Scission Products Research Articles

Thermal decomposition kinetics and mechanism of poly(ethylene 2,5-furan dicarboxylate) Nanocomposites for food packaging applications

Poly(ethylene 2,5-furan dicarboxylate) (PEF) based nanocomposites containing different nanoparticles like Ag, TiO2, ZnO, ZrO2 Ce-Bioglass, have been synthesized via in-situ polymerization techniques targeting food packaging applications. Zeta potential measurements showed an increase in the negative zeta potential value due to an increase in the surface charge density of the nanocomposites. Thermogravimetric analysis results proved that, except PEF-ZnO nanocomposite, all the other nanocomposites exhibited good resistance to thermal degradation without serious mass loss until 330 °C. Thermal decomposition kinetic analysis and the dependence of activation energy on the degree of conversion (α), indicated that the presence of ZnO nanoparticles influences, the degradation mechanism of PEF. In contrast, the presence of Ce-Bioglass nanoparticles leads to a slower degradation process, contributing to the enhanced resistance to thermal degradation of the PEF-Bioglass nanocomposite. The thermal degradation mechanism of PEF nanocomposites analyzed by pyrolysis‒gas chromatography/mass spectrometry (Py-GC/MS) indicated that the primary thermal degradation mechanism for the studied nanocomposites was β-hydrogen bond scission, while to a lesser extent, α-hydrogen bond scission products were noted in PEF-TiO2 and PEF-ZrO2 nanocomposites.

Oxidative degradation and possible interactions of coexisting decabromodiphenyl ether (BDE-209) on polystyrene microplastics in UV/chlorine process

This work was to investigate the transformation of coexisting decabromodiphenyl ether (BDE-209) on microplastics and their possible interactions in UV/chlorine process. Compared with pristine microplastics, the highly aged polystyrene (PS) showed an inhibitory effect on degradation of BDE-209. Increasing initial concentration of BDE-209 on PS inhibited degradation, while the chlorine concentration and pH did not affect the final degradation efficiency. Moreover, the presence of NO3−, SO42−, HCO3− and HA in water was unfavorable for BDE-209 degradation. According to the experimental and calculation results, the contribution to the degradation of BDE-209 was ranked as direct photolysis > HO• > •Cl in the UV/ chlorine system. Chlorination products released by PS during UV/chlorination were detected. Four possible reaction pathways of BDE-209 were proposed, which mainly involved debromination, hydroxylation, chlorine substitution, cleavage of ether bond, and intramolecular elimination of HBr. It was worth noting that PS microplastics not only inhibited the degradation of BDE-209, but also affected the type and abundance of its transformation products. Meanwhile, interaction products of PS and BDE-209 were determined, which was attributed to reactions of PS-derived radicals with •Br/•C6Br5 and •Cl. Results of toxicity evaluation showed that the introduction of carbon-halogen bonds, especially C-Br bond, increased the toxicity of chain scission products of PS. This work provides some new insights into transformation, interaction, and associated ecological risks of coexisting microplastics and surface adsorbed contaminants in the UV/chlorine process of drinking water treatment plants (DWTPs) and wastewater treatment plants (WWTPs).

Para-Acetamidobenzoylglutamate Is a Suitable Indicator of Folate Catabolism in Rats

The amount of biologically active folate excreted in the urine corresponds to a small fraction of the recommended dietary allowance, suggesting that a large amount of folate is excreted as its catabolites. A strategy of assessing folate requirement by measuring the daily urinary levels of products of folate catabolism depends on the demonstration of an exclusive mechanism of breakdown as well as a suitable marker of the catabolic process. Rats were given [3H] and [14C]folic acid by gastric intubation daily for 10 d to simulate normal dietary intake of the vitamin. Total urine was collected throughout this period as well as for the following 10 d. Reverse-phase HPLC of the radiolabeled urinary products revealed the presence of a variety of intact folates as well as products of C9-N10 scission of the folate molecule, pteridines, para-aminobenzoylglutamate and para-acetamidobenzoylglutmate. We detected no other N10-containing catabolites, nor did we find the oxidized folate derivative ‘4α-hydroxy-5-methyltetrahydrofolate’. Of all the urinary folate metabolites, only para-acetamidobenzoylglutmate persisted at high levels up to 10 d after radiolabel treatment was withdrawn. We conclude that folate catabolism occurs exclusively through C9-N10 cleavage and that measurement of urinary para-acetamidobenzoylglutmate provides a suitable indicator of daily folate turnover.

