perfluoroalkyl nitroxldes at room temperature in CFCl2-CF2Cl.

SYNTHESIS OF ACYCLIC ANALOGS OF BENZOTRIAZOLE AND INDOLE NUCLEOSIDE CONTAINING PERFLUOROALKYL GROUP

1-[(2-hydroxyethoxy)methyl]benzotriazole and -indole containing perfluoroalkyl group have been synthesized.

Meta-Analysis on the associations between Prenatal Perfluoroalkyl Substances Exposure and Adverse Birth Outcomes

The epidemiological associations between the prenatal perfluoroalkyl substances(PFASs)exposure and the reproductive outcomes remain controversial.A continuous evaluation is needed to combine the inconsistent results.In this study,we explored the associations between PFASs exposure and the low birth weight(LBW),preterm birth and small for gestational age(SGA).The quality of selected literature,quantitative estimates,publication bias and subgroup analysis were performed on the basis of 17 retrieved articles published before December 2020.The results showed a significant positive association between the perfluorooctane sulfonate(PFOS)exposure and the risk of LBW[Odds ratio(OR)=1.17;95%confidence interval(CI):1.01,1.36;heterogeneity:P=0.30,I2=17%].The positive association was also observed between the PFOS and the risk of preterm birth(OR=1.19;95%CI:1.01,1.39,P=0.007;I2=62%).There was a paucity of evidence regarding the negative effects of perfluorooctanoic acid(PFOA),perfluorohexanesulfonic acid(PFHxS)and perfluorononanoic acid(PFNA)on the pregnancy outcomes.The findings from the subgroup analysis(the sampling period,the birth gender and biologic specimens)did not substantially altered the results of the overall pooled estimate ORs.The increased prevalence of negative birth outcomes with gestational PFASs exposure warrants further explorations from biological process perspective.

Chemistry and Application of Phosphonium and Arsonium Ylide(ⅩⅧ)——Stereoselective Syntheses of (Z)-3-Perfluoroalkyl--4-(3-Carboethoxy-2-f uranyl )-3-Butenoates

The stereoselective syntheses of (Z)-methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-3-butenoates 5a-c were investigated. The reaction of (3-carboethoxy-2-fu-ranyl)-methyltriphenylphosphonium bromide 1 with methyl 2-perfluoroalkynoates 2a-c in the presence of K2CO3 at room temperature gives two adducts, (E)-methyl 3-per-fluoroalkyl-4-( 3-carboethoxy-2-furanyl )-2-triphenylphosphoranylidene-3-butenoates 3a-c and (E)-methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-4-triphenylphos-phoranylidene-2-butenoates 4a-c. (Z)-Methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-3-butenoates 5a-c can be synthesized stereoselectively with high yields when an aqueous DMF solution of 3c, 4c or a mixture of 3a-b and 4a-b was heated at 140℃ for 8 h.

ORGANOPHOSPHINE INITIATED REACTION OF PERFLUOROALKYL IODIDES WITH ALKENES

perfluoroalkyl iodides reacted with alkenes in acetonitrile solu- tion containing catalytic amount of organophosphine under mild condition to give the corresponding adducts in moderate to good yields.Reaction was shown to involve a free radical mechanism.

Reaction of 4-Ethoxyl-1,1,1-trifluoromethyl-3-butenone with perfluorophenyl hydrazine and perfluoroalkyl hydrazides

The presence of fluorine in biologically active compounds can impart a profound influence on their biological active. This influence has lead to the development of several potent agricultural and therapeutic agents[1]. During the study on the reactions of 4 - ethoxyl - 1, 1, 1 -trifluoromathyl-3-butenone 1, we found which is a very useful building-block in synthesis of fluoro-containing heterocyclic compounds[2]. Compound 1 can react with perfluorophenyl hydrazine and afford 1- perfluorophenyl-5-trifluoromethyl- 5 -hydroxy-4, 5 -2H- pyrazole 2 in excellent yield. It’s structure is further supported by X-ray diffraction.

Perfluoroalkyl acids(PFAAs) in urban surface water of Shijiazhuang, China: Occurrence, distribution,sources and ecological risks

It is extremely important to analyze the contaminative behaviors of Perfluoroalkyl acids(PFAAs) due to their serious threats to urban environments which are closely related to humans. Current study aimed to explore the distribution, source apportionment and ecological risk assessment of PFAAs in surface water from Shijiazhuang, China. The concentrations of ΣPFAAs ranged from 19.5 to 125.9 ng/L in the investigation area. Perfluorobutanesulfonic acid(PFBS) and perfluoropentanoic acid(PFPeA) were the predominant contaminants(mean value: 14.3 ng/L and 16.6 ng/L, respectively). The distribution of PFAAs according to geospatial analysis and hierarchical clustering analysis(HCA) showed that higher levels of ΣPFAAs were detected in the southern surface water of Shijiazhuang and there was a stepwise decrease from the wet season to the dry season. Furthermore, based on source apportionment,the dominant potential sources were found to be wastewater treatment plant(WWTP) effluents and industrial discharge. The risk quotients(RQs) revealed low ecological risks of all PFAAs for aquatic organisms in Shijiazhuang surface water. Collectively, this study provided basic data for regulatory strategies for controlling PFAA pollutions in urban surface water.

