MGO origin in Manuka honey

The scientific paper that I have written is outlined here.

This paper provides a telling blow to the whole MGO story.

Kinetics of the conversion of dihydroxyacetone to methylglyoxal in New Zealand mānuka honey: Part II--Model systems - PubMed (nih.gov)

Megan N C Grainger 1, Merilyn Manley-Harris 2, Joseph R Lane 1, Richard J Field 3

Abstract

The irreversible dehydration reaction of dihydroxyacetone (DHA) to methylglyoxal (MGO) in a honey model system has been examined to investigate the influence of added perturbant species on the reaction rate. The secondary amino acid proline, primary amino acids (alanine, lysine and serine), and iron, or combinations of these perturbants, were added to artificial honey with either DHA or MGO and stored at 20, 27 and 37°C. These systems were monitored over time. A 1:1 conversion of DHA to MGO was not observed in any system studied, including the control system with no added perturbants. Addition of proline to the matrix increased consumption of DHA but did not produce any more MGO than the control sample. Lysine and serine behaved similarly. Alanine enhanced the conversion of DHA to MGO and had the best efficiency of conversion of DHA to MGO for the amino acids studied. An iron II salt enhanced the conversion of DHA to MGO, even in the presence of proline.

Keywords: Artificial honey; Conversion; Dihydroxyacetone; Methylglyoxal; Model system; Mānuka.

The conclusion that was drawn was DHA in Manuka honey does not turn into MGO. The reason for this is really quite simple. DHA in the nectar when it is turned into honey by the bees becomes a dimer. It no longer is a monomer. The dimer cannot under conversion to MGO. The dimer is stable in the honey because of the low water availability in the honey. It is a hydrophobic environment.

Figure 1: Glyoxal. 

You can see that these compounds are able to bind together to form polymers through a condensation reaction which removes water when two hydroxyls come together to form a bond.

The paper outlines that alanine is a potential source of MGO and not DHA. There appears to be an internal reaction with the carboxylic acid hydroxyl group with the alpha amino carbon where the amino group leaves.

Other references

  • Dissecting the Antimicrobial Composition of Honey.
    Nolan VC, Harrison J, Cox JAG. Nolan VC, et al. Antibiotics (Basel). 2019 Dec 5;8(4):251. doi: 10.3390/antibiotics8040251. Antibiotics (Basel). 2019. PMID: 31817375 Free PMC article. Review.

It appears that MGO does not come from DHA collected by the bees from the nectar. The new discovery is discussed in the following videos.

 This video shows that the natural pollen germination processes taking place within Manuka honey is what is resulting in the development of a polymeric glyoxal. This glyoxal polymeric material appears to be highly fluorescent.  I opened a can of worms in terms of the prior scientific information related to DHA conversion into MGO within the Manuka honey. The ability to explore the new ideas suggests we have to use comparative analysis to compare the two ideas and see which one makes more sense. On one hand DHA conversion into MGO. We need water so that the DHA is in a monomeric form, so that the conversion can take place.

Issue 1) Manuka honey has a high sugar content and low water availability. What this means is that the DHA in the nectar is in a dimeric form. A condensation reaction has taken place leading to the formation of a DHA dimer. In this structure the DHA cannot convert to MGO. It needs water. You add water during the analysis step to dissolve the Manuka honey and determine the concentration of DHA and MGO and 5-HMF. All of the conversion of DHA to MGO could be occurring during the sample preparation. Is it an artifact of the analysis method. 

These are not easy questions to ask and answer. It is not so straight forward. If we think that DHA converts into MGO from the nectar, then we develop techniques to measure DHA conversion from the nectar. We ignore other potential sources. So the pollen origin has been ignored completely.

However, the industry in New Zealand has already identified that high MGO containing honey has low pollen counts and vice versa, which indicates that pollen counts may correlate with MGO formation in an inversely proportional way. This ties in nicely with the evidence I have developed over the years on the basis of identifying the polymeric glyoxal within the broken pollen grain that was highly fluorescent. The idea that photo-Fenton chemistry in involved in pollen tube formation and the breaking open the tube to allow the sperm to interact with the ovum within the flower is something that makes sense. This appears to be what is happening within the Manuka honey during maturation. Finding an alternative source of MGO from the pollen appears to be a key discovery for the industry. I am happy to share this because it assists the industry to concentrate on ways to improve the health-giving benefits of Manuka honey.

 

Pollen is very strong. It is difficult to break apart. The photo-Fenton chemistry has the ability to generate of hydroxyl radical and is involved pollen tube formation. The polymeric glyoxal breaks down and gets released into Manuka honey as the honey is aged during long-term storage. The coordination chemistry is important in the functioning of the photo-Fenton chemistry system. 

Duan, Q., Kita, D., Johnson, E. et al. Reactive oxygen species mediate pollen tube rupture to release sperm for fertilization in Arabidopsis. Nat Commun 5, 3129 (2014). https://doi.org/10.1038/ncomms4129

 

 Glyoxal and its dimer and trimer and the presence of polymeric glyoxal. Turning phenolics in pollen into CO2 and water. A system that pollen uses during fertilisation.

 

The photo Fenton chemistry used to convert pollen phenolics into CO2 and water. Pollen germination system requires CO2 and water. Iron + light and the phenolics as well as hydrogen peroxide generates OH*. Part of our natural death and regeneration system called apoptosis.

Returning biological molecules into CO2 and water. It is a light-based photo-reduction of iron. OH BEE HAVE empowering healing takes advantage of the Senolytic benefits of the royal jelly proteins isolated from Manuka honey to provide the basis for the rejuvenating skin care serum.

 

Manuka honey is prized for its health-giving benefits. It is a magical product. MGO was identified many years ago as the molecule responsible for the biological activity. However, Peter Molan (The God Father of Manuka honey research in New Zealand) rightly suggested that it was more than just MGO. A synergy was responsible for the antimicrobial properties. The current story was being told that dihydroxyacetone (DHA) collected by the bees from the Manuka flower nectar gets converted into MGO on prolonged storage of the Manuka honey. Scientific research suggests that Manuka honey has too little water in it for this conversion to occur effectively. I discovered an alternative mechanism that involves the Manuka honey pollen that the bees collect from the Manuka flower. The pollen undergoes a process that generates a polymer containing glyoxal and this is a natural process that occurs during pollen germination. It uses hydroxyl radicals and photo-Fenton chemistry. The new story identifies that pollen is the natural origin of MGO during Manuka honey aging and not nectar DHA. #MGO #Manuka #honey #DHA #polymer #pollen #germination https://www.ohbeehave.co.nz