Role of reactive carbonyls and superoxide radicals in protein damage by cigarette smoke extracts: Comparison of Heat-not-Burn e-cigarettes to conventional cigarettes.

Oxidative protein damage involving carbonylation of respiratory tract proteins typically accompanies exposure to tobacco smoke. Such damage can arise via multiple mechanisms, including direct amino acid oxidation by reactive oxygen species or protein adduction by electrophilic aldehydes. This study investigated the relative importance of these pathways during exposure of a model protein to fresh cigarette emission extracts. Briefly, protein carbonyl adducts were estimated in bovine serum albumin following incubation in buffered solutions with whole cigarette emissions extracts prepared from either a single 1R6F research cigarette or a single "Heat-not-Burn" e-cigarette. Although both extracts caused concentration-dependent protein carbonylation, conventional cigarette extracts produced higher adduct yields than e-cigarette extracts. Superoxide radical generation by conventional and e-cigarette emissions was assessed by monitoring nitro blue tetrazolium reduction and was considerably lower in extracts made from "Heat-Not-Burn" e-cigarettes. The superoxide dismutase/catalase mimic EUK-134 strongly suppressed radical production by whole smoke extracts from conventional cigarettes, however, it did not diminish protein carbonyl adduction when incubating smoke extracts with the model protein. In contrast, edaravone, a neuroprotective drug with strong carbonyl-trapping properties, strongly suppressed protein damage without inhibiting superoxide formation. Although these findings require extension to appropriate cell-based and in vivo systems, they suggest reactive aldehydes in tobacco smoke make greater contributions to oxidative protein damage than smoke phase radicals.

Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements.

The impact of organometallic chemistry on the terpene field only really blossomed in the 1960s and 1970s with the realisation that carbon-carbon bond formation under mild conditions could be achieved by using nickel or iron carbonyls as synthetic reagents. Concomitantly, the development of palladium derivatives capable of the controlled coupling of isoprene units attracted the attention of numerous highly talented researchers, including future Nobel laureates. We discuss briefly how early work on the syntheses of simple monoterpenes soon progressed to sesquiterpenes and diterpenes of increasing complexity, such as humulene, flexibilene, vitamin A, or pheromones of commercial value, in particular those used in perfumery (muscone, lavandulol), or grandisol and red scale pheromone as replacements for harmful pesticides. As the field progressed, there has been more emphasis on developing organometallic routes to enantiopure rather than racemic products, as well as gaining precise mechanistic data on the transformations, notably the course of metal-promoted molecular rearrangements that have long been a feature of terpene chemistry. We note the impact of the enormously enhanced analytical techniques, high-field NMR spectroscopy and X-ray crystallography, and their use to re-examine the originally proposed structures of terpenes and their organometallic derivatives. Finally, we highlight the very recent ground-breaking use of the crystalline sponge method to acquire structural data on low-melting or volatile terpenes. The literature cited herein covers the period 1959 to 2023.

ß-caryophyllene attenuates oxidative stress and hepatocellular mitochondrial dysfunction in type-2 diabetic rats induced with high fat and fructose diets.

Objective: Hyperglycemia, hyperlipidemia, and systemic resistance to insulin are typical manifestations of type 2 diabetes mellitus. One of the main pathophysiological alterations in insulin-sensitive organs is mitochondrial malfunction associated with oxidative stress and diminished fuel utilization. ß-Caryophyllene (BCP) has qualities that are anti-inflammatory, anti-tumor, antioxidant, hypolipidemic, and hypoglycemic. In this work, rats suffering from type 2 diabetes were given a diet high in fat and sugar with the aim of examining the ameliorative effects of BCP on oxidative stress-mediated hepatic mitochondrial dysfunction. Methods: The diabetic condition was experimentally induced by feeding rats a high-calorie diet. The rats were then administered the recommended doses of BCP and metformin (MET) once every day for 30 days at 200 mg and 50 mg concentrations per kg of body weight, respectively, to prove the hypothesis of the study that BCP ameliorates mitochondrial dysfunction induced by oxidative stress in diabetic rats. Mitochondrial dysfunction can be identified by indicators such as oxidative stress, cardiolipin dienes, membrane phospholipid concentration, and mitochondrial enzymes. Results: The mitochondria in the liver of rats with diabetes exhibit elevated redox imbalance-related parameters and malfunctioning mitochondria with peroxided cardiolipin, while their amounts of glutathione and phospholipids are lowered. Oxidative stress indices, ameliorated mitochondrial activities, and peroxided cardiolipin were drastically decreased in rats with diabetes treated with BCP or MET. Conclusions: The present research demonstrated that BCP improved the vital role of mitochondria by reducing free radical dominance in type 2 diabetic experimental rats fed high-fat and high-sugar diets.

