Stability of antioxidants in cosmetic products

edited October 2016 in Ask the Beauty Brains
Many companies are adding different kinds of antioxidants to cosmetic products, like Tocopherol, ECGC, Resveratrol, Green Tea Extract, Quercetin, Superoxide Dismutase. But from what I've learned antioxidants are unstable and must be packaged airless, and preferably stored refrigerated. Some of them are more stable than others, but still. Shipping the product to a distribution center takes some time (during which the product may be exposed to heat) and maybe the product will last 2-3 months, so enough time after production for the "actives" to degrade.

I have some toners, serums and moisturizers from Paula's Choice they all contain mixtures of well researched antioxidants, but none of them is packaged airless. Even some serums/moisturizers with retinol are not airless. So what do you think, do these products still offer the benefits of the researched actives? Or will they be oxidized and ineffective? Why doesn't Paula use better packaging? If the Resveratrol or Green Tea for example will be oxidized by the time I open the product, I can just as well buy a less expensive product.

Comments

  • "Superoxide Dismutase and Catalase do not guarantee sufficient stability to survive manufacturing procedures and shelf life in cosmetic consumer products" (Draelos, 2016 - Cosmetic Procedures: Products and Procedures, p. 315).
  • edited October 2016
    Good question Peter, it has been bugging me too!

    I am hesistant to buy from Skin Actives as I experienced the antioxidants going bad the last time I purchased the products. Yes I refrigerated them. Although they only went bad at the end, it was a sign that powerful antioxidants require proper storage and proper packaging. Skin Actives used jars and regular pump bottles.

    Most commercial products are not at risk because they never included enough antioxidants in the 1st place to even have this concern.

    The other concern is warehousing and transport. The summer is coming and Skin Actives is in Arizona (desert), I would feel more comfortable ordering when the weather in both Australia & USA is not hot, lest my products get stuck in a heated truck or warehouse And get damaged in transit. So I have to wait until summer is over now before I place my next order.

    3rd concern is ordering the products "fresh". Instead of adding it to my stash and queueing to use it. I prefer to buy it WHEN I know I will use it immediately when it arrives. So this "just in time" purchase style is required which is difficult since I use up their products each at different speeds.

    @Peter thank you for starting this thread and articulating my fears.

    I have noticed that even Skin Actives ELS serum which is essentially a mixture of oils and antioxidant is beginning to turn rancid despite refrigerator storage. Pao is 6 months.

    The general rule I find with antioxidant ingredients are the higher than antioxidant value, the higher the oxidative instability. :( there are a few exceptions but 95% of the time there is an inverse relationship with antioxidant property and stability.

    Sometimes when looking at good products, I often hesitate purchases because of their packaging. Derma E comes to mind. I own Derma E vitamin C product in a jar. Will Decant that when I get it. I have purchased refillable tubes for my thicker creams.


    On another note:


    I have fallen in love with a local company called ABFE (AUSTRALIAN BUSH FLOWER ESSENCES). They store even their cleanser in an airless bottle, And there is a lid for the pump. It smells amazing and it is full of antioxidants.


    image
    Australian Bush Flower Essences LOVE SYSTEM was judged the WINNER in the coveted ‘Organic Range’ category in the UK’s Natural Health International Beauty Awards 2015.


  • @preciousia
    I've asked the customer service at paula's choice again, they assured me all active ingredients (like antioxidants, resveratrol, green tea) are used in effective amount, and remain stable and potent after shipping and after opening it and storing it in your bathroom...

    Well I know the ingredient are very unstable, and all kind of techniques have to be taken to keep them stable. But I'm no cosmetic chemist, so I knowing with 100% certainty what's the truth is difficult.
  • @Peter they must include very minuscule amounts then.

    I never formulated with resveratrol or green tea but I know both are vvv good!
  • edited December 2016
    @Peter the technical functions of this forum here is really good to save my reply... i was shopping at Bulk Actives... and wanted to buy Green Tea and Resveratrol! I'll formulate and let you know

    I noticed Paula's Begoun's Beautypedia referencing this website (the link was broken), nonetheless, they have so many articles on airless bottles.

    here's one that will interest you.

    if a skincare brand formulas with idebenone or Ellagic acid/pomegranate extract, you know the color of the product will definitely change if sufficient quantities were added. For the colourless ingredients, it's hard to tell.

