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Using Niacinamide in an acidic formulation

July 8, 2015

I have been having an interesting discussion with one of my clients this week about formulations containing Niacinamide and AHA’s.  Niacinamide is also known as Vitamin B3 and it is a great skin care ingredient as it has scientific evidence behind it to back up claims ranging from improving skin tone and down-regulating sebum production to acne control and barrier repair.  I use it quite a bit in my skin care formulations.   While Niacinamide is very stable it can break down when it is in extreme acid or alkaline environments.  In fact it breaks down to release Ammonia (NH3) which is a rather stinky gas that you wouldn’t want tainting your skin care formulations, leaving Niacin behind.  Niacin is also a member of the Vitamin B3 family but unlike Niacinamide which is usually (and I say USUALLY and not always) well tolerated, Niacin can cause facial flushing which isn’t something many people want from an ingredient.  Because of this Niacinamide + Acid = Niacin (and facial flushing) THING many people have decided that Niacinamide and AHA’s can’t play together which is a shame as it probably isn’t true!

There haven’t been that many studies into the stability of Niacinamide over various pH’s but one study I did find looked at this very thing by heating up Niacinamide solutions with acid and measuring what happened – how much Niacin was produced.  The conversion from Niacinamide to Niacin is called NON ENZYMATIC HYDROLYSIS.  Basically that means splitting a molecule up to release water without using a biological enzyme to cleave the molecule.  This type of hydrolysis reaction is quite common in organic chemistry.

The paper that I am referring to is called “Rate Studies on the Hydrolysis of Niacinamide” and they were using hydrochloric acid to perform the experiment in the acid region (which is all we care about here).  This is a significant detail as hydrochloric acid is a strong acid whereas AHA’s are weak acids.   Acid strength is not just about how much you put in a formula – 10%, 20%, 2% etc – it is also about how readily the acid let’s go of its hydrogen ion – its dissociation constant.  Strong acids completely dissociate in water meaning that even at low % concentrations the acid is quite potent. Weak acids have only a tiny part of themselves raring to go meaning that even at high concentrations they won’t be quite so aggressive.   The above study found that a 10% Niacinamide solution heated to around 89C and then taken to a pH of below 4.5 with a STRONG acid did start to hydrolyse and form Niacin and that this conversion was a first order reaction which basically means it went from Niacinamide to Niacin without turning into anything else first.  The study found that between pH 4.5-6 very little of this crazy game of shape shifting occurred.  In fact at pH 4.5 – 6 the half-life of the solution was found to be 1000 days which probably means that the average cosmetic formulator has little to worry about.

I’ve noticed several blogs and web-based publications cautioning people about using Niacinamide with Acids because of this hydrolysis reaction and even noted that the manufacturer technical data sheet includes the warning about pH too which was interesting as  it seems like many people have taken a quick look at the above paper  (which was written in 1962 and is available to read online for just $6 US) and jumped to the conclusion that acids and Niacinamide don’t go.   To that I’d say ‘it pays to be fascinated, to really try to understand what is being said and to think wider and deeper than what is in front of you’.

That said it doesn’t mean that a formula containing  Niacinamide and AHA’s will suit everybody.

Niacinamide may well be a darling ingredient but several in-vivo studies have reported skin reactions from itching to burning from simple serums using the ingredient (one study recorded negative outcomes for 4 out of 38 trial members. That is 10% which is highly significant although the study reported this as ‘minor’ as the dermatological review at the end of the study found that the negative outcomes were temporary and not serious (not likely to cause allergic reactions or ongoing discomfort or damage).  This particular study used 4% Niacinamide.

So if a relatively simple Niacinamide formula can cause a burning or tingling sensation in some people it stands to reason that a formula containing AHA’s and Niacinamide could do the same given that some people are just sensitive to AHA formulations without adding anything else in.

But if we step back for a moment and think about this don’t many things that work cause a little irritation at times?  AHA’s,  Retinol products, High strength Vitamin C products and now Niacinamide serums and creams?