Formation of phenazines, phenoxazines, and benzoxazoles in the browning reactions of o-quinones.

Quinone-induced browning is widely produced in foods and is mostly considered a consequence of quinone/nucleophile reactions. However, even in the absence of amino acids or proteins, o-quinones develop browning. In an attempt to better understand the reaction pathways involved in this browning development, this study describes the reactions of 4-methyl-1,2-benzoquinone with alcohols, ammonia, and short chain aldehydes. These reaction mixtures developed browning at 37 °C and the main produced compounds were isolated by semipreparative HPLC and characterized by NMR and MS as phenazines, phenoxazines, and benzoxazoles. A reaction pathway that explains the formation of all these compounds is proposed. The formation of phenazines is responsible, at least partially, for the produced browning, and the formation of benzoxazoles inhibits such browning. Browning development seems to be a consequence of a competition among the reactions of formation of phenazines, phenoxazines, and benzoxazoles, which appear to be produced from a single intermediate.

Assessing the Impact of Pomegranate Peel Extract Active Packaging and High Hydrostatic Pressure Processing on Color and Oxidative Stability in Sliced Nitrate/Nitrite-Reduced Iberian Dry-Cured Loins.

Our study aimed to assess the impact of active packaging with pomegranate peel extract (0.06 mg gallic acid eq./cm2) and/or high-pressure treatment (600 MPa, 7 min) on the instrumental color, lipid, and protein oxidation of Iberian dry loins formulated with reduced nitrate/nitrite levels (0, 37.5, and 150 mg/kg) during 100-day refrigerated storage (4 °C). CIE L*a*b* coordinates were measured, and malondialdehyde, carbonyls, and free thiol contents served as markers for lipid and protein oxidation. Active packaging lowered CIE L* (35.4 vs. 34.1) and a* (15.5 vs. 14.5) and increased yellowness (15.6 vs. 16.3) and hue (45.2 vs. 48.4), while pressurization increased CIE L* (33.1 vs. 36.3) and diminished a* values (16.1 vs. 13.9). Ongoing nitrate/nitrite amounts significantly influenced lipid peroxidation, protein carbonyl formation, and free thiol loss. Active packaging and high-pressure processing had varying effects on carbonyl and thiol contents. Neither pressurization nor active packaging impacted malondialdehyde formation. Pressurization enhanced the formation of 4-HNE (503 vs. 697 pg/g). Protein oxidation proved more sensitive to changes, with active packaging offering protection against protein carbonylation (15.4 vs. 14.7 nmol carbonyls/mg protein), while pressurization induced thiol loss (34.3 vs. 28.0 nmol Cys eq./mg protein). This comprehensive understanding provides essential insights for the meat industry, emphasizing the necessity for customized processing conditions to enhance color stability, lipid preservation, and protein integrity in dry-cured loin slices.

Mitigation of lens opacification by a functional food in a diabetic rodent model.