    Just wondering, what have you done with the Niacinamide you bought from Bulk Actives. What else did you get?


  • edited December 2016
    @preciousia
    The question on airless packaging remains: is it for marketing purposes (due to the growing competition) or is it really necessary to stabilize the product. I prefer airless packaging, but if a tube or dropper is fine for certain products, I don't want to skip those products.
    I've asked Deciem another time if their products really are stable and don't degrade ;-) (I know I'm an annoying customer haha). Their reply:

    By "stable" my colleague meant that our formulations are made to not degrade when exposed to air for short periods of time. All of the Ordinaries have a 12 month shelf life once opened. We are aware our consumers will be opening and closing these products constantly, thus exposing the products to air. With that in mind we've formulated this products to preserve their integrity even when expose to air regularly. 

    Our Vitamin C products, are either in water free formulations(Vitamin C Suspension 23%) or derivatives of Vitamin C(Ascorbyl Glucoside Solution 12%,Ascorbyl Tetraisopalmitate Solution 20% in Vitamin F, Magnesium Ascorbyl Phosphate 10%) so that they can be formulated in a water base because, being derivatives they are less likely to oxidize in water. They are bottled in UV packing to further protect their integrity. 


  • edited December 2016
    I know there are many ingredients that will cause a weird color to the product. Most companies use the lowest concentration possible to reduce cost. Certainly now Paula's Choice isn't owned by Paula Begoun anymore, I really think many products are formulated not for their efficiency, but to earn as much money possible. Retinol at 0.01% really is low, as Brandon Truaxe explained (which is true) many actives don't penetrate very well in a silicone base, which is used often in PC products, also many of the ingredients are added below the recommended levels at PC.

    I bought Niacinamide, Panthenol, Green Tea Powder, Clay Powder (for a facial mask), Allantoin and Bisabolol. I've formulated a 10% Niacinamide, 2% Panthenol, 0.2% Allantoin toner a couple of times. But to be honest I'm a bit hesitant at formulating DIY cosmetics, you never know for sure if its good if you don't understand the chemistry completely. It is very attractive to do of course, it's so easy to buy all kind of different actives and put them together in one product, but the uncertainty if ingredients are stable, at what temperatures you can mix ingredients, if bacteria will grow, if the pH is at the right level for every ingredient and in general the reaction between ingredients during the formulation, makes me wonder if it is wise to do.
  • edited December 2016
    @Peter I don't think you are an annoying customer and if anything, you are kinda AWESOME. Lol esp that you share the reply so the rest of us who do NOT care to email them get our answers replied. ❤️ thank you for sharing!

    Airless is not marketing that is for certain!

    Using airless reduces the need for more preservatives (in other words, I read from their reply). In a formulation need to add MORE preservatives to account for dropper bottles/opening closing/hygiene from introducing bacteria ... that means more preservatives eg BHT yuck.

    If using my dermatologist's private label skincare for a decade has taught me anything... it is everything came in Airless!

    I appreciate airless for the precision in dispensing (control the quantity used), hygiene, better integrity of the product preserved and best of all klutzproof (I don't know how many times I have spilled dropper bottles! )

    I just bought an autoclave with heat/UV so my decanting has just gone up another level.
  • edited December 2016
    @Peter

    The factors affecting products going bad...

    light, heat, air, bacteria

    Airless does help with oxidation!!

    I am experimenting with DIY vitamin C serums in my refrigerator to compare the difference with the degradation of the Vitamin C.

    - one in a regular opaque bottle (no air protection)
    - one in clear dropper bottle (no uv, air protection)
    - one in a Super duper completely airless bottle (Not even the sprout is an issue) , upcycle derm's products
    - one in clear airless bottle (no uv protection)

    And bearing in mind that I have isolated heat... which is the worst deteriorating factor of LAA vitamin C serums (in water, not Anhydrous).

