scholarly journals Dependency of the photocatalytic and photochemical decomposition of per- and polyfluoroalkyl substances (PFAS) on their chain lengths, functional groups, and structural properties

Author(s):  
Nusrat Chowdhury ◽  
Srinivas Prabakar ◽  
Hyeok Choi

Abstract This study reports the removal of per- and polyfluoroalkyl substances (PFAS) in water using various photocatalytic and photochemical processes. PFAS were chosen, based on chain lengths, functional groups, and structural properties: 4 perfluorocarboxylic acids (PFCAs) including perfluorooctanoic acid (PFOA), 3 perfluorosulfonic acids (PFSAs) including perfluorooctanesulfonic acid (PFOS), hexafluoropropylene oxide dimer (GenX), and 6:2 fluorotelomer sulfonate (6:2 FTS), and investigated dependency of the photocatalytic decomposition of PFAS on their properties. Oxidants and reductants were introduced to study the photochemical decomposition of PFAS, and reactive species and reaction byproducts were identified to elucidate the decomposition mechanism of PFAS. Some notable findings include long chain PFCAs (95% in 48 h) and 6:2 FTS (100%) were removed via chemical decomposition in TiO2/UVC while GenX (37%), long chain PFSAs (60%), short chain PFSAs (0–10%) and short chain PFCAs (5–18%) were removed via physical adsorption. Sulfate radicals generated with persulfate (PS) played an important role in decomposing PFCAs (60–90%). Sulfite activated by UVC worked for defluorination of PFOA (75%) and PFOS (80%). PFOA was removed faster by UVC/sulfite > UVC/TiO2/sulfite ≈ UVC/TiO2/PS ≥ UVC/PS > UVC/TiO2 while PFOS was removed faster by UVC/sulfite ≫ UVC/TiO2/sulfite ≈ UVC/TiO2/PS ≈ UVC/TiO2 ≫ UVC/PS. Susceptibility of PFAS to the chemical reactions could be explained with their properties and the reactive species produced in each system.

Polymers ◽  
2021 ◽  
Vol 13 (16) ◽  
pp. 2660
Author(s):  
Zibo Zhou ◽  
Guozhang Wu

This study aimed to improve polydimethylsiloxane (PDMS) conversion in the preparation of polycarbonate (PC)–polydimethylsiloxane (PDMS) copolymer through melt polycondensation. We examined the transesterification process of PDMS with diphenyl carbonate (DPC) and its copolymerization products with bisphenol-A (BPA) for different chain lengths of PDMS. The key factors affecting PDMS conversion were investigated. Results showed that long-chain PDMS required a higher critical transesterification level (38.6%) to improve miscibility with DPC. During polycondensation, side reactions were more prone to occur when the equilibrium transesterification level of long-chain PDMS was lower. PDMS conversion was also lower when more short-chain PDMS was fed. Increasing the chain length of PDMS also reduced PDMS conversion. Notably, increasing the amount of KOH can significantly improve PDMS conversion throughout the polycondensation stage by increasing the equilibrium transesterification level of long-chain PDMS, thereby inhibiting the occurrence of side reactions.


2019 ◽  
Vol 87 (3) ◽  
Author(s):  
Yifan Zhou ◽  
Wenlei Zhang ◽  
Jian Hu ◽  
Jingda Tang ◽  
Chenyu Jin ◽  
...  

Abstract Stiffness and fatigue threshold are important material parameters in load-carrying applications. However, it is impossible to achieve both high stiffness and high threshold for single-network elastomers and single-network hydrogels. As the polymer chain length increases, the stiffness reduces, but the threshold increases. Here, we show that this stiffness-threshold conflict is resolved in double-network hydrogels, where the stiffness depends on the short-chain network, but the threshold depends on the long-chain network. Experimental data in the literature have shown that the stiffness of the hydrogels is inversely proportional to chain length of the short-chain network. In this paper we measure the threshold of PAAm-PAMPS hydrogels with five different chain lengths of the long-chain network. We find that the threshold is proportional to 1/2 power of the chain length of the long-chain network. The resolution of the conflict enables the design of elastomers and hydrogels to achieve both high stiffness and high threshold.


