fbpx
Wikipedia

Hydroxymethylfurfural

January 01, 1970

Hydroxymethylfurfural (HMF), also known as 5-(hydroxymethyl)furfural, is an organic compound formed by the dehydration of reducing sugars.[4][5] It is a white low-melting solid (although commercial samples are often yellow) which is highly soluble in both water and organic solvents. The molecule consists of a furan ring, containing both aldehyde and alcohol functional groups.

Hydroxymethylfurfural
Names
Preferred IUPAC name
5-(Hydroxymethyl)furan-2-carbaldehyde[1]
Other names
5-(Hydroxymethyl)-2-furaldehyde[1]
5-(Hydroxymethyl)furfural[1]
Identifiers
  • 67-47-0 Y
3D model (JSmol)
  • Interactive image
110889
ChEBI
  • CHEBI:412516 Y
ChEMBL
  • ChEMBL185885 Y
ChemSpider
  • 207215 Y
ECHA InfoCard 100.000.595
EC Number
  • 200-654-9
278693
KEGG
  • C11101 Y
  • 237332
UNII
  • 70ETD81LF0
  • DTXSID3030428
  • InChI=1S/C6H6O3/c7-3-5-1-2-6(4-8)9-5/h1-3,8H,4H2 Y
    Key: NOEGNKMFWQHSLB-UHFFFAOYSA-N Y
  • InChI=1/C6H6O3/c7-3-5-1-2-6(4-8)9-5/h1-3,8H,4H2
    Key: NOEGNKMFWQHSLB-UHFFFAOYAB
  • c1cc(oc1CO)C=O
Properties
C6H6O3
Molar mass 126.111 g·mol−1
Appearance Low melting white solid
Odor Buttery, caramel
Density 1.29 g/cm3
Melting point 30 to 34 °C (86 to 93 °F; 303 to 307 K)
Boiling point 114 to 116 °C (237 to 241 °F; 387 to 389 K) (1 mbar)
UV-vis (λmax) 284 nm[2]
Related compounds
Related furan-2-carbaldehydes
 Furfural

Methoxymethylfurfural

Hazards
GHS labelling:
[3]
Warning[3]
H315, H319, H335[3]
P261, P305+P351+P338, P310[3]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)

HMF can form in sugar-containing food, particularly as a result of heating or cooking. Its formation has been the topic of significant study as HMF was regarded as being potentially carcinogenic to humans. However, so far in vivo genotoxicity was negative. No relevance for humans concerning carcinogenic and genotoxic effects can be derived.[6] HMF is classified as a food improvement agent [7] and is primarily being used in the food industry in form of a food additive as a biomarker as well as a flavoring agent for food products.[8][9] It is also produced industrially on a modest scale[10] as a carbon-neutral feedstock for the production of fuels[11] and other chemicals.[12]

Production and reactions edit

HMF was first reported in 1875 as an intermediate in the formation of levulinic acid from sugar and sulfuric acid.[13] This remains the classical route, with 6-carbon sugars (hexoses) such as fructose undergoing acid catalyzed poly-dehydration.[14][15] When hydrochloric acid is used 5-chloromethylfurfural is produced instead of HMF. Similar chemistry is seen with 5-carbon sugars (pentoses), which react with aqueous acid to form furfural.

 
fructopyranose 1, fructofuranose 2, two intermediate stages of dehydration (not isolated) 3,4 and finally HMF 5

The classical approach tends to suffer from poor yields as HMF continues to react in aqueous acid, forming levulinic acid.[4] As sugar is not generally soluble in solvents other than water, the development of high-yielding reactions has been slow and difficult; hence while furfural has been produced on a large scale since the 1920s,[16] HMF was not produced on a commercial scale until over 90 years later. The first production plant coming online in 2013.[10] Numerous synthetic technologies have been developed, including the use of ionic liquids,[17][18] continuous liquid-liquid extraction, reactive distillation and solid acid catalysts to either remove the HMF before it reacts further or to otherwise promote its formation and inhibit its decomposition.[19]

Derivatives edit

HMF itself has few applications. It can however be converted into other more useful compounds.[12] Of these the most important is 2,5-furandicarboxylic acid, which has been proposed as a replacement for terephthalic acid in the production of polyesters.[20][21] HMF can be converted to 2,5-dimethylfuran (DMF), a liquid that is a potential biofuel with a greater energy content than bioethanol. Hydrogenation of HMF gives 2,5-bis(hydroxymethyl)furan. Acid-catalysed hydrolysis converts HMF into gamma-hydroxyvaleric acid and gamma-valerolactone, with loss of formic acid.[5][4]

Occurrence in food edit

HMF is practically absent in fresh food, but it is naturally generated in sugar-containing food during heat-treatments like drying or cooking. Along with many other flavor- and color-related substances, HMF is formed in the Maillard reaction as well as during caramelization. In these foods it is also slowly generated during storage. Acid conditions favour generation of HMF.[22] HMF is a well known component of baked goods. Upon toasting bread, the amount increases from 14.8 (5 min.) to 2024.8 mg/kg (60 min).[5] It is also formed during coffee roasting, with up to 769 mg/kg.[23]

