The role of 5-hydroxymethylfurfural in food and recent advances in analytical methods.

The thermal processing, storage, and transportation of foodstuffs (e.g., fruit juices, coffee, honey, and vinegar) generate 5-hydroxymethylfurfural (HMF). The food industry uses this compound as a quality marker, thus increasing the demand for fast and reliable analytical methods for its determination. This review focuses on the formation of HMF in food, its desirable and toxic effects, and recent advances in analytical methods for its determination in foodstuffs. The advantages and limitations of these analytical approaches are discussed relative to the main analytical features.

Maillard reaction products and guaiacol as production process and raw material markers for the authentication of sesame oil.

BACKGROUND: Sesame oil has an excellent flavor and is widely appreciated. It has a higher price than other vegetable oils because of the high price of its raw materials, and different processing techniques also result in products of different quality levels, which can command different prices. In the market, there is a persistent problem of adulteration of sesame oil, driven by economic interests. The screening of volatile markers used to distinguish the authenticity of sesame oil raw materials and production processes is therefore very important. RESULTS: In this work, six markers related to the production processes and raw materials of sesame oil were screened by gas chromatography-tandem mass spectrometry (GC-MS/MS) combined with chemometric analysis. They were 3-methyl-2-butanone, 2-ethyl-5-methyl-pyrazine, guaiacol, 2,6-dimethyl-pyrazine, 5-methyl furfural, and ethyl-pyrazine. The concentration of these markers in sesame oil is between 10 and1000 times that found in other vegetable oils. However, only 3-methyl-2-butanone and 2-ethyl-5-methyl-pyrazine differed significantly as the result of the use of different production processes. Except for guaiacol, which was mainly derived from raw materials, the other five compounds mentioned above all result from the Maillard reaction during thermal processing. The six compounds mentioned above are sufficient to distinguish fraud involving sesame oil raw materials and production processes, and can identify accurately adulteration levels of 30% concentration. CONCLUSION: In this study, the classification markers can identify the adulteration of sesame oil accurately. These six compounds are therefore important for the authenticity of sesame oil and provide a theoretical basis for the rapid and accurate identification of the authenticity of sesame oil. © 2021 Society of Chemical Industry.

Effect of various roasting, extraction and drinking conditions on furan and 5-hydroxymethylfurfural levels in coffee.

Furan and 5-hydroxymethylfurfural (5-HMF) were quantified in 108 coffee models prepared considering the species/origin of the coffee beans, roasting temperature/time, mesh size used to sieve the ground coffee beans, type of extraction water and extraction method. The effect of drinking conditions, such as adding sugar or cream, on furan and 5-HMF levels, was also studied. The range of furan and 5-HMF in coffee samples were 5-362 ppb and 51-1143 ppm, respectively. Furan levels were increased by 198-560% with increasing roasting temperature/time and by 106-399% in cold-brew extracts compared with espresso extracts. Among the mesh sizes used, 500 µm with espresso extraction, and 710 µm with cold-brew extraction led to maximal furan levels. 5-HMF concentration was highest in Robusta coffee and espresso extracts, and decreased by 17-76% with increasing roasting temperature/time. In a drinking condition study, furan level was remained unchanged, even when sugar or cream were added.

A novel UHPLC method for determining the degree of coffee roasting by analysis of furans.

The aim of this study was to develop a multi-analyte UHPLC method for furans and to apply it to commercial coffee samples as well as commercial roasting trials. Furans, as rising time-temperature indicators (TTIs), promised to be an alternative to unsatisfactory roasting temperature measurements. Consequently, a UHPLC-UV method for the determination of 5-hydroxymethyl-2-furfural (HMF), 5-hydroxymethyl-2-furoic acid (HMFA), 2-furfural (F), 5-methylfurfural (MF), 2-furyl methyl ketone (FMC), 2-furoic acid (FA), and for 3-caffeoylquinic acid (3-CQA) was developed and validated. Commercial roasted coffee beans contained 77.7-322 mg/kg HMF, 73.3-158 mg/kg HMFA, 109-200 mg/kg 2-F, 157-209 mg/kg MF, 12.3-32.8 mg/kg FMC, and 137-205 mg/kg FA. Roasting trial samples showed strong rising HMF contents (max.: Arabica: 769 mg/kg, Robusta: 364 mg/kg) followed by a distinct decline. Only MF and FA appeared as steady rising TTIs in the roasting process in Arabica and Robusta beans. 3-CQA fitted well as a decreasing TTI as expected.

