Analysis of F-53B,Gen-X,ADONA, and emerging fluoroalkylether substances in environmental and biomonitoring samples: A review

The persistent, bioaccumulative, and toxic properties of certain per- and polyfluoroalkyl substances (PFAS) raise concerns for environmental and human health. This has led to the gradual phase-out from production and commerce of some legacy PFAS. Fluoroalkylether compounds (ether-PFAS) are among the fluorinated alternative chemicals that are beginning to be reported in impacted and background environments. Extensive monitoring activities were conducted since 2015–2019 to bridge knowledge gaps on the environmental fate and effects of ether-PFAS including F-53B (6:2 chlorinated polyfluoroalkyl ether sulfonate [6:2 Cl-PFAES] and 8:2 Cl-PFAES), Gen-X (hexafluoropropylene oxide dimer acid [HFPO-DA]), and ADONA (dodecafluoro-3H-4,8-dioxanonanoate). In recent years, advances in nontarget screening using high-resolution mass spectrometry have revealed the identities of other infrequently monitored ether-PFAS. In this critical review, we provide an up-to-date inventory of the structures of ether-PFAS discovered in the recent literature. Their environmental occurrence, fate, and effects are discussed on a comparative perspective with some legacy PFAS such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Information on the methods employed for the quantitative and semi-quantitative analysis of ether-PFAS is also provided, including sample preparation and mass spectrometry analysis, analytical performance, and limitations. In particular, the compiled database of MS/MS fragment ions (n = 111) can be useful in spectrum interpretation of novel ether-PFAS. The concluding remarks open on possible research avenues and the challenges that remain to be addressed.     

Improvement of capacitance activity for Cu‐doped Ni‐based metal–organic frameworks by adding potassium hexacyanoferrate into KOH electrolyte

Cu‐doped Ni‐based metal–organic frameworks (MOFs) nanomaterials fabricated through a one‐pot hydrothermal reaction were characterized, and their performance as supercapacitor electrode materials was further studied for the first time. The results indicated that the doping of foreign metals and the introduction of K₃[Fe(CN)₆] in the KOH electrolyte significantly improve the performance of the supercapacitor. The results indicated that the Ni_2.6Cu_0.4 MOFs material shows the highest specific capacitance (1282 F g^?1 at 1 A g^?1 in mixed 2 M KOH and 0.1 M K₃[Fe(CN)₆]) and optimal capacitance retention (85.7% after 2000 cycles). This work provides a feasible optimization strategy for the construction of MOFs‐based supercapacitor electrode materials with excellent performance, and also provides a reliable experimental and theoretical basis for practical industrial production.     

Entropic effect implication for change in polymer coils swelling state in the demixing enthalpy recovery of aqueous poly(vinyl methyl ether) solutions

Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151     

Synthesis,cytotoxicity, apoptosis and cell cycle arrest of a monoruthenium(II)-substituted Dawson polyoxotungstate

By 5-h reaction of cis-[Ru^IICl₂(DMSO)₄] (M2) with K₁₀[α₂-P₂W₁₇O₆₁] (M3) in ice-cooled, HCl-acidic aqueous solution, a water-soluble 1:2-type diamagnetic ruthenium(II) complex of formula K₁₈[Ru^II(DMSO)₂(P₂W₁₇O₆₁)₂]·35H₂O (M1) was unexpectedly obtained as an analytically pure, homogeneous tan-colored solid, in which two DMSO ligands are coordinated to the ruthenium(II) atom. The cytotoxic potential of the complex was tested on C33A, DLD-1, and HepG-2 cancer cells and human normal embryonic lung fibroblasts cell MRC-5; the viability of the treated cells was evaluated by MTT assay. The mode of cell death was assessed by morphological study of DNA damage and apoptosis assays. Compound M1 induced cell death in a dose-dependent manner, and the mode of cell death was essentially apoptosis though necrosis was also noticed. Cell cycle analysis by flow cytometry indicated that M1 caused cell cycle arrest and accumulated cells in S phase.     

Novel palladium nanoparticles supported on β‐cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross‐coupling reaction with two different approaches in bio‐based solvents

A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.     

