Chiroptical Studies on Supramolecular Chirality of Molecular Aggregates

The attempts of applying chiroptical spectroscopy to supramolecular chirality are reviewed with a focus on vibrational circular dichroism (VCD). Examples were taken from gels, solids, and monolayers formed by low‐molecular mass weight chiral gelators. Particular attention was paid to a group of gelators with perfluoroalkyl chains. The effects of the helical conformation of the perfluoroalkyl chains on the formation of chiral architectures are reported. It is described how the conformation of a chiral gelator was determined by comparing the experimental and theoretical VCD spectra together with a model proposed for the molecular aggregation in fibrils. The results demonstrate the potential utility of the chiroptical method in analyzing organized chiral aggregates. Chirality 27:659–666, 2015. © 2015 Wiley Periodicals, Inc.     

Metabolic products and pathways of fluorotelomer alcohols in isolated rat hepatocytes

Fluorotelomer alcohols (FTOHs; CF(3)(CF(2))(x)C(2)H(4)OH; where x=3, 5, 7, 9) are a novel class of polyfluorinated contaminants, recently detected in the North American atmosphere, that are possible precursors to the series of perfluoroalkyl carboxylates (PFCAs) in human blood. An in vivo rat study validated earlier independent work that poly- and per-fluoroalkyl carboxylates were metabolites of FTOHs, but our detection of several novel metabolites prompted us to examine their pathways in greater detail using isolated rat hepatocytes. Using 8:2 FTOH (i.e. where x=7) as a model compound, the metabolic products formed by isolated rat hepatocytes were identified, and three synthesized intermediates were incubated separately to elucidate the metabolic pathways. For 8:2 FTOH, a major fate was direct conjugation to form the O-glucuronide and O-sulfate. Using 2,4-dinitrophenylhydrazine (DNPH) trapping, the immediate oxidation product of 8:2 FTOH was identified as 8:2 fluorotelomer aldehyde (8:2 FTAL; CF(3)(CF(2))(7)CH(2)C(H)O). 8:2 FTAL was transient and eliminated HF non-enzymatically to yield 8:2 fluorotelomer alpha,beta-unsaturated aldehyde (8:2 FTUAL; CF(3)(CF(2))(6)CFCHC(H)O) which was also short-lived and reacted GSH and perhaps other endogenous nucleophiles. Four polyfluorinated acid intermediates were also detected, including 8:2 fluorotelomer carboxylate (8:2 FTCA; CF(3)(CF(2))(7)CH(2)C(O)O(-)), 8:2 fluorotelomer alpha,beta-unsaturated carboxylate (8:2 FTUCA; CF(3)(CF(2))(6)CFCHC(O)O(-)), tetrahydroperfluorodecanoate (CF(3)(CF(2))(6)(CH(2))(2)CO(2)(-)), and dihydroperfluorodecenoate (CF(3)(CF(2))(6)CHCHCO(2)(-)). The pathways leading to 8:2 FTCA and FTUCA involve oxidation of 8:2 FTAL, however, the pathways leading to the latter two polyfluorinated acids remain inconclusive. The fate of the unsaturated metabolites, 8:2 FTUAL and FTUCA, included conjugation with GSH and dehydrofluorination to yield alpha,beta-unsaturated GSH conjugates, and GS-8:2 FTUAL which was subsequently reduced to the corresponding alcohol. Perfluorooctanoate (PFOA) and minor amounts of perfluorononanoate (PFNA) were confirmed as metabolites of 8:2 FTOH, and the respective roles of beta- and alpha-oxidation mechanisms are discussed. The analogous acids, aldehydes, and conjugated metabolites of 4:2, 6:2, and 10:2 FTOH (i.e. where x=3, 5, and 9, respectively) were also detected, and metabolite profiles among FTOHs generally differed only in the length of their perfluoroalkyl chains. Preincubation with aminobenzotriazole, but not pyrazole, inhibited the formation of metabolites from all FTOHs, suggesting that their oxidation was catalyzed by P450, not alcohol dehydrogenase.     

Leonidas Zervas award lecture: Abiotic ligands for new quaternary architectures of peptides and proteins

This review is the result of a kind invitation to provide a report on the basis of the Leonidas Zervas award lecture at the 32nd European Peptide Society in Athens, Greece, September 2012. The lecture covered several topics including contributions toward new methods for the assembly of peptides and chemical modification of proteins. The present review will focus on another topic from the Zervas lecture, namely, our recent efforts at creating new, artificial architectures for the organization of the quaternary structure of proteins. Crucially, this is achieved with abiotic ligands and not protein surface engineering. This concept was demonstrated for the important biopharmaceutical peptide insulin, by using both abiotic metal ion binding ligands and perfluoroalkyl chains. Copyright © 2013 European Peptide Society and John Wiley & Sons, Ltd.     