Ultrasound-assisted extraction extracts from Stemona japonica (Blume) Miq. and Cnidium monnieri (L.) Cuss. could be used as potential Rhipicephalus sanguineus control agents.

Nicotiana tabacum, Stemona japonica, and Cnidium monnieri are common plants that are widely used for their anti-parasitic properties. The purpose of this study was to evaluate the acaricidal activity of extracts from these plants against the brown dog tick, Rhipicephalus sanguineus. A composition analysis of crude extracts by GC-MS was conducted to discover compounds with acaricidal effects. The toxicity of extraction against the engorged nymphs of R. sanguineus was evaluated by an immersion test. The results showed that the crude extracts of S. japonica and C. monnieri in varying ratios, concentrations, and from different extraction methods, had a killing effect on R. sanguineus. Lethality reached 76.67% ± 0.04410 when using a 1:1 extract of S. japonica:C. monnieri in 75% ethanol with ultrasonic extraction; the crude extract was determined at a concentration of 0.5 g/mL. GC-MS results showed that osthole and 5-hydroxymethylfurfural (5-HMF) are the main components of the extract. These results suggested that ultrasound-assisted extraction (UAE) extracts contained acaricidal components acting against R. sanguineus, which may result in the development of effective extracts of S. japonica and C. monnieri as a source of low-toxicity, plant-based, natural acaricidal drugs.

Hydrazone chemistry mediated toehold strand displacement cascade and its application for 5-hydroxymethylfurfural analysis.

Hydrazone chemistry has been firstly explored as capturing mode for interface supported toehold strand displacement cascade (TSDC). The method has been further established for analysis of 5-hydroxymethylfurfural (HMF) based on hydrazone chemistry-mediated TSDC. HMF containing aldehyde group can be covalently captured by hydrazine group around magnetic bead through the formation of hydrazone bond, so as to inhibit the immobilization of hybrid duplex and the occurrence of TSDC. Thereby, HMF will cause the change of the fluorescence of modified magnetic bead. With simplicity, specificity, and sensitivity, the method has been successfully applied to analyze HMF in food samples. This paper gives a new insight to explore capturing mode for interface supported TSDC and the established method can be extended for analysis of saccharic derivatives.

Simultaneous quantification of six indicator compounds in Wen-Qing-Yin by high-performance liquid chromatography-diode array detection.

A simple gradient high-performance liquid chromatography with diode array detection (HPLC-DAD) method was used to simultaneously to analyze characteristics of six indicator compounds in the traditional Chinese medicine (TCM) formulation Wen-Qing-Yin (WQY). Separate optimization was performed using a Cosmosil C18 column gradient method with 0.1% formic acid in both mobile phases of aqueous and acetonitrile (ACN), at a flow rate, detection wavelength, and sample volume of 1.8 mL/min, 268 nm, and 10 µL, respectively. The linear regression of six active compounds berberine (BER), baicalin (BAI), ferulic acid (FER), geniposide (GEN), hydorxymethoxylfurfural (HMF), and paeoniflorin (PAE) was produced at the concentration range of 10-2000 µg/mL. The method validation revealed an acceptable precision (intra- and inter-day precision < 3.39% and 4.11%, respectively) and recovery (85.60-110.45% and 86.58-110.90%), a recovery range of 86.61-109.42%, and sensitivity (limit of detection [LOD] and limit of quantification [LOQ] values were in the range of 0.03-3.13, and 0.08-9.38 µg/mL, respectively) while the calibration curves were linear with a correlation coefficient (R2) ranging from 0.9966 to 0.9989. The qualitative and quantitative analyses were performed by direct comparison of the peaks of the WCY extract to retention times of reference standards. Additionally, principal component analysis (PCA) successfully discriminated four purchased commercial samples of all six indicator constituents, and the present results indicate their comprehensive potential usefulness for qualitative and quantitative analyses of the WQY decoction and its commercial products.

