Brewer's Spent Grain-Cellulose-Coated Copper Electrode-Based Extended Gate Field-Effect Transistor for Nonenzymatic Glucose Detection toward Diagnosis of Diabetes Mellitus.

The demand for environmentally friendly, reliable, and cost-effective electrodes for glucose sensor technology has become a major research area in the paradigm shift toward green electronics. In this regard, cellulose has emerged as a promising flexible biopolymer solution with unique properties such as biocompatibility, biodegradability, nontoxicity, renewability, and sustainability. Because of their large surface area and porous structure, fibrous cellulose substrates quickly adsorb and disperse analytes at detection sites. This work focuses on utilizing glyoxal-treated cellulose (derived from brewer's spent grain (BSG)) for the fabrication of extended gate field-effect transistor (EGFET)-based glucose sensors. This investigation extends to the utilization of BSG-cellulose for glucose detection in biomimicking electrolytes (phosphate buffer saline) to facilitate glucose detection in human blood samples. The fabricated electrode demonstrates a linear range of glucose detection from 1 to 13.5 mM with a Langmuir adsorption coefficient (K) of 0.102. Also, its selectivity toward glucose over interfering molecules such as sucrose, fructose, ascorbic acid, and uric acid under physiological conditions has been demonstrated. This cellulose-based EGFET electrode exhibits a sensitivity of 6.5 µA mM-1 cm-2 with a limit of detection (LOD) of 0.135 mM. Computational studies by density functional theory calculations confirmed the higher binding affinity of glucose molecules with glyoxal-modified cellulose (-0.95 eV) than with pristine cellulose (-0.46 eV). Here, the novelty lies in the fabrication of electrodes with biodegradable catalysts and their integration into the EGFET configuration.

Investigating vertical distributions and photochemical indications of formaldehyde, glyoxal, and NO2 from MAX-DOAS observations in four typical cities of China.

Formaldehyde (HCHO), glyoxal (CHOCHO), and nitrogen dioxide (NO2) are crucial in atmospheric photochemical processes at both surface and elevated altitudes. This study presents synchronous multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of the vertical distributions of summertime HCHO, CHOCHO and NO2 in four representative megacities within the Beijing-Tianjin-Hebei (BTH), Yangtze River Delta (YRD), Sichuan Basin (SB), and Pearl River Delta (PRD) regions of China. The vertical distributions of HCHO and CHOCHO tended to occur at higher altitudes compared to NO2, influenced by both primary emissions near the ground and photochemical oxidation processes at elevated altitudes. Source separation regression analysis using the CO-CHOCHO trace pair identified secondary formation as the predominant source of ambient HCHO. In urban areas, the ratio of CHOCHO to secondary HCHO (RGFsec) serves as a more reliable metric at ground level for diagnosing VOC precursor sources, excluding the interference of primary and background HCHO. The increase in RGF values at higher altitudes highlights the relative contribution of VOCs favoring CHOCHO production. Moreover, four indicators (e.g. FNR, FNRsec, GNR, and MNR) were utilized to characterize O3 formation sensitivity at different altitudes. The range of FNR, FNRsec, GNR, and MNR marking the O3 formation sensitivity regime varies regionally, highlighting the need for localized assessments. The VOC-limited regime dominated at the ground level, whereas the contribution of the NOx-limited regime increased with altitude. Therefore, a comprehensive control strategy addressing both VOC and NOx emissions across different altitudes is essential for effectively mitigating photochemical pollution in urban areas of China.

The Role of Natural Low Molecular Weight Dicarbonyls in Atherogenesis and Diabetogenesis.

This review summarises the data from long-term experimental studies and literature data on the role of oxidatively modified low-density lipoproteins (LDL) in atherogenesis and diabetogenesis. It was shown that not "oxidized" (lipoperoxide-containing) LDL, but dicarbonyl-modified LDL are atherogenic (actively captured by cultured macrophages with the help of scavenger receptors), and also cause expression of lectin like oxidized low density lipoprotein receptor 1 (LOX-1) and nicotinamide adenine dinucleotide phosphate (NADPH) oxidase 1 (NOX-1) genes in endotheliocytes, which stimulate apoptosis and endothelial dysfunction. The obtained data allowed us to justify new approaches to pharmacotherapy of atherosclerosis and diabetes mellitus.