It is a good wine storage time−temperature marker,[24] especially in sweet wines such as Madeira[25] and those sweetened with grape concentrate arrope.[26]

 
Phallus indusiatus. Cooktown, Queensland, Australia. The fruiting body contains hydroxymethylfurfural

HMF can be found in low amounts in honey, fruit-juices and UHT-milk. Here, as well as in vinegars, jams, alcoholic products or biscuits, HMF can be used as an indicator for excess heat-treatment. For instance, fresh honey contains less than 15 mg/kg—depending on pH-value and temperature and age,[27] and the codex alimentarius standard requires that honey have less than 40 mg/kg HMF to guarantee that the honey has not undergone heating during processing, except for tropical honeys which must be below 80 mg/kg.[28]

Higher quantities of HMF are found naturally in coffee and dried fruit. Several types of roasted coffee contained between 300 – 2900 mg/kg HMF.[29] Dried plums were found to contain up to 2200 mg/kg HMF. In dark beer 13.3 mg/kg were found,[30] bakery-products contained between 4.1 – 151 mg/kg HMF.[31]

It can be found in glucose syrup.

HMF can form in high-fructose corn syrup (HFCS), levels around 20 mg/kg HMF were found, increasing during storage or heating.[27] This is a problem for American beekeepers because they use HFCS as a source of sugar when there are not enough nectar sources to feed honeybees, and HMF is toxic to them. Adding bases such as soda ash or potash to neutralize the HFCS slows the formation of HMF.[27]

Depending on production-technology and storage, levels in food vary considerably. To evaluate the contribution of a food to HMF intake, its consumption-pattern has to be considered. Coffee is the food that has a very high relevance in terms of levels of HMF and quantities consumed.

HMF is a natural component in heated food but usually present in low concentrations. The daily intake of HMF may underlie high variations due to individual consumption-patterns. It has been estimated that the intakes range between 4 mg - 30 mg per person per day, while an intake of up to 350 mg can result from, e.g., beverages made from dried plums.[6][32]

Biomedical edit

A major metabolite in humans is 5-hydroxymethyl-2-furoic acid (HMFA), also known as Sumiki's acid, which is excreted in urine.

HMF bind intracellular sickle hemoglobin (HbS). Preliminary in vivo studies using transgenic sickle mice showed that orally administered 5HMF inhibits the formation of sickled cells in the blood.[33] Under the development code Aes-103, HMF has been considered for the treatment of sickle cell disease.[34]

Quantification edit

Today, HPLC with UV-detection is the reference-method (e.g. DIN 10751–3). Classic methods for the quantification of HMF in food use photometry. The method according to White is a differential UV-photometry with and without sodium bisulfite-reduction of HMF.[35] Winkler photometric method is a colour-reaction using p-toluidine and barbituric acid (DIN 10751–1). Photometric test may be unspecific as they may detect also related substances, leading to higher results than HPLC-measurements. Test-kits for rapid analyses are also available (e.g. Reflectoquant HMF, Merck KGaA).[36][37]

Other edit

HMF is an intermediate in the titration of hexoses in the Molisch's test. In the related Bial's test for pentoses, the hydroxymethylfurfural from hexoses may give a muddy-brown or gray solution, but this is easily distinguishable from the green color of pentoses.

Acetoxymethyl furfural (AMF) is also bio-derived green platform chemicals as an alternative to HMF.[38]