Migration of terephthalate from scraps of poly(ethylene terephthalate) (PET) in water and artificial seawater

We report the migration of terephthalate and some low molecular weight organic compounds from poly(ethylene terephthalate) (PET) scraps in Milli-Q water and artificial seawater (ASW). The photochemical processes and the subsequent dark reactions were investigated using PET scraps obtained from postconsumer bottles of commercial non‑carbonated mineral water. Concentrations of terephthalate exponentially increased with irradiation time, reaching approximately 6–8 μmol L−1 in ASW after 80 h irradiation. The photochemical migrations of compounds related to terephthalate were also observed. Concentrations of terephthalate and related compounds reached higher concentrations in ASW than in Milli-Q water. After 80 h irradiation, two dark experiments were conducted: one on the solutions after irradiation without PET scraps, and the other on photochemically damaged PET scraps. In ASW in the dark without PET scraps, the terephthalate concentration increased, and concentrations of other compounds related to terephthalate also changed. The results suggested that terephthalate was generated by hydrolytic reaction in dark ASW from the scission products of PET which were generated during the irradiation of PET scraps. Photochemically damaged PET scraps released terephthalate and related compounds in the dark. The half-life of the photo-irradiated PET scraps in the dark is approximately 205 years. Our results show that PET bottles in marine environments can continuously release terephthalate and other low molecular weight organic compounds during the day at the sunny surface, at the dark ocean floor, and during the night.

Palladium catalyzed liquid phase oxidation of glycerol under alkaline conditions - Kinetic analysis and modelling

Glycerol is a major by-product of bio-diesel production and hence its utilization has been an area of high interest in the scientific community. Oxidizing glycerol to high-value products can improve the economics of bio-diesel production. In the present work, we study glycerol oxidation in alkaline medium using an activated carbon supported Palladium catalyst. Kinetic studies have been performed in a batch reactor to study the effect of different parameters such as NaOH concentration, temperature, and pressure. Our results point to product inhibition by adsorbing reactant and product species. We also observe a relative insensitivity of product yields at a given conversion, to the temperature. Our observations further suggest that higher NaOH concentration gives better C3 selectivity while higher oxygen pressure results in lower C3 selectivity. Based on our own studies and the literature available, the most likely kinetic pathway and a kinetic model have been proposed. Our results suggest the possibility that C–C cleavage occurs directly from the primary intermediate aldehydic species, as a result of which, carbon chain scission products (including CO2) form from very early stages of the reaction. Various strategies such as pooling temperature data to estimate rate ratios prior to full parameter estimation, use of statistical significance tests to reduce model parameters etc have been used to arrive at a minimalistic model still capable of explaining all features of the oxidation. Confidence bounds on the model parameters have been estimated.

The β-carotene–oxygen copolymer: its relationship to apocarotenoids and β-carotene function

β-carotene spontaneously copolymerizes with molecular oxygen to form a β-carotene–oxygen copolymer compound (“copolymer”) as the main product, together with small amounts of many apocarotenoids. Both the addition and scission products are interpreted as being formed during progression through successive free radical β-carotene–oxygen adduct intermediates. The product mixture from full oxidation of β-carotene, lacking both vitamin A and β-carotene, has immunological activities, some of which are derived from the copolymer. However, the copolymer’s chemical makeup is unknown. A chemical breakdown study shows the compound to be moderately stable but nevertheless the latent source of many small apocarotenoids. GC–MS analysis with mass-spectral library matching identified a minimum of 45 structures, while more than 90 others remain unassigned. Newly identified products include various small keto carboxylic acids and dicarboxylic acids, several of which are central metabolic intermediates. Also present are glyoxal and methyl glyoxal dialdehydes, recently reported as β-carotene metabolites in plants. Although both compounds at higher concentrations are known to be toxic, at low concentration, methyl glyoxal has been reported to be potentially capable of activating an immune response against microbial infection. In plants, advantage is taken of the electrophilic reactivity of specific apocarotenoids derived from β-carotene oxidation to activate protective defenses. Given the copolymer occurs naturally and is a major product of non-enzymatic β-carotene oxidation in stored plants, by partially sequestering apocarotenoid metabolites, the copolymer may serve to limit potential toxicity and maintain low cellular apocarotenoid concentrations for signaling purposes. In animals, the copolymer may serve as a systemic source of apocarotenoids.