The current study was designed to test a functional food (FF) mixture containing aldose reductase inhibitors and antiglycation bioactive compounds for suppressing the onset and progression of cataracts in a diabetic rat model. Two-month-old Sprague Dawley rats were grouped as control (C), diabetes untreated (D), and diabetic rats treated with FF at two doses (FF1 = 1.35 g and FF2 = 6.25 g/100g of diet). Diabetes was induced by a single injection of streptozotocin. The FF is a mixture of amla, turmeric, black pepper, cinnamon, ginger, and fenugreek added to the rodent diet. The status of cataracts was monitored weekly by a slit lamp examination for 20 weeks, after which animals were sacrificed to collect eye lenses. Feeding FF1 and FF2 to diabetic rats yielded a significant anti-hyperglycaemic effect and marginally prevented body weight loss. FF delayed cataract progression, and FF2 showed better efficacy than FF1. FF prevented the loss of lens crystallins and their insolubilization in diabetic rats. The antioxidant potential of FF was evident with the lowered protein carbonyls, lipid peroxidation, and prevention of altered antioxidant enzyme activities induced by diabetes. These studies demonstrate the efficacy of plant-derived dietary supplements against the onset and progression of cataracts in a well-established rat model of diabetic eye disease.

Cobalt-Catalyzed Enantioselective Reductive α-Chloro-Carbonyl Addition of Ketimine to Construct the ß-Tertiary Amino Acid Analogues.

ß-Tertiary amino acid derivatives constitute one of the most frequently occurring units in natural products and bioactive molecules. However, the efficient asymmetric synthesis of this motif still remains a significant challenge. Herein, we disclose a cobalt-catalyzed enantioselective reductive addition reaction of ketimine using α-chloro carbonyl compound as a radical precursor, providing expedient access to a diverse array of enantioenriched ß-quaternary amino acid analogues. This protocol exhibits outstanding enantioselectivity and broad substrate scope with excellent functional group tolerance. Preliminary mechanism studies rule out the possibility of Reformatsky-type addition and confirm the involvement of radical species in stereoselective addition process. The synthetic utility has been demonstrated through the rapid assembly of iterative amino acid units and oligopeptide, showcasing its versatile platform for late-stage modification of drug candidates.

A Metallomicellar Catalyst for Controlled Oxidation of Alcohols and Lignin Mimics in Water using Open Air as Oxidant.

Alcohol groups and ß-O-4 (C-C) linkages are widespread in biomass feedstock that are abundant renewable resource for value-added chemicals. The development of sustainable protocols for direct oxidation or oxidative cleavage of feedstock materials in a controlled fashion, using open air as an oxidant is an intellectually stimulating task to produce industrially important value-added carbonyls. Further, the oxidative depolymerization of lignin into fine chemicals has evoked interest in recent times. Herein, we report the first example of a catalyst system that could activate molecular oxygen from atmospheric air for controlled oxidation and oxidative cleavage/depolymerization of feedstock materials such as alcohols, ß-O-4 (C-C) linkages and real lignin in water under open air conditions. The selectivity of carbonyl products is controlled by altering the pH between ~7.0 and ~12.0. The current strategy highlights the non-involvement of any external co-catalyst, oxidant, radical additives, and/or destructive organic solvents. The catalyst shows a wide substrate scope and eminent functional group tolerance. The upscaled multigram synthesis using an inexpensive catalyst and easily available oxidant evidences the practical utility of the developed protocol. A plausible mechanism has been proposed with the help of a few controlled experiments, and kinetic and computational studies.

Pressure Induced Alteration and Stabilization of Intermolecular Stacking in Square-planar Osmium tetracarbonyl.

Osmium carbonyls are well known to form stable 18-electron complexes like Os(CO)5 , Os2 (CO)9 and Os3 (CO)12 having both bridging and terminal carbonyls. For osmium tetra-carbonyl, Os(CO)4 solid-state packing significantly alters the ground-state structure. The gas-phase stable see-saw geometry converts to a square-planar structure in solid state. Highly efficient intermolecular stacking between Os(CO)4 units assists this transformation. Each Os(CO)4 molecule is stacked in a staggered orientation with respect to each other. Pressure induces a [Xe]4f14 5d6 6s2 (S=2)→[Xe]4f14 5d8 (S=0) electronic transition in osmium stabilize a square planar osmium tetra-carbonyl. Under the influence of isotropic pressure, the molecules not only come closer to each other but their relative orientations also get significantly altered. Calculations show that at P=1 GPa and above, the eclipsed orientation for the intermolecular stacking gets preferred over the staggered form. The staggered→eclipsed intermolecular stacking orientation under pressure is shown to be controlled by London dispersion interactions.