References edit

  1. ^ a b c "Front Matter". Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 911. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
  2. ^ The Determination of HMF in Honey with an Evolution Array UV-Visible Spectrophotometer. Nicole Kreuziger Keppy and Michael W. Allen, Ph.D., Application note 51864, Thermo Fisher Scientific, Madison, WI, USA (article)
  3. ^ a b c d Sigma-Aldrich Co., 5-(Hydroxymethyl)furfural.
  4. ^ a b c van Putten, Robert-Jan; van der Waal, Jan C.; de Jong, Ed; Rasrendra, Carolus B.; Heeres, Hero J.; de Vries, Johannes G. (2013). "Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources". Chemical Reviews. 113 (3): 1499–1597. doi:10.1021/cr300182k. ISSN 0009-2665. PMID 23394139.
  5. ^ a b c Rosatella, Andreia A.; Simeonov, Svilen P.; Frade, Raquel F. M.; Afonso, Carlos A. M. (2011). "5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications". Green Chemistry. 13 (4): 754. doi:10.1039/c0gc00401d. ISSN 1463-9262.
  6. ^ a b Abraham, Klaus; Gürtler, Rainer; Berg, Katharina; Heinemeyer, Gerhard; Lampen, Alfonso; Appel, Klaus E. (2011-04-04). "Toxicology and risk assessment of 5-Hydroxymethylfurfural in food". Molecular Nutrition & Food Research. 55 (5): 667–678. doi:10.1002/mnfr.201000564. ISSN 1613-4125. PMID 21462333.
  7. ^ PubChem. "EU Food Improvement Agents - PubChem Data Source". pubchem.ncbi.nlm.nih.gov. Retrieved 2018-06-25.
  8. ^ Commission Implementing Regulation (EU) No 872/2012 of 1 October 2012 adopting the list of flavouring substances provided for by Regulation (EC) No 2232/96 of the European Parliament and of the Council, introducing it in Annex I to Regulation (EC) No 1334/2008 of the European Parliament and of the Council and repealing Commission Regulation (EC) No 1565/2000 and Commission Decision 1999/217/EC Text with EEA relevance, 2012-10-02, retrieved 2018-06-25
  9. ^ Pubchem. "5-(Hydroxymethyl)-2-furaldehyde". pubchem.ncbi.nlm.nih.gov. Retrieved 2018-06-25.
  10. ^ a b Kläusli, Thomas (2014). "AVA Biochem: commercialising renewable platform chemical 5-HMF". Green Processing and Synthesis. 3 (3): 235–236. doi:10.1515/gps-2014-0029. ISSN 2191-9550. S2CID 100848139.
  11. ^ Huber, George W.; Iborra, Sara; Corma, Avelino (2006). "Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering". Chem. Rev. 106 (9): 4044–98. doi:10.1021/cr068360d. PMID 16967928.MIT Technology Review
  12. ^ a b Lewkowski, J. (2001). "Synthesis, chemistry and applications of 5-hydroxymethyl-furfural and its derivatives". Arkivoc. 1: 17–54. doi:10.3998/ark.5550190.0002.102. hdl:2027/spo.5550190.0002.102. ISSN 1424-6376.
  13. ^ Grote, A. Freiherrn V.; Tollens, B. (1875). "Untersuchungen über Kohlenhydrate. I. Ueber die bei Einwirkung von Schwefelsäure auf Zucker entstehende Säure (Levulinsäure)". Justus Liebig's Annalen der Chemie. 175 (1–2): 181–204. doi:10.1002/jlac.18751750113. ISSN 0075-4617.
  14. ^ Yuriy Román-Leshkov; Juben N. Chheda; James A. Dumesic (2006). "Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose". Science. 312 (5782): 1933–1937. Bibcode:2006Sci...312.1933R. doi:10.1126/science.1126337. PMID 16809536. S2CID 38432592.
  15. ^ Simeonov, Svilen (2016). "Synthesis of 5-(Hydroxymethyl)furfural (HMF)". Organic Syntheses. 93: 29–36. doi:10.15227/orgsyn.093.0029.
  16. ^ Brownlee, Harold J.; Miner, Carl S. (1948). "Industrial Development of Furfural". Industrial & Engineering Chemistry. 40 (2): 201–204. doi:10.1021/ie50458a005. ISSN 0019-7866.
  17. ^ Zakrzewska, Małgorzata E.; Bogel-Łukasik, Ewa; Bogel-Łukasik, Rafał (2011). "Ionic Liquid-Mediated Formation of 5-Hydroxymethylfurfural—A Promising Biomass-Derived Building Block". Chemical Reviews. 111 (2): 397–417. doi:10.1021/cr100171a. ISSN 0009-2665. PMID 20973468.
  18. ^ Eminov, Sanan; Wilton-Ely, James D. E. T.; Hallett, Jason P. (2 March 2014). "Highly Selective and Near-Quantitative Conversion of Fructose to 5-Hydroxymethylfurfural Using Mildly Acidic Ionic Liquids". ACS Sustainable Chemistry & Engineering. 2 (4): 978–981. doi:10.1021/sc400553q. hdl:10044/1/31478.
  19. ^ Teong, Siew Ping; Yi, Guangshun; Zhang, Yugen (2014). "Hydroxymethylfurfural production from bioresources: past, present and future". Green Chemistry. 16 (4): 2015. doi:10.1039/c3gc42018c. ISSN 1463-9262.
  20. ^ Sousa, Andreia F.; Vilela, Carla; Fonseca, Ana C.; Matos, Marina; Freire, Carmen S. R.; Gruter, Gert-Jan M.; Coelho, Jorge F. J.; Silvestre, Armando J. D. (2015). "Biobased polyesters and other polymers from 2,5-furandicarboxylic acid: a tribute to furan excellency". Polym. Chem. 6 (33): 5961–5983. doi:10.1039/C5PY00686D. ISSN 1759-9954.
