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Sex toy inspection

Dear Reader,

It has come to my attention that the Swedish chemical authority have decided to inspect some items which might be known as “adult toys” or “sex toys”. I do have a problem with this use of the word “adult” as some of the things in “adult entertainment” sector are anything but adult. To me adult means mature, sensible, reasonable and decent. The true meanings of these four words “mature, sensible, reasonable and decent” are often polar opposites of some of the things in the “adult entertainment industry”. But I think that we will leave this topic alone.

What Kemikalieinspektionen did was to consider a total of 44 items from 16 compaines, now I am not going to discuss the intended use of the items or what they are. If you feel the urge to read that then I suggest you look elsewhere. What I am going to discuss is some of the chemistry involved.

Now the Swedish body choose to consider “phthalates, short chain chlorinated paraffins, azo dyes, nickel and the metals and flame retardants that are restricted for electrical products“. While the topic and the items might be controversial I think that it was a reasonable choice to make.

Now the start of the method explains how XRF was used to screen for a range of harmful metals, it will also detect bromine. But care needs to be taken with the measurement of bromine by XRD as one of the L lines (1.48043 1.48043 1.52590 keV) for bromine are very close to the line for aluminium (K lines at 1.48670, 1.48627 and 1.55745 keV). The items which were regarded as being interesting were then sent for further examination.

The problem with the report was that it was not totally clear which analytical method was used to determine the metal or the organics in the items. What was found in one study by Gerald Fowles which is mentioned in the wonderful book “Chemistry in the Marketplace” is that the nature of the mechanical pretreatment before leaching will alter the amount of a metal which can be released from an item. The key message is that chewing a plastic children’s toy was very effective as a means of releasing the metals in them while other mechanical pretreatments tended to lock in the metals. Also sucking on toys is not that dangerous but chewing and gnawing at them does release cadmium.

He also found that the use of hydrochloric acid which contains mercury(II) chloride as a preservative also inhibited the release of cadmium from cadmium sulfide and cadmium selenide. The reason is that an even more insoluble layer of the mercury chalcogenide will form on the surface of a pigment particle thus preventing any further reaction. It is a bit like the problem of sulfuric acid and marble chips, there a layer of insoluble calcium sulfate forms on the marble chips thus preventing any further reaction from occuring.

Gerald Wilfred Albert Fowles also did some very interesting work on lead and chromium in children’s comic books when he was at Reading University in the 1970s. In Diana F. Eaton, Gerald W. A. Fowles, Michael W. Thomas, G. Brian Turnbull, Environ. Sci. Technol., 1975, 9 (8), pp 768–770 he reports on how much lead and chromium can be leached from comic books when they are leached in a simulated stomach acid.

A different approach would be to use a wet combustion of the plastic by digesting it in a Parr bomb with nitric acid. Here the plastic would be totally degraded by the oxidant (nitric acid). Then we would get all of the metal contents released from the object. It is interesting to note that simple burning can result in the loss of some semivolatile metals such as lead.

What would have been interesting to know is if the items were leached with some chemical reagent or were they digested / burnt to release the entire inventory of the metals. One interesting problem is that while when PVC and latex are heated under oxidizing conditions that they are converted totally into gases, when silicone is burnt it forms a large amount of silicone dioxide. It is possible that attempts to liberate metals from silicone objects will be hampered by the formation of silica. In the worst cases the silica may form a crust over the metals thus locking them in.

Toxic lubes ?

Dear Reader,

As I suspect that most of my readers will understand how and when they have sex and with who is a very personal matter. Now it has come to my attention that Gwyneth Paltrow has been condemning the use of “lube” as her naturopathic doctor told her that “lube” is dangerous. Now I would like for the record to point out that I do not work for the “Drug Industry” and have no other vested interest in the “Drug Industry“. Nor do I work in the “lube industry” or get any money from them.

Maggie Ney her doctor had condemned “lubes” such as KY gel because they contain parabens, she claimed that

Parabens have actually been found inside breast tumor cells. And while we cannot conclude that parabens cause breast cancer, we can certainly argue that our bodies do not efficiently metabolize and eliminate it from our bodies. So when the FDA (which does not even regulate what goes into our lubricants) claims that the amounts of parabens are too low to pose a toxic effect in the body, they may be correct if we’re talking about a single exposure. The problems is, parabens are in our moisturizers, makeup, shaving creams, and facial cleansers. With multiple, daily use of these products, parabens and other chemicals are accumulating in our bodies, being passed onto our children, and playing a significant role in the health of our reproductive system.

Lets consider the ideas in this paragraph, we will start with the orange text. Now if I was to take a cancer cell regardless if it was lung, skin, liver or breast it would contain water. Maggie claims parabens have been found in breast cancer cells and then suggests that these substances could be responsible for the cancer. This might be an attempt to confuse the reader.

To my mind with the general public, they are almost always going to misunderstand the letter of the text as meaning “parabens can cause cancer”. I would say that a responsible doctor or medical scientist should take care to avoid leading the reader down a wrong path.

The great problem with cancer is that it originates in a single cell, this mutant cell keeps on dividing so it will be impossible to find this cell in a person who has clinical symptoms of cancer. So the substances in the cell at the moment it is removed from a person as part of a sample of a tumor will not be the substances present in the cell when it turned into a cancer cell. Also she has failed to show that the parabens were responsible for the cancer. Her link between the presence of parabens in cancer cells and the suggestion that they were part of the carcinogenic (cancer forming) process is on the same level as a person claiming that the water in cancer cells was responsible for the origin of the cancer.

