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General Category => Yeast and Fermentation => Topic started by: mabrungard on April 10, 2016, 04:59:55 PM

Title: Methyl anthranilate (Grape Ester)
Post by: mabrungard on April 10, 2016, 04:59:55 PM
Is anyone on the forum familiar with this ester and its formation in beer?

I recently brewed a Helles that had a significant corny DMS aroma and flavor when it was young. Through lagering, that corn has been replaced with a light concord grape flavor and aroma. I'm curious if that genesis was via the DMS?

I've noted that this grape ester shows up more often in German lager styles, but I'm not sure why. Maybe because they tend to be malt focused and not hop focused?
Title: Re: Methyl anthranilate (Grape Ester)
Post by: HoosierBrew on April 10, 2016, 05:13:23 PM
I wonder if it's more a pilsner malt thing than strictly a lager thing, Martin. I've noticed it occasionally even in beers like cream ale that get some pils malt. I only notice it now and then and it's subtle, but I've only noticed it when using pils malt in lager or ale.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: mabrungard on April 10, 2016, 09:32:16 PM
Well, its interesting that Pils may be the cause of this. Maybe it has something to do with the SMM or the subsequent DMS. I had not made the correlation with lightly kilned malt previously.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: HoosierBrew on April 10, 2016, 09:37:35 PM
I don't have any experiments or specific data to back it up, Martin. But I've never encountered it when not using Pils. Don't notice it often even then.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: klickitat jim on April 10, 2016, 09:50:15 PM
Isnt this the grape-lollipop ester that S Cerv. talks about in some British strains?
Title: Re: Methyl anthranilate (Grape Ester)
Post by: Frankenbrew on April 10, 2016, 10:01:41 PM
This might be what I am getting in my Maibock. I described it on another thread as the flavor I used to get as a kid with those paper straw sugar candies. I thought I got it from the S-189 yeast, but it certainly could have come from the pilsner malt. The recipe had 67% pilsner malt.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: erockrph on April 10, 2016, 10:05:43 PM
I don't know if this is the same one. Methyl anthranilate is the flavoring in grape Koolaid. There's not a lot of info about this ester's presence in beer, at least within the limits of my Google-fu. Anthranilic acid is a precursor of amino acids, so I'd guess that this is coming from the malt. There's no sulfur in it, so it's hard to picture the chemistry of how DMS could form it.

Sent from my XT1585 using Tapatalk

Title: Re: Methyl anthranilate (Grape Ester)
Post by: HoosierBrew on April 10, 2016, 10:18:24 PM
I couldn't begin to guess at the mechanism forming it, it just seems that sometimes I get a touch when I use pils. Not even maltster specific that I've seen. I've used all the major maltsters' pils (including Belgian) and no one brand seems to produce this consistently. And I could be wrong, though it does seem to correlate with pils. Maybe (like with hops) it's a perception thing - what I perceive as a light grape note someone else might get as just light malty sweetness.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: beersk on April 11, 2016, 12:47:54 PM
So, do you suppose this is a mash, boil, or fermentation thing causing this flaw? I've gotten what someone in my brew club described as sweet kettle corn in some lighter lagers before with mostly pils malt. They said it wasn't DMS though. I attributed most of this to fermentation and underpitching/fermenting too warm. But perhaps it was really the same thing as being described here. It's a sweetness that I can't quite put my finger on what it tastes like. It crops up once in a while. I think since I started acidifying my boil it has gone away though. Knock on wood...
Title: Re: Methyl anthranilate (Grape Ester)
Post by: hopfenundmalz on April 11, 2016, 12:55:20 PM
I associate grape with Munich I malt heavy beers. Traditional Bocks for example. If it from the malt or a compound that the yeast produce from malt is something I can't answer.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: beersk on April 11, 2016, 01:23:41 PM
I associate grape with Munich I malt heavy beers. Traditional Bocks for example. If it from the malt or a compound that the yeast produce from malt is something I can't answer.
And I've especially noticed it when using Munich in my helles beers. So there could be something to that as well.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: blair.streit on April 11, 2016, 01:38:09 PM
Is anyone on the forum familiar with this ester and its formation in beer?