  21. ^ Zhang, Daihui; Dumont, Marie-Josée (1 May 2017). "Advances in polymer precursors and bio-based polymers synthesized from 5-hydroxymethylfurfural". Journal of Polymer Science Part A: Polymer Chemistry. 55 (9): 1478–1492. Bibcode:2017JPoSA..55.1478Z. doi:10.1002/pola.28527. hdl:20.500.11794/100964.
  22. ^ Arribas-Lorenzo, G; Morales, FJ (2010). "Estimation of dietary intake of 5-hydroxymethylfurfural and related substances from coffee to Spanish population". Food and Chemical Toxicology. 48 (2): 644–9. doi:10.1016/j.fct.2009.11.046. hdl:10261/82147. PMID 20005914.
  23. ^ Macheiner, Lukas; Schmidt, Anatol; Karpf, Franz; Mayer, Helmut K. (2021). "A novel UHPLC method for determining the degree of coffee roasting by analysis of furans". Food Chemistry. 341 (Pt 1): 128165. doi:10.1016/j.foodchem.2020.128165. ISSN 0308-8146. PMID 33038777.
  24. ^ Serra-Cayuela, A.; Jourdes, M.; Riu-Aumatell, M.; Buxaderas, S.; Teissedre, P.-L.; López-Tamames, E. (2014). "Kinetics of Browning, Phenolics, and 5-Hydroxymethylfurfural in Commercial Sparkling Wines". J. Agric. Food Chem. 62 (5): 1159–1166. doi:10.1021/jf403281y. PMID 24444020.
  25. ^ Pereira, V. (2011). "Evolution of 5-hydroxymethylfurfural (HMF) and furfural (F) in fortified wines submitted to overheating conditions". Food Research International. 44: 71–76. doi:10.1016/j.foodres.2010.11.011. hdl:10400.14/7635.
  26. ^ Amerine, Maynard A. (1948). "Hydroxymethylfurfural in California Wines". Journal of Food Science. 13 (3): 264–269. doi:10.1111/j.1365-2621.1948.tb16621.x. PMID 18870652.
  27. ^ a b c Ruiz-Matute, AI; Weiss, M; Sammataro, D; Finely, J; Sanz, ML (2010). "Carbohydrate composition of high-fructose corn syrups (HFCS) used for bee feeding: effect on honey composition". Journal of Agricultural and Food Chemistry. 58 (12): 7317–22. doi:10.1021/jf100758x. PMID 20491475.
  28. ^ Shapla, UM; Solayman, M; Alam, N; Khalil, MI; Gan, SH (2018). "5-Hydroxymethylfurfural (HMF) levels in honey and other food products: effects on bees and human health". Chem Cent J. 12 (1): 35. doi:10.1186/s13065-018-0408-3. PMC 5884753. PMID 29619623.
  29. ^ Murkovic, M; Pichler, N (2006). "Analysis of 5-hydroxymethylfurfual in coffee, dried fruits and urine". Molecular Nutrition & Food Research. 50 (9): 842–6. doi:10.1002/mnfr.200500262. PMID 16917810.
  30. ^ Husøy, T; Haugen, M; Murkovic, M; Jöbstl, D; Stølen, LH; Bjellaas, T; Rønningborg, C; Glatt, H; Alexander, J (2008). "Dietary exposure to 5-hydroxymethylfurfural from Norwegian food and correlations with urine metabolites of short-term exposure". Food and Chemical Toxicology. 46 (12): 3697–702. doi:10.1016/j.fct.2008.09.048. PMID 18929614.
  31. ^ Ramírez-Jiménez, A; Garcı́a-Villanova, Belén; Guerra-Hernández, Eduardo (2000). "Hydroxymethylfurfural and methylfurfural content of selected bakery products". Food Research International. 33 (10): 833. doi:10.1016/S0963-9969(00)00102-2.
  32. ^ Abraham, Klaus; Gürtler, Rainer; Berg, Katharina; Heinemeyer, Gerhard; Lampen, Alfonso; Appel, Klaus E. (May 2011). "Toxicology and risk assessment of 5-Hydroxymethylfurfural in food". Molecular Nutrition & Food Research. 55 (5): 667–678. doi:10.1002/mnfr.201000564. ISSN 1613-4133. PMID 21462333.
  33. ^ Abdulmalik, O; Safo, MK; Chen, Q; Yang, J; Brugnara, C; Ohene-Frempong, K; Abraham, DJ; Asakura, T (2005). "5-hydroxymethyl-2-furfural modifies intracellular sickle haemoglobin and inhibits sickling of red blood cells". British Journal of Haematology. 128 (4): 552–61. doi:10.1111/j.1365-2141.2004.05332.x. PMID 15686467. S2CID 22342114.
  34. ^ "Aes-103 for Sickle Cell Disease". National Center for Advancing Translational Sciences. 2015-03-18. Retrieved 2022-01-20.
  35. ^ White Jr., J. W. (1979). "Spectrophotometric method for hydroxymethylfurfural in honey". Journal of the Association of Official Analytical Chemists. 62 (3): 509–514. doi:10.1093/jaoac/62.3.509. PMID 479072.
  36. ^ Schultheiss, J.; Jensen, D.; Galensa, R. (2000). "Determination of aldehydes in food by high-performance liquid chromatography with biosensor coupling and micromembrane suppressors". Journal of Chromatography A. 880 (1–2): 233–42. doi:10.1016/S0021-9673(99)01086-9. PMID 10890522.
  37. ^ Gaspar, Elvira M.S.M.; Lucena, Ana F.F. (2009). "Improved HPLC methodology for food control – furfurals and patulin as markers of quality". Food Chemistry. 114 (4): 1576. doi:10.1016/j.foodchem.2008.11.097.
  38. ^ Kang, Eun-Sil; Hong, Yeon-Woo; Chae, Da Won; Kim, Bora; Kim, Baekjin; Kim, Yong Jin; Cho, Jin Ku; Kim, Young Gyu (13 April 2015). "From Lignocellulosic Biomass to Furans via 5-Acetoxymethylfurfural as an Alternative to 5-Hydroxymethylfurfural". ChemSusChem. 8 (7): 1179–1188. doi:10.1002/cssc.201403252. ISSN 1864-564X. PMID 25619448.