One of the problems with the paper in 2004 in which P.D. Darbre, A. Aljarrah, W.R. Miller, N.G. Coldham, M.J. Sauer and G.S. Pope reported the concentrations of paraben esters in breast cancer tumors (Journal of Applied Toxicology, 2004, 24(1), 5-13) was that they failed to give any data for normal healthy breast tissue. This was pointed out by the editors of the journal. So already the significance of the finding of parabens in breast cancer samples has been called into doubt. This weakness in the paper which is a key part of Maggie’s argument is something which we should also consider when deciding what sort of under arm sprays to use or lubes to smear on our bodies.

For those of you who want to see what methyl paraben looks like then here is a diagram of the molecule.

Methyl paraben, methyl 4-hydroxybenzoate

Methyl paraben, methyl 4-hydroxybenzoate

Those of you who want to see the shape of the molecule through the miracle of x-ray crystallography should consult D. Vujovic and L.R. Nassimbeni, Cryst.Growth Des. , 2006, 6, 1595.

Next my English grammar expert points out that the use of the “and” I highlighted in red, is an example of rather bad written english. But we will not be making this post an english language lesson.

Next we look at the statement in blue, now this is an example of poor writing. Firstly the text is too informal and poorly defined. The text So when the FDA (which does not even regulate what goes into our lubricants) can be understood in several different ways.

Firstly I was to make a “lube” and market it only in Sweden then the FDA would not regulate it at all, so it would be correct for me to write “The FDA does not regulate my lube”. Equally if someone was to buy a lube which was made and marketed in Denmark and use it on holiday in France then they could quite correctly write “The FDA does not regulate my lube”. Instead of a single person writing (or talking) we were to have a group of people expressing an opinion then they could write (or say) under those conditions

“The FDA does not regulate our lube”

An alternative and meaning which could be understood from the text is the claim that the “FDA does not regulate what substances are used in lube”. I think that as a “doctor” that Maggie should be very careful with the way in which she writes and speaks. She should aim to avoid speaking in an ambigous manner, I would advise her for many reasons to make sure she writes clearly. But then when I looked at the FDA web site and made a search there for “sexual lubricant” then I found this group of documents bundled together into a single pdf. This is one of many such collections of documents, I do not want to endorse any particular brand and this is given as an example of some letters which have gone between companies which wish to market lube and the FDA.

After reading the documents in the pdf I have given a link to, I came to the conclusion that the FDA does regulate the marketing of “lube”. Part of this regulatory process includes a consideration of what is added to the lube. Keep in mind that multiple licenses are required for a drug to be brought to the market and sold or issued to people.

Consider for a moment as an example an asthma inhaler, now I am sure that some of my readers will be aware that cold air, infections, exposure to allergens, running, chopping wood, vigorous dancing or even sex can trigger breathing trouble in people who have asthma.

The drug must be shown to be safe and effective before a license is issued for the drug to be allowed as a treatment for a condition. For example salbutamol has been shown to be a safe and effective drug.

The drug must be made by a company which has a series of licenses (GMP etc etc) to be able to make pharma grade batches of the chemical which is intended to be used as the drug. The drug has to be made under special clean conditions, rather than being made under “normal” conditions.

The device which delivers the drug to the person taking it needs to have a license before it can be put on the market. Questions such as how well does it manage to deliver the same dose each time to the user need to be considered. Also how much of the drug is delivered to the lungs and how much is lost in the mouth could be an important issue with an asthma inhaler.

I see the same thing with the marketing of a “lube”, the substances in it must be ones which are regarded as “safe” in their intended use. Also the product must be able to deliver the substance in a safe way, issues such as microbiology need to be considered.

Next we will look at her statement in green, this is on the subject of how long these will stay in our bodies. I have already sent an email to Maggie Ney via the comments form on the website of her medical practice regarding the biological half lifes of the parabens. So far she has failed to reply. It so happens that two papers have been published in which the safety case for human exposure to two paraben esters have been reviewed. For methyl paraben, M.G. Soni, S.L. Taylor, N.A. Greenberg and G.A. Burdock wrote a paper entitled “Evaluation of the health aspects of methyl paraben: a review of the published literature”, (Food and Chemical Toxicology, 2002, 40(issue 10), pages 1335-1373) was the review on the substance. The abstract of the review contained the important phrase methyl paraben “is hydrolyzed to p-hydroxybenzoic acid, conjugated, and the conjugates are rapidly excreted in the urine. There is no evidence of accumulation.”

For those of you who might wounder what a paraben is, then it is an ester of 4-hydroxybenzoic acid. This is a carboxylic acid which is found in a range of fruits as a natural product. For example it was detected in coconuts by G. Dey, A. Sachan, S. Ghosh and A. Mitra, Industrial Crops and Products, 2003, 18(2),  pages 171-176. While in currants this carboxylic acid was found by K. Maatta, A. Kamal-Eldin and R. Torronen, Antioxidants & Redox Signaling, 2001, 3(6), 981-993. It gets even better, methyl paraben has been isolated from countless plants, reports of its isolation as a natural product go back into the 1960s.

While for propyl paraben the same authors reported very similar results in their survey of the literature in Food and Chemical Toxicology, 2001, 39(issue 6), pages 513-532.

I hold the view that if Maggie wants to continue to make these claims about parabens she should provide some evidence to show how M.G. Soni et. al. are wrong, her personal view that parabens are harmful is far less important than a pair of reviews which each cite over 100 papers. We should be striving towards evidence based medicine, here I see a conflict between Maggie and her claims (not supported with evidence) and the scientific literature.