Occurrence and Health Risk of Perfluoroalkyl Acids in Popular Shellfish from a Typical Coastal Area of the East China

As crucial homologous members of per-and polyfluoroalkyl substances(PFASs),perfluoroalkyl acids(PFAAs)have aroused wide public concern because of their unique properties(persistence,bioaccumulation,long-distance migration and toxicity).Studies have shown their potential hazard to wildlife and humans,with food consumption as one of the primary routes of PFAA exposure for general population,especially seafood intake.In this study,17 PFAAs were quantified in 9 shellfish species from Yuhuan City,a typical coastal area of the East China.The total mean concentrations of PFAAs were in the range of 5.03–381 ng/g dry weight(dw),with the highest concentration found in Neverita didyma and the lowest in Babylonia lutosa.Concentrations and composition profiles of PFAAs varied significantly among different species,indicating differences in the bioaccumulation potential of PFAAs among species.Perfluorooctanoic acid(PFOA)was presented as the most abundant PFAA in this study,followed by perfluorobutanoic acid(PFBA).Significant positive correlations were observed among some individual PFAAs(p<0.05),indicating that they may share similar pollution sources or undergo similar compound behaviors.Health risk assessment indicated a relatively high threat for local residents exposed to PFAAs through shellfish consumption.

Insights into the enzymatic degradation of DNA expedited by typical perfluoroalkyl acids

Perfluoroalkyl acids(PFAAs)are considered forever chemicals,gaining increasing attention for their hazardous impacts.However,the ecological effects of PFAAs remain unclear.Environmental DNA(eDNA),as the environmental gene pool,is often collected for evaluating the ecotoxicological effects of pollutants.In this study,we found that all PFAAs investigated,including perfluorohexanoic acid,perfluorooctanoic acid,perfluorononanoic acid,and perfluorooctane sulfonate,even at low concentrations(0.02 and 0.05 mg/L),expedited the enzymatic degradation of DNA in a nonlinear dose–effect relationship,with DNA degradation fragment sizes being lower than 1,000 bp and 200 bp after 15 and 30 min of degradation,respectively.This phenomenon was attributed to the binding interaction between PFAAs and AT bases in DNA via groove binding.van der Waals force(especially dispersion force)and hydrogen bonding are the main binding forces.DNA binding with PFAAs led to decreased base stacking and right-handed helicity,resulting in loose DNA structure exposing more digestion sites for degrading enzymes,and accelerating the enzymatic degradation of DNA.The global ecological risk evaluation results indicated that PFAA contamination could cause medium and high molecular ecological risk in 497 samples from 11 contamination-hot countries(such as the USA,Canada,and China).The findings of this study show new insights into the influence of PFAAs on the environmental fates of biomacromolecules and reveal the hidden molecular ecological effects of PFAAs in the environment.

Levels and trends of poly-and perfluoroalkyl substances in the Arctic environment-An update

Poly-and perfluoroalkyl substances(PFASs)are important environmental contaminants globally and in the early 2000s they were shown to be ubiquitous contaminants in Arctic wildlife.Previous reviews by Butt et al.and Letcher et al.have covered studies on levels and trends of PFASs in the Arctic that were available to 2009.The purpose of this review is to focus on more recent work,generally published between 2009 and 2018,with emphasis on PFASs of emerging concern such as perfluoroalkyl carboxylates(PFCAs)and short-chain perfluoroalkyl sulfonates(PFSAs)and their precursors.Atmospheric measurements over the period 2006e2014 have shown that fluorotelomer alcohols(FTOHs)as well as perfluorobutanoic acid(PFBA)and perfluoroctanoic acid(PFOA)are the most prominent PFASs in the arctic atmosphere,all with increasing concentrations at Alert although PFOA concentrations declined at the Zeppelin Station(Svalbard).Results from ice cores show generally increasing deposition of PFCAs on the Devon Ice cap in the Canadian arctic while declining fluxes were found in a glacier on Svalbard.An extensive dataset exists for long-term trends of long-chain PFCAs that have been reported in Arctic biota with some datasets including archived samples from the 1970s and 1980s.Trends in PFCAs over time vary among the same species across the North American Arctic,East and West Greenland,and Svalbard.Most long term time series show a decline from higher concentrations in the early 2000s.However there have been recent(post 2010)increasing trends of PFCAs in ringed seals in the Canadian Arctic,East Greenland polar bears and in arctic foxes in Svalbard.Annual biological sampling is helping to determine these relatively short term changes.Rising levels of some PFCAs have been explained by continued emissions of long-chain PFCAs and/or their precursors and inflows to the Arctic Ocean,especially from the North Atlantic.While the effectiveness of biological sampling for temporal trends in long-chain PFCAs and PFSAs has been demonstrated,this does not apply to the C4eC8ePFCAs,perfluorobutane sulfonamide(FBSA),or perfluorobutane sulfonate(PFBS)which are generally present at low concentrations in biota.In addition to air sampling,sampling abiotic media such as glacial cores,and annual sampling of lake waters and seawater would appear to be the best approaches for investigating trends in the less bioaccumulative PFASs.