Evaluation of PBN spin-trapped radicals as early markers of lipid oxidation in mayonnaise

Quality deterioration of mayonnaise is caused by lipid oxidation, mediated by radical reactions. Assessment of radicals would enable early lipid oxidation assessment and generate mechanistic insights. To monitor short-lived lipid-radicals, N-tert-butyl-α-phenylnitrone (PBN), a spin-trap, is commonly used. In this study, the fate of PBN-adducts and their impact on lipid oxidation mechanisms in mayonnaise were investigated. The main signals detected by Electron Spin Resonance (ESR) were attributed to L-radicals attached to 2-methyl-2-nitrosopropane (MNP), one of three degradation products of the PBN-peroxy-adduct. The second degradation product, benzaldehyde, was detected with Nuclear Magnetic Resonance (1H NMR), in line with MNP-L adduct generation. For the third class of degradation products, LO-radicals, their scission products were detected with 1H NMR and indicated that LO-radicals have a major impact on downstream oxidation pathways. This precludes mechanistical studies in presence of PBN. Degradation products of PBN-adducts can, however, be used for early assessment of antioxidants efficacy in oil-in-water emulsions.

Significance of Squalene in Rice Bran Oil and Perspectives on Squalene Oxidation.

As an intermediate metabolite during the biosynthesis of sterols, squalene is found ubiquitously in plants and animals. In rice, squalene is contained in rice bran, and consequently, squalene in rice bran oil has gained attention. Studies have shown that the intake of squalene from food sources demonstrate various physiological benefits such as the prevention of cancer and cardiovascular disease. Squalene is also known as an effective antioxidant in edible oils. However, due to its chemical structure, squalene is susceptible to oxidation, which may cause a decline in the nutraceutical and antioxidative effects of squalene in edible oils. Oxidative degradation of squalene also results in the formation of scission products (i.e., aldehydes and ketones) which may lead to off-flavor. Since the rate of squalene oxidation depends on the factors that induce its oxidation (i.e., light or heat), emphasis on oxidation mechanisms is necessary. It has been demonstrated in previous studies that the oxidation products formed by the singlet oxygen oxidation and free radical oxidation of squalene are different, and more recently, we demonstrated that different squalene monohydroperoxide isomers are formed by each oxidation mechanism. We herein discuss the significance of squalene in rice bran oil as well as the oxidative degradation of squalene in edible oils with focus on oxidation mechanisms.

Simultaneous Analysis of Epoxidized and Hydroperoxidized Triacylglycerols in Canola Oil and Margarine by LC-MS.

The progress of lipid oxidation in foods is evaluated by measuring the peroxides and their scission products. However, hydrogen abstraction-independent pathways are not considered by commonly applied methods despite the known reactivity of epoxides toward biomolecules. Herein, a novel liquid chromatography tandem-mass spectrometry method was developed to detect hydroperoxidized and epoxidized triacylglycerols (TAGs) without derivatization or hydrolyzation of food samples. Epoxidized TAGs could be detected in refined canola oil at concentrations of 96.8 ± 2.08 μM, while only 5.77 ± 0.04 μM hydroperoxidized TAGs could be determined. In contrast to canola oil, margarine was more resistant to lipid oxidation since generation of epoxidized TAGs could only be marginally enhanced from 21.7 ± 0.48 to 28.8 ± 0.64 μM in margarine after treatment at 180 °C for 60 min, as also reflected by a peroxide value of 0.80 ± 0.00 mequiv O2/kg, which remained unchanged. The new method allows the assessment of food safety by the simultaneous measurement of hydroperoxidized and epoxidized TAGs without hydrolysis and laborious sample preparation.