Maggie also makes the interesting comment that anything which is safe to eat is generally safe to smear on one’s body before sex. Now lets explore this, now before some of you might think that this is going to be an exercise in school boy smut should understand that they will be disappointed if they expect Dr Foreman to be writing about something obscene.

We will start off with sugar containing products, now I know that many of us like sugar. It contributes to the taste of many nice and yummy products. It is found in fruit, sweets and many other products. I know that the food industry is accused of over using it, but when used in moderation it makes things taste very nice.

The problem I see is that sugar in the wrong place can result in mayhem, I would be interested to know if Maggie has considered the problem of Candida type yeasts. If one was to use some sugar rich substance as a lube, I see a danger that it might disturb the microbiology of the private parts. This could result in some rather unpleasant effects.

I also considered the possibility that Candida can feed on starch, I checked the academic literature and quickly I found an example of a form of Candida which can feed on starch. It so happens that the Candida tropicalis BPU1 isolated from goats can feed on potato, tapioca, or jack seed starch to form polyhydroxybutyrate (PHB). If you want to read the paper then see P. Priji, S. Sajith, S. Sreedevi, K.N. Unni, S. Kumar and S. Benjamin, Starch-Starke, 2016, 68(1-2), 57-66.

I looked in the literature for papers about starch and the yeast (Candida albicans) which is the form of candida common in humans, I found one by K. Bramono, R. Tsuboi and H. Ogawa (Mycoses, 1995, 38(9-10), 349-353) in which the authors reported that this yeast did not form alpha-amylase but it did form alpha-glucosidase. This is an enzyme which is able to break down starch into glucose. Also the yeast was able to grow on maltose which is a disaccharide. This suggests to me that it is possible that starch containing foods could cause something to happen, the final comment I will make on this organism is that by treatment with UV light and ethidium bromide it was possible to form a version of this yeast which was very good at converting starch into alcohol (ethanol). This was reported by A. Aruna, M. Nagavalli, V. Girijashankar, S.P.D. Ponamgi, V. Swathisree and L.V. Rao, Lettters in Applied Microbiology, 2015, 60(3), 229-236. While I hope it is unlikely that this mutant yeast would ever be able to escape from the lab or industry and establish itself in humans it does suggest that the parent version of the yeast can feed on starch.

In case you want to find out what ethidium bromide is then here is a picture of it, it is a nasty mutagenic dye used in DNA research.

Ethidium bromide

Ethidium bromide

I note that the KY liquid and the jelly both contain hydroxyethyl cellulose, in general cellulose is much harder to digest than a starch. This alone will make the KY gel much less likely to act as a food for the yeasts and bacteria. There are some organisms which have the enzymes needed to digest cellulose but many lifeforms are unable to do this. The paper by A. Martinez-Richa (Polymer, 1998, 39(14), 3115-3119) indicates that as the hydroxy groups in cellulose are replaced with 2-hydroxyethyl groups the rate of digestion by cytolase decreases. A series of products are sold under the names of cytolases, these are enzymes for the digestion of things like celluloses.

Now I can not claim to be an expert on the biology of Candida but this paper does raise a great concern. I think any of my readers who are concerned about starch based products being used for sexual purposes might be well advised to ask either a gynecologist or a microbiologist about this issue.

KY jelly as that sold in the UK contains some glycerol (propane-1,2,3-triol, Glycerin) which can be used by many microbes as a source of food but with the preservatives present in the gel I suspect that it will not be much of a problem. Glycerol can be used as a food by some bacteria, for example see A. Murarka, Y. Dharmadi, S.S. Yazdani and R. Gonzalez, Appl Environ Microbiol., 2008, 74(4), 1124–1135 explains how E. Coli can be used to convert glycerol into some industrial chemicals. It can also be used by some yeasts as a source of energy, but I suspect that the preservatives in the gel will stop this glycerol causing any problems.

Glycerol

Glycerol

The KY liquid also contains sorbitol and propylene glycol, these are polyalcohols which are non toxic. The sorbitol is a sugar which is slightly different to glucose, it provides less energy per gram and I suspect that it is a poorer fuel for bacteria / yeast than glucose would be. As it will only be present in a small amount I suspect that a small amount of this sugar will be less likely to cause some microbiological mayhem than a strong sugar solution such as honey.

D-Sorbitol (also known as D-Glucitol)

D-Sorbitol (also known as D-Glucitol)

The propylene glycol is a non toxic replacement for ethylene glycol which is used in both food and antifreezes. The reason it is far less toxic than ethylene glycol is that it can not be converted into oxalic acid or some other toxic C2 compound such as glycolaldehyde and glycolate (glycolic acid).

Propylene glycol

Propylene glycol

Likewise some gels such as KY jelly contain some gluconolactone which is a sugar, I do not know how much is present in the gel but due to the fact that the gel contains some antibacterials I suspect that this small trace of sugar will not pose a problem. This additive may be present to squester any unwanted trace metals which appear in the gel, this substance can chelate to a metal ion using the hydroxyl group which is alpha to the carboxylic acid which exists when it is in the open chain form. The addition of this to the product will be likely to increase the shelf life of it.

I have looked and the open chain version of this lactone has been converted into crystaline solids which have been investigated with X-ray crystallography, T. Lis, Acta Crystallogr.,Sect.B:Struct.Crystallogr.Cryst.Chem., 1979, 35, 1699 reports a polymeric manganese compound. Here two carboxylic acid groups (COOH) have lost a proton, these forms a negatively charged species which binds to the manganese cation (positive ion). At the same time an alcohol on the next carbon to the carboxylic acid binds to the manganese, two waters are attached to the manganese atom and to complete the metal complex an alcohol from the acid binds to the metal. I was going to draw a picture of it and then I saw the hydrogen bonding network, as I can not do justice to it I will not try to draw it.

