Hydroxymethylfurfural

From Wikipedia, the free encyclopedia

This is an old revision of this page, as edited by ZéroBot (talk | contribs) at 03:30, 14 January 2012 (r2.7.1) (Robot: Adding fr:Hydroxyméthylfurfural). The present address (URL) is a permanent link to this revision, which may differ significantly from the current revision.

Hydroxymethylfurfural
Hydroxymethylfurfural
Names
IUPAC name
5-(hydroxymethyl)-2-furaldehyde
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.595 Edit this at Wikidata
KEGG
  • InChI=1S/C6H6O3/c7-3-5-1-2-6(4-8)9-5/h1-3,8H,4H2 checkY
    Key: NOEGNKMFWQHSLB-UHFFFAOYSA-N checkY
  • 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 126.11 g/mol
Density 1.29 g/cm3
Melting point 30–34 °C
Boiling point 114–116 °C (1 mbar)
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Hydroxymethylfurfural (HMF), also 5-(Hydroxymethyl)furfural, is an organic compound derived from dehydration of certain sugars.[1] This yellow low-melting solid is highly water-soluble. The molecule consists of a furan ring, containing both aldehyde and alcohol functional groups. HMF has been identified in a wide variety of heat-processed foods including milk, fruit juices, spirits, honey, etc. HMF, which is derived from cellulose without use of fermentation, is a potential "carbon-neutral" feedstock for fuels and chemicals.[2]

Production

Related to the production of furfural, HMF is produced from sugars. It arises via the dehydration of fructose.[3] Treatment of fructose with acids followed by liquid-liquid extraction into organic solvents such as methyl isobutyl ketone. The conversion is affected by various additives such as DMSO, 2-butanol, and Poly vinyl pyrrolidone, which minimize the formation of side product. In an optimized system for fructose (but not raw biomass), conversion is 77%, with half the HMF ending up in the organic phase. Ionic liquids also facilitate the conversion of fructose to HMF.[4]

New method for production of hydroxymethylfurfural from fructose

In the image above are displayed in a series of chemical equilibria: fructopyranose 1, fructofuranose 2, two intermediate stages of dehydration (not isolated) 3,4 and finally HMF 5.

Chromous chloride catalyzes the direct conversion of both fructose (yielding 90%+) and glucose (yielding 70%+) into an HMF.[5] Subsequently cellulose has been directly converted into HMF (yielding 55% at 96% purity).[6] The chromium chloride catalyzes the conversion of glucose into fructose.

Uses

HMF can be converted to 2,5-dimethylfuran (DMF), which is a liquid biofuel that in certain ways is superior to ethanol.[which?] Oxidation of HMF also gives 2,5-furandicarboxylic acid, which has been proposed as a replacement for terephthalic acid in the production of polyesters.

5-Hydroxymethyl-2-furfural (5HMF) has been found to bind specifically with 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.[7]

As a component in food

HMF is practically not present 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 colour-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.[8]

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 only has low amounts of HMF—less than 15 mg/kg—depending on pH-value and temperature and age,[9] 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.

Higher quantities of HMF are found naturally in coffee and dried fruit. Several types of roasted coffee contained between 300 – 2900 mg/kg HMF.[10] Dried plums were found to contain up to 2200 mg/kg HMF. In dark beer 13.3 mg/kg were found,[11] bakery-products contained between 4.1 – 151 mg/kg HMF.[12]

HMF can form in high-fructose corn syrup (HFCS), levels around 20 mg/kg HMF were found, increasing during storage or heating.[9] 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 down the formation of HMF.[9]

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 in a western diet, in the order of magnitude of 5 – 10 mg of HMF are ingested per day from food.[8]

In former times, HMF was used in food for flavoring purposes, but in Europe this practice now is suspended. HMF is also found in cigarette smoke.[13]

Metabolism

A major metabolite in humans is 5-hydroxymethyl-2-furoic acid (HMFA), which is excreted in urine. HMF can also be metabolized to 5-sulfoxymethylfurfural (SMF), which is highly reactive and can form adducts with DNA or proteins. In vitro tests and studies on rats suggest potential toxicity and carcinogenicity of HMF.[14] In humans, no correlation of intakes of HMF and disease could be demonstrated yet.

Quantification

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 bisulphite-reduction of HMF (AOAC 980.23). 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. Refelctoquant HMF, Merck KGaA).[15][16]

History

This organic compound was studied by French chemist Louis Maillard in 1912 in studies on non-enzymatic reactions of glucose.

References

  1. ^ Andreia A. Rosatella, Svilen P. Simeonov, Raquel F. M. Frade, Carlos A. M. Afonso "Critical Review 5-Hydroxymethylfurfural (HMF) as a building block platform: Biological Properties, Synthesis and Synthetic Applications" Green Chem., 2011, volume 13, 754. doi:10.1039/c0gc00401d
  2. ^ Huber, George W.; Iborra, Sara; Corma, Avelino (2006). "Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering". Chem. Rev. 106 (9): 4044. doi:10.1021/cr068360d.MIT Technology Review
  3. ^ Yuriy Román-Leshkov, Juben N. Chheda, James A. Dumesic (2006). "Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose". Science. 312 (5782): 1933–1937. doi:10.1126/science.1126337. PMID 16809536.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  4. ^ Ståhlberg, T.; Fu, W.; Woodley, J. M.; Riisager, A.; Synthesis of 5-(Hydroxymethyl)furfural in Ionic Liquids: Paving the Way to Renewable Chemicals. ChemSusChem. 2011, n/a. DOI: 10.1002/cssc.201000374
  5. ^ Haibo Zhao, Johnathan E. Holladay, Heather Brown, Z. Conrad Zhang (2007). "Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural". Science. 316 (5782): 1597–1600. doi:10.1126/science.1141199. PMID 17569858.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  6. ^ Su, Yu; Brown, Heather M.; Huang, Xiwen; Zhou, Xiao-Dong; Amonette, James E.; Zhang, Z. Conrad (2009). "Single-step conversion of cellulose to 5-hydroxymethylfurfural (HMF), a versatile platform chemical". Applied Catalysis A: General. 361: 117. doi:10.1016/j.apcata.2009.04.002.
  7. ^ 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.
  8. ^ a b 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. PMID 20005914.
  9. ^ 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.
  10. ^ 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.
  11. ^ 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.
  12. ^ Ramírez-Jiménez, A (2000). "Hydroxymethylfurfural and methylfurfural content of selected bakery products". Food Research International. 33 (10): 833. doi:10.1016/S0963-9969(00)00102-2.
  13. ^ Rufían-Henares, JA; De La Cueva, SP (2008). "Assessment of hydroxymethylfurfural intake in the Spanish diet". Food Additives & Contaminants: Part A: Chemistry, Analysis, Control, Exposure & Risk Assessment. 25 (11): 1306–12. doi:10.1080/02652030802163406. PMID 19680837.
  14. ^ Husøy, T.; Haugen, M.; Murkovic, M.; Jöbstl, D.; Stølen, L.H.; 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. doi:10.1016/j.fct.2008.09.048. PMID 18929614.
  15. ^ 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: 233. doi:10.1016/S0021-9673(99)01086-9.
  16. ^ 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.
Retrieved from "https://en.wikipedia.org/w/index.php?title=Hydroxymethylfurfural&oldid=471259737"