Isomer sieving and the selective formation of terminal methyl isomers in reactions of linear alkanes on one-dimensional zeolites

Diffusional hurdles enhance secondary interconversions of monomethyl isomers formed as primary products in bifunctional metal-acid isomerization of n-alkanes. One-dimensional medium-pore zeolites preferentially place methyl branches near the end of the isoalkane chains in what has been described as “pore mouth catalysis”; they also lead to low β-scission selectivities compared with three-dimensional frameworks similar in void size. n-Heptane and n-hexane reactions on acid forms of aluminosilicates of different channel size and connectivity (Al-MCM-41, FAU, SFH, BEA, MFI, MEL, SVR, TON, MTT; as mixtures with a Pt function) and crystallite size and proton density show that intracrystalline alkene concentration gradients are more consequential for larger and more branched molecules, as a result of their higher reactivity and lower diffusivity, and that the products form using all intracrystalline protons instead of only those near pore mouths. For both C6 and C7 reactants, 2-methyl to 3-methyl isoalkane ratios are those expected from equilibrium on large-pore zeolites (FAU, SFH, BEA). In contrast, these isomer ratios reflect the preferential sieving of the faster diffusing 2-methyl isomers from isoalkene products present as equilibrated mixtures within crystallites on medium-pore (10-MR) zeolites. These sieving effects are most evident for one-dimensional 10-MR frameworks because their void structures lead to stronger concentration gradients and more selective sieving of the faster diffusing isoalkenes. These effects are weaker on three-dimensional 10-MR structures because of less severe diffusional constraints, but the intersecting channels in these frameworks create local cage-like structures that favor β-scission through the preferential retention of dimethylpentenes, which act as the sole precursors to scission products. One-dimensional structures lack such channel undulations and cage-like intersections; as a result, one-dimensional medium-pore TON and MTT frameworks lead to low β-scission selectivities. This work demonstrates the essential, yet often overlooked, coupling between reactive and diffusive properties of zeolite materials in determining reactivity and selectivity in practice.

Association with Polyamines and Polypeptides Increases the Relative Yield of 2-Deoxyribonolactone Lesions in Radiation-Damaged DNA.

The production of 2-deoxyribonolactones (C1'-oxidation product), C4'-oxidized abasic sites and C5'-carbonyl terminated strand scission products was investigated in complexes of double-stranded DNA with protamine, poly-L-lysine and spermine exposed to X-ray radiation. The lesions were quantified by high-performance liquid chromatography through the release of the corresponding low-molecular-weight products 5-methylenefuran-2(5H)-one, N-(2'-hydroxy-ethyl)-5-methylene-D3-pyrrolin-2-one and furfural, respectively. All binders were found to increase the relative yield of C1' oxidation up to 40% of the total 2-deoxyribose damage through the indirect effect versus approximately 18% typically found in homogeneous solutions by the same technique. On the contrary, the yield of C5'-oxidation was found to be suppressed almost completely, while in homogeneous solutions it constituted approximately 14% of the total. The observed change in end product distribution is attributed to free valence transfer to and from the complexing agent, although the mechanisms associated with this process remain unclear.

Identification of β scission products from free radical polymerizations of butyl acrylate at high temperature

Unsaturated low molar mass species were identified via ESI-MS after fractionation of poly(butyl acrylate) from high temperature radical polymerization.

Monitoring anthocyanin degradation in Hibiscus sabdariffa extracts with multi-curve resolution on spectral measurement during storage

This study aims to monitor composition changes in an anthocyanin-rich beverage during storage by the means of UV–VIS measurements associated with a multi-curve resolution procedure. Hibiscus sabdariffa extract was stored at 37 °C for 50 days and UV–VIS spectra were measured on the extract and the fractions of the extract every 5 days. MCR was carried out in two steps, first with the fraction and then the extract spectra. The results enabled the main polyphenols initially present to be identified, anthocyanins and chlorogenic acid, but also found the nature of the main degradation products: the polymers from anthocyanin condensation and scission products. In addition, comparison with HPLC analysis results showed that the MCR procedure recovered the correct shapes of the concentration profiles particularly of anthocyanin and polymer kinetics during storage. This work gives perspective for the use of a rapid and efficient technique to monitor pigment-rich beverage processing or storage.