The complex of this acid with a tris-(2-aminoethyl) amine complex of cobalt is more manageable, this is a simple complex which was documented by M.Pfister, S.Illi and P.Klufers, Z.Naturforsch.,B:Chem.Sci. , 2013, 68, 739 which explains clearly how I imagine that this molecule can bind to a metal. One of the advantages of binding to a metal is that it can make the metal less available for bacteria and other microbes to use. One of the ways in which a human body suppresses the growth of “germs” is by keeping its iron locked up in chemical forms which the germs can not access.

The KY jelly contains some chlorhexidine, this is an antibacterial agent which is used in mouth washes and many other antibacterial products. One interesting thing about chlorhexidine is that it can not be used at the same time as normal soap or an anionic detergent. This is due to the fact that the anionic detergents inactivate the chlorhexidine becuase the chlorhexidine is a cationic surfactant. The best detergents to use with chlorhexidine are neutral ones such as block copolymers of ethylene oxide and propylene oxide.

The gel also contains some sodium hydroxide, this might sound horrible but a small amount of sodium hydroxide when added to starch has an interesting effect. It causes the starch to swell up. This is because starch is a mild acid, starch is slightly more acidic than water so a slurry of starch will react with sodium hydroxide to form the sodium salt of the starch. I suspect that with the vast number of hydroxy groups present in hydroxyethyl cellulose that it can also bind to sodium ions in a similar way to corn starch.

So far I think that KY gel or another similar product designed and marketed by a mainstream drug company is going to provide you with a safe experience. Sadly no pharma company can offer a warranty that your sexual relationships will go perfectly and that you will live happily ever after with your partner. Well if only they could offer you such a deal !

I would also like to point something else out, those of my readers who are easily horrified should stop reading this post now ! Trust me this one is nasty with a capital N ! So not read the text in yellow if you are squeamish.

Many years ago as a PhD student I read of a nasty product tampering case in the USA. A man held an extreme belief that people who use contraception are going to bun in hell, regardless of how outlandish and offensive we might find this belief we can not criminalize a person’s belief or their thoughts. However acting on these beliefs or thoughts can be criminal. What this man did was to get a job in a condom factory, he decided to give the users of condoms an early taste of hell by smuggling an extra hot chili sauce into the factory which he later applied to the condoms while they are being packed.

He was convicted of a crime, and I think he was lucky to get away with probation. My father holds the view that this person should have got jail time as it was a hate crime. His reasoning is that a hate crime should earn the criminal a more lengthy stay inside. I have to agree with him on that. My legal adviser comments that a hate crime is a crime against society as a whole and not just the person or company which is being attacked.

Those of you of a sensitive nature can start reading again, this horrible story clearly shows that Maggie’s claim “When it comes to lube, if it is safe to eat, it is generally safe to apply” is clearly wrong. I think that the word “generally” is a funny word, it can have two meanings. It can either mean that the majority of things in a class are safe or it can mean all things in the class have the same characteristics, one can say that a chemical reaction is so general such that all substances of a given class will do reaction X. For example all secondary alcohols can react with chromium(VI) oxidants to form ketones. To my mind the use of “generally safe to apply is bad scientific writing as it can be understood in two very different ways. A good scientist or even a reasonable one will attempt to write and communicate in such a way that it is impossible to misunderstand the message.

While I might have picked an extreme example in the form of the capsaicins and the related compounds in chilli peppers, other foods contain substances which when taken in a particular way can cause injury. For example I know the inhalation of cinnamon powder his harmful (look up the cinnamon challenge and please for goodness sake do not try it).

I hold the view that many food substances might be safe to swallow in moderate amounts but when applied to the wrong part of the body the results can be rather disagreeable. Another example would be the fumes from onions and horseradish, while eating an onion or putting horseradish sauce on your beef might be OK. Exposing your eyes to the fumes from either is rather disagreeable.

It was interesting that Maggie Ney suggests oils as a alternative to these lubes made by the big companies, I have to question how good an idea this is. One sorry tale I know about is that relates to cosmetic breast implants. Now years ago as we all know silicone was marketed for breast implants. What happened was that a series of high profile court cases occurred when women claimed that their silicone implants harmed their health. Now I do not want to take sides over this matter. As a result of the court cases the world’s leading producer of silicone withdrew from the medical / cosmetic market so a search started anew for a new material for filling breast implants. One of the materials which was used was soy oil. Now we might think that something which is a food substance would be harmless for use in an implant and for smearing on our bodies. But there is a nasty sting in the tail in this case.

The subject has been reviewed by S. Monstrey, A. Christophe, J. Delanghe, S. De Vriese, M. Hamdi, K. Van Landuyt, and P. Blondeel, Plastic and Reconstructive Surgery, 2004, page 847. Here it is explained that the super refined soy oil used in the implants tends to react with oxygen to form new products including some which are carcinogenic. The idea of substances such as malondialdehyde sodium (3-hydroxy-2-propenal) forming inside my body is not a welcome or comforting idea. This compound is a dielectrophile which could crosslink biomolecules in a similar way to glyoxal. The malondialdehyde would be formed by the oxidation of the linoleic acid groups which are present in the soy oil. Other horrible oxidation products could form in the oil, I would like to know if Maggie knows about the problem of the instability of biodiesel, when compared with traditional road diesel fuel (DERV) made from petroleum the FAME biodiesel is more unstable. I have seen some papers in which oxidation processes which involve the carbon double bonds (unsaturation) are involved in some oxidation processes which are not possible in mixtures of alkanes or most alkyl aromatics (normal diesel fuel). I will assume that no one is going to try to create a diesel fuel which contains large amounts of cumene (isopropyl benzene) or similar compounds. Cumene is a rare example of a alkylarene which is very able to react with the oxygen of the air.