Multi-response kinetic study of Maillard reaction hazards in the glucose-lysine model system.

BACKGROUND: Nε-carboxymethyllysine (CML), Nε-carboxyethyllysine (CEL) and α-aminoadipic acid (AAA) are important foodborne hazards and their intake can cause a variety of diseases in humans. It is extremely important to investigate the formation mechanism of CML, CEL and AAA, as well as their association with each other when aiming to control their production. RESULTS: A multi-response kinetic model was developed within the glucose-lysine Maillard reaction model system. The concentrations of glucose, lysine, glyoxal (GO), methylglyoxal (MGO), CML, CEL and AAA were quantified at different temperature (100-160 °C) and at different intervals (0-60 min). The experimental data were fitted to the proposed model to calculate kinetic parameters for the corresponding steps. The results indicated that the production of CML was primarily relied on the direct oxidative cleavage of the Amadori product, rather than the reaction between GO and Lys, whereas CEL and AAA were generated through the reaction of MGO with Lys. Significantly, the reaction between α-dicarbonyl compounds and Lys preferentially generated CML and CEL, resulting in the lower concentrations of AAA compared to CML and CEL. CONCLUSION: The multi-response kinetic model developed in the present study can be applied well to the Maillard reaction. The relationship between the formation mechanisms of CML, CEL and AAA is also explained. © 2024 Society of Chemical Industry.

A Polarizable Forcefields for Glyoxal Acetals as Electrolyte Components for Lithium-Ion Batteries.

In this work we have derived the parameters of an AMOEBA-like polarizable forcefield for electrolytes based on tetramethoxy and tetraethoxy-glyoxal acetals, and propylene carbonate. The resulting forcefield has been validated using both ab-initio data and the experimental properties of the fluids. Using molecular dynamics simulations, we have investigated the structural features and the solvation properties of both the neat liquids and of the corresponding 1 M LiTFSI electrolytes at the molecular level. We present a detailed analysis of the Li ion solvation shells, of their structure and highlight the different behavior of the solvents in terms of their molecular structure and coordinating features.

Women suffering from systemic lupus erythematosus are characterized by low blood levels of α-dicarbonyl compounds.

Introduction: Systemic lupus erythematosus (SLE) is a chronic, autoimmune disease, often characterised by severe course and unclear etiopathogenesis. The reaction of protein glycoxidation, also known as glycation, may be linked to etiopathogenesis of SLE. Advanced glycation end-products (AGEs) exhibit cytotoxic properties, affect cellular signalling, impair functions of extracellular proteins, and may act as neoepitopes. Glucosone (GS), glyoxal (GO), and methylglyoxal (MGO) are examples of α-dicarbonyl compounds (α-DCs) partaking in glycoxidation. The study aimed to evaluate concentrations of these three compounds in blood serum of SLE patients, and to compare the results with healthy individuals. Material and methods: 31 women suffering from SLE and 26 healthy individuals were included in the study. High-performance liquid chromatography with fluorescence detection was applied to evaluate concentrations of α-DCs in their serum samples. Correlations between the results and parameters such as disease duration time, age, glomerular filtration rate (GFR), Systemic Lupus Erythematosus Disease Activity Index 2000 (SLEDAI-2K), and creatinine were analysed. Results: The SLE patients exhibited lower concentrations of glucosone, glyoxal, and methylglyoxal than the control group. Analysis of correlations showed a difference between the examined groups. Conclusions: In women suffering from SLE the course of α-DCs metabolism is altered. SLE patients are characterised by low serum levels of α-DCs. We hypothesise that either hindered proteasomal degradation or fast consumption of α-DCs in oxidative conditions may cause the observed low concentration of these compounds.

Coordination and diffusion in glyoxal-based electrolytes for potassium-ion batteries.