Significant contribution of carbonyls to atmospheric oxidation capacity (AOC) during the winter haze pollution over North China Plain.

Atmospheric carbonyl compounds play significant roles in the cycling of radicals and have exhibited surprisingly high levels in winter that were well correlated to particulate matter, for which the reason have not been clearly elucidated. Here we measured carbonyl compounds and other trace gasses together with PM2.5 over urban Jinan in North China Plain during the winter. Markedly higher carbonyl concentrations (average: 14.63 ± 4.21 ppbv) were found during wintertime haze pollution, about one to three-times relative to those on non-haze days, with slight difference in chemical composition except formaldehyde (HCHO). HCHO (3.68 ppbv), acetone (3.17 ppbv), and acetaldehyde (CH3CHO) (2.83 ppbv) were the three most abundant species, accounting for ∼75% of the total carbonylson both haze and non-haze days. Results from observational-based model (OBM) with atmospheric oxidation capacity (AOC) indicated that AOC significantly increased with the increasing carbonyls during the winter haze events. Carbonyl photolysis have supplied key oxidants such as RO2 and HO2, and thereby enhancing the formation of fine particles and secondary organic aerosols, elucidating the observed haze-carbonyls inter-correlation. Diurnal variation with carbonyls exhibiting peak values at early-noon and night highlighted the combined contribution of both secondary formation and primary diesel-fuel sources. 1-butene was further confirmed to be the major precursor for HCHO. This study confirms the great contribution of carbonyls to AOC, and also suggests that reducing the emissions of carbonyls would be an effective way to mitigate haze pollution in urban area of the NCP region.

Aerosol Emissions from Heated Tobacco Products: A Review Focusing on Carbonyls, Analytical Methods, and Experimental Quality.

We provide an extensive review of 17 independent and industry-funded studies targeting carbonyls in aerosol emissions of Heated Tobacco Products (HTPs), focusing on quality criteria based on the reproducibility of experiments, appropriate analytic methods, and puffing regimes. Most revised studies complied with these requirements, but some were unreproducible, while others failed to consider analytical variables that may have affected the results and/or produced unrealistic comparisons. We also provide a review of the literature on the physicochemical properties of heated tobacco and HTP aerosols, as well as the evaluation of HTPs by regulatory agencies, addressing various critiques of their relative safety profile. The outcomes from the revised studies and regulatory evaluations tend to agree with and converge to a general consensus that HTP aerosols expose users to significantly lower levels of toxicity than tobacco smoke.

Food Polyphenols as Preventive Medicine.

Reactive oxygen species (ROS) are the initiators in foods and in the stomach of oxidized dietary lipids, proteins, and lipid-oxidation end-products (ALEs), inducing in humans the development of several chronic diseases and cancer. Epidemiological, human clinical and animal studies supported the role of dietary polyphenols and derivatives in prevention of development of such chronic diseases. There is much evidence that polyphenols/derivatives at the right timing and concentration, which is critical, acts mostly in the aerobic stomach and generally in the gastrointestinal tract as reducing agents, scavengers of free radicals, trappers of reactive carbonyls, modulators of enzyme activity, generators of beneficial gut microbiota and effectors of cellular signaling. In the blood system, at low concentration, they act as generators of electrophiles and low concentration of H2O2, acting mostly as cellular signaling, activating the PI3K/Akt-mediated Nrf2/eNOS pathways and inhibiting the inflammatory transcription factor NF-κB, inducing the cells, organs and organism for eustress, adaptation and surviving.

Impact of more intense smoking parameters and flavor variety on toxicant levels in emissions of a Heated Tobacco Product.