FAME biodiesel is a refined plant oil which has been converted into methyl esters. I would like to know how Maggie and the people who might follow her plan to keep the oils fresh without using things like BHT as a stabilizer. I know that many oils contain tocopherols but the more the oil is refined then the lower the greater the chance that these will be removed by the refining process. I would like to know if the natural tocopherol content of the oil will be sufficient to keep it from forming nasty chemicals by going rancid during storage. Again this is an example of how a food substance is not universally safe for humans.

Now while I have concentrated on American products, I would like to consider for a moment some Swedish products. Now some of my readers might misunderstand the Swedes and their attitude to sex, rather than either being rather repressed or sex mad what the Swedes are is “open” about sex. This does not mean that they do it in the open or public places, what this means is that they are willing to talk more openly about it than the British.

In Sweden there is an organisation named RFSU (Swedish Association for Sexuality Education) sell condoms, pregnancy tests and other sex related items. Now while some of their products are things which I would rather not discuss here they do sell lube. It is interesting that the Swedish version of the RFSU site has a link to the RFSU shop which is absent from the English version, I will have to tell RFSU about this. RFSU market a range of lubes, some of which are aqueous based products while they also market a silicone based lube. They also market a product which is both water and silicone based. I suspect that the product based on both silicone and water will be an emulsion. An emulsion is a combination of two liquids which are not miscible. I will not discuss the silicone based products any further in this post. We will save those for another day.

It is interesting that RFSU market some products which are free of parabens, for a list of what the Kick range contain see here. I considered the question of how does a paraben free product stay stable and I noticed that the aqueous product contains the following substances.

Aqua, Propylene Glycol, Glycerin, Hydroxyethylcellulose, Phenoxyethanol, Lactic Acid, Sodium Saccharin, Benzoic Acid, Sodium Hydroxide, Dehydroacetic Acid

This list might look long and scary, but lets go through it step by step.

Aqua is water, unless you are nervous of “dihydrogen monoxide” then I would not worry about this substance. We have already discussed propylene glycol and glyerin, they are similar to each other in their purpose and relatively harmless.

The hydroxyethyl cellulose is a version of cellulose which we have already considered. The phenoxyethanol is an interesting one. It is an antibacterial, while it is not paraben it is still a preservative.

phoch2ch2oh

Phenoxyethanol

The lactic acid and sodium hydroxide are likely to be there to control the pH. I know that in a normal woman that lactic acid is found in the vagina so the use of lactic acid plus some sodium hydroxide to set the pH of the product seems to be a very reasonable choice by the designers of the Swedish product.

lactic-acid

Lactic acid (2-hydroxypropanoic acid)

The sodium saccharin appears to be an odd choice of chemical, it is a sweetening agent used commonly in foods. But a quick search of the literature does reveal that it is able to inhibit bacteria. So it may be present to prevent microbes from spoiling the product. I also notice that benzoic acid is present, this is a substance which prevents the growth of yeasts, again a substance intended to make the product be more stable.

The last substance is dehydroacetic acid which has some antibacterial properties, it has been reported that Collie as a young man made some interesting discoveries about this substance. He found that it could be converted into orcinol. Sadly I know very little else about this substance other than the fact that it is a cyclic compound which is a masked polycarbonyl. The interesting thing is that both the Cambridge database and Wikipedia both have data which suggets that dehydroacetic acid is C8H8Owhile a book (Chemistry of Plant Natural Products: Stereochemistry, Conformation by Sunil Kumar Talapatra and Bani Talapatra) suggets that it is a slightly smaller molecule.

dehydroacetic-acid

Dehydroacetic acid and the ring opening reaction with water

But when we think about this moelcule it is clear that on heating under acidic conditions that it will lose carbon dioxide (decarboxylate) to form a triketone with the formula C7H8O3 which then undergoes an aldol reaction with itself followed by some minor reactions to form the orcinol. The triketone can form a cyclic compound with a formula of C7H8O2 which the book labeled as dehydroacetic acid.

The aldol reaction will form 3,5-dihydroxy-5-methylcyclohex-2-en-1-one which can dehydrate and then undergo a keto-enol tautomerism to become aromatic and thus form orcinol. Here is part of the reaction in the following figure.

steps towards orcinol.png

Formation of 3,5-dihydroxy-5-methylcyclohex-2-en-1-one from dehydroacetic acid.

What will happen next is that the dehydration and the keto-enol tautomerism will form the diphenol (orcinol).

orcinol-formation

Final stages of the formation of orcinol

While the formation of orcinol from dehydracetic acid is interesting, it is a bit of a diversion. I would like to point out that I know too little about dehydroacetic acid to be able to make a judgement as to how much is good or bad to put in a product. However looking at the Swedish product it does appear to be a product where none of the ingredients are screaming danger to me.

Lastly I would like to point out that soy oil will degrade condoms and also stain the sheets / clothing more than a water / hydroxyethyl cellulose based lube.

So far I am not convinced that “lube” is dangerous, unless you smear it on the vines which Tarzan swings from tree to tree with. I have taken the time to contact Maggie to see if she wishes to reply to some of the comments raised in this blog. But so far she has not chosen to comment.