Glyoxal-based electrolytes have been identified as promising for potassium-ion batteries (PIBs). Here we investigate the properties of electrolytes containing bis(fluorosulfonyl)imide (KFSI) in 1,1,2,2-tetra-ethoxy-ethane (tetra-ethyl-glyoxal, TEG) using density functional theory (DFT) calculations, Raman spectroscopy, and impedance spectroscopy. The coordination and configuration of the complexes possible to arise from coordination of the K+ ions by FSI and TEG were investigated both from an energetic point of view as well as qualitatively determined via comparing experimental and artificial Raman spectra. Overall, the K+ coordination depends heavily on the electrolyte composition with contributions both from FSI and TEG. Energetically the coordination by both the trans FSI anion conformer and the TEG solvent with four z-chain conformation is preferrable. From the spectroscopy we find that at lower concentrations, the predominant coordination is by TEG, whereas at higher concentrations, K+ is coordinated mostly by FSI. Concerning the diffusion of ions, investigated by impedance spectroscopy, show that the diffusion of the potassium salt is faster as compared to lithium and sodium salts in comparable electrolytes.

Energetics of the OH radical H-abstraction reactions from simple aldehydes and their geminal diol forms.

CONTEXT: Carbonyl compounds, especially aldehydes, emitted to the atmosphere, may suffer hydration in aerosols or water droplets in clouds. At the same time, they can react with hydroxyl radicals which may add or abstract hydrogen atoms from these species. The interplay between hydration and hydrogen abstraction is studied using density functional and quantum composite theoretical methods, both in the gas phase and in simulated bulk water. The H-abstraction from the aldehydic and geminal diol forms of formaldehyde, acetaldehyde, glycolaldehyde, glyoxal, methylglyoxal, and acrolein is studied to determine whether the substituent has any noticeable effect in the preference for the abstraction of one form or another. It is found that abstraction of the H-atom adjacent to the carbonyl group gives a more stable radical than same abstraction from the geminal diol in the case of formaldehyde, acetaldehyde, and glycolaldehyde. The presence of a delocalizing group in the Cα (a carbonyl group in glyoxal and methylglyoxal, and a vinyl group in acrolein), reverts this trend, and now the abstraction of the H-atom from the geminal diol gives more stable radicals. A further study was conducted abstracting hydrogen atoms from the other different positions in the species considered, both in the aldehydic and geminal diol forms. Only in the case of glycolaldehyde, the radical formed by H-abstraction from the -CH2OH group is more stable than any of the other radical species. Abstraction of the hydrogen atom in one of the hydroxyl groups in the geminal diol is equivalent to the addition of the •OH radical to the aldehyde. It leads, in some cases, to decomposition into a smaller radical and a neutral molecule. In these cases, some interesting theoretical differences are observed between the results in gas phase and (simulated) bulk solvent, as well as with respect to the method of calculation chosen. METHODS: DFT (M06-2X, B2PLYP, PW6B95), CCSD(T), and composite (CBS-QB3, jun-ChS, SCVECV-f12) methods using Dunning basis sets and extrapolation to the CBS limit were used to study the energetics of closed shell aldehydes in their keto and geminal-diol forms, as well as the radical derived from them by hydrogen abstraction. Both gas phase and simulated bulk solvent calculations were performed, in the last case using the Polarizable Continuum Model.

Fenfuro®-mediated arrest in the formation of protein-methyl glyoxal adducts: a new dimension in the anti-hyperglycemic potential of a novel fenugreek seed extract.

The fenugreek plant (Trigonella foenum-graecum) is traditionally known for its anti-diabetic properties owing to its high content of furostanolic saponins, which can synergistically treat many human ailments. Non-enzymatic protein glycation leading to the formation of Advanced Glycation End products (AGE) is a common pathophysiology observed in diabetic or prediabetic individuals, which can initiate the development of neurodegenerative disorders. A potent cellular source of glycation is Methyl Glyoxal, a highly reactive dicarbonyl formed as a glycolytic byproduct. We demonstrate the in vitro glycation arresting potential of Fenfuro®, a novel patented formulation of Fenugreek seed extract with clinically proven anti-diabetic properties, in Methyl-Glyoxal (MGO) adducts of three abundant amyloidogenic cellular proteins, alpha-synuclein, Serum albumin, and Lysozyme. A 0.25% w/v Fenfuro® was able to effectively arrest glycation by more than 50% in all three proteins, as evidenced by AGE fluorescence. Glycation-induced amyloid formation was also arrested by more than 36%, 14% and 15% for BSA, Alpha-synuclein and Lysozyme respectively. An increase in MW by attachment of MGO was also partially prevented by Fenfuro® as confirmed by SDS-PAGE analysis. Glycation resulted in enhanced aggregation of the three proteins as revealed by Native PAGE and Dynamic Light Scattering. However, in the presence of Fenfuro®, aggregation was arrested substantially, and the normal size distribution was restored. The results cumulatively indicated the lesser explored potential of direct inhibition of glycation by fenugreek seed in addition to its proven role in alleviating insulin resistance. Fenfuro® boosts its therapeutic potential as an effective phytotherapeutic to arrest Type 2 diabetes.

