Is there an industrial chemist in the house?

[Vocalek]

Received this comment to one of my blog posts.

Hi Vocal EK; no offense, but the fact that you hadn't heard that nicotine is transformed into niacin, really has nothing to do with the facts. If you look into it, you'll find that is how your medicinal niacin is actually made. Don't guess; check. Don't ask a doctor, ask an industrial chemist. And anybody who is living in a modern city, breathing mostly car exhausts, eating mostly processed foods, and getting essentially no exercise, has a lot more to worry about than cigarette smoke. Fix up those other things first. You might even find that when your health returns, you don't need to smoke anymore.

The original comment he left included this text:

Nicotine for one could never survive the process of burning because it's flash point is well below the temperature of the idle cigarette ash. What they do inhale is a transformed chemical known as nicotinic acid you might know this as niacin or vitamin B3.

To which I responded:

To Anonymous who left the comment May 9th at 5:32 -- You make some good points about not knowing any more what is truth and which are lies when we have caught not just ALA, but all of the 3-letter health organizations, in several lies. However, this is the first I have heard that nicotine is transformed into niacin in cigarette smoke.

If anyone wants to read the blog post and the entire comment string here's the link:
The Truth About Nicotine: Lung Association Recommends Smoking

I was unable to find anything on the web that verifies his claim about the transformation of nicotine into niacin by burning. Can a chemist please step forward and provide me with some definitive information?

 

[kinabaloo]

Hi Vocalek,

Off top of my head response - the nicotine evaporates from either pure form (freebase) or salt form (these decompose readily under heating, quite a low temperature to release the nicotine) as the heat of the burning tip approaches - most is not actually burned; and the flash point is largely irrelevant because the concentration is too low. In short, quite a bit of the nicotine survives and is released intact; about 10% of the total in the leaf survives and makes it all the way to bloodstream. Much of the wastage is because a cig burns even when we're not inhaling; otherwise efficiency of release of nicotine might be close to 50% (my estimate). The nicotine is not necessarily undegoing vaporisation (which would largely occur before burning) but also through transfer by carrier particles such as ash and vapor droplets sucked past nicotine in liquid phase.

Next; while nicotinic acid is one possible oxidation product (and also one path step in metabolism) of nicotine, the psychoactive effects of smoking as relate to nicotine are due to nicotine and not nicotinic acid. In short, the nicotine is certainly not all changed to nicotinic acid, if any. Nicotinic acid is not even a main oxidation product of nicotine; industrially that is achieved with reagents such as permanganate. Simple heating in air or air exposure is much more likely to produce acetaldehyde, nicotinaldehyde and cotinine (also the main metabolite).

To sum up, grains of truth but very largely erroneous in conclusions.

Tceight or DVap could give a better answer. I'm a bit pressed for time to dot all the I-s right now.

-----

Btw, I will not be around much for the next two months or so. Will try to look in now and then but hopefully posting again properly around december time.

 

[Vocalek]

Thanks, Kin. I did find one article that explained that within a plant, nicotine is created from niacin coming together with another chemical. I guess the question is whether, when burned, the chemicals pull back apart again. My guess (from nothing more than H.S. chemistry) would be no.

 

[Mister]

I'm working on a comprehensive reply with references to appropriate scientific articles. Will post it to your blog's comments later today.

 

[kinabaloo]

In brief, to oxidise nicotine to nicotinic acid requires special oxidising agents and does not happen in a cigarette; some other oxidation products may be formed though.

About 10% of the available nicotine in the leaf reaches the bloodstream, chemically unchanged (other than heat activated release from the salt forms (and perhaps aided also by ammonia)).

###

Vocalek - right, by heat alone no. Nicotine is released by heat; only some that did not escape by heat alone ends up getting burned (severe oxidation to say formaldehyde, or carbon or CO2 or CO, water vapor etc)

 

[Mister]

Vocalek, I don't see the comment with " no offense, but the fact that you hadn't heard that nicotine is transformed into niacin, really has nothing to do with the facts" on your blog at The Truth About Nicotine: Lung Association Recommends Smoking. The last comment displaying for me is from June 2. Was it a private mail or am I looking in the wrong place or ...?

Anyway, here's what I wanted to post, please feel free to post or use any or all of this as you wish:


On May 3 2010 Anonymous said "Nicotine for one could never survive the process of burning because it's flash point is well below the temperature of the idle cigarette ash. What they do inhale is a transformed chemical known as nicotinic acid you might know this as niacin or vitamin B3."