Oh So Crazy part II

Dear Reader,

I have been informed by a senior figure at the University of Lagos (Prof. L.O. Oyekunle) that the work of Mr S. Amalaha is not sanctioned or supported by the university. They have published a statement condemning the work and pointing out that it is not related to his course of study.

I hold the view that some persons on the internet have been unfair towards the University of Lagos, the questionable “work” on magnets appears to have been done independently of his studies in chem eng. Maybe the “magnet genius” is misusing his association with the university to propagate his crack pot ideas.

I will be writing something shortly about the limits of academic freedom and freedom of thought in the near future but for the mean time here is the statement from the University of Lagos. I have to say that while I generally support the freedom to hold and express ideas different to my own, in this case I hold the view that Mr S. Amalaha has crossed a line into hate speech. We should commend the University of Lagos for their firm statement which I am now reproducing below.

DISCLAIMER OF THE PUBLICATION OF MR. STANLEY AMALAHA – Part Time Postgraduate Diploma Student of Chemical Engineering

Our attention has been drawn to a publication containing research purportedly written by one of the Part Time Postgraduate Diploma Students in the Department of Chemical Engineering, University of Lagos – Stanley Amalaha, titled “Science of Gay Marriage” in THISDAY Newspapers of 5th September, 2013 and on several blogs on the Internet.

The University of Lagos writes to dissociate itself in its entirety from the actions, publications and research of this individual. We further state, for the avoidance of doubt, that his publication has nothing to do with his programme and has no relationship to his studentship of the University. Indeed our postgraduate diploma students ordinarily only take conversion courses to improve their capability for the chosen specialization and do not undertake research. The case of the writer who has a background in Education (Chemistry) is not different.

Although the University is a market place of different views and ideas, its platform should not be used for the propagation of ill-conceived, unsubstantiated and ill-digested opinions that have no basis in rigorous empirical research. The University of Lagos, which stands for excellence in teaching and research, cannot and should not be associated with such puerile and pseudo-scientific postulations.

The University reaffirms its mission, which is to be a top-class institution for the pursuit of excellence in knowledge through learning and research as well as in character and service to humanity.

 

Toyin Adebule,

Deputy Registrar

(Information)

The swedish version of the spanner case

Dear Reader,

On friday by chance we were discussing fire control equipment which uses something called Argonite, this is a trade name for a 50/50 mixture of argon and nitrogen which is used as a fire extinguishing system. One of the students talked about suffocation with Argonite, I then pointed out that lack of oxygen (Inert gas asphyxiation) has totally different biology in humans to suffocation which involves a high level of carbon dioxide in the lungs and blood.

Now while reading the news I read that a man in Sweden has been convicted of a crime against the person relating to erotic asphyxiation (strangulation). The Swedish court of appeal has upheld the man’s conviction but they downgraded the crime. I think that the court should have considered the man’s actions to be very grave crimes. Alex Comfort in his book (The Joy of Sex) strongly condemes this practice as very dangerous, so I am not alone in being opposed to this activity.

Some years ago (1987) in the UK there was a case known as the “spanner case”. As this blog is a family show I will not tell you of the worst of the sexual tortures which occurred during S&M sex, But this case revolved around should a person be able to consent to an assault committed against them. One of the judges who had to deal with the case commented “Society is entitled and bound to protect itself against a cult of violence. Pleasure derived from the infliction of pain is an evil thing. Cruelty is uncivilised”, he also expressed the view that the convictions of the S&M fanatics should be upheld.

One argument is that a person should be free to consent to what ever they like, I have an alternative argument. While the people do not intend to seriously injure each other there is a problem. Their conduct is jolly reckless and it should be clear to a “reasonable man” that a large risk exists of a fatal outcome or another outcome which causes some permanent disability.

I assume that a lot of people will find the sexual practises in both cases offensive and very immoral, but if we leave our morals out of it for a moment another compelling argument exists for banning “choke sex” and the dire extreme S&M seen in the spanner case.

A citizen does not live in isolation, those who work should all pay into a common fund (through tax) which allows society to take care of people who need help. It provides funds for fire fighting, police, hospital treatment for ill people, education for children, pensions for old people and other social care. If a person takes a reckless risk with their wellbeing such as riding a motorcycle with no helmet then they place themselves at risk of changing themselves from a person who generates money to run society into a person who is a drain on society.

A brain injured motorcyclist may well need expensive special health and social care for the rest of their live, while I do not advocate a refusal of care for people who injure themselves doing something I think is stupid or immoral I do think that it is reasonable for the state to use criminal law to deter or punish people who place themselves in grave danger under some conditions.

The key thing is that riding a motorcycle with no helmet, driving a car without wearing a seat belt and the horrible S&M sex are reckless acts which offer no reward to either the individual or society which outweighs the risks. So I think that we should use criminal law to ban these activities.

On the other hand, cheese rolling contests, sleeping in a bed and dog ownership are all activities which do carry a risk of physical harm but the rewards to society and the individual strongly outweight the risks. We should not allow “health and safety” to be used as an excuse to ban these things.

For example it is possible for me to roll out of my bed and crash onto the floor breaking some part of my body this is a remote but plausible risk, the reward of sleeping in a bed is that I do not have to sleep on the floor and get cold. I think that the majority of my readers would agree that the benefits of sleeping in a bed outweigh the risks. So we should never have a law banning normal beds, maybe beds which are surrounded with spikes or lethal 2000 volt fences should be outlawed but my normal bed should remain legal !

While performing emergency repair work on my dog (pulling a bone which was stuck in the dog’s mouth out), I have been slightly injured by a panicking dog (a couple of small cuts to the hands). This is an example of a risk of dog ownership, on the other hand the social and emotional benefits of dog ownership outweigh the risk of a minor injury occurring during ECM (emergency canine maintenance not electronic counter measures).