Fenfuro^® is a novel patented formulation of Fenugreek seed extract with more than 45% furostanolic saponins and anti-diabetic property free from any side effect as established through clinical study.In the present study, the role of Fenfuro® in arresting in vitro AGE formation and glycation-induced amyloid formation has been demonstrated with the help of three amyloidogenic proteins, namely Human Lysozyme, Human alpha-synuclein and Bovine Serum Albumin using Methyl Glyoxal as the glycating agent.A 0.25% (w/v) ethanolic solution of Fenfuro® resulted in more than 50% arrest in glycation with simultaneous prevention of aggregation as demonstrated by native PAGE, DLS and inhibition of development of Thio-T positive amyloid like entities.The studies collectively aim toward the development of a safe therapeutic method for arresting protein glycation through direct physical intervention.

Glyoxal-methyl-ethylene sulfonic acid fixative enhances the fixation of cytoskeletal structures for Förster resonance energy transfer measurements.

Förster resonance energy transfer (FRET) serves as a tool for measuring protein-protein interactions using various sensor molecules. The tension sensor module relies on FRET technology. In our study, this module was inserted within the actinin molecule to measure the surface tension of the cells. Given that the decay curve of FRET efficiency correlates with surface tension increase, precise and accurate efficiency measurement becomes crucial. Among the methods of FRET measurements, FRET efficiency remains the most accurate if sample fixation is successful. However, when cells were fixed with 4% paraformaldehyde (PFA), the actinin-FRET sensor diffused across the cytoplasm; this prompted us to explore fixation method enhancements. Glyoxal fixative has been reported to improve cytoskeletal morphologies compared to PFA. However, it was not known whether glyoxal fits FRET measurements. Glyoxal necessitates an acetic acid solution for fixation; however, acidic conditions could compromise fluorescence stability. We observed that the pH working range of glyoxal fixative aligns closely with MES (methyl-ethylene sulfonic acid) Good's buffer. Initially, we switched the acidic solution for MES buffer and optimized the fixation procedure for in vitro and in vivo FRET imaging. By comparing FRET measurements on hydrogels with known stiffness to tumor nodules in mouse lung, we estimated in vivo stiffness. The estimated stiffness of cancerous tissue was harder than the reported stiffness of smooth muscle. This discovery shed lights on how cancer cells perceive environmental stiffness during metastasis.

Development of environmentally friendly glyoxal-based adhesives with outstanding water repellency utilizing wheat gluten protein.

To reduce the release of volatile organic compounds (VOCs) from formaldehyde-based adhesives at the source, the use of low-toxicity and biodegradable glyoxal instead of formaldehyde for the preparation of novel urea-glyoxal resins is a simple and promising strategy. The limited water resistance and adhesive strength of the new urea-glyoxal resins (UG) restrict their extensive application. This study prepared a high-performance, water-resistant WP-UG wood adhesive by combining UG prepolymer with wheat gluten protein (WP). FTIR, XRD, and XPS confirmed the existence of a chemical reaction between the two components, and thermal analysis showed that WP-UG plywood had better thermal stability. Evaluation of the gluing properties revealed that the dry and wet strengths of WP-UG adhesive bonded plywood reached 1.39 and 0.87 MPa, respectively, which were significantly higher than those of UG resin by 35 % and 314 %. The bond strength increased from 0 to 0.89 MPa after immersion in water at 63 °C for 3 h. The results indicated that the introduction of WP promoted the formation of a more complex and tightly packed crosslinking network and developed a glyoxal-based adhesive with high bond strength and water resistance. This study provides a new green pathway for novel urea-formaldehyde binders to replace harmful formaldehyde-based binders, which helps to increase their potential application value in the wood industry.