I've noted that this grape ester shows up more often in German lager styles, but I'm not sure why. Maybe because they tend to be malt focused and not hop focused?
Martin by chance did the recipe include any CaraPils?
Title: Re: Methyl anthranilate (Grape Ester)
Post by: blatz on April 11, 2016, 01:39:02 PM
Is anyone on the forum familiar with this ester and its formation in beer?

I recently brewed a Helles that had a significant corny DMS aroma and flavor when it was young.

have one on tap right now that has some of that.   never had the corny DMS aroma or flavor though.  just a light hint on concord grape.  that same yeast (830) was used on a marzen before it and a Vienna after the helles, and neither of those have the grape ester at a detectable level.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: majorvices on April 11, 2016, 01:48:55 PM
I associate grape with Munich I malt heavy beers. Traditional Bocks for example. If it from the malt or a compound that the yeast produce from malt is something I can't answer.

This is exactly what I was thinking. In fact I cut the Munich malt with pilsner malt to avoid that grape character.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: Thirsty_Monk on April 11, 2016, 01:49:26 PM
Is anyone on the forum familiar with this ester and its formation in beer?

I recently brewed a Helles that had a significant corny DMS aroma and flavor when it was young.

have one on tap right now that has some of that.   never had the corny DMS aroma or flavor though.  just a light hint on concord grape.  that same yeast (830) was used on a marzen before it and a Vienna after the helles, and neither of those have the grape ester at a detectable level.
Paul, Munich light will give you hints of grape flavor.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: blair.streit on April 11, 2016, 03:14:00 PM
I've experienced significant cherry esters with beers heavy on Munich and CaraMunch. Cutting back on the CaraMunich has reduced this for me but I don't pretend that I fully understand what happened and would like to experiment more.

I'm wondering if there's something similar in the Pils/CaraPils family that lends grape rather than cherry esters.

I realize I'm way out in speculation-land here, but it strikes me that the kilning temperature and process could lend certain precursors in the wort that then produce elevated levels of these esters during fermentation.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: narcout on April 11, 2016, 04:14:01 PM
Isnt this the grape-lollipop ester that S Cerv. talks about in some British strains?

Per the last blog post, that is ethyl heptanoate.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: morticaixavier on April 11, 2016, 07:13:23 PM
I get grape and candy from pils malt. particularly german pils malt. not noticed a relation to DMS though.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: mabrungard on April 12, 2016, 12:37:56 PM
Per the last blog post, that is ethyl heptanoate.

I've just been alerted that methyl anthranilate is more typically found in wine and ethyl heptanoate is more typically the source of the grape ester in beer. So, let's consider my concern is with ethyl heptanoate!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: blair.streit on April 12, 2016, 12:47:04 PM
Per the last blog post, that is ethyl heptanoate.

I've just been alerted that methyl anthranilate is more typically found in wine and ethyl heptanoate is more typically the source of the grape ester in beer. So, let's consider my concern is with ethyl heptanoate!
This suggests it's a fatty acid ester and that it will dissipate with time. Still no hint at the source, but this is fun so I'll keep digging:

http://www.ymdb.ca/compounds/YMDB01474
Title: Re: Methyl anthranilate (Grape Ester)
Post by: blair.streit on April 12, 2016, 01:20:44 PM
Saccharomyces' blog on Experimental Brewing seems to suggest that it's more common among certain yeasts:

http://www.experimentalbrew.com/blogs/saccharomyces/have-you-seen-ester

Ethyl heptanoate is my all-time favorite ale ester. It smells like one of those grape lollipops that were often given to children by bank tellers and medical office receptionists when I was young. Ales fermented with the Young’s Ram Brewery strain usually contain high levels of this ester when young, which is why I refer to ethyl heptanoate as the British lollipop ester.