Simultaneous Determination of Acrylamide and Hydroxymethylfurfural in Extruded Products by LC-MS/MS Method.

The aim of this study was to develop a liquid chromatography/tandem mass spectrometry LC-MS/MS method for the simultaneous determination of acrylamide and hydroxymethylfurfural (HMF) in corn snack products enriched with food industry by-products: brewer's spent grain (BSG), sugar beet pulp (SBP) and apple pomace (AP). Development of the method included the study of different sources for ionization, different mobile phases, different extraction conditions as well as different methods of sample preparation. Finally, the single LC-MS/MS method was developed for the analysis of both analytes in one step with a duration of 20 min using a simple single-step extraction. The method with apparent recoveries of 91.4 and 90.4 for acrylamide and HMF, respectively, was applied for the analysis of non-extruded and extruded samples. The obtained results shown that the acrylamide content was

Maillard reaction derived from oil-tea camellia seed through roasting.

BACKGROUND: The Maillard reaction products (MRPs) formed after roasting of oil-tea camellia seeds (camellia seeds) were investigated. Camellia seeds are inevitably heated during processing, but the effect of heating or roasting on the physicochemical properties of camellia seed or oil-tea camellia seed oil (camellia oil) has been seldom studied, especially with respect to the Maillard reaction. RESULTS: Changes in reducing sugars, free amino acids, pH, color, browning intensity and MRP (furosine, glyoxal, methylglyoxal, 5-hydroxymethylfurfural and furural) concentrations were examined in camellia seeds during roasting at 120-160 °C for 20-120 min. Results showed that roasting leads first to a decrease and then to a considerable increase in free amino groups and, at the same time, to a reduction in moisture content and decrease in pH. The sucrose content of the seeds decreased, while that of glucose and fructose increased reciprocally during roasting. On the other hand, the observed changes concerning glyoxal were negligible. Furthermore, 5-hydroxymethylfurfural and furfural have been found at the end of the roasting process, with maximum values of 572.26 ± 1.91 mg kg-1 dry wt and 0.46 ± 0.003 mg kg-1 dry wt, at 160 °C for 120 min, respectively. CONCLUSION: This investigation provides the initial groundwork necessary for the development and implementation of green and efficient technology that could be applied to obtain high-quality camellia oil. Future research is necessary to assess antioxidant capacity, quality and safety of oil after thermal processing of camellia seeds. © 2019 Society of Chemical Industry.

Spatial distributions of furan and 5-hydroxymethylfurfural in unroasted and roasted Coffea arabica beans.

For the first time, the spatial distributions of the highly volatile compounds furan and 5-hydroxymethylfurfural (HMF) have been determined in cross sections of green and roasted Coffea arabica beans. The image maps were revealed by laser ablation DART imaging mass spectrometry (LADI-MS). The presence of these compounds was independently confirmed by GC-MS as well as argon DART-MS. Quantification of furan by GC-MS was completed with the final concentrations in roasted and unroasted beans determined to be 96.5 and 4.1 ng/g, respectively. Furan was observed to be distributed throughout the tissue of both green and roasted beans, while HMF was localized to the silver skin in green beans. Following roasting, the appearance of HMF was more diffuse. The implications of the broad distribution of furan on the one hand, and localization of HMF on the other, are discussed.

Reduction of 5-hydroxymethylfurfural formation by flavan-3-ols in Maillard reaction models and fried potato chips.