Catalytic mechanism of sulfuric acid in cellulose pyrolysis: A combined experimental and computational investigation

Sulfuric acid (H2SO4) is widely used as a strong acid catalyst in biomass pyrolysis process, and exhibits prominent catalytic effects on the pyrolytic reactions and product distribution. In this study, the fundamental catalytic mechanism of H2SO4 on cellulose pyrolysis process was investigated via combined experimental and computational methods. Both thermographic analysis (TGA) and pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) experiments were performed to reveal the pyrolytic characteristics and product distribution in the H2SO4-catalyzed pyrolysis of cellulose. In addition, quantum chemistry methods were employed to build the reaction models and investigate the major H2SO4-assisted reactions in initial cellulose pyrolysis process, i.e., depolymerization of the cellulose chain, bridged dehydration, ring-opening, ring-contraction and dehydration of the free hydroxyl groups. The results indicate that the H2SO4-assisted depolymerization via C1-O1 bond scission and bridged dehydration reactions take place in a two-step mechanism involving a sulfate ester intermediate. While other reactions occur via a one-step mechanism involving only hydroxyl group or both hydroxyl and sulfonic groups of H2SO4. The activation energies of above reactions are all decreased by adding H2SO4, and thus lowering the degradation temperature of cellulose. Among all initial pyrolytic reactions, dehydration reactions which are inconspicuous in the non-catalytic process, become very important in the catalytic process, because their activation energies are decreased dramatically by adding H2SO4 (from 322.7 to 372.1 to 152.2–237.7 kJ/mol). The promoting effect on the dehydration reactions plays a vital role in the increased char yield and significant change of organic volatile product distribution. Through the promoted dehydration reactions, unsaturated structures of cellulose are formed, which is favorable for the formation of certain dehydrated products at the expense of depolymerized and ring scission products.

Identification of Chain Scission Products Released to Water by Plastic Exposed to Ultraviolet Light

Buoyant plastic in the marine environment is exposed to sunlight, oxidants, and physical stress, which may lead to degradation of the plastic polymer and the release of compounds that are potentially hazardous. We report the development of a laboratory protocol that simulates the exposure of plastic floating in the marine environment to ultraviolet light (UV) and nontarget analysis to identify degradation products of plastic polymers in water. Plastic pellets [polyethylene, polypropylene, polystyrene, and poly(ethylene terephthalate)] suspended in water were exposed to a UV light source for 5 days. Organic chemicals in the water were concentrated by solid phase extraction and then analyzed by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry using a nontarget approach with a C18 LC column coupled to a Q Exactive Orbitrap HF mass spectrometer. We designed a data analysis scheme to identify chemicals that are likely chain scission products from degradation of the plas...

Techniques for the Analysis of Minor Lipid Oxidation Products Derived from Triacylglycerols: Epoxides, Alcohols, and Ketones.

Lipid oxidation can lead to flavor and safety issues in fat-containing foods. In order to measure the extent of lipid oxidation, hydroperoxides and their scission products are normally targeted for analytical purposes. In recent years, the formation of rarely monitored oxygenated products, including epoxides, alcohols, and ketones, has also raised concerns. These products are thought to form from alternative pathways that compete with chain scissions, and should not be neglected. In this review, a number of instrumental techniques and approaches to determine epoxides, alcohols, and ketones are discussed, with a focus on their selectivity and sensitivity in applications to food lipids and oils. Special attention is given to methods employing gas chromatography (GC), high-performance liquid chromatography (HPLC), and nuclear magnetic resonance (NMR). For characterization purposes, GC-mass spectrometry (GC-MS) provides valuable information regarding the structures of individual oxygenated fatty acids, typically as methyl esters, isolated from oxygenated triacylglycerols (TAGs), while the use of liquid chromatography-MS (LC-MS) techniques allows analysis of intact oxygenated TAGs and offers information about the position of the oxygenated acyl chain on the glycerol backbone. For quantitative purposes, traditional chromatography methods have exhibited excellent sensitivity, while spectroscopic methods, including NMR, are superior to chromatography for their rapid analytical cycles. Future studies should focus on the development of a routine quantitative method that is both selective and sensitive.