January 01, 1970
hydroxymethylfurfural, also, known, hydroxymethyl, furfural, organic, compound, formed, dehydration, reducing, sugars, white, melting, solid, although, commercial, samples, often, yellow, which, highly, soluble, both, water, organic, solvents, molecule, consis. Hydroxymethylfurfural HMF also known as 5 hydroxymethyl furfural is an organic compound formed by the dehydration of reducing sugars 4 5 It is a white low melting solid although commercial samples are often yellow which is highly soluble in both water and organic solvents The molecule consists of a furan ring containing both aldehyde and alcohol functional groups Hydroxymethylfurfural Names Preferred IUPAC name 5 Hydroxymethyl furan 2 carbaldehyde 1 Other names 5 Hydroxymethyl 2 furaldehyde 1 5 Hydroxymethyl furfural 1 Identifiers CAS Number 67 47 0 Y 3D model JSmol Interactive image Beilstein Reference 110889 ChEBI CHEBI 412516 Y ChEMBL ChEMBL185885 Y ChemSpider 207215 Y ECHA InfoCard 100 000 595 EC Number 200 654 9 Gmelin Reference 278693 KEGG C11101 Y PubChem CID 237332 UNII 70ETD81LF0 CompTox Dashboard EPA DTXSID3030428 InChI InChI 1S C6H6O3 c7 3 5 1 2 6 4 8 9 5 h1 3 8H 4H2 YKey NOEGNKMFWQHSLB UHFFFAOYSA N YInChI 1 C6H6O3 c7 3 5 1 2 6 4 8 9 5 h1 3 8H 4H2Key NOEGNKMFWQHSLB UHFFFAOYAB SMILES c1cc oc1CO C O Properties Chemical formula C 6H 6O 3 Molar mass 126 111 g mol 1 Appearance Low melting white solid Odor Buttery caramel Density 1 29 g cm3 Melting point 30 to 34 C 86 to 93 F 303 to 307 K Boiling point 114 to 116 C 237 to 241 F 387 to 389 K 1 mbar UV vis lmax 284 nm 2 Related compounds Related furan 2 carbaldehydes Furfural Methoxymethylfurfural Hazards GHS labelling Pictograms 3 Signal word Warning 3 Hazard statements H315 H319 H335 3 Precautionary statements P261 P305 P351 P338 P310 3 Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Y verify what is Y N Infobox references HMF can form in sugar containing food particularly as a result of heating or cooking Its formation has been the topic of significant study as HMF was regarded as being potentially carcinogenic to humans However so far in vivo genotoxicity was negative No relevance for humans concerning carcinogenic and genotoxic effects can be derived 6 HMF is classified as a food improvement agent 7 and is primarily being used in the food industry in form of a food additive as a biomarker as well as a flavoring agent for food products 8 9 It is also produced industrially on a modest scale 10 as a carbon neutral feedstock for the production of fuels 11 and other chemicals 12 Contents 1 Production and reactions 1 1 Derivatives 2 Occurrence in food 3 Biomedical 4 Quantification 5 Other 6 ReferencesProduction and reactions editHMF was first reported in 1875 as an intermediate in the formation of levulinic acid from sugar and sulfuric acid 13 This remains the classical route with 6 carbon sugars hexoses such as fructose undergoing acid catalyzed poly dehydration 14 15 When hydrochloric acid is used 5 chloromethylfurfural is produced instead of HMF Similar chemistry is seen with 5 carbon sugars pentoses which react with aqueous acid to form furfural nbsp fructopyranose 1 fructofuranose 2 two intermediate stages of dehydration not isolated 3 4 and finally HMF 5 The classical approach tends to suffer from poor yields as HMF continues to react in aqueous acid forming levulinic acid 4 As sugar is not generally soluble in solvents other than water the development of high yielding reactions has been slow and difficult hence while furfural has been produced on a large scale since the 1920s 16 HMF was not produced on a commercial scale until over 90 years later The first production plant coming online in 2013 10 Numerous synthetic technologies have been developed including the use of ionic liquids 17 18 continuous liquid liquid extraction reactive distillation and solid acid catalysts to either remove the HMF before it reacts further or to otherwise promote its formation and inhibit its decomposition 19 Derivatives edit HMF itself has few applications It can however be converted into other more useful compounds 12 Of these the most important is 2 5 furandicarboxylic acid which has been proposed as a replacement for terephthalic acid in the production of polyesters 20 21 HMF can be converted to 2 5 dimethylfuran DMF a liquid that is a potential biofuel with a greater