It is correct that nicotine cannot survive the temperature at the burning point of a lit cigarette. Nonetheless a large number of studies (at least in the hundreds) have measured nicotine absorbed from cigarette smoke by testing blood plasma during and soon after smoking. Just one example is at http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1463714/pdf/brjclinpharm00149-0085.pdf. Methods for detecting and measuring nicotine in cigarette smoke are well understood and the results are indisputable. For example here's how Health Canada measures it: Determination of "Tar", Nicotine and Carbon Monoxide in Mainstream Tobacco Smoke.

Roughly 10% of the nicotine in cigarette tobacco survives the burning of a cigarette and is transported to the body with the smoke. There are a number of ways it can avoid oxidation and pyrolysis at the burning point of the cigarette, e.g. escaping with vapor and smoke particles which leave the cigarette at the elevated temperatures which occur as the point of combustion approaches.

On May 3 2010 Anonymous said "What they do inhale is a transformed chemical known as nicotinic acid you might know this as niacin or vitamin B3."

It is not true that any significant amount of nicotinic acid (niacin) is present in cigarette smoke. Nicotine does not oxidize to niacin without other elements being involved in the reaction. An example is an old method of producing niacin which uses nicotine and nitric acid, see Organic Syntheses Prep. Another method involves the use of potassium dichromate. But these are not reactions of significance in smoking.

On September 9 2010 Anonymous said "no offense, but the fact that you hadn't heard that nicotine is transformed into niacin, really has nothing to do with the facts. If you look into it, you'll find that is how your medicinal niacin is actually made."

This is incorrect. See http://www.lonza.com/group/en/compa...-DownloadFile.pdf/7_Nicotinate_articleRod.pdf for a detailed description of methods currently used to produce niacin. None of them involve nicotine.

 

[kinabaloo]

Vocalek, I don't see the comment with " no offense, but the fact that you hadn't heard that nicotine is transformed into niacin, really has nothing to do with the facts" on your blog at The Truth About Nicotine: Lung Association Recommends Smoking. The last comment displaying for me is from June 2. Was it a private mail or am I looking in the wrong place or ...?

Anyway, here's what I wanted to post, please feel free to post or use any or all of this as you wish:


On May 3 2010 Anonymous said "Nicotine for one could never survive the process of burning because it's flash point is well below the temperature of the idle cigarette ash. What they do inhale is a transformed chemical known as nicotinic acid you might know this as niacin or vitamin B3."

It is correct that nicotine cannot survive the temperature at the burning point of a lit cigarette. Nonetheless a large number of studies (at least in the hundreds) have measured nicotine absorbed from cigarette smoke by testing blood plasma during and soon after smoking. Just one example is at http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1463714/pdf/brjclinpharm00149-0085.pdf. Methods for detecting and measuring nicotine in cigarette smoke are well understood and the results are indisputable. For example here's how Health Canada measures it: Determination of "Tar", Nicotine and Carbon Monoxide in Mainstream Tobacco Smoke.

Roughly 10% of the nicotine in cigarette tobacco survives the burning of a cigarette and is transported to the body with the smoke. There are a number of ways it can avoid oxidation and pyrolysis at the burning point of the cigarette, e.g. escaping with vapor and smoke particles which leave the cigarette at the elevated temperatures which occur as the point of combustion approaches.

On May 3 2010 Anonymous said "What they do inhale is a transformed chemical known as nicotinic acid you might know this as niacin or vitamin B3."

It is not true that any significant amount of nicotinic acid (niacin) is present in cigarette smoke. Nicotine does not oxidize to niacin without other elements being involved in the reaction. An example is an old method of producing niacin which uses nicotine and nitric acid, see Organic Syntheses Prep. Another method involves the use of potassium dichromate. But these are not reactions of significance in smoking.

On September 9 2010 Anonymous said "no offense, but the fact that you hadn't heard that nicotine is transformed into niacin, really has nothing to do with the facts. If you look into it, you'll find that is how your medicinal niacin is actually made."

This is incorrect. See http://www.lonza.com/group/en/compa...-DownloadFile.pdf/7_Nicotinate_articleRod.pdf for a detailed description of methods currently used to produce niacin. None of them involve nicotine.

Agreed.

 

[Whistle_Pig]

Tceight or DVap could give a better answer. I'm a bit pressed for time to dot all the I-s right now.

Or Old Chemist or Kurt.

 

[Vocalek]

Mister: My bad, I had not clicked the Publish button on the comment. It is there now. Would you be willing to post what you have written as your own comment, rather than having me put it in as my comment?

 

[DVap]

Nicotine survives precisely in the manner described previously by Kin: Due to the heat of the advancing hot coal volatilizing nicotine from the tobacco matrix.