It also pays to step back and review what we are trying to do here.  Niacinamide has many anti-ageing benefits as well as benefits for acne prone skin and ditto AHA’s although they tackle the problems in a different way.  Most high-tech cosmaceuticals use a bevy of complimentary ingredients to ensure the product delivers results and so it is easy to see why combining these two actives sounds attractive especially when targeting premature ageing or acne – both of which require more than one dysfunction to be addressed.  What this does highlight for me is the need to use these high-strength, multi-faceted active-skincare products under guidance from a trained professional who can monitor how the skin reacts to treatment and modify the treatment regimen accordingly.

The bottom line from me is that I feel it is unlikely that non-enzymatic hydrolysis will occur under when Niacinamide and AHA’s are used together in a typical cosmetic formulation.  I feel that anyone using AHA’s in their formulations needs to be mindful of their power and needs to have a good grasp on the safety and chemistry of their products before they go to market and ditto for people using other highly potent cosmetic actives such as Niacinamide and Retinol.

Keep Calm and Study Chemistry

6 Comments leave one →
  1. Lisa permalink
    August 26, 2016 12:41 pm

    Hi. I would like to make alpha arbutin+niacinamide cream. Does it matter if the end product is not ph 6? Would you recommend the percentage of each product to be used for skin lightening? I have 10 years tan that just would not go away. Hence, i would like to try this. As i havr never done any DIY cream using raw powder before, i need help. Thank you so much in advance.

    • RealizeBeautyEd permalink*
      August 26, 2016 12:49 pm

      The blog post I wrote was with relation to Niacinamide and AHA’s and I concluded that Niacinamide can probably work in a product with AHA’s, especially where the pH was around 4-4.5. Now at this pH AHA’s have lost some of their effectiveness but in many cases this will be OK (AHA’s work best at pH under 4). I can’t give you specific formulating advice on here as that is not what the blog is for (that is what I do for my business as often the whole formula needs to be considered to make an accurate appraisal of the situation) but I hope knowing that you can alter the pH a bit helps you somewhat.

  2. Khanh Bee permalink
    May 13, 2017 10:14 pm

    But… I tried. I always use BHA after toner because of acne-prone skin. BHA and AHA (once a week) helped me a lot. My skin was less acne and better. Then I added Paula’s Choice Resist 10% Niacinamide Booster to my routine. Oh, my face got redness and flushing and at that time I did not know why. Now, it’s still red and I am looking for the reason on internet and finally I know that the combination of BHA/AHA & Niacinamide did. So terrible and suprised !! no warning from Paula’s Choice. Mrs. Paula is not always right !

    • RealizeBeautyEd permalink*
      May 14, 2017 6:24 pm

      HI there Khanh,
      Thanks for your feedback, I would say that 10% Niacinamide is way too high anyway, regardless of whether you use AHA/ BHA with it. The other thing to keep in mind is that everyone is different so one person might flush while another won’t feel anything at all. The skin is a wonderful and confusing thing 🙂

      • Khanh Bee permalink
        May 16, 2017 4:25 am

        I think the main problem is I used Skin Balancing Pore-Reducing Toner that contains the ingredient Niacinamide right before BHA/AHA, of course no waiting between 2 these steps. After BHA/AHA I always wait about 15 minutes and jump to 10% Niacinamide Booster. I did not use it alone, i mixed it with Timeless B5 Hydration Serum so I think this must be fine. But the result made me dissapointed, the skin got redness and even darker / dull skin. You know the benefits of Niacinamide is making the skin brighter, improving redness, reducing wrinkles… But i received nothing but worse result. Now I changed another toner (with no Niacinamide) and wait up to 30 minutes to use 10% Niacinamide Booster after BHA/AHA. Fortunately, everything seems to be getting better… As a result, in my opinon, using Niacinamide in acidic formulation destroyed their huge benefits, made them useless. The time waiting is very important if we use acidic ingredients with Niacinamide.

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