INTRODUCTION: IQOS HEETS are promoted as reduced risk alternatives to cigarettes. Although some studies have investigated the chemical composition of HEETS emissions, little is known on whether toxicant levels in such emissions are affected by different puffing parameters and flavor varieties. This has important implications when assessing actual human exposure, since IQOS users develop a specific and personalized puffing behavior and may use different HEETS variants. METHODS: This study measured the levels of nicotine, Total Particulate Matter (TPM), carbonyl compounds and tobacco-Specific Nitrosamines (TSNAs) in the emissions of nine differently flavored HEETS and two cigarettes (1R6F and Marlboro Red, MR). Emissions from Yellow HEETS, 1R6F and MR were collected using the World Health Organization Intense (WHOI) smoking regime and four more intense smoking regimes. RESULTS: Yellow HEETS aerosol contained lower levels of toxicants compared to 1R6F and MR smoke. More intense smoking regimes increased carbonyls release in cigarette smoke, whereas only higher puff frequency led to lower levels of toxicants in Yellow HEETS aerosol. Some HEETS varieties exhibited higher levels of formaldehyde and TSNAs in their aerosol compared to Yellow HEETS. CONCLUSIONS: Puff frequency was identified as the only smoking parameter that significantly lowered the release of almost all toxicants in Yellow HEETS, whereas a combination of higher puff volume and puff duration led to increased levels of some carbonyls. Differences in toxicants levels between various commercially-available HEETS have important implications when assessing their health impact, as their consumption might induce different toxicant exposure and health effects. IMPLICATIONS: HEETS release about half as much nicotine and substantially lower levels of toxicants compared to cigarettes. Literature data showed that puffing intensity is increased in cigarette smokers switching to HEETS, maybe in reaction to these lower nicotine levels. Our results show a differential impact of increased puff frequency, puff duration and puff volume in the release of toxicants from HEETS. Thus, industry-independent studies on puff topography are critical to make choices for the most relevant puffing regime for HTP regulation. Regulators should consider evaluating the health impact of multiple HEETS varieties, as the tobacco filler composition significantly affects the release of certain toxicants.

Altered Lipid Moieties and Carbonyls in a Wistar Rat Dietary Model of Subclinical Fatty Liver: Potential Sex-Specific Biomarkers of Early Fatty Liver Disease?

Non-alcoholic fatty liver disease (NAFLD) is a condition in which excess fat builds up in the liver. To date, there is a lack of knowledge about the subtype of lipid structures affected in the early stages of NAFLD. The aim of this study was to analyze serum and liver lipid moieties, specifically unsaturations and carbonyls, by nuclear magnetic resonance (NMR) in a subclinical Wistar rat model of NAFLD for detecting early alterations and potential sex dimorphisms. Twelve weeks of a high-fat diet (HFD) induced fat accumulation in the liver to a similar extent in male and female Wistar rats. In addition to total liver fat accumulation, Wistar rats showed a shift in lipid subtype composition. HFD rats displayed increased lipid carbonyls in both liver and serum, and decreased in unsaturated fatty acids (UFAs) and polyunsaturated fatty acids (PUFAs), with a much stronger effect in male than female animals. Our results revealed that the change in fat was not only quantitative but also qualitative, with dramatic shifts in relevant lipid structures. Finally, we compared the results found in Wistar rats with an analysis in a human patient cohort of extreme obesity. For the first time to our knowledge, lipid carbonyl levels and lipoproteins profiles were analyzed in the context of subclinical NAFLD. The association found between lipid carbonyls and alanine aminotransferase (ALT) in a human cohort of extremely obese individuals further supports the potential role of lipid moieties as biomarkers of early NAFLD.

Torpid 13-lined ground squirrel liver mitochondria resist anoxia-reoxygenation despite high levels of protein damage.