Theanine Capture of Reactive Carbonyl Species in Humans after Consuming Theanine Capsules or Green Tea.

Acrolein (ACR), methylglyoxal (MGO), and glyoxal (GO) are a class of reactive carbonyl species (RCS), which play a crucial role in the pathogenesis of chronic and age-related diseases. Here, we explored a new RCS inhibitor (theanine, THE) and investigated its capture capacity on RCS in vivo by human experiments. After proving that theanine could efficiently capture ACR instead of MGO/GO by forming adducts under simulated physiological conditions, we further detected the ACR/MGO/GO adducts of theanine in the human urine samples after consumption of theanine capsules (200 and 400 mg) or green tea (4 cups, containing 200 mg of theanine) by using ultraperformance liquid chromatography-time-of-flight-high-resolution mass spectrometry. Quantitative assays revealed that THE-ACR, THE-2ACR-1, THE-MGO, and THE-GO were formed in a dose-dependent manner in the theanine capsule groups; the maximum value of the adducts of theanine was also tested. Furthermore, besides the RCS adducts of theanine, the RCS adducts of catechins could also be detected in the drinking tea group. Whereas, metabolite profile analysis showed that theanine could better capture RCS produced in the renal metabolic pathway than catechins. Our findings indicated that theanine could reduce RCS in the body in two ways: as a pure component or contained in tea leaves.

Investigation of formation of AGEs precursors, hydroxymethylfurfural and malondialdehyde in oleogel added cakes using an in vitro simulated gastrointestinal digestive system.

The baking process has the potential to generate health-risk compounds, including products from lipid oxidation and Maillard reaction. Pre- and post-digestion levels of hydroxymethylfurfural (HMF), malondialdehyde (MDA), glyoxal (GO), and methylglyoxal (MGO) were studied in cakes formulated with hazelnut and sunflower oil, along with their oleogels as margarine substitutes. The concentration of HMF in oil and oleogel-formulated cakes increased after digestion compared to cakes formulated with margarine. The MDA values were between 82 and 120 µg/100 g in oil and oleogel formulated cakes before digestion and a decrease was observed after digestion. The substitution of margarine with oil and oleogels resulted in the production of high amounts of GO and MGO in cakes. However, the highest bioaccessibility as 318.2% was found in cakes formulated by margarine for GO. Oleogels may not pose a potential health benefit compared to margarines due to the formation of HMF, MDA, GO, and MGO.

Changes in α-Dicarbonyl Compound Contents during Storage of Various Fruits and Juices.

α-Dicarbonyl compounds (α-DCs) are commonly present in various foods. We conducted the investigation into concentration changes of α-DCs including 3-deoxyglucosone (3-DG), glyoxal (GO), and methylglyoxal (MGO) in fresh fruits and decapped commercial juices during storage at room temperature and 4 °C, as well as in homemade juices during storage at 4 °C. The studies indicate the presence of α-DCs in all samples. The initial contents of 3-DG in the commercial juices (6.74 to 65.61 µg/mL) are higher than those in the homemade ones (1.97 to 4.65 µg/mL) as well as fruits (1.58 to 3.33 µg/g). The initial concentrations of GO and MGO are normally less than 1 µg/mL in all samples. During storage, the α-DC levels in the fruits exhibit an initial increase followed by a subsequent decrease, whereas, in all juices, they tend to accumulate continuously over time. As expected, 4 °C storage reduces the increase rates of the α-DC concentrations in most samples. From the viewpoint of the α-DC contents, fruits and homemade juices should always be the first choice for daily intake of nutrients and commercial juices ought to be mostly avoided.

Investigation of Advanced Glycation End Products in Liver, Adipose, and Renal Tissue of Mice on a High-Fat Diet.