energy content than bioethanol Hydrogenation of HMF gives 2 5 bis hydroxymethyl furan Acid catalysed hydrolysis converts HMF into gamma hydroxyvaleric acid and gamma valerolactone with loss of formic acid 5 4 Occurrence in food editHMF is practically absent in fresh food but it is naturally generated in sugar containing food during heat treatments like drying or cooking Along with many other flavor and color related substances HMF is formed in the Maillard reaction as well as during caramelization In these foods it is also slowly generated during storage Acid conditions favour generation of HMF 22 HMF is a well known component of baked goods Upon toasting bread the amount increases from 14 8 5 min to 2024 8 mg kg 60 min 5 It is also formed during coffee roasting with up to 769 mg kg 23 It is a good wine storage time temperature marker 24 especially in sweet wines such as Madeira 25 and those sweetened with grape concentrate arrope 26 nbsp Phallus indusiatus Cooktown Queensland Australia The fruiting body contains hydroxymethylfurfural HMF can be found in low amounts in honey fruit juices and UHT milk Here as well as in vinegars jams alcoholic products or biscuits HMF can be used as an indicator for excess heat treatment For instance fresh honey contains less than 15 mg kg depending on pH value and temperature and age 27 and the codex alimentarius standard requires that honey have less than 40 mg kg HMF to guarantee that the honey has not undergone heating during processing except for tropical honeys which must be below 80 mg kg 28 Higher quantities of HMF are found naturally in coffee and dried fruit Several types of roasted coffee contained between 300 2900 mg kg HMF 29 Dried plums were found to contain up to 2200 mg kg HMF In dark beer 13 3 mg kg were found 30 bakery products contained between 4 1 151 mg kg HMF 31 It can be found in glucose syrup HMF can form in high fructose corn syrup HFCS levels around 20 mg kg HMF were found increasing during storage or heating 27 This is a problem for American beekeepers because they use HFCS as a source of sugar when there are not enough nectar sources to feed honeybees and HMF is toxic to them Adding bases such as soda ash or potash to neutralize the HFCS slows the formation of HMF 27 Depending on production technology and storage levels in food vary considerably To evaluate the contribution of a food to HMF intake its consumption pattern has to be considered Coffee is the food that has a very high relevance in terms of levels of HMF and quantities consumed HMF is a natural component in heated food but usually present in low concentrations The daily intake of HMF may underlie high variations due to individual consumption patterns It has been estimated that the intakes range between 4 mg 30 mg per person per day while an intake of up to 350 mg can result from e g beverages made from dried plums 6 32 Biomedical editA major metabolite in humans is 5 hydroxymethyl 2 furoic acid HMFA also known as Sumiki s acid which is excreted in urine HMF bind intracellular sickle hemoglobin HbS Preliminary in vivo studies using transgenic sickle mice showed that orally administered 5HMF inhibits the formation of sickled cells in the blood 33 Under the development code Aes 103 HMF has been considered for the treatment of sickle cell disease 34 Quantification editToday HPLC with UV detection is the reference method e g DIN 10751 3 Classic methods for the quantification of HMF in food use photometry The method according to White is a differential UV photometry with and without sodium bisulfite reduction of HMF 35 Winkler photometric method is a colour reaction using p toluidine and barbituric acid DIN 10751 1 Photometric test may be unspecific as they may detect also related substances leading to higher results than HPLC measurements Test kits for rapid analyses are also available e g Reflectoquant HMF Merck KGaA 36 37 Other editHMF is an intermediate in the titration of hexoses in the Molisch s test In the related Bial s test for pentoses the hydroxymethylfurfural from hexoses may give a muddy brown or gray solution but this is easily distinguishable from the green color of pentoses Acetoxymethyl furfural AMF is also bio derived green platform chemicals as an alternative to HMF 38 References edit a b c Front Matter Nomenclature of Organic Chemistry IUPAC Recommendations