Martin, I assume this is a new flavor for you (and you didn't mention trying out anything unique in this brew). Maybe someone can ping Saccharomyces and get him to weigh in on potential sources?
Title: Re: Methyl anthranilate (Grape Ester)
Post by: Hooper on April 12, 2016, 04:04:20 PM
Not kidding...I just dumped 2 cans of frozen white grape juice at 0 in the kettle in my latest Soma Saison...I guess I won't be too upset if get a touch of grape flavor...1st time I've tried this so I have no idea what I will get...
Title: Re: Methyl anthranilate (Grape Ester)
Post by: beersk on April 12, 2016, 04:22:52 PM
Saccharomyces' blog on Experimental Brewing seems to suggest that it's more common among certain yeasts:

http://www.experimentalbrew.com/blogs/saccharomyces/have-you-seen-ester

Ethyl heptanoate is my all-time favorite ale ester. It smells like one of those grape lollipops that were often given to children by bank tellers and medical office receptionists when I was young. Ales fermented with the Young’s Ram Brewery strain usually contain high levels of this ester when young, which is why I refer to ethyl heptanoate as the British lollipop ester.

Martin, I assume this is a new flavor for you (and you didn't mention trying out anything unique in this brew). Maybe someone can ping Saccharomyces and get him to weigh in on potential sources?
Interesting. Wonder where it comes into play in terms of something like a pilsner or helles.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: blair.streit on April 12, 2016, 04:30:13 PM
Interesting. Wonder where it comes into play in terms of something like a pilsner or helles.
I know. Martin was talking about a Helles so likely a lager yeast. Sacc's post mentions a specific ale yeast.

However, looking at this MBAA paper on esters in wheat beers, it indicates that it is more prevalent in lager yeast:

http://www.mbaa.com/districts/MidSouth/Events/Documents/2010-03-13Wheat_Beer_Yeast__Fermentation2.pdf

Sorry, still not any closer to an answer on what conditions might cause increased production....
Title: Re: Methyl anthranilate (Grape Ester)
Post by: mabrungard on April 12, 2016, 08:06:43 PM
A smart birdy landed on my shoulder this morning and whispered some sage information to me.

It turns out that malt contains a precursor to this ester. Its an alkyl aldehyde called heptanal. There are journal articles that show that the heptanal content of barley is dependent upon the cultivar. I would also have to assume that it's concentration might change during malting and kilning. I see that the Kovats retention index for that compound is fairly low, so it is likely to be driven off to some degree during kilning. Paler malts are therefore more likely to contain this precursor.

Heptanal is converted to ethyl heptanoate through the metabolic action of yeast. Ale yeasts are most prone to this metabolic action. Interestingly, this Helles I'm referring to was fermented with US-05 at 52F. So it is possible that this is the source of that ester in my beer.

Thanks, Mark!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: klickitat jim on April 12, 2016, 08:57:00 PM
Isnt this the grape-lollipop ester that S Cerv. talks about in some British strains?
Winner winner chicken dinner
Title: Re: Methyl anthranilate (Grape Ester)
Post by: beersk on April 12, 2016, 09:34:18 PM
A smart birdy landed on my shoulder this morning and whispered some sage information to me.

It turns out that malt contains a precursor to this ester. Its an alkyl aldehyde called heptanal. There are journal articles that show that the heptanal content of barley is dependent upon the cultivar. I would also have to assume that it's concentration might change during malting and kilning. I see that the Kovats retention index for that compound is fairly low, so it is likely to be driven off to some degree during kilning. Paler malts are therefore more likely to contain this precursor.

Heptanal is converted to ethyl heptanoate through the metabolic action of yeast. Ale yeasts are most prone to this metabolic action. Interestingly, this Helles I'm referring to was fermented with US-05 at 52F. So it is possible that this is the source of that ester in my beer.