Mechanism of Perfluoroalkyl Halide Toxicity: Catalysis of Perfluoroalkylation by Reduced Forms of Cobalamin (Vitamin B12)

Perfluoroalkyl halides (PFHs) are synthetic products widely used in various fields. Perfluorooctyl bromide (PFB) is used in medicine as a component of blood substitutes and for artificial lung ventilation. In both cases, it is considered a completely inert compound acting as a solvent for oxygen. However, there are many reports of PFH-induced intoxication, including lethal cases. Mechanisms underlying toxic effects of this compound remain unknown. In this study, we demonstrate that the reduced form of cobalamin (vitamin B12) typical for B12-dependent enzymes can catalyze the reactions of perfluoroalkylation, aromatic substitution, or addition by double bonds. Synthesis of perfluoro derivatives from PFHs during catalysis by cob(I)alamin-like super nucleophiles is a new possible mechanism responsible for in vivo formation of highly toxic compounds from "chemically inert" substances widely used in medicine. Catalytic perfluoroalkylation might possibly contribute to nitric oxide depletion and modulation of activity of guanylate cyclase, cytochromes, NO-synthases, and other heme-containing proteins.     

Spontaneous multiscale phase separation within fluorinated xerogel coatings for fouling-release surfaces

Four-component xerogel films consisting of 1 mole-% n-octadecyltrimethoxysilane (C18) and 50 mole-% tetraethoxysilane (TEOS) in combination with 1–24 mole-% tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (TDF) and 25–48 mole-% n-octyltriethoxysilane (C8) and a 1:49:50 mole-% C18/TDF/TEOS were prepared. Settlement of barnacle cyprids and removal of juvenile barnacles, settlement of zoospores of the alga Ulva linza, and strength of attachment of 7-day sporelings (young plants) of Ulva were compared amongst the xerogel formulations. Several of the xerogel formulations were comparable to poly(dimethylsiloxane) elastomer with respect to removal of juvenile barnacles and removal of sporeling biomass. The 1:4:45:50 and 1:14:35:50 C18/TDF/C8/TEOS xerogels displayed some phase segregation by atomic force microscopy (AFM) pre- and post-immersion in water. Imaging reflectance infrared microscopy showed the formation of islands of alkane-rich and perfluoroalkane-rich regions in these same xerogels both pre- and post-immersion in water. Surface energies were unchanged upon immersion in water for 48 h amongst the TDF-containing xerogel coatings. AFM measurements demonstrated that surface roughness on the 1:4:45:50 and 1:14:35:50 C18/TDF/C8/TEOS xerogel coatings decreased upon immersion in water.     

Helical Inversion of Gel Fibrils by Elongation of Perfluoroalkyl Chains as Studied by Vibrational Circular Dichroism

Vibrational circular dichroism (VCD) spectroscopy was applied to gelation by a chiral low‐molecular mass weight gelator, N,N’‐diperfluoroalkanoyl‐1,2‐trans‐diaminocyclohexane. Attention was focused on the winding effects of (–CF₂)_n chains on the gelating ability. For this purpose, a series of gelators were synthesized with perfluoroalkyl chains of different length (n = 6–8). When gelation was studied using acetonitrile as a solvent, the fibrils took different morphologies, depending on the chain length: twisted saddle‐like ribbon or helical ribbon from fibril (n = 6) and a helical ribbon from platelet (n = 8). The signs of VCD peaks assigned to the couplet of C=O stretching and to the C‐F stretching were also dependent on n, indicating that a gelator molecule changed conformation on elongating perfluoroalkyl chains. A model is proposed for the aggregation modes in fibrils. Chirality 28:361–364, 2016. © 2016 Wiley Periodicals, Inc.     

全氟辛酸在沉积物-水界面污染及吸附迁移行为研究进展

全氟辛酸(PFOA)是一种重要的全氟化表面活性剂,具有环境持久性、高毒性和生物累积性等特征,成为当前备受关注的新污染物。沉积物是PFOA的重要环境储蓄库,被污染后的沉积物可作为长期污染源造成上覆地表水及周边地下水污染。本文结合近年来国内外研究,对地表水和沉积物中PFOA的来源、污染现状和界面吸附迁移行为进行了综述。结果表明: 地表水体和沉积物中PFOA最主要的污染来源为工业废水排放。全球范围地表水体和沉积物中PFOA污染水平普遍为ng·g^-1和ng·L^-1数量级,且国内部分地区污染形势更为严峻。沉积物组分、水化学条件、有机质及表面活性剂等因素均影响沉积物中PFOA的吸附行为,但目前在吸附主控机制方面仍然存在争议。沉积物中PFOA迁移行为的研究正处于起步阶段,相关报导还较为缺乏,对于迁移机理的认识还很不足,今后需在该方面加大研究力度。