CoFe2O4@SiO2‐CPTES‐Guanidine‐Cu(II): A novel and reusable nanocatalyst for the synthesis of 2,3‐dihydroquinazolin‐4(1H)‐ones and polyhydroquinolines and oxidation of sulfides

CoFe₂O₄@SiO₂‐CPTES‐Guanidine‐Cu(II) magnetic nanoparticles were synthesized and used as a new, inexpensive and efficient heterogeneous catalyst for the synthesis of polyhydroquinolines and 2,3‐dihydroquinazoline‐4(1H)‐ones and for the oxidation of sulfides. The structure of this nanocatalyst was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, X‐ray diffraction and inductively coupled plasma optical emission spectrometry. Simple preparation, high catalytic activity, simple operation, high yields, use of green solvents, easy magnetic separation and reusability of the catalyst are some of the advantages of this protocol.     

Convergence of solutions for the fractional Cahn–Hilliard system

This paper deals with the Cauchy–Dirichlet problem for the fractional Cahn–Hilliard equation. The main results consist of global (in time) existence of weak solutions, characterization of parabolic smoothing effects (implying under proper condition eventual boundedness of trajectories), and convergence of each solution to a (single) equilibrium. In particular, to prove the convergence result, a variant of the so-called ?ojasiewicz–Simon inequality is provided for the fractional Dirichlet Laplacian and (possibly) non-analytic (but $C^1$) nonlinearities.     

Kinetics and mechanism of trichloroisocyanuric acid/NaNO2-triggered nitration of aromatic compounds under acid-free and Vilsmeier-Haack conditions

Kinetics and mechanism of nitration of aromatic compounds using trichloroisocyanuric acid (TCCA)/NaNO₂, TCCA-N,N-dimethyl formamide (TCCA-DMF)/NaNO₂, and TCCA-N,N-dimethyl acetamide (TCCA-DMA)/NaNO₂ under acid-free and Vilsmeier-Haack conditions. Reactions followed second-order kinetics with a first-order dependence on [Phenol] and [Nitrating agent] ([TCCA], [(TCCA-DMF)], or [(TCCA-DMA)] >> [NaNO₂]). Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but did not fit well into the Hammett's theory of linear free energy relationship or its modified forms like Brown-Okamoto or Yukawa-Tsuno equations. Rate data were analyzed by Charton's multiple linear regression analysis. Isokinetic temperature (β) values, obtained from Exner's theory for different protocols, are 403.7 K (TCCA-NaNO₂), 365.8 K (TCCA-DMF)/NaNO₂, and 358 K (TCCA-DMA)/NaNO₂. These values are far above the experimental temperature range (303-323 K), indicating that the enthalpy factors are probably more important in controlling the reaction.     

4D Printing based piezoelectric composite for medical applications

Additive manufacturing (AM), otherwise known as three‐dimensional (3D) printing, is driving major innovations in many areas, such as engineering, manufacturing, art, education, and medicine. Although a considerable amount of progress has been made in this field, additional research work is required to overcome various remaining challenges. Recently, one of the actively researched areas lies in the AM of smart materials and structures. Electroactive materials incorporated in 3D printing have given birth to 4D printing, where 3D printed structures can perform as actuating and/or sensing systems, making it possible to deliver electrical signals under external mechanical stimuli and vice versa. In this paper, we present a lightweight, low cost piezoelectric material based on the dispersion of inorganic ferroelectric submicron particles in a polymer matrix. We report on how the proposed material is compatible with the AM process. Finally, we discuss its potential applications for healthcare, especially in smart implants prostheses. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 109–115     

Short Syntheses of some ‘Decalin‐1,8‐diones’ and their Derivatives: Breaking the Pretended Symmetry

A cheap synthesis of the so‐called ‘decalin‐1,8‐diones’ started with the conjugate (1,4‐) addition of cyclohex‐2‐en‐1‐one derivatives to the γ‐position of the dilithium derivative (buta‐1,3‐diene‐1,1‐bis(olate)) of crotonic acid. Hydrogenation of these ‘1,4‐γ’ adducts and final cyclization afforded the enol tautomers of decalin‐1,8‐diones. Nucleophilic substitutions at these 3‐oxoenols by NH₃ or primary amines created only monoamino products (namely, 3‐oxoenamines) whose reactions with OPCl₃ yielded dihydro(1,3,2)oxazaphosphinin‐2‐one derivatives. The two regioisomers of a trimethyl‐3‐oxoenamine served as models for the constitutional assignments of the two rapidly interconverting (hence, individually NMR‐invisible), tautomeric trimethyl‐3‐oxoenols. Such methyl substitutions served to break the ‘pretended’ symmetry of ‘decalin‐1,8‐dione’. Hydrazine and 3‐oxoenols furnished oxygen‐free indazole derivatives whose N?H bonds exchanged with t_1/2=ca. 0.00035 s at ca. ?58(9) °C.