Thanks, Mark!
Wow, US-05 at 52F? Dang. And that ain't no helles! ;)

Thanks for posting that info, Martin.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: HoosierBrew on April 12, 2016, 09:39:16 PM
Thanks for the info, Martin. I felt since the correlation seemed strong with pils malt, that malt had to play some part. Good to know.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: erockrph on April 12, 2016, 11:05:45 PM
A smart birdy landed on my shoulder this morning and whispered some sage information to me.

It turns out that malt contains a precursor to this ester. Its an alkyl aldehyde called heptanal. There are journal articles that show that the heptanal content of barley is dependent upon the cultivar. I would also have to assume that it's concentration might change during malting and kilning. I see that the Kovats retention index for that compound is fairly low, so it is likely to be driven off to some degree during kilning. Paler malts are therefore more likely to contain this precursor.

Heptanal is converted to ethyl heptanoate through the metabolic action of yeast. Ale yeasts are most prone to this metabolic action. Interestingly, this Helles I'm referring to was fermented with US-05 at 52F. So it is possible that this is the source of that ester in my beer.

Thanks, Mark!
Wow, US-05 at 52F? Dang. And that ain't no helles! ;)

Thanks for posting that info, Martin.
Call it a lollipop blonde? ;)

Sent from my XT1585 using Tapatalk

Title: Re: Methyl anthranilate (Grape Ester)
Post by: jeffy on April 13, 2016, 12:55:30 AM
This has been fun and educational to read.  I have experienced that flavor described as grape before, but had never associated it with actual grape flavor in my pallet.  I kind of think of the flavor as an under-fermented Pilsner malt flavor - kind of sour, but not really.  Nice to put a name and origin on it.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: ynotbrusum on April 13, 2016, 01:52:32 AM
I judged a recent Vienna and Marzen category with another judge and in two beers we both noticed the grape issue and I suspected Munich malt as the culprit.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: Saccharomyces on April 14, 2016, 04:11:47 AM
As I explained to Martin yesterday, the conversion of heptanal to ethyl heptonoate requires multiple reactions.   The first reaction involves the conversion of the alkyl aldehyde heptanal to the higher alcohol heptanol (CH3(CH2)5CH2OH or C7H16O).  The conversion of heptanal to heptanol results in the production of the carboxylic acids heptanoic acid and 2-hydroxyheptanoic acid. Anyone who has read "Have You Seen Ester?" knows that a carboxylic acid is an acid whose formula ends in COOH, which is also known as a carboxyl group.

(http://i699.photobucket.com/albums/vv356/tonestack/Brewing/heptanal-to-hetanol_zpss8a43txv.png)

As one can clearly see, the formulas for heptanoic acid and 2-hydroxyheptanoic acid both end in COOH.


Ethyl heptanoate is the condensation reaction between ethanol and heptanoic acid.

C2H6O + CH3(CH2)5COOH → C9H18O2 + H2O

The above reaction reads one molecule of ethanol plus one molecule of heptanoic acid yields one molecule of ethyl heptanoate plus one molecule of water.

I have the links to the publications that I provided to Martin if anyone is interested.

Title: Re: Methyl anthranilate (Grape Ester)
Post by: hopfenundmalz on April 14, 2016, 04:53:20 AM
As I explained to Martin yesterday, the conversion of heptanal to ethyl heptonoate requires multiple reactions.   The first reaction involves the conversion of the alkyl aldehyde heptanal to the higher alcohol heptanol (CH3(CH2)5CH2OH or C7H16O).  The conversion of heptanal to heptanol results in the production of the carboxylic acids heptanoic acid and 2-hydroxyheptanoic acid. Anyone who has read "Have You Seen Ester?" knows that a carboxylic acid is an acid whose formula ends in COOH, which is also known as a carboxyl group.

(http://i699.photobucket.com/albums/vv356/tonestack/Brewing/heptanal-to-hetanol_zpss8a43txv.png)

As one can clearly see, the formulas for heptanoic acid and 2-hydroxyheptanoic acid both end in COOH.