    All stored in the refrigerator.

    TBH the UV protected Airless bottle is amazing ! I sent a decant of a 4month old Vitamin C Serum & mailed it to a Friend (was sitting in the post office all weekend) and she got it still effective! I used a UV protected Airless bottle to store it. During warm weather last month too. She said it was still effective when she got it. I tested it prior to mailing it out & yes, still effective. I used 1% phenoxyethanol as preservative.




  • edited December 2016
    @Peter yup. I can confirm someone else said that Paula Begoun has sold her shares... Paula Choice has been sold again recently.., some capital company owns it now. Nathan who used to work there joined Drunk Elephant (in talks of buy over by Estee Lauder). Brian is also a part owner, not sure if he is still there. You see these guys in the PC's videos.

    Run like a corporation. The marketing now are sexier and I am getting afraid to trust their claims. I use one Paula Choice's product and that is Paula's Begoun's fave BHA. The other ones I wanted to get, were reformulated. One was a moisturiser Paula used under her eyes (richer) phased out after they started selling eye creams. Another was a hand cream with SPF she shared she used on her face (she forgot to bring sunscreen).


    Their antioxidant serum was crap. Tried it. Hated it. I am comparing it with my derm's antioxidant products. world of difference!

    She did well for herself, good nest egg, I would sell out too if I was her! I still love Paula Begoun but I don't trust PC entirely anymore.

    interesting how her blog which I shared with you said that it was an avenue for her to share everything she was not allowed on Paula Choice. She has since removed and updated that statement.

    Silicones are the bane of my product selection. I recently bought a product and thought it had silicones. I wanted to get rid of it immediately. It is an Asian Essence supposed to be used as the 1st step before using any serums. Silicone in the product will obstruct my skin from receiving/absorbing any actives from other serums subsequently applied. Thankfully the supplier made a mistake & sent me the wrong item, a variant of the product, different ingredient list, no silicones.

    If I see any form of silicones in serums, I avoid it! The only exception is the Ordinary Azelaic acid which I bought out of curiousity
  • edited December 2016
    @Peter interesting how you did not get N Acetyl Glucosamine, it goes very well with B3. I am hesitant to use their NAG as it is not plant derived,

    Bisabolol has been on my watch list. Wow you got that & Allantonin. BulkActives bisabolol is expensive! Skin Essential Actives used to sell it much cheaper.

    Your questions for DIY are valid.

    My shortcoming is my lack of chemistry knowledge, if you follow a tried and tested "recipe" it should be ok. I can send u a tried and tested Niacinamide recipe to experiment if you like.

    I don't know if Niacinamide makes a good toner as the pH isn't best suited. I prefer a lower pH toner to prepare my skin for LAA/BHA. Doesn't matter now that I am using Paula Choice as the pH is adjusted much higher. Certainly Niacinamide as a Essence or even mixed in an emulsion is good.




    pH
    For pH it is critical to check as some actives are unstable in certain pH! Get a Digital pH pen. Calibration is important too! I got one. Just bought my 2nd (something better)

    Temperature:
    check the MSDS or research the ingredient. Eg Niacinamide info can easily be found on Wikipedia. Synthetic ingredients are mostly similar. Natural ingredients may vary greatly from source to source (do check with supplier).

    Bacteria.
    Even labs are not 100% bacteria free. I bought an autoclave (thank you Escherida) and say hello to my new BFF alcohol. Cleanliness in DIY is impertinent!

    Testing
    You need to stress test the product and subject the formula to heat etc eg in a bathroom before sharing your products with others. I minimise UV/air using airless bottles.

    Reaction between ingredients.
    Lol that is the billion dollar question. Use medical journals. And read. Eg Copper + LAA Don't play nice. Even companies do not know 100% for certain if a formula is good, so testing is required! If you are not prepared the risks (sometimes it can be minimised) then don't DIY. Sometimes I read the ingredients list of products I like to get inspiration.

    Costs
    DIY ain't cheap. I had opted to DIY only if the product I want is better as a DIY vs store bought. If it costs cheaper or even just s little more, I prefer to buy. Time is precious too.