The flashpoint argument is misplaced as flashpoint refers to the temperature that a liquid (typically a pure material) will generate sufficient vapor pressure to burn under a normal atmosphere in proximity to an external ignition source under a standardized testing protocol. It doesn't have any meaning in the context of a tobacco matrix and the resultant particulate stream (smoke).

One industrial method of synthesizing nicotinic acid (niacin) does involve nicotine as a starting material. Nicotine is oxidized to nicotinonitrile (typically with the help of a catalyst), which can then be easily hydrolized to nicotinic acid (niacin). I didn't really get the impression that this is a particularly common method of production. (And kudos to mister for illustrating this with the article discussing industrial nicotinic acid synthesis).

However, I seriously doubt that pyrolysis of nicotine is an effective direct route to nicotinic acid. If this were the case, smoking would have saved many from the ravages of the disease (pellagra) caused by chronic nicotinic acid deficiency. The typical pellagra sufferer had easy access to corn and tobacco. Corn must be specially treated (high pH) to make it's nicotinic acid bio-available, and if we're to believe the blog comment, one needs only smoke cigarettes to get all the nicotinic acid they could want.

I did find a source that made the claim that nicotine is converted in significant amounts to nicotinic acid during smoking. This source made the bold claim that it's not nicotine that we're craving, but nicotinic acid (niacin), and cigarettes readily provide it. The source, of course, claims that the "truth" of this claim has been ignored, suppressed, you name it. (Funny how when I was taking nicotinic acid at a gram/day for cholesterol control, it didn't cut down on my urge to smoke).

This is a good time to remember that much information found on the Internet is worth precisely what we've paid for it, I.E. nothing. Or, in other words, Kook-alert!

The blog commenter is full of crap misguided, and has perhaps been influenced by an uncritical acceptance of this nicotinic acid "conspiracy".

 

[Mister]

Would you be willing to post what you have written as your own comment, rather than having me put it in as my comment?

Sure, done! Now pending publication. I modified the post a bit to be more correct re Kin's and DVap's notes (thank you!) and to address the possibility raised by DVap:

One industrial method of synthesizing nicotinic acid (niacin) does involve nicotine as a starting material ... I didn't really get the impression that this is a particularly common method of production.

I didn't see that during my searches so went looking. I found a description of that approach related to making use of tobacco industry waste products. I didn't find anything regarding its use in production. Along the way I did find something useful though. It is a 1998 article which lists global production of niacin among other things. It states that 98% of the world production of niacin was by the four companies whose production methods are described in the article I previously referenced. It therefore quite substantiates your impression that this isn't a common method of production and I've added a reference to it in the comment I've posted. It is at http://www.agecon.purdue.edu/staff/...amins Conspiracy Sanctions and Deterrence.pdf

 

[Kate51]

The role of niacin in detoxification

I've never seen a production method for Niacin that incorporated Nicotine, or any reference to Nicotine reverting into any form of niacin ~ Niacin is a water-soluble B vitamin – vitamin B3 - and the common name for 2 very different compounds: "nicotinic acid" and its amine "niacinamide".
Niacin is a mirror-molecule of Nicotine. It is not the same molecular structure, but does it's work as a detox agent for nicotine addiction by binding to neurons the same way nicotine does, or by preventing nicotine molecules. That's my understanding. Simplified to niacin 101.

Niacin (vitamin B3, nicotinic acid), Niacinamide: MedlinePlus Supplements

Some very complete lists of detox and Niacin or B3 vitamin.
I take 200mg per day, should raise the level. The Flashing or Flushing kind.
I will also do some more searching, but I think to say one is made from the other I think is a falacy. I will try to keep an open mind.

From "DETOX" by Rhodes:

• Niacin is known to be one of the most powerful Cholesterol treating
drugs in the world. Low-density lipoprotein (LDL) is a type of Cholesterol.
When LDL accumulates inside the arteries it can oxidize which causes
inflammation and triggers some changes that lead to immune cells and blood
clotting proteins entering the arteries where they turn into a sticky substance
called plaque. Build ups of plaque block the arteries and lead to blood clots
and heart attack.
Smoking has been found to increase the oxidation of LDL. Niacin can and
dose decrease LDL Cholesterol and at the same time increases your “good
cholesterol” high-density lipoprotein (HDL). Nicotine increases bad cholesterol
and lowers good cholesterol while Niacin does the opposite. Here we see
clearly that Niacin does the opposite to nicotine. Due to all the years of
smoking your blood vessels have become clogged with plaque. As soon as
you start taking niacin your arteries and blood vessels will start being cleared
out.• Niacin opens blood vessels wider. In fact this increase can be quite large,
between 2 and 3 times their normal width for small blood vessels. The effect
of this is a huge increase in blood flow which is most beneficial to very small
blood vessels called capillaries. Some capillaries such as those near the skin
or those around the lungs are so small that blood cells can only go through
one at a time. In fact the smallest capillaries are often blocked completely
and blood cells cannot fit through. As Niacin expands the capillaries and blood
vessels the flow of blood is increased dramatically and can cause a flushing of
the skin which is caused by the increase in blood flow. As the blood flows
through previously clogged arteries the waste products and toxins present are
released into the bloodstream and therefore processed out of the body. Here
again we see clearly the opposite effect to nicotine. Smoking reduces
circulation and restricts blood vessels while niacin increases blood flow and
expands blood vessels. That’s exactly what you need to begin clearing your
lungs of tar and toxins…
• Cardiovascular problems such as triglyceride levels, strokes and heart
attacks are all significantly reduced with niacin. This has been studied in
clinical trials and was found to be substantiated numerous times. Nicotine
does the opposite! Nicotine increases triglyceride levels and the chance of
strokes and heart attacks.

Sorry, this got long, but illustrates my feeble attempt to define "mirror molecule" of Nicotine.

 

[Vocalek]

Maybe it isn't the nicotine. It's the smoke.

Swedish snus Information

• The risk of myocardial infarction is not increased in Snus users.
• No significant elevation of diastolic blood pressure, hemoglobin concentrations, white cell count, serum cholesterol or triglyceride levels has been found in Snus users. This is in contrast with findings for cigarette smokers.

So if the nicotine in snus isn't elevating cholesterol, it would seem that the nicotine in e-liquid would not do so.

 

[Vocalek]

"Thanks, Mister." (I've always wanted to use that line.)

 

[Kate51]

Nothing is being combusted or "oxidized" it may be ok to assume we don't absorb nicotine at sufficient levels to be harmful enough to even cause vascular constriction more than minimally. My BP is about the same as it's ever been, 110/62 or in that range, at 63 years I'm not worried about those kind of numbers. Maybe people would be more affected at higher density nicotine, above 24mg/ml. Would make an interesting study to track from smokers to "new to 1 year" vapers. A lot of other things can affect blood pressure so would be speculative at best, but interesting.
I'm going to keep taking my Niacin just to make sure!!

 

[kinabaloo]

Kate51 - There are a few things thought by some able to reverse arterial plaque, and niacin is one of these. It is good that you have raised this. B6 and B12 also help the LDL - HDL ratio favorably and because the B vits in some ways act together, it would be good to combine niacin with a B-group vit, of suitably 'high' dosage.

Regarding the effect of nicotine - it has the temporary effect of restricting blood vessels and thereby raising BP, but the long term arterial reduction and blocking would be due almost entirely to free-radicals in smoke; in this regard vaping should not present other than a minor long-term effect in this regard (as far as I know), if any.

 

[Kurt]

Anonymous is, to my mind, rather chemically ignorant and rather arrogant. Even a wiki search on niacin (Niacin - Wikipedia, the free encyclopedia) states that it takes an oxidizer compound to make it from nicotine, with nitric acid being the early one used...DVap mentioned others. It was likely a matter of chemical convenience, since nicotine has a pyridine with C-functionality at the 2-position, and nicotine is readily available for cheap. There is as far as I can tell no metabolism paths from nicotine to niacin.

And Kin is exactly right, nicotine, as well as other free-base alkaloids, vaporize in the hot air being sucked from the cigarette cherry. Much does pyrolyze, but a good amount just evaporates.

I am always amazed when I see posts like Anon's, with a derisive tone, and yet stating things that make zero chemical sense, and certainly cannot be cited. I'm with DVap on this one, as long as he removes the cross-out line...lol.

 

[TWISTED VICTOR]

Thanks kin, Kurt and Dvap for the clarification on this. I was afraid I might have to step in and straighten this out with a server choking blog, but I see my services aren't needed. Phoow!!....

 

[Kurt]

TV, you ol' clog blogger! Stick around, the misinfo gargoyles seem to be getting more creative.

Cleaning out the chem trash with:
Roda Lacket
Pipe Tobacco Essense
Water...wait wrong thread...where ARE those emoticons??? :/

 

[TWISTED VICTOR]

TV, you ol' clog blogger! Stick around, the misinfo gargoyles seem to be getting more creative.

Cleaning out the chem trash with:
Roda Lacket
Pipe Tobacco Essense
Water...wait wrong thread...where ARE those emoticons??? :/

Heehee...gotchya . Now if I could just finish my corruption of Dvap my evil plan will be complete. Bwaahahaha...........