Obesity is a complex condition associated with disruptions in carbohydrate, protein, and fat metabolism, linked to increased insulin resistance and glucose intolerance. High levels of Advanced Glycation End-products (AGEs) are associated with a range of chronic diseases, including kidney diseases, diabetic complications, cardiovascular diseases, and neurodegenerative diseases. Our study aims to investigate the accumulation of AGEs in the liver, renal and adipose tissues of mice fed a high-fat diet, contributing to a deeper understanding of obesity and its related metabolic disorders. Our study consists of three different groups fed with diets containing 60% and 10% fat. The Experiment 1 group was maintained on their diet for 12 weeks, while the obese 2 and control groups continued their diets for 24 weeks. AGEs in the liver and kidney tissues obtained were measured using the High-performance liquid chromatography grade (HPLC) method. Higher accumulation of AGEs has been observed in kidney tissue compared to adipose and liver tissues (p < 0.05). Moreover, the GO levels were notably higher in liver tissue than in adipose tissue of the D1 and D2 groups (p < 0.0001). Our results suggest that particularly in kidney tissue, increased filtration burden, functional impairment, and receptor interaction due to obesity may be effective. The lower levels of AGEs detected, especially in the obese groups compared to the control, can be attributed to the inability to metabolize AGEs due to tissue damage caused by obesity.

Determination of toxic α-dicarbonyl compounds in sesame oils using dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry.

Glyoxal, methylglyoxal, and diacetyl are toxic α-dicarbonyl compounds found in heat-processed foods, including edible oils. Dispersive liquid-liquid microextraction was combined with gas chromatography mass spectrometry to determine the glyoxal, methylglyoxal, and diacetyl contents in sesame oil. Chloroform and methanol were selected as the optimal extraction and dispersive solvents, respectively. The maximum derivatization efficiency was obtained using 500 µg of the derivatization agent, o-phenylenediamine. The derivatization of glyoxal was completed in 1 h, whereas those of methylglyoxal and diacetyl were completed immediately. The optimized method was validated, and was found to exhibit a good linearity, recovery, intraday repeatability, and interday reproducibility. The α-dicarbonyl compound concentrations in the oils were dependent on the roasting temperature. The sesame oil concentrates contained 0-175.4, 0-990.5, and 0-220.9 ng g-1 of glyoxal, methylglyoxal, and diacetyl, respectively. For the perilla oils, the respective concentrations were 0-96.4, 0-410.8, and 0-197.5 ng g-1.

The unanti-cipated oxidation of a tertiary amine in a tetra-cyclic glyoxal-cyclam condensate yielding zinc(II) coordinated to a sterically hindered amine oxide.

The complex, tri-chlorido-(1,4,11-tri-aza-8-azonia-tetra-cyclo-[6.6.2.04,16.011,15]hexa-decane 1-oxide-κO)zinc(II) monohydrate, [ZnCl3(C12H23N4O)]·H2O, (I), has monoclinic symmetry (space group P21/n) at 120 K. The zinc(II) center adopts a slightly distorted tetra-hedral coordination geometry and is coordinated by three chlorine atoms and the oxygen atom of the oxidized tertiary amine of the tetra-cycle. The amine nitro-gen atom, inside the ligand cleft, is protonated and forms a hydrogen bond to the oxygen of the amine oxide. Additional hydrogen-bonding inter-actions involve the protonated amine, the water solvate oxygen atom, and one of the chloro ligands.

Investigations of Major α-Dicarbonyl Content in U.S. Honey of Different Geographical Origins.

α-Dicarbonyls are significant degradation products resulting from the Maillard reaction during food processing. Their presence in foods can indicate the extent of heat exposure, processing treatments, and storage conditions. Moreover, they may be useful in providing insights into the potential antibacterial and antioxidant activity of U.S. honey. Despite their importance, the occurrence of α-dicarbonyls in honey produced in the United States has not been extensively studied. This study aims to assess the concentrations of α-dicarbonyls in honey samples from different regions across the United States. The identification and quantification of α-dicarbonyls were conducted using reverse-phase liquid chromatography after derivatization with o-phenylenediamine (OPD) and detected using ultraviolet (UV) and mass spectrometry methods. This study investigated the effects of pH, color, and derivatization reagent on the presence of α-dicarbonyls in honey. The quantification method was validated by estimating the linearity, precision, recovery, method limit of detection, and quantification using known standards for GO, MGO, and 3-DG, respectively. Three major OPD-derivatized α-dicarbonyls including methylglyoxal (MGO), glyoxal (GO), and 3-deoxyglucosone (3-DG), were quantified in all the honey samples. 3-Deoxyglucosone (3-DG) was identified as the predominant α-dicarbonyl in all the U.S. honey samples, with concentrations ranging from 10.80 to 50.24 mg/kg. The total α-dicarbonyl content ranged from 16.81 to 55.74 mg/kg, with the highest concentration measured for Southern California honey. Our results showed no significant correlation between the total α-dicarbonyl content and the measured pH solutions. Similarly, we found that lower amounts of the OPD reagent are optimal for efficient derivatization of MGO, GO, and 3-DG in honey. Our results also indicated that darker types of honey may contain higher α-dicarbonyl content compared with lighter ones. The method validation results yielded excellent recovery rates for 3-DG (82.5%), MGO (75.8%), and GO (67.0%). The method demonstrated high linearity with a limit of detection (LOD) and limit of quantitation (LOQ) ranging from 0.0015 to 0.002 mg/kg and 0.005 to 0.008 mg/kg, respectively. Our results provide insights into the occurrence and concentrations of α-dicarbonyl compounds in U.S. honey varieties, offering valuable information on their quality and susceptibility to thermal processing effects.