The cheese rolling is clearly an activity in which people can get hurt, but the cultural significance of a pack of men (and women) chasing a cheese down a steep hill is so great that it should remain legal !

Estrogen chemistry

Dear Reader,

I was going to write about the case of Julian Assange but I think that rather than reading about how the UK courts are trying to choose what to do with an alleged sex criminal you would rather read about some organic chemistry. For those of you who have spotted this blog because the word “sex” appears in it I am sorry to disappoint you but this is not going to be a lurid blog post all about sex.

Instead of a crude post we have an frank, blunt, explicit and no holds barred bit of organic chemistry. Do not worry it is safe for work !

Recently my lovely female westie (Rosie) has been not quite right, in the interests of canine medical privacy I am not going to discuss what is right and wrong with her body on my blog. But today she had to go off to see the vet, after being examined by the vet she has been put on a course of estrogen pills.

This made me think about estrogen, the estrogens are a series of steroidal compounds which has an important role in female mammals. It is part of the system of hormones which regulate a series of bodily functions. By the way if you are still reading, you will have a good laugh at those who went to the red hot action site expecting to see something rude, it was a page devoted to blacksmithing. Well blacksmiths tend to beat red hot steel into shape which is a bit macho.

One example of the estrogens is estradiol. Estradiol is an aromatic compound, it is like the other steroids a tetracyclic compound. It has an aromatic ring at the opposite end to the five membered ring. It is important to understand that the two hydroxyl groups in the molecule will be very different. Different because of the electronic effects of the aromatic system.

Now before we get onto estrogen, you should cast your mind back to that blog post on overgrown snakes, like that German one which had grabbed his tail (Ouroboros). Always bear in mind that a aromatic system has to have a pi cloud which is a ring which goes on and on for ever. The story is that one chemist (Kekulé) was sitting beside a fire and he had a dream about snakes which grabbed hold of their tails and pulsated about (resonance) which is very close to what we know from modern science about benzene rings.

Before we go any further it is important to bear in mind how estrogen is made in the lab, one way is to use a combination of cobalt carbonyl chemistry and a Diels-Alder reaction. Do not worry about the cobalt step, that is some very advanced chemistry (organometallic chemistry), the important parts are the next two steps.

 

The core of a lab synthesis for estrogen type steroids using the Peter C. Vollhardt method.

The core of a lab synthesis of a steroid using Peter Vollhardt’s method.

Those of you who have been on my course may recall that anything with a unsaturated ring which has four electrons in it has the clear potential to be antiaromatic. The easy way to understand what
antiaromaticity does to a molecule’s stability is to imagine aromaticity as an almighty virtue. Think of the nicest person you can think of, think of all their good points as being like the super stable calmness of an aromatic molecule like benzene.

Now think of the worst person you can imagine, think of a person who is the total opposite of the best person you can imagine.

OK I will tell you about someone I admire, Verka the nun. She is kind, well read, keen to pass on the good things she knows to others, generous and a joy to know. Now imagine anti-Verka she would be cruel, ignorant (and proud of it), keen to never pass on anything useful to another soul, mean minded and a total nightmare to know. If aromatic is all the good things you can think of then antiaromatic is all the worst things about human nature you can think of.

In the case of the ring opening which converts the benzocyclobutane into the thing which does the [4+2] the ring opening reaction occurs via a transition state which has a cyclic pi system with four electrons. To avoid having an antiaromatic transition state the pi system gives its self a twist to end up being like a Möbius strip. If you do advanced organic chemistry then you may get to learn about this sort of thing.

The [4+2] reaction (Diels-Alder) goes via an aromatic transition state which has 4n+2 pi electrons (n=1) so it should not come to be too much of a shock to know that the transition state has a
conventional aromatic nature. It only exists for a small moment and then it is gone !

In the biosynthesis of steroids it starts with a simple monoterpene which is related to 2-methylbutadiene, this is converted via a series of intermediates to form squalene (hexaterpene) which is cyclised to form lanosterol

Fruitbat sex again

Recently the Irish high court ruled on the case of Dylan Evans. It gave a ruling which can be divided into three parts. The story can be read at http://www.timeshighereducation.co.uk/story.asp?sectioncode=26&storycode=414495

1. Dylan Evans was guilty of ‘sexual harassment under the university’s “dignity of respect” and “right to dignity” policies.’

2. But the punishment imposed by the university was  “disproportionate” and should be lifted.

3. That the university is free to investigate Dylan Evans for “alleged breach of confidentiality” regarding the leaking of the case papers to the public domain.

Now before we get going I would like to say that I am not equipped to comment on point two as I have no idea what the correct penalty should be or how the university court came to their choice of penalty. I can also not comment on point three as the university must be left free to consider the matter without commentators remarking on every step of the process. But I do feel equipped to consider Dylan’s reaction to the case.

I read with interest on Dylan’s web site (http://www.dylan.org.uk/fruitbat_freedom.html) how he thought that he had been the unlucky victim of “extreme feminists”. He asserted that this group of “extreme feminists” viewed other women as weak fragile persons who can not make choices for themselves.

I thought about this, I know that occasional extremist such as Valerie Solanas (The woman who shot Andy Warhol). But it is unreasonable to define the entire movement or gender because of the views and acts of a small minority. To my mind Emmeline Pankhurst and the other suffragettes were early feminists, I have no problem with what the suffragettes wanted. What they wanted was equal political rights no matter which gender you were. From what I know about Emmeline Pankhurst she did not seem to be a person who regarded other women as being weak minded persons who are unable to makes choices for themselves.