    So far, I have only the DIY vitamin C & a toner with fermented Essence mixed with ACV. My Mother in law just asked for repeats for the toner, lol she likes a milder version so I customise it for her. My sister is lazy, one doesn't use skincare, one skips steps... she has my toner which I advised for night use only.

    Gearing up in 2017 for DIY.
    I got borosilicate beakers, glass funnels, autoclave, googles, cleaning alcohol, digital scale (2 decimal places), digital pH pen, something to heat the product if required, pipettes,airless bottles, plenty of upcycled packaging, buying a couple more ingredients, waiting for my glass rods.

    I am going to DIY as many ingredients esp antioxidants are better "fresh" and I get to avoid nasty ingredients and customise for my needs.

  • @preciousia

    Is Brian co owner of PC, didn't know that. Interesting things on Paula Begoun. The cosmetic industry if difficult to understand sometimes, everyone wants to be different and unique. I also believe most companies pay for studies (proctor and gamble on niacinamide for example) or pay for not publishing studies, I think we as consumers are often brainwashed. Ingredients from far away countries and new technologies, they all want you to believe that they are selling the new miracle. The whole concept of Brandon Truaxe company is also very clever, but many of his explanations are not really backed up by real science. I guess you've read the post on Reddit, which is quite accurate on sciencewashing..

    I formulated my DIY toner at a pH of 5.5, this is okay for Niacinamide. Also I made it fresh every other day. Now I've bought green clay, and I want to do a clay mask once a week. I think I'm going to add some honey, allantoin, bisabolol, panthenol whatever I have. Making it fresh for single use reduces some of the risks with DIY cosmetics.
  • edited December 2016
    @Peter Not sure if Brian had sell out yet... do you still see him on videos? Yes, in Paula Begoun's book. she said, medical studies can be bought. They can publish anything you ask. almost kindda. There are many "tricks" of the trade. I emphasise to always check independent sources from reputable journals.

    so when i see a claim by a company (an australian company had a claim recently from medical research of before/after done in an european country, was it poland (sorry i forget)... i did find it odd that they had to do it overseas in that country... and of course, i tried it... and did not even get anything close to the results they were claiming.

    >they all want you to believe that they are selling the new miracle.

    a DIY shop owner told me the key ingredients required for anti-aging. And... truth is... it's not sexy... people want something else, and they do not believe the reality is as simple as it really is. Sadly, the shop has closed now :(

    Brandon Truaxe majored in computer i heard?! lol He's a smart dude, he sold his first company, had a non compete. I bought a product from his first company which Caroline Hirons raved about. meh for me.

    hmmm. i will checkout the reddit post. i haven't read it, i may have seen it. 

    For DIY, for lower "risk" items... masks are good. you don't even need an elegant formula. Niacinamide is stable at pH 4-6.... 5.5 is a good pH! :) You do know your pH. How do you check your pH? 

    Fresh is awesome... but i don't know how oxidative unstable Niacinamide is. I was thinking of formulating a facial mist with some hydrating/skin moisturising factors, any thoughts on that? What preservatives do you use?

    DIY is fun. What else are you making? I am planning to do a LAA+Vitamin E+Ferulic Acid+Kojic Acid for a "mask" equivalent. Low pH, like a mild chemical peel. Not buffering.

    what packaging do you use?
  • @Preciousia
    I have a digital pH-meter, and a very accurate scale. I didn't want to use preservatives, so I used distilled water, 5% Niacinamide, 2% Panthenol, 0.2% Allantoin. Very simple but very stable, I also used a dropper bottle. But I stored it in the fridge.

  • @Peter can you share a photo of your pH meter? I want one that doesn't require too much product to test. The one I use now unfortunately requires much more product. Maybe I should get a test tube too... so less is required.

    I heard bacteria can start growing within a few hours...need to double check. preservatives are important. You should use one?

    Look into NAG? Plays well with b3. My
  • @Peter can you share a photo of your pH meter? I want one that doesn't require too much product to test. The one I use now unfortunately requires much more product. Maybe I should get a test tube too... so less is required.