2014 ◽  
Vol 16 (40) ◽  
pp. 21988-21998 ◽  
Author(s):  
Samantha Micciulla ◽  
Samuel Dodoo ◽  
Chloé Chevigny ◽  
André Laschewsky ◽  
Regine von Klitzing

Optimization of the layer-by-layer growth of short chain (∼30 repeat units per chain) polyelectrolyte multilayers and comparison with classical long chain systems.


1977 ◽  
Vol 55 (12) ◽  
pp. 2404-2410 ◽  
Author(s):  
Douglas M. Chen ◽  
Fred Y. Fujiwara ◽  
Leonard W. Reeves

The degree of order of solubilized molecules and ions in oriented lyomesophases has been determined at specifically deuterated C—D bond axes from the quadrupole splitting of the deuterium magnetic resonance. Mixtures at low concentration of specifically deuterated alkanes, alcohols, carboxylic acids, and carboxylates of different chain length have been observed in host cationic and anionic lyomesophases. The degree of order of a given C—D position in alcohols increases strongly with chain length up to a length comparable with the host detergent. A broad series of carboxylic acids and carboxylate ions from C2 to C16 have been deuterated in the α position. The α-C—D bond axis in the solubilisate increases in order with chain length, the anion having lower order than the parent acid. An accurately linear increase in the degree of order of the α position is observed for intermediate chain lengths. At chain lengths approximately equal to the host chain lengths the α position reaches a limiting value in the degree of order and further segments do not influence the order. At short chain lengths the degree of order is less than that predicted from extrapolation of order in the linear region. This has been interpreted in terms of distribution into the aqueous compartment by the solubilisates of short chain length. Acetic acid and the acetate, propionate, butanoate, and pentanoate ions spend an appreciable amount of time in the aqueous region. An estimate has been made of these distributions based on reasonable assumptions.


2000 ◽  
Vol 13 (2) ◽  
pp. 185-214 ◽  
Author(s):  
Geoffrey Livesey

AbstractAlthough stearic acid is a saturated fatty acid, its influence on plasma cholesterol acid other health variables is neutral; possibly owing in part to poor absorption. Reduced absorption of stearic acid from particular triacylglycerols, cocoa butter and novel fats formulated with short- and long-chain acid triacylglycerol molecules (Salatrims) has been attributed to high intakes. However, the circumstances and causes of poor stearic acid digestion from triacylglycerols are unclear; published data were therefore collected and analysed, with emphasis on human studies. Of twenty-eight studies conducted in adults, most are in men (>90%). The assertion that reduced absorption is due to a high intake of stearoyl groups is not supported: dietary intakes of stearoyl of 0·05–0·65 g stearic acid equivalent/kg body weight (cf typical intake of 0·2 g stearic acid equivalent/kg body weight in the Western diet) indicate that the ‘true’ digestibility of stearoyl is 0·98 (SE 0·01) g/g, with apparent digestibility less than this value at low intakes owing to endogenous stearic acid excretion and to inter-publication variation of unidentified cause. The neutral health impact of stearic acid must be due to factors other than availability. Exceptions include cocoa butter, Salatrims and tristearin, for which digestibility is an additional factor. The efficiency with which human subjects digest stearoyl from cocoa butter still remains uncertain, while the digestion of total long-chain fat from this source is 0·89–0·95 g/g, high in comparison with 0·33 g/g for Salatrim 23CA and 0·15 g/g for tristearin in their prepared states. Salatrims contain the highest proportion of long-chain fatty acids that are stearic acid-rich other than tristearin, which is the main component of fully-hydrogenated soyabean and rapeseed oil. Analysis shows that apparent digestibility of stearic acid is associated with stearoyl density within the triacylglycerol molecule and that, in Salatrims, the occurrence of short-chain fatty acids in place of long-chain fatty acids increases this density. Soap formation appears not to be a major factor in the reduced digestion of stearic acid from tristearin under regular dietary circumstances, but both microcrystallinity and reduced digestibility of tri-, di- and monostearoylglycerols appears to be important. Solubilisation of high-melting-point tristearin in low-melting-point oils improves the digestibility of its stearic acid, particularly when emulsified or liquidized at above melting point. However, without such artificial aids, the digestive tracts of the rat, dog and man have a low capacity for emulsifying and digesting stearic acid from tristearin. Reduced digestibility of stearic acid from Salatrim 23CA also appears to be attributable to reduced digestibility of di- and monostearoylglycerols and is particularly due to remnants with the 1- or 3-stearoylglycerol intact after initial hydrolytic cleavage. Short-chain organic acid in Salatrim 23CA, which is readily hydrolysed, leaves such remnants. Unlike tristearin, Salatrim 23CA melts at body temperature and mixing it with low-melting-point oils is not expected to cause further disruption of microcrystalline structures to aid digestibility of its stearoyl groups. The low digestibility of stearoyl in Salatrim 23CA, together with the occurrence of short-chain organic acids in this product, account for its relatively low nutritional energy value (about 20 kJ (5 kcal)/g) compared with traditional fats (37 kJ (9 kcal)/g) and low fat value (<20:37 kJ/kJ; <5:9 kcal/kcal) relative to traditional fats. In part these differences are because of minor effects of Salatrim 23CA on the excretion of other fat and protein, due to the bulking properties of this poorly-digestible fat.