and Preferred Names 2013 Blue Book Cambridge The Royal Society of Chemistry 2014 p 911 doi 10 1039 9781849733069 FP001 ISBN 978 0 85404 182 4 The Determination of HMF in Honey with an Evolution Array UV Visible Spectrophotometer Nicole Kreuziger Keppy and Michael W Allen Ph D Application note 51864 Thermo Fisher Scientific Madison WI USA article a b c d Sigma Aldrich Co 5 Hydroxymethyl furfural a b c van Putten Robert Jan van der Waal Jan C de Jong Ed Rasrendra Carolus B Heeres Hero J de Vries Johannes G 2013 Hydroxymethylfurfural A Versatile Platform Chemical Made from Renewable Resources Chemical Reviews 113 3 1499 1597 doi 10 1021 cr300182k ISSN 0009 2665 PMID 23394139 a b c Rosatella Andreia A Simeonov Svilen P Frade Raquel F M Afonso Carlos A M 2011 5 Hydroxymethylfurfural HMF as a building block platform Biological properties synthesis and synthetic applications Green Chemistry 13 4 754 doi 10 1039 c0gc00401d ISSN 1463 9262 a b Abraham Klaus Gurtler Rainer Berg Katharina Heinemeyer Gerhard Lampen Alfonso Appel Klaus E 2011 04 04 Toxicology and risk assessment of 5 Hydroxymethylfurfural in food Molecular Nutrition amp Food Research 55 5 667 678 doi 10 1002 mnfr 201000564 ISSN 1613 4125 PMID 21462333 PubChem EU Food Improvement Agents PubChem Data Source pubchem ncbi nlm nih gov Retrieved 2018 06 25 Commission Implementing Regulation EU No 872 2012 of 1 October 2012 adopting the list of flavouring substances provided for by Regulation EC No 2232 96 of the European Parliament and of the Council introducing it in Annex I to Regulation EC No 1334 2008 of the European Parliament and of the Council and repealing Commission Regulation EC No 1565 2000 and Commission Decision 1999 217 EC Text with EEA relevance 2012 10 02 retrieved 2018 06 25 Pubchem 5 Hydroxymethyl 2 furaldehyde pubchem ncbi nlm nih gov Retrieved 2018 06 25 a b Klausli Thomas 2014 AVA Biochem commercialising renewable platform chemical 5 HMF Green Processing and Synthesis 3 3 235 236 doi 10 1515 gps 2014 0029 ISSN 2191 9550 S2CID 100848139 Huber George W Iborra Sara Corma Avelino 2006 Synthesis of Transportation Fuels from Biomass Chemistry Catalysts and Engineering Chem Rev 106 9 4044 98 doi 10 1021 cr068360d PMID 16967928 MIT Technology Review a b Lewkowski J 2001 Synthesis chemistry and applications of 5 hydroxymethyl furfural and its derivatives Arkivoc 1 17 54 doi 10 3998 ark 5550190 0002 102 hdl 2027 spo 5550190 0002 102 ISSN 1424 6376 Grote A Freiherrn V Tollens B 1875 Untersuchungen uber Kohlenhydrate I Ueber die bei Einwirkung von Schwefelsaure auf Zucker entstehende Saure Levulinsaure Justus Liebig s Annalen der Chemie 175 1 2 181 204 doi 10 1002 jlac 18751750113 ISSN 0075 4617 Yuriy Roman Leshkov Juben N Chheda James A Dumesic 2006 Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose Science 312 5782 1933 1937 Bibcode 2006Sci 312 1933R doi 10 1126 science 1126337 PMID 16809536 S2CID 38432592 Simeonov Svilen 2016 Synthesis of 5 Hydroxymethyl furfural HMF Organic Syntheses 93 29 36 doi 10 15227 orgsyn 093 0029 Brownlee Harold J Miner Carl S 1948 Industrial Development of Furfural Industrial amp Engineering Chemistry 40 2 201 204 doi 10 1021 ie50458a005 ISSN 0019 7866 Zakrzewska Malgorzata E Bogel Lukasik Ewa Bogel Lukasik Rafal 2011 Ionic Liquid Mediated Formation of 5 Hydroxymethylfurfural A Promising Biomass Derived Building Block Chemical Reviews 111 2 397 417 doi 10 1021 cr100171a ISSN 0009 2665 PMID 20973468 Eminov Sanan Wilton Ely James D E T Hallett Jason P 2 March 2014 Highly Selective and Near Quantitative Conversion of Fructose to 5 Hydroxymethylfurfural Using Mildly Acidic Ionic Liquids ACS Sustainable Chemistry amp Engineering 2 4 978 981 doi 10 1021 sc400553q hdl 10044 1 31478 Teong Siew Ping Yi Guangshun Zhang Yugen 2014 Hydroxymethylfurfural production from bioresources past present and future Green Chemistry 16 4 2015 doi 10 1039 c3gc42018c ISSN 1463 9262 Sousa Andreia F Vilela Carla Fonseca Ana C Matos Marina Freire Carmen S R Gruter Gert Jan M Coelho Jorge F J Silvestre Armando J D 2015 Biobased polyesters and other polymers from 2 5 furandicarboxylic acid a tribute to furan excellency Polym Chem 6 33 5961 5983 doi 10 1039 C5PY00686D ISSN 1759 9954 Zhang Daihui Dumont Marie Josee 1 May 2017 Advances in polymer precursors and bio based polymers synthesized from 5 hydroxymethylfurfural Journal of