Ethyl heptanoate is the condensation reaction between ethanol and heptanoic acid.

C2H6O + CH3(CH2)5COOH → C9H18O2 + H2O

The above reaction reads one molecule of ethanol plus one molecule of heptanoic acid yields one molecule of ethyl heptanoate plus one molecule of water.

I have the links to the publications that I provided to Martin if anyone is interested.

Good to have some advanced knowledge laid on us!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: narcout on April 14, 2016, 04:58:38 AM
I have the links to the publications that I provided to Martin if anyone is interested.

Cool. Please post.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: klickitat jim on April 14, 2016, 06:30:18 AM
As I explained to Martin yesterday, the conversion of heptanal to ethyl heptonoate requires multiple reactions.   The first reaction involves the conversion of the alkyl aldehyde heptanal to the higher alcohol heptanol (CH3(CH2)5CH2OH or C7H16O).  The conversion of heptanal to heptanol results in the production of the carboxylic acids heptanoic acid and 2-hydroxyheptanoic acid. Anyone who has read "Have You Seen Ester?" knows that a carboxylic acid is an acid whose formula ends in COOH, which is also known as a carboxyl group.

(http://i699.photobucket.com/albums/vv356/tonestack/Brewing/heptanal-to-hetanol_zpss8a43txv.png)

As one can clearly see, the formulas for heptanoic acid and 2-hydroxyheptanoic acid both end in COOH.


Ethyl heptanoate is the condensation reaction between ethanol and heptanoic acid.

C2H6O + CH3(CH2)5COOH → C9H18O2 + H2O

The above reaction reads one molecule of ethanol plus one molecule of heptanoic acid yields one molecule of ethyl heptanoate plus one molecule of water.

I have the links to the publications that I provided to Martin if anyone is interested.
Howdy sir!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: jeffy on April 14, 2016, 11:28:19 AM
As I explained to Martin yesterday, the conversion of heptanal to ethyl heptonoate requires multiple reactions.   The first reaction involves the conversion of the alkyl aldehyde heptanal to the higher alcohol heptanol (CH3(CH2)5CH2OH or C7H16O).  The conversion of heptanal to heptanol results in the production of the carboxylic acids heptanoic acid and 2-hydroxyheptanoic acid. Anyone who has read "Have You Seen Ester?" knows that a carboxylic acid is an acid whose formula ends in COOH, which is also known as a carboxyl group.

(http://i699.photobucket.com/albums/vv356/tonestack/Brewing/heptanal-to-hetanol_zpss8a43txv.png)

As one can clearly see, the formulas for heptanoic acid and 2-hydroxyheptanoic acid both end in COOH.


Ethyl heptanoate is the condensation reaction between ethanol and heptanoic acid.

C2H6O + CH3(CH2)5COOH → C9H18O2 + H2O

The above reaction reads one molecule of ethanol plus one molecule of heptanoic acid yields one molecule of ethyl heptanoate plus one molecule of water.

I have the links to the publications that I provided to Martin if anyone is interested.
Howdy sir!
We missed you.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: HoosierBrew on April 14, 2016, 12:06:49 PM
Welcome back!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: beersk on April 14, 2016, 01:18:28 PM
That's some crazy science-y sh*t! Welcome back!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: AmandaK on April 14, 2016, 02:24:19 PM
This has been fun and educational to read. I have experienced that flavor described as grape before, but had never associated it with actual grape flavor in my pallet.  I kind of think of the flavor as an under-fermented Pilsner malt flavor - kind of sour, but not really.  Nice to put a name and origin on it.

Totally agree. Thanks guys!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: Saccharomyces on April 16, 2016, 01:57:39 PM
I have the links to the publications that I provided to Martin if anyone is interested.

Cool. Please post.