Scavenging Glyoxal and Methylglyoxal by Synephrine and Neohesperidin from Flowers of Citrus aurantium L. var. amara Engl. in Mice and Humans.

There is considerable research evidence that α-dicarbonyl compounds, including glyoxal (GO) and methylglyoxal (MGO), are closely related to many chronic diseases. In this work, after comparison of the capture capacity, reaction pathway, and reaction rate of synephrine (SYN) and neohesperidin (NEO) on GO/MGO in vitro, experimental mice were administrated with SYN and NEO alone and in combination. Quantitative data from UHPLC-QQQ-MS/MS revealed that SYN/NEO/HES (hesperetin, the metabolite of NEO) could form the GO/MGO-adducts in mice (except SYN-MGO), and the levels of GO/MGO-adducts in mouse urine and fecal samples were dose-dependent. Moreover, SYN and NEO had a synergistic scavenging effect on GO in vivo by promoting each other to form more GO adducts, while SYN could promote NEO to form more MGO-adducts, although it could not form MGO-adducts. Additionally, human experiments showed that the GO/MGO-adducts of SYN/NEO/HES found in mice were also detected in human urine and fecal samples after drinking flowers of Citrus aurantium L. var. amara Engl. (FCAVA) tea using UHPLC-QTOF-MS/MS. These findings provide a novel strategy to reduce endogenous GO/MGO via the consumption of dietary FCAVA rich in SYN and NEO.

Green infant formula analysis: Optimizing headspace solid-phase microextraction of carbonyl compounds associated with lipid peroxidation using GC-MS and pentafluorophenylhydrazine derivatization.

The refinement and optimization of a method combining headspace solid-phase microextraction (HS-SPME) with gas chromatography-mass spectrometry (GC-MS) was successfully performed for the first time to determine seven carbonyl and dicarbonyl compounds, including glyoxal, methylglyoxal, dimethylglyoxal, and malondialdehyde in infant formulae, related to lipid peroxidation. HS-SPME was utilized for simultaneous extraction and derivatization with pentafluorophenylhydrazine (PFPH). Critical parameters such as temperature, pH, extractive phase, and salting-out were meticulously investigated and fine-tuned by an asymmetrical 2232//9 screening design to ensure the method's efficacy and reliability. Optimal conditions included a PFPH concentration of 5 g/L, pH 5.0, head-space extraction at 60 °C within 10 min, utilizing a DVB/CAR/PDMS coating, and a 20% w/w salting-out. The analytical validation of this method, compliant with FDA guidelines, demonstrated exceptional linearity, sensitivity, specificity, precision (RSD ≤13.8%), and accuracy (84.8% ≤ recovery ≤111.5%). The metric approach AGREEprep confirms its eco-friendliness, marking a significant step towards an environmentally conscious approach in infant formula analysis. An occurrence study conducted on 25 infant formula samples revealed widespread carbonyl and dicarbonyl compounds in both powdered and liquid variants. ANOVA results exhibited variations in compound concentrations among different sample groups. Clustering analyses delineated distinct groups based on carbonyl content, indicating the potential of these compounds as markers for lipid peroxidation and food quality assessment. This method serves as a valuable tool for evaluating infant formula quality, stability towards oxidation, and safety.