I would like to consider the question of what is disgusting and offensive.

I hold the view that it is possible for papers in the scientific literature to be horrible, disgusting and offensive. I have read some things which in some people would inspire horror and disgust, for instance in some scholarly works I have seen serious (fatal) examples of radiological injury. I will not give you a link here as some of you might rather not have such disturbing images in their minds. Putting aside for a while papers which contain graphic pictures of serious injury I would also like to point out that some papers will contain ideas or text which is offensive to some people. For example a person who is ideologically opposed to the nuclear industry might find the idea of a new reprocessing method as offensive. This alone is not a justification for condemning the paper as offensive and as being worthy of being banned.

Material should never be regarded as offensive because the reader did not like it, instead a more fair test is required. We could consider the Miller test.

The Miller test is a test which is used in the USA to decide if pornography is legal or not. The Miller test (http://caselaw.lp.findlaw.com/scripts/printer_friendly.pl?page=us/413/15.html) has three points. To be obscene to the point of needing to be banned you need to ask three questions about a work.

A.  Does “the average person, applying contemporary community standards” would find that the work, taken as a whole, appeals to the prurient interest ?

B. Whether the work depicts or describes, in a patently offensive way, sexual conduct ?

C.  Does the work, taken as a whole, lacks serious literary, artistic, political, or scientific value ?

After having read the paper about the sex lives of bats I would have to say that it would not be banned if we use the logic of the miller test as the answer to question C is not yes. The paper does have some scientific valve. However after reading the paper I hold the view that it is not suitable for universal reading. I would not dream of supplying a copy of this work to a child, a student or a coworker in the same way as I would not dream of quoting the Marquis de Sade’s books when I teach organic chemistry. After getting a quick no for question C, I gave up and stopped thinking about the other two.

I have to supervise PhD students, I have several people in my research group who are working on topics such as iodine chemistry and recycling polymers. When I was a student, I was once given a reference to look up by a member of staff (not my normal tutor or supervisor. I will refuse to name names so do not bother asking). I went to the library and I looked in the lancet and discovered that the paper was a reference to some sexual injuries. I then asked myself the question “what has this got to do with my studies ? Answer: Nothing, it was someone’s idea of a joke (Not funny).

The incident made me think, one  pedagogy prof calls this “using critical incidents” (http://gup.ub.gu.se/gup/record/index.xsql?pubid=103790), this is the idea of looking at an event in the past using a given method (http://www.apa.org/pubs/databases/psycinfo/cit-article.pdf). I thought long and hard about it, some years ago during the obscenity trial of a book ( Lady Chatterley’s Lover,  D. H. Lawrence) a remark was made by prosecutor (Mervyn Griffith-Jones) when he asked “if it were the kind of book ‘you would wish your wife or servants to read ?’ “. To be blunt with you I am not bothered what my PhD students read in their spare time as long as it does not adversely affect their work. But “What should I require my students to read ?” is an important question.

I would not go as far as to apply the all the ideas of the Hays code (http://productioncode.dhwritings.com/multipleframes_productioncode.php) to my work and their reading lists, but I will say that the Hay’s code has some good points such as……

Salacious, indecent, or obscene titles shall not be used. (Teaching events should never have rude names)

I do not have an easy or good answer to this question yet, but I would like to state that so far the concept of “need to know” does apply, the idea of “need to know” is based on an idea from the military sector.

Does my student need to read papers about sexual injury ? do they need to read how bats have sex with each other ? Do they need to read how to make MDMA ? I would say that somethings there are things which are interesting but might have clear potential to offend or be close to the dividing line between what should be allowed and what should be outlawed. Before I supply a copy to a student or encourage them to read it, I need to make sure that there is a good reason for the person to be reading this borderline matter.

Bat sex

In the recent past, an almighty debate has risen up over academic freedom. In Ireland, an academic has been investigated for having shown a female co-worker a paper on the subject of the sex lives of bats. As this blog is a family show, I will not describe what the bats have been doing.

Dr Dylan Evans has argued that the fact that the paper was from a peer reviewed science journal to defend his actions. For the moment, at least I do not want to sit in judgement on Dr Evans. However, I want to explore some of the issues with you. I think that the fact that it is “peer reviewed science” does not make a paper universally acceptable to show to a co-worker.

Years ago I was told a story of a man who escaped from a mental hospital, he broke out of the hospital and being a clever lad stole some clothing from a washing line and then started to walk down the road wearing his new suit of clothes. He then had a thought (a paranoid thought) that the first person who encounters him would think he was insane and therefore an escaped psychiatric patient. Therefore, he resolved to say to the first person something, which was so universally accepted to be true that no person would doubt his sanity.

Five minutes later a woodcutter, his girlfriend and their handsome Westie dog were walking the opposite way along the leafy country lane. (I like to aspire to be poetic and romantic sounding). The escaped man then said to them as he passed “The earth is round, and it orbits the sun”. The woodcutter asked “What?” The man repeated, “The earth is round, and it orbits the sun”. The woodcutter’s young lady then recalled hearing that a someone had escaped from “St Elsewhere’s”; she then lured the man into the nearby café. While he was drinking some tea, the police arrived and took his back to hospital.

What the escaped man said might have been true but it was grossly inappropriate, he would have been better saying “Oh what a delightful day, and what a sweet looking dog you have”.

What Dylan Evans showed the woman might have been “peer reviewed science” but in my opinion, it was  reading material which is very inappropriate in most circumstances. I have read the paper on the bats and I can tell you