    I heard bacteria can start growing within a few hours...need to double check. preservatives are important. You should use one?

    Look into NAG? Plays well with b3. My
  • edited December 2016
    I buy not very expensive pH meters (like this), if you put your product just above the sensing electrode they already work, and I calibrate them with the supplied test solutions. Although they are cheap, they are very accurate. All the products I already knew the pH of, this meter exactly showed the same pH value, so I think this one is perfect. Disadvantage of more expensive ones is you have to calibrate regularly (so you have to buy test solutions) and I'm not using it often enough to justify the price difference. 

    I know bacteria start growing very quickly, that's why I use distilled water, sanitize everything with 96% alcohol solution, store it in the fridge and make a fresh one every two days. But because I'm too lazy, and really at home you can't do the testings professional laboratories can do, I don't want to bother with formulating my own cosmetics. I've seen the testings they do at brands like L'Oreal, you can't do that at home. You will never know if there might be crossreations between substances, or some sort of yeast or bacteria growing inside your product. Also you can't be completely sure if the ingredients you buy have the same quality as larger brands. The most difficult thing you need to know is at what pH each ingredient has to be formulated, if they work well together, how you have to dissolve them. I know there are some really odd ones, you can only formulate with at unusual pH values (a common one which everyone knows of is Ascorbic Acid, it has to be at a pH lower than 3.6). I think there are too many uncertainties to formulate your own cosmetics. I even have seen profesional brands, where bacteria started growing, which had to be taken of the market. 

    Although I do like to make a simply toner or clay mask once in a while, I will only use it once. Also you can make a toner with regular green tea bags, nothing wrong with that. A tip might be, just buy a simple fragrance free toner, and add some ingredients. You can't go wrong with Niacinamide, Panthenol or Allantoin for example. This is a nice video on "pimping" your toner, its in german so perhaps the text is a bit difficult to read.

  • Hey...that is exactly the same as my pH meter! How do you test liquids and use less? I did buy some solutions to calibrate my pH meter. when it was brand new, the pH was wrong.

    >But because I'm too lazy
    rubbish. you are not lazy.
    humanely not possible to formulate skincare everyday for usage.

    >you can't do the testings professional laboratories can do
    Damn straight

    >Also you can't be completely sure if the ingredients you buy have the same quality as larger brands. 
    try reputable companies. Avoid dodgy sources.

    >Also you can't be completely sure if the ingredients you buy have the same quality as larger brands.
    synthetic stuff - maybe not
    natural - 100% YES
  • @Peter gosh the limit for text is not very long. i keep getting prompted the message is too long.

    continued

    >The most difficult thing you need to know is at what pH each ingredient has to be formulated,
    wrong. check the MSDS, they will advise for each ingredient what pH it is stable in.

    >if they work well together
    billion dollar question. companies are built on 1 successful product. lol
    no one knows either. discover the next best combination and make buck loads.

    >how you have to dissolve them.
    easy. medical journals. forums. MSDS
    many of your fave ingredients are TOUGH to dissolve. you may need to use solvents or heat/hold.

    >I think there are too many uncertainties to formulate your own cosmetics.
    if it is too easy, i lose interest lol. take the challenge and make it fun.

    >I even have seen professional brands, where bacteria started growing, which had to be taken of the market.
    bingo. even the pros are not perfect.
    i have seen home labs better than professional factories.

  • @Peter

    >Also you can make a toner with regular green tea bags, nothing wrong with that.
    I saw a video of Korea top makeup artist skincare trick... using green tea to rinse the face. :) even better. Aussie tap water is filled with gunk, i see it constantly in my distiller.

    > A tip might be, just buy a simple fragrance free toner, and add some ingredients. 
    toners are really good margin products. i'll make that simple toner if you want... for you at cost. i wouldn't pay too much for >90% water.