Polymer Science Part A Polymer Chemistry 55 9 1478 1492 Bibcode 2017JPoSA 55 1478Z doi 10 1002 pola 28527 hdl 20 500 11794 100964 Arribas Lorenzo G Morales FJ 2010 Estimation of dietary intake of 5 hydroxymethylfurfural and related substances from coffee to Spanish population Food and Chemical Toxicology 48 2 644 9 doi 10 1016 j fct 2009 11 046 hdl 10261 82147 PMID 20005914 Macheiner Lukas Schmidt Anatol Karpf Franz Mayer Helmut K 2021 A novel UHPLC method for determining the degree of coffee roasting by analysis of furans Food Chemistry 341 Pt 1 128165 doi 10 1016 j foodchem 2020 128165 ISSN 0308 8146 PMID 33038777 Serra Cayuela A Jourdes M Riu Aumatell M Buxaderas S Teissedre P L Lopez Tamames E 2014 Kinetics of Browning Phenolics and 5 Hydroxymethylfurfural in Commercial Sparkling Wines J Agric Food Chem 62 5 1159 1166 doi 10 1021 jf403281y PMID 24444020 Pereira V 2011 Evolution of 5 hydroxymethylfurfural HMF and furfural F in fortified wines submitted to overheating conditions Food Research International 44 71 76 doi 10 1016 j foodres 2010 11 011 hdl 10400 14 7635 Amerine Maynard A 1948 Hydroxymethylfurfural in California Wines Journal of Food Science 13 3 264 269 doi 10 1111 j 1365 2621 1948 tb16621 x PMID 18870652 a b c Ruiz Matute AI Weiss M Sammataro D Finely J Sanz ML 2010 Carbohydrate composition of high fructose corn syrups HFCS used for bee feeding effect on honey composition Journal of Agricultural and Food Chemistry 58 12 7317 22 doi 10 1021 jf100758x PMID 20491475 Shapla UM Solayman M Alam N Khalil MI Gan SH 2018 5 Hydroxymethylfurfural HMF levels in honey and other food products effects on bees and human health Chem Cent J 12 1 35 doi 10 1186 s13065 018 0408 3 PMC 5884753 PMID 29619623 Murkovic M Pichler N 2006 Analysis of 5 hydroxymethylfurfual in coffee dried fruits and urine Molecular Nutrition amp Food Research 50 9 842 6 doi 10 1002 mnfr 200500262 PMID 16917810 Husoy T Haugen M Murkovic M Jobstl D Stolen LH Bjellaas T Ronningborg C Glatt H Alexander J 2008 Dietary exposure to 5 hydroxymethylfurfural from Norwegian food and correlations with urine metabolites of short term exposure Food and Chemical Toxicology 46 12 3697 702 doi 10 1016 j fct 2008 09 048 PMID 18929614 Ramirez Jimenez A Garci a Villanova Belen Guerra Hernandez Eduardo 2000 Hydroxymethylfurfural and methylfurfural content of selected bakery products Food Research International 33 10 833 doi 10 1016 S0963 9969 00 00102 2 Abraham Klaus Gurtler Rainer Berg Katharina Heinemeyer Gerhard Lampen Alfonso Appel Klaus E May 2011 Toxicology and risk assessment of 5 Hydroxymethylfurfural in food Molecular Nutrition amp Food Research 55 5 667 678 doi 10 1002 mnfr 201000564 ISSN 1613 4133 PMID 21462333 Abdulmalik O Safo MK Chen Q Yang J Brugnara C Ohene Frempong K Abraham DJ Asakura T 2005 5 hydroxymethyl 2 furfural modifies intracellular sickle haemoglobin and inhibits sickling of red blood cells British Journal of Haematology 128 4 552 61 doi 10 1111 j 1365 2141 2004 05332 x PMID 15686467 S2CID 22342114 Aes 103 for Sickle Cell Disease National Center for Advancing Translational Sciences 2015 03 18 Retrieved 2022 01 20 White Jr J W 1979 Spectrophotometric method for hydroxymethylfurfural in honey Journal of the Association of Official Analytical Chemists 62 3 509 514 doi 10 1093 jaoac 62 3 509 PMID 479072 Schultheiss J Jensen D Galensa R 2000 Determination of aldehydes in food by high performance liquid chromatography with biosensor coupling and micromembrane suppressors Journal of Chromatography A 880 1 2 233 42 doi 10 1016 S0021 9673 99 01086 9 PMID 10890522 Gaspar Elvira M S M Lucena Ana F F 2009 Improved HPLC methodology for food control furfurals and patulin as markers of quality Food Chemistry 114 4 1576 doi 10 1016 j foodchem 2008 11 097 Kang Eun Sil Hong Yeon Woo Chae Da Won Kim Bora Kim Baekjin Kim Yong Jin Cho Jin Ku Kim Young Gyu 13 April 2015 From Lignocellulosic Biomass to Furans via 5 Acetoxymethylfurfural as an Alternative to 5 Hydroxymethylfurfural ChemSusChem 8 7 1179 1188 doi 10 1002 cssc 201403252 ISSN 1864 564X PMID 25619448 Retrieved from https en wikipedia org w index php title Hydroxymethylfurfural amp oldid 1193140129, wikipedia, wiki, book, books, library,

article

, read, download, free, free download, mp3, video, mp4, 3gp, jpg, jpeg, gif, png, picture, music, song, movie, book, game, games.