BACKGROUND: 5-Hydroxymethylfurfural (HMF) is regarded as a thermal process contaminant in foods. Six flavan-3-ol fractions were isolated or semisynthesized from sorghum, cranberry and grape seed. Their unit compositions, interflavan linkages and degree of polymerization were characterized. The aim of this study was to investigate the effect of flavan-3-ols on the formation of HMF in chemical reaction models and fried potato chips. RESULTS: Results showed that all flavan-3-ols significantly mitigated the HMF formation at concentrations of 50, 100 and 200 µg mL-1 in the chemical model system, and the inhibition was positively related to dose. Using the food model, HMF content was reduced by about 50% when potato chips were soaked in an optimal concentration of 0.1 mg mL-1 flavan-3-ol solutions before frying. Based on the same mass concentration, B-type flavan-3-ols mitigated more HMF than A-type, and oligomeric proanthocyanidins had stronger inhibitory activity than polymers. At suitable addition levels (0.01-0.1 mg mL-1 ), the browning of auto-oxidized flavan-3-ols under high temperature compensated the anti-browning effect along with the supression of the Maillard reaction; therefore, the color of fried potato chips was not affected. CONCLUSION: This study demonstrates that flavan-3-ols could be effective additives for reducing HMF levels in fried potato chips without changing sensory properties. © 2018 Society of Chemical Industry.

An 1H NMR-based metabolomic approach to compare the chemical profiling of retail samples of ground roasted and instant coffees.

The present non-targeted 1H NMR-based fingerprinting approach along with multivariate analysis established differences between representative aqueous extracts of commercial ground roasted coffee (GRC) and instant (soluble) coffee (IC) samples. The latter were prepared either by spray drying or freeze drying. When comparing a total of 33 compounds between GRC and IC, the latter product contained a remarkable increase in 5-(hydroxymethyl)furfural and carbohydrates, as well as a clear decrease in trigonelline, N-methylpyridinium, caffeine, caffeoylquinic acids and 2-furylmethanol. Furthermore, the current protocol was able to detect the subtle chemical differences between spray-dried and freeze-dried IC. The aforementioned metabolites could serve as target molecules in the attempt to preserve, as much as possible, the organoleptic and nutraceutical properties of GRC during the industrial drying processes used in the production of the two commercial types of IC.

Determination of volatile organic compounds in eucalyptus fast pyrolysis bio-oil by full evaporation headspace gas chromatography.

This paper reports a full evaporation (FE) headspace gas chromatographic (HS-GC) method for the determination of the volatile organic compounds (VOCs) in bio-oil (i.e. methanol, ethanol, acetone, acetic acid and furfural). The method uses a 4µL sample of bio-oil in a headspace vial (ca. 20mL). Complete evaporation of the compounds was achieved after seven minutes at 90°C. The method showed good precision and accuracy for methanol, ethanol, acetone and acetic acid. The recovery of furfural was low (74.3%). The results showed that the protocol can be applied for the determination of methanol, ethanol, acetone and acetic acid in bio-oil. Detection limits ranged from 0.13 to 0.16µg. Acetic acid was the dominant analyte in the heavy bio-oil and light bio-oil analysis (113. 3 and 85.1µgmg-1, respectively), followed by methanol, ethanol, and acetone. The polymerisation of furfural was suspected as the cause of its poor quantification.

Chemical Composition and Antioxidant Properties of Powders Obtained from Different Plum Juice Formulations.

Among popular crops, plum (Prunus domestica L.) has received special attention due to its health-promoting properties. The seasonality of this fruit makes it impossible to consume it throughout the year, so new products in a powder form may offer an alternative to fresh consumption and may be used as high-quality natural food ingredients. A 100% plum (cultivar "Valor") juice was mixed with three different concentrations of maltodextrin or subjected to sugars removal by amberlite-XAD column, and dried using the freeze, spray, and vacuum (40, 60, and 80 °C) drying techniques. The identification and quantification of phenolic acids, flavonols, and anthocyanins in plum powders was performed by LC-MS QTof and UPLC-PDA, respectively. l-ascorbic acid, hydroxymethylfurfural, and antioxidant capacity were measured by the Trolox equivalent antioxidant capacity (TEAC) ABTS and ferric reducing antioxidant potential (FRAP) methods in order to compare the influence of the drying methods on product quality. The results indicated that the profile of polyphenolic compounds in the plum juice powders significantly differed from the whole plum powders. The drying of a sugar free plum extract resulted in higher content of polyphenolic compounds, l-ascorbic acid and antioxidant capacity, but lower content of hydroxymethylfurfural, regardless of drying method applied. Thus, the formulation of plum juice before drying and the drying method should be carefully selected in order to obtain high-quality powders.