Bioconversion of heptanal to heptanol by Saccharomyces cerevisiae, http://onlinelibrary.wiley.com/doi/10.1002/yea.1750/pdf


Characterization of volatile aroma compounds in different brewing barley cultivars,
https://www.researchgate.net/publication/273755180_Characterization_of_volatile_aroma_compounds_in_different_brewing_barley_cultivars
Title: Re: Methyl anthranilate (Grape Ester)
Post by: 69franx on April 16, 2016, 02:46:32 PM
All great info. Thanks saccharomyces
Title: Re: Methyl anthranilate (Grape Ester)
Post by: RPIScotty on April 16, 2016, 02:59:57 PM
As I explained to Martin yesterday, the conversion of heptanal to ethyl heptonoate requires multiple reactions.   The first reaction involves the conversion of the alkyl aldehyde heptanal to the higher alcohol heptanol (CH3(CH2)5CH2OH or C7H16O).  The conversion of heptanal to heptanol results in the production of the carboxylic acids heptanoic acid and 2-hydroxyheptanoic acid. Anyone who has read "Have You Seen Ester?" knows that a carboxylic acid is an acid whose formula ends in COOH, which is also known as a carboxyl group.

(http://i699.photobucket.com/albums/vv356/tonestack/Brewing/heptanal-to-hetanol_zpss8a43txv.png)

As one can clearly see, the formulas for heptanoic acid and 2-hydroxyheptanoic acid both end in COOH.


Ethyl heptanoate is the condensation reaction between ethanol and heptanoic acid.

C2H6O + CH3(CH2)5COOH → C9H18O2 + H2O

The above reaction reads one molecule of ethanol plus one molecule of heptanoic acid yields one molecule of ethyl heptanoate plus one molecule of water.

I have the links to the publications that I provided to Martin if anyone is interested.

Glad to have you back.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: ynotbrusum on April 18, 2016, 10:15:48 PM
It's so nice when knowledgeable people share information relating to a topic here.  Thanks, Mark!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: brewinhard on April 18, 2016, 10:40:50 PM
It's so nice when knowledgeable people share information relating to a topic here.  Thanks, Mark!

And when it is freely offered without any smug replies.  Welcome back Mark!
Title: Re: Methyl anthranilate (Grape Ester)
Post by: bucketbiochemist on May 11, 2016, 04:06:24 AM
I've had a "grape" flavor noted at the AHA comp. for Kolsch made with WLP029.  Do people think this is the same flavor?  Is WLP029 (or other Kolsch strains) known for this compound?

Title: Re: Methyl anthranilate (Grape Ester)
Post by: HoosierBrew on May 11, 2016, 11:55:35 AM
I've had a "grape" flavor noted at the AHA comp. for Kolsch made with WLP029.  Do people think this is the same flavor?  Is WLP029 (or other Kolsch strains) known for this compound?



Yeah, I get a white grape character from kolsch strains, especially in WY2565. I prefer that character in kolsch.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: hopfenundmalz on May 11, 2016, 12:07:31 PM
I've had a "grape" flavor noted at the AHA comp. for Kolsch made with WLP029.  Do people think this is the same flavor?  Is WLP029 (or other Kolsch strains) known for this compound?
It may be the same, but I perceive it as white wine, in other beers I have gotten a Welches grape juice flavor. Are those the same? IDK.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: HoosierBrew on May 11, 2016, 12:18:24 PM
I've had a "grape" flavor noted at the AHA comp. for Kolsch made with WLP029.  Do people think this is the same flavor?  Is WLP029 (or other Kolsch strains) known for this compound?
It may be the same, but I perceive it as white wine, in other beers I have gotten a Welches grape juice flavor. Are those the same? IDK.


I agree with the white wine description for kolsch as opposed to juice. I should've been more specific.
Title: Re: Methyl anthranilate (Grape Ester)
Post by: brewinhard on May 11, 2016, 12:40:13 PM
I think I got this flavor in my last Helles towards the very tail end of it.  Most likely due to oxidation of pilsner malt possibly? It was very subtle, and almost slightly enjoyable. It was a mix of concord grape and wine notes.