2012 ◽  
Vol 52 (9) ◽  
pp. 795-803 ◽  
Author(s):  
Giovanni M. Turchini ◽  
Peter D. Nichols ◽  
Colin Barrow ◽  
Andrew J. Sinclair

1996 ◽  
Vol 1996 ◽  
pp. 98-98
Author(s):  
B M L McLean ◽  
R W Mayes ◽  
F D DeB Hovell

Alkanes occur naturally in all plants, although forage crops tend to have higher alkane contents than cereals. N-alkanes have odd-numbered carbon chains. They are ideal for use as markers in feed trials, because, they are inert, indigestible and naturally occurring, and can be recovered in animal faeces. Synthetic alkanes (even-numbered carbon chains) are available commercially and can also used as external markers. Dove and Mayes (1991) cite evidence indicating that faecal recovery of alkanes in ruminants increases with increasing carbon-chain length. Thus the alkane “pairs” (e.g. C35 & C36, and C32 & C33) are used in calculating intake and digestibility because they are long chain and adjacent to each other. However, recent work by Cuddeford and Mayes (unpublished) has found that in horses the faecal recovery rates are similar regardless of chain lengths.


2008 ◽  
Vol 71 (7) ◽  
pp. 1401-1405 ◽  
Author(s):  
JEREMY A. OBRITSCH ◽  
DOJIN RYU ◽  
LUCINA E. LAMPILA ◽  
LLOYD B. BULLERMAN

The antimicrobial activities of four long-chain food-grade polyphosphates were studied at concentrations allowed in the food industry (&lt;5,000 ppm) in defined basal media by determining the inhibition of growth of three gram-negative and four gram-positive spoilage and pathogenic bacteria. Both generation time and lag phase of Escherichia coli K-12, E. coli O157: H7, and Salmonella Typhimurium were increased with all of the polyphosphates tested. Bacillus subtilis and Staphylococcus aureus were more sensitive to polyphosphates, but not in all cases, with multiphased growth. The growth of Lactobacillus plantarum was inhibited by polyphosphates at concentrations above 750 ppm, but the lag time of Listeria monocytogenes was shortened by the presence of polyphosphates. No single polyphosphate was maximally inhibitory against all bacteria. Polyphosphates with chain lengths of 12 to 15 were significantly different from those with chain lengths of 18 to 21 depending on the organism and concentrations of polyphosphate used. Overall, higher polyphosphate concentrations resulted in greater inhibition of bacterial growth.


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