Non-polyphenolic compounds of a specific kind of dried grape (Maviz) inhibit memory impairments induced by beta-amyloid peptide.

OBJECTIVES: Although grape has been recently the topic of many investigations, Maviz (a kind of dried one) has remained neglected. The aim of this study was to assess anti-Alzheimer activity of Maviz. METHODS: To reach this goal, total phenolic content (TPC) of ethanolic (Eth) and aqueous (Aq) extracts were determined and radical scavenging activity was assayed by 2,2-diphenyl-1-picrylhydrazyl. Chemical compositions of each extract were also determined via GC-Mass. Behavioral changes were studied via passive avoidance and Morris water maze in Aß-induced model of Alzheimer's disease. Catalase (CAT) and superoxide dismutase (SOD) determination were also done on rats' hippocampus. RESULTS: The results showed that seed Eth extract has a high level of TPC and radical scavenging activity. However, this extract had surprisingly no effect on memory and CAT and SOD activities. In contrast, fruit Aq and Eth extracts (containing furfurals as major compounds) inhibited memory impairment (P < 0.001) and elevated brain levels of CAT and SOD(P < 0.05). CONCLUSION: It seems that Maviz non-phenolic compounds-most probably 5-hydroxymethylfurfural and other similar derivatives-are responsible for these actions.

Effect of hydroxytyrosol and olive leaf extract on 1,2-dicarbonyl compounds, hydroxymethylfurfural and advanced glycation endproducts in a biscuit model.

The antiglycative activity of hydroxytyrosol (HT) and olive leaf extract (OLE) was investigated in wheat-flour biscuits. Quercetin (QE) and gallic acid (GA) were used as reference of antiglycative activity of phenolic compounds. HT, OLE, QE and GA were added in the range of 0.25-0.75% (w/w). Samples were compared against a control recipe baked at 180°C/20min. HT biscuit was able to inhibit efficiently the formation of hydroxymethylfurfural (HMF) and 3-deoxyglucosone (3-DG), as well as reduced the formation of overall free fluorescent AGEs and pentosidine. The inhibition of the 3-DG and HMF formation was directly and significantly correlated under controlled baking conditions. However, samples formulated with OLE exerted similar antiglycative capacity against pentosidine and Nε-carboxyethyl-lysine, although the amount of HT in the biscuit was 100-fold lower than the biscuit formulated with HT. Methylglyoxal, 3-DG, and glyoxal were the predominant 1,2-dicarbonyl compounds after baking but only 3-DG was significantly reduced by HT.

Microwave-assisted chemical pre-treatment of waste sorghum leaves: Process optimization and development of an intelligent model for determination of volatile compound fractions.

This study reports the profiling of volatile compounds generated during microwave-assisted chemical pre-treatment of sorghum leaves. Compounds including acetic acid (0-186.26ng/g SL), furfural (0-240.80ng/g SL), 5-hydroxymethylfurfural (HMF) (0-19.20ng/g SL) and phenol (0-7.76ng/g SL) were detected. The reducing sugar production was optimized. An intelligent model based on Artificial Neural Networks (ANNs) was developed and validated to predict a profile of 21 volatile compounds under novel pre-treatment conditions. This model gave R2-values of up to 0.93. Knowledge extraction revealed furfural and phenol exhibited high sensitivity to acid- and alkali concentration and S:L ratio, while phenol showed high sensitivity to microwave duration and intensity. Furthermore, furfural production was majorly dependent on acid concentration and fit a dosage-response relationship model with a 2.5% HCl threshold. Significant non-linearities were observed between pre-treatment conditions and the profile of various compounds. This tool reduces analytical costs through virtual analytical instrumentation, improving process economics.