家用活性炭滤芯与反渗透膜滤芯对饮用水中全氟化合物的去除性能试验

饮用水中普遍检出全氟化合物(PFASs)。该研究以4种典型的PFASs,即全氟丁基羧酸(PFBA)、全氟己基磺酸(PFHxS)、全氟辛基羧酸(PFOA)及全氟辛基磺酸(PFOS)为目标物质,以活性炭滤芯及反渗透(RO)膜滤芯两种常用家庭净水部件为研究对象,测试两种净水材料对PFASs自来水加标水样的去除性能及过滤前后相关水质参数。结果表明,对于活性炭滤芯,PFHxS、PFOA、PFOS在7倍额定总净水量内去除率为72%~86%,PFBA去除率相对较低,且通水量超过2倍额定总净水量后,去除率呈明显下降趋势;PFASs的去除率与高锰酸盐指数、溶解性总固体、无机阴离子等水质参数不相关;对于RO膜滤芯,PFASs的去除率可达90%~100%,PFBA去除率在通水后期呈现缓慢下降趋势;PFHxS、PFOA及PFOS的去除率与溶解性总固体、氯化物、硫酸盐等无机阴离子浓度呈较好的相关性。因此,家用活性炭滤芯、RO膜滤芯对饮用水中的PFASs具有良好的去除效果。研究可为家庭净水装置去除PFASs提供使用参考。

质谱技术在食品及食品接触材料的典型有机污染物中的应用研究进展

食品及食品接触材料有机污染物种类繁多,给环境和消费者健康带来诸多影响。质谱技术具有灵敏度高、分析速度快等特点,在分析检测领域发挥着重要作用。本文主要介绍了液相色谱-质谱联用技术在近年来比较关注的全氟多氟化合物(PFASs)、双酚类化合物(BPs)、季铵盐类化合物(QACs)3类典型有机污染物中的应用研究进展,并对未来发展趋势进行了展望。

多孔材料吸附全氟烷基化合物的应用进展

全氟烷基化合物(PFASs)属于新兴有机污染物的范畴,自身具有毒性、生物累积性且难降解,其广泛分布于全球水环境中,严重威胁着生态平衡与人类健康。吸附法作为一种物理化学方法,其成本低、能耗低、效率高且操作简便,常用于水体中PFASs的去除,然而目前有关水体中PFASs的吸附去除的全面总结较少。从吸附剂角度出发,首先归纳总结了近年来用于水体中PFASs吸附去除的各类多孔材料吸附剂,然后对主要吸附作用机制及影响吸附效果的关键因素进行梳理分析,最后对这一领域未来的发展方向及前景进行展望。

Perfluoroalkylation of benzo crown ethers with sodium perfluoroalkanesulfinates in the presence of oxidant

Using Ce(SO4)2 or Mn(OAc)3 as oxidant, dibenzo crown ethers such as dibenzo-18-crown-6 (1) and dibenzo-24-crown-8 (5) and benzo-12-crown-4 (7) reacted smoothly with sodium perfluoroalkanesulfinates (2a-2e) to give the corresponding perfluoroalkylated products (3,4,6,7) in good yields with two isomers obtained in the case of dibenzo crown ethers. This provides a facile synthesis of perfluoroalkyl-containing crown ethers.