Radicals initiated by gamma-rays in collagen and its main components

Radical products generated by gamma-rays were identified in collagen and in microcrystalline powders of glycyne, L-proline and L-hydroksyproline. Reagents irradiated at 77K were studied by EPR spectroscopy in the range of 100–350K using temperature control system. Two radical centers found in collagen were localized in proline ring at α and γ positions to the carbonyl group. There were neither terminal radicals generated by chain scission nor transient products disrupting hydrogen bonding system of irradiated collagen.

Tea polyphenols: absorption, bioavailability and potential toxicity.

Abstract Tea polyphenols (catechins) have various reported properties that may benefit health and lower risk of non-communicable disease. However, their bioavailability is low. There is rapid metabolism and elimination of most absorbed catechins, and they do not accumulate beyond nanomolar amounts in plasma, even with regular intake. There is extensive biotransformation of unabsorbed catechins by colonic microflora, which produces ring scission products that, if included, increase bioavailability from an average of <4% to around 40%. Strategies exist to increase bioavailability, such as taking tea catechins in the fasting state, or taking more concentrated, purified, stable or bioaccessible formulations of catechins. However, catechins demonstrate pro-oxidant activity under certain conditions, and administration of high levels induces toxic effects on liver and kidney. In humans catechins are generally well tolerated at up to 400 mg/day, but even this dose can cause gastrointestinal upset and in some people induces hepatic toxicity. Furthermore, catechins bind iron and high doses can interfere with iron absorption, and catechins ingestion affects pharmacokinetics and action of some drugs used to treat hypertension and cardiovascular disease. Therefore, strategies to overcome low bioavailability of catechins must be viewed with caution, and very high doses should be avoided. In this article, absorption, metabolism and bioavailability of green tea catechins, in particular epigallocatechin gallate, are reviewed, focusing mainly on human data. Issues of potential toxicity of catechins are examined, and a recommendation in regard to 'safe' intake is given.

Anthocyanins degradation during storage of Hibiscus sabdariffa extract and evolution of its degradation products

Degradation parameters of two main anthocyanins from roselle extract (Hibiscus sabdariffa L.) stored at different temperatures (4–37°C) over 60days were determined. Anthocyanins and some of their degradation products were monitored and quantified using HPLC–MS and DAD. Degradation of anthocyanins followed first-order kinetics and reaction rate constants (k values), which were obtained by non-linear regression, showed that the degradation rate of delphinidin 3-O-sambubioside was higher than that of cyanidin 3-O-sambubioside with k values of 9.2·10−7s−1 and 8.4·10−7s−1 at 37°C respectively. The temperature dependence of the rate of anthocyanin degradation was modeled by the Arrhenius equation. Degradation of delphinidin 3-O-sambubioside (Ea=90kJmol−1) tended to be significantly more sensitive to an increase in temperature than cyanidin 3-O-sambubioside (Ea=80kJmol−1). Degradation of these anthocyanins formed scission products (gallic and protocatechuic acids respectively) and was accompanied by an increase in polymeric color index.

Selective Synthesis and Derivatization of Germasilicon Hydrides.

Mixed Si/Ge hydrides SixGeyHz are valuable precursors for the deposition of binary Si-Ge alloys. This work describes the synthesis and full characterization of the previously unknown germaisotetrasilane Ph3GeSi(SiH3)3 (2) on a multigram scale from the reaction of the lithium silanide LiSi(SiH3)3 with Ph3GeCl. The stability of the Si-Ge bond in 2 versus electrophiles and nucleophiles has been investigated with the primary aim of developing new approaches to mixed sila-H-germanes (H3Ge)xSi(SiH3)4-x. With 1 equiv of MeLi, 2 reacted cleanly under cleavage of one Si-Si bond to give Ph3GeSi(SiH3)2Li, which is a valuable synthon for further derivatization. In contrast, the dephenylation reaction of 2 with 1 or 2 equiv of CF3SO3H/iBu2AlH proceeded much less selectively and afforded the desired Ph/H-germasilanes Ph2HGeSi(SiH3)3 and PhH2GeSi(SiH3)3 along with considerable amounts of Si-Ge scission products.