    >You can't go wrong with Niacinamide, Panthenol or Allantoin for example. 
    + NAG hee


    >This is a nice video on "pimping" your toner, its in german so perhaps the text is a bit difficult to read.
    lol google translate can't help... i'll check that out. i got so much homework to read from u ... lol
  • >Also you can't be completely sure if the ingredients you buy have the same quality as larger brands.
    There's difference between purities of pure ingredients. They don't mention it on the packaging. But in professional labs they test for the quality of ingredients, even natural oils or things like niacinamide for example may contain trace amounts of all kind of different elements.

    >How do you test liquids and use less
    you need to calibrate a pH-meter quite regularly. Most of those yellow cheap pH-meter come with a pH4 and pH6.86 test sollution. I put the product I want to test in a small cup and if the electrode is inside the product, it works very well, so in my experience you don't have to stick it till the recommended immersion level.

    >The most difficult thing you need to know is at what pH each ingredient has to be formulated
    Well I've found the right pH for many ingredients, but I couldn't find it for things like Resveratrol or Green Tea for example. Those MSDS pH values are just the pH what you get if you dissolve the ingredient. That doesn't have to be the pH at which the ingredient is most stable.
  • edited December 2016
    >I think there are too many uncertainties to formulate your own cosmetics.
    >if it is too easy, i lose interest lol. take the challenge and make it fun.
    Well I have had some chemistry classes, if I don't completely understand which chemical reactions are taking place, I'm not going to do it. For example perhaps you've read there's an interaction between ascorbic acid and niacinamide, it forms a complex. But do you know what will happen if you mix Superoxide Dismutase with Resveratrol, I don't.

    I mean dissolving it, perhaps knowing at what pH an ingredient is stable, storing it in the fridge is the first step, many things are described on the internet, but exactly knowing what you're doing, what is happening chemically inside the product is another story. It's way more complex than you think, and many things you simply can't know or read from the internet. Professional cosmetic companies use techniques like multidimensional gas chromatography, or electrospary ioniation mass spectometry. I don't think you have that at your home. Perhaps you can read this book.

    Besides a face mask or a product with some simple oils and some ingredients I'm not going to formulate my own cosmetics ;-)
  • edited December 2016
    @Peter

    > so in my experience you don't have to stick it till the recommended immersion level.
    Aha! So how much is ok to get away with my pH meter. I need a smidgen with pH strips.
    Yes I have those calibration solution.

    Purity of ingredients: I thought the companies I. It ingredients... eg bulk Actives lotion rafter etc do state they essay/purity ... sometimes the % of Actives in the Extract.

    Green tea /Resveratrol : oh yeah, these are not provided. I remember having no luck finding more on Resveratrol. A good question for Perry's forum Chemist corner.

    Chemistry :
    Duh no. But I do safe stuff. And seek inspiration by products already formulated and tested. You can also try asking at chem corner if some actives play nice, they may have better experience tho the person with better experience with superoxide dismisses is Dr Sivak. You can check the products she has, good chance you'll find them ... if not post directly in their forum and ask. Sounds like a dream team combo, check their products to see if this 2 ingredients appear in the same product? I don't remember but I rem Dragon fr Skinactives told me to DIY slow. Not too many actives at a time. no more than 3 Actives ideally. I hope she is ok, she closed her shop Skin Essential Actives. I'll send an email, pray it doesn't bounce.

    >mean dissolving it, perhaps knowing at what pH an ingredient is stable, storing it in the fridge is the first step, many things are described on the internet, but exactly knowing what you're doing, what is happening chemically inside the product is another story.
    I only follow recipes/instructions so far.

    Btw I read this we were discussing:

    "If the active is not soluble in water or in oil, I may have to find an alternative solvent, because the skin will not absorb the un-dissolved active.

    The physical properties of an ingredient, including its capacity to dissolve in a particular solvent, are fixed. The capacity to dissolve depends on the relationships that the molecule can establish with the molecules of the solvent." Dr Sivak


    >It's way more complex than you think, and many things you simply can't know or read from the internet.
    Agreed. But it is not difficult to make something simple with ingredients with an abundant of information already available,

    >Professional cosmetic companies use techniques like multidimensional gas chromatography, or electrospary ioniation mass spectometry. I don't think you have that at your home. Perhaps you can read this book.
    Thanks.
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