成都市典型湿地公园全氟化合物的污染特征及风险评估

全氟化合物(PFASs)因其潜在的危害性而引起社会的广泛关注,但国内鲜有关于湿地公园中PFASs的研究报道.本文以青龙湖湿地公园水体、沉积物和水生植物(芦苇、美人蕉和香蒲)为研究对象,设置18个采样点位,对12种典型PFASs的污染特征和潜在生态风险进行分析.结果表明,水样中全氟丁烷羧酸(perfluorobutanoic acid,PFBA)、全氟己烷羧酸(perfluorohexanoic acid,PFHxA)和全氟辛酸(perfluorooctanoic acid,PFOA)的检出率较高,分别为100%、100%和94.4%,其中PFOA含量最高(47.9 ng·L^(-1)),为青龙湖湿地水相中的主要PFASs.S4和S8点位PFASs浓度最高,分别为455 ng·L^(-1)和467 ng·L^(-1),且存在餐饮旅游设施和建筑施工,说明人类活动对青龙湖PFASs的分布起到重要影响.沉积物中PFASs长碳链物质检出率较高如全氟壬烷羧酸(perfluorononanoic acid,PFNA)为100%,PFOA为94.4%,全氟癸烷羧酸(perfluorodecanoic acid,PFDA)为83.3%,全氟辛烷磺酸(perfluorooctane sulfonic acid,PFOS)的总检出浓度最高,为19.5 ng·g^(-1),占∑12PFASs的26.9%.PFOA和PFBA是植物中主要PFASs,含量分别为58.7 ng·g^(-1)和15.5 ng·g^(-1).芦苇对PFASs吸收能力最强,PFASs总含量为45.7 ng·g^(-1),富集系数为3.13,可作为青龙湖湿地全氟化合物生态修复的备选植物.青龙湖水相中PFOA和PFOS的风险熵(RQ)均小于0.01,处于低风险状态,但沉积物中PFOS的RQ值最高达0.184,属于中等风险,需引起重视.

船舶污水及压载水中PFASs及其新型替代品的含量及赋存特征

为了解船舶压载水以及生活污水中的全氟/多氟化合物(PFASs)及其新型替代品对海洋环境中PFASs污染的影响,针对16个港口,46艘船舶的黑水、灰水、黑灰混合水和压载水系统采集了56个样品,并对其中17种传统PFASs及2种新型替代品进行了分析.结果表明,船舶压载水中ΣPFASs浓度范围为45.6~97.4ng/L;船舶生活污水中ΣPFASs浓度范围为24~14681ng/L,ΣPFASs浓度最高值出现在灰水样品中.不同类型船舶之间PFASs含量及赋存情况没有明显差异.传统PFASs中,全氟辛酸(PFOA)和全氟丁烷磺酸(PFBS)是大部分样品中占比较高的化合物;新型替代品中,全氟壬烯氧基苯磺酸钠(OBS)浓度相对较高,6:2氯代多氟醚磺酸(6:2Cl-PFESA)检出频率较低.经过处理的船舶生活污水ΣPFASs浓度高于未处理的,归因于船舶生活污水的处理过程中有前体物质发生了向PFASs的转化.

氟调酸在我国典型城市污水处理厂中的浓度分布及排放

氟调酸(fluorotelomer carboxylic acids,FTCAs)是全氟烷基羧酸(perfluoroalkyl carboxylates,PFCAs)的前体物,同时也是替代加工助剂.本研究应用固相萃取-液相色谱-三重四极杆质谱仪联用的检测分析方法,探究了中国5个城市9座城市污水处理厂进水、二沉池出水、三级处理出水和污泥中6种FTCAs和12种PFCAs的分布及排放特征.FTCAs在城市污水处理厂进水中的浓度为0.52—2.00×10^(3) ng·L^(-1),受纳工业废水的城市污水处理厂进水中FTCAs的浓度高于其他主要受纳生活污水的城市污水处理厂,表明工业废水的排放会影响城市污水处理厂中FTCAs的浓度水平.生物处理工艺对FTCAs和PFCAs的去除率分别为43%—93%和-40%—69%.∑FTCAs在三级处理出水及污泥中的总排放量为13.6 g·d^(-1),6:2 FTCA和8:2 FTCA为主要的组成物质.三级处理出水中FTCAs及PFCAs的风险商分析表明三级处理出水中6:2 FTCA、PFHxA、PFOA、PFNA和PFDA可能对鱼类存在潜在风险.本研究为我国城市污水处理厂中新污染物的管控提供了数据基础.

Occurrence of perfluoroalkyl substances in matched human serum,urine,hair and nail

The purpose of this study was to determine perfluoroalkyl substances（PFASs） in human serum, urine, hair and nail from general populations, and to investigate the possibility for human urine, hair and nail used as the biomonitoring sample for PFASs exposure. We detected the concentrations of PFHx A, PFOA, PFNA, PFDA, PFUn DA, PFDo A, PFHx S and PFOS in 39 matched human serum, urine, hair and nail samples from Shenzhen in China. The detection frequency and the median level of PFOS were all higher than that of the other PFASs in four matrices. The median concentration of PFOS in serum, urine, hair, and nail were 9.24 ng/mL, 13.96 ng/L, 0.58 ng/g and 0.63 ng/g, respectively. The results of spearman correlation test indicated that nail was an ideal matrix for biomonitoring PFOS rather than human urine and hair in general populations for the non-invasive sampling.