Quality evaluation of Shenmaidihuang Pills based on the chromatographic fingerprints and simultaneous determination of seven bioactive constituents.

In this study, we aimed to establish a comprehensive and practical quality evaluation system for Shenmaidihuang pills. A simple and reliable high-performance liquid chromatography coupled with photodiode array detection method was developed both for fingerprint analysis and quantitative determination. In fingerprint analysis, relative retention time and relative peak area were used to identify the common peaks in 18 samples for investigation. Twenty one peaks were selected as the common peaks to evaluate the similarities of 18 Shenmaidihuang pills samples with different manufacture dates. Furthermore, similarity analysis was applied to evaluate the similarity of samples. Hierarchical cluster analysis and principal component analysis were also performed to evaluate the variation of Shenmaidihuang pills. In quantitative analysis, linear regressions, injection precisions, recovery, repeatability and sample stability were all tested and good results were obtained to simultaneously determine the seven identified compounds, namely, 5-hydroxymethylfurfural, morroniside, loganin, paeonol, paeoniflorin, psoralen, isopsoralen in Shenmaidihuang pills. The contents of some analytes in different batches of samples indicated significant difference, especially for 5-hydroxymethylfurfural. So, it was concluded that the chromatographic fingerprint method obtained by high-performance liquid chromatography coupled with photodiode array detection associated with multiple compounds determination is a powerful and meaningful tool to comprehensively conduct the quality control of Shenmaidihuang pills.

Characterization of Coffea arabica monofloral honey from Espírito Santo, Brazil.

In this study, samples of coffee honey produced in Espírito Santo State, Brazil, were characterized based on their melissopalynology, physicochemical and nutritional properties, and mineral and caffeine contents. The caffeine content in the nectar from coffee flowers was measured by high performance liquid chromatography (HPLC). Blends of honey were obtained from three Coffea arabica crops, each with 10 colonies of Africanized Apis mellifera. All honey samples contained monofloral (75-78%) pollen belonging to C. arabica. Physicochemical parameters (total acidity, pH, moisture, dry matter, ash, and qualitative hydroxymethylfurfural) were within the approved limits established by EU legislation. Coffee honey contains high levels of ascorbic acid (294.68 mg kg(-1)) and low amounts of total flavonoids (3.51 ± 0.18 mg QE kg(-1)). The most abundant minerals were potassium and calcium (962.59 ± 154.3 and 343.75 ± 25.56 mg kg(-1), respectively). The caffeine content in coffee nectar (1.64 mg kg(-1)) was approximately 8-fold lower than that in honey (12.02 ± 0.81 mg kg(-1)).

An investigation of process contaminants' formation during the deep frying of breadcrumbs using a bread coat model.

The formation of acrylamide, hydroxymethylfurfural (HMF) and furfural was investigated in a deep fried breadcrumb coat model resembling the coat batter of breaded foods. The influence of the composition of the breadcrumb and the frying conditions on the formation of these contaminants was evaluated. Six wheat-based flour formulations of breadcrumbs were deep fried in sunflower oil at temperatures between 170-200 °C and for frying times of 1-5 minutes. Results showed significant differences in the levels of contaminants according to the concentration of the potential precursors in the breadcrumbs. HMF was influenced by the sugar content in the breadcrumbs whereas levels of acrylamide were significantly correlated with the ratio between asparagine and reducing sugars. Acrylamide, HMF and furfural were directly related to the frying time and temperature. The composition of the breadcrumb and the compounds formed during frying contributed to the total antioxidant capacity of the fried samples. The bread coat model is a useful tool in the formulation of breaded foods since it allows the evaluation of the contribution of breadcrumbs in the formation of process contaminants after frying.