Hibernation confers resistance to ischemia-reperfusion injury in tissue, but the underlying mechanisms remain unclear. Suppression of mitochondrial respiration during torpor may contribute to this tolerance. To explore this concept, we subjected isolated liver mitochondria from torpid, interbout euthermic (IBE) and summer 13-lined ground squirrels (Ictidomys tridecemlineatus) to 5 min of anoxia, followed by reoxygenation (A/R). We also included rat liver mitochondria as a non-hibernating comparison group. Maximum respiration rates of mitochondria from torpid ground squirrels were not affected by A/R, but in IBE and summer, these rates decreased by 50% following A/R and in rats they decreased by 80%. Comparing net ROS production rates among groups, revealed seasonal differences; mitochondria from IBE and torpor produced 75% less ROS than summer ground squirrels and rats. Measurements of oxidative damage to these mitochondria, both freshly isolated, as well as pre- and post-A/R, demonstrated elevated damage to protein, but not lipids, in all groups. Hibernation likely generates oxidative stress, as freshly isolated mitochondria had greater protein damage in torpor and IBE than in summer and rats. When comparing markers of damage pre- and post-A/R, we found that when RET was active, rat macromolecules were more damaged than when RET is inhibited, but in TLGS markers of damage were similar. This result suggests that suppression of RET during hibernation, both in torpor and IBE, lessens oxidative stress produced during arousal. Taken together our study suggests that ischemia-reperfusion tolerance at the mitochondrial level is associated with metabolically suppressed oxidative phosphorylation during hibernation.

Induction of Vesicular Trafficking and JNK-Mediated Apoptotic Signaling in Mononuclear Leukocytes Marks the Immuno-Proteostasis Response to Uremic Proteins.

INTRODUCTION: Uremic retention solutes have been alleged to induce the apoptotic program of different cell types, including peripheral blood mononuclear leukocytes (PBL), which may contribute to uremic leukopenia and immune dysfunction. METHODS: The molecular effects of these solutes were investigated in uremic PBL (u-PBL) and mononuclear cell lines (THP-1 and K562) exposed to the high molecular weight fraction of uremic plasma (u-HMW) prepared by in vitro ultrafiltration with 50 kDa cut-off microconcentrators. RESULTS: u-PBL show reduced cell viability and increased apoptotic death compared to healthy control PBL (c-PBL). u-HMW induce apoptosis both in u-PBL and c-PBL, as well as in mononuclear cell lines, also stimulating cellular H2O2 formation and secretion, IRE1-α-mediated endoplasmic reticulum stress signaling, and JNK/cJun pathway activation. Also, u-HMW induce autophagy in THP-1 monocytes. u-PBL were characterized by the presence in their cellular proteome of the main proteins and carbonylation targets of u-HMW, namely albumin, transferrin, and fibrinogen, and by the increased expression of receptor for advanced glycation end-products, a scavenger receptor with promiscuous ligand binding properties involved in leukocyte activation and endocytosis. CONCLUSIONS: Large uremic solutes induce abnormal endocytosis and terminal alteration of cellular proteostasis mechanisms in PBL, including UPR/ER stress response and autophagy, ultimately activating the JNK-mediated apoptotic signaling of these cells. These findings describe the suicidal role of immune cells in facing systemic proteostasis alterations of kidney disease patients, a process that we define as the immuno-proteostasis response of uremia.

Effect of Repeated Bolus and Continuous Glucose Infusion on DNA Damage and Oxidative Stress Biomarkers in Healthy Male Volunteers.

Glucose variability (GV), which describes fluctuations in blood glucose levels within the day, is a phenomenon that is increasingly becoming the target of scientific attention when it comes to increased risk of coronary heart disease. Effects of GV may contribute to the development of metabolic syndrome and type 2 diabetes. Hyperglycemia can lead to oxidative stress resulting in molecular damage due to accumulation of reactive oxygen species (ROS). To discover more about the immediate effects of GV, continuous vs. bolus intravenous glucose administration was applied to 10 healthy men aged 21-30 years over a time frame of 48 h. Whole blood and plasma were analyzed for DNA damage using a comet assay with 3 different treatments (lysis buffer, H2O2, and the lesion-specific enzyme formamidopyrimidine DNA glycosylase (FPG)) as well as for the oxidative stress markers protein carbonyls (PC), unconjugated bilirubin (UCB), and ferric reducing antioxidant power (FRAP). A significant time effect was found in the three DNA damage treatments as well as in PC and UCB possibly due to circadian changes on oxidative stress, but no intervention group effect was observed for any of the markers. In conclusion, bolus vs. continuous glucose administration had no significant acute effect on DNA damage and markers of oxidative stress in healthy men.

Determination of chemical constituent yields in e-cigarette aerosol using partial and whole pod collections, a comparative analysis.

Literature reports the chemical constituent yields of electronic nicotine delivery systems (ENDS) aerosol collected using a range of aerosol collection strategies. The number of puffs to deplete an ENDS product varies widely, but collections often consist of data from the first 50-100 puffs. However, it is not clear whether these discrete puff blocks are representative of constituent yields over the life of a pod. We aimed to assess the effect of differing aerosol collection strategies on reported yields for select chemical constituents in the aerosol of closed pod-based ENDS products. Constituents analyzed were chosen to reflect important classes of compounds from the Final Premarket Tobacco Product Application Guidance. Yields were normalized to total device mass loss (DML). Collection strategies that consisted of partial pod collection were valid for determining yields of constituents whose DML normalized yields were consistent for the duration of pod life. These included primary aerosol constituents, such as propylene glycol, glycerol, and nicotine, and whole pod yields could be determined from initial puff blocks. However, changes were observed in the yields of some metals, some carbonyl compounds, and glycidol over pod life in a chemical constituent and product dependent manner. These results suggest that collection strategies consisting of initial puff block collections require validation per chemical constituent/product and are not appropriate for chemical constituents with variable yields over pod life. Whole pod collection increased sensitivity and accuracy in determining metal, carbonyl, and glycidol yields compared to puff block-based collection methodologies for all products tested.

Peptidomics Analysis of Soy Protein Hydrolysates-Antioxidant Properties and Mechanism of their Inhibition of the Oxidation of Palm Olein during Frying Cycles.

This study determined for the first time the structure of the peptides (i.e., peptidomics) in soy protein hydrolysates and elucidated their effects on an oil's oxidative stability during frying cycles. The oil investigated was palm olein during 0, 4, 8, and 12 frying cycles of plantain banana chips. Proteins were extracted and hydrolyzed with two proteases. Trypsin hydrolysate (HTRY) exhibited higher anti-radical activity (DPPH, 70.2%) than the control (unhydrolyzed proteins, 33.49%) and pepsin hydrolysate (HPEP, 46.1%) at 200 µg/mL. HPEP however showed a 4.6-fold greater reduction of ferric ions (FRAP) while also possessing a higher peroxyl radical scavenging ability (716 ± 30 µM Trolox Eq/g) than HTRY (38.5 ± 35 µM Trolox Eq/g). During oil oxidative stability tests, HPEP improved the oxidative stability of the palm olein oil after 8 and 12 frying cycles, characterized by lower concentrations of hydroperoxides, and carbonyl and volatile compounds. HTRY however exerteda pro-oxidant activity. Structural data from SDS-PAGE and tandem mass spectrometry showed that the mechanism for the greater activity of the pepsin hydrolysate occurred due to unique structural features and a higher percentage of short-chain peptides. This was justified by a 25, 31, and 48% higher contents of tryptophan, histidine, and methionine, respectively (important amino acids with hydrogen atom transfer and electron-donating capacities) in the peptides identified in the pepsin hydrolysate.

Effect of Wort Boiling System and Hopping Regime on Wort and Beer Stale-Flavor Aldehydes.

The main factor responsible for the sensory aging of beer is the increase in off-flavor aldehydes during beer storage. In pilot brews (200 L) of pale lager beer with different hopping regimes and wort boiling systems, 15 carbonyls were monitored using the GC-MS method. Factor analysis revealed several groups of aldehydes with similar behavior during wort boiling. The concentration of most of them decreased with atmospheric wort boiling and increased with the time and energy-saving pressurized boiling system. Wort clarification was a critical step because of the increase in carbonyl concentration, with the level of most carbonyls being higher in the final wort compared to sweet wort. The hopping regimes only affected the level of 3-methylbutan-2-one in the wort. The concentration of carbonyls decreased significantly (30-90%) during fermentation, except for trans-2-butenal, which increased by 59% on average, likely due to the release from imine complex. The concentration of free aldehydes in the fresh beers was similar for all variants used, but the pressurized wort boiling system could result in lower sensory stability of the beer due to the release of aldehydes from inactive complexes formed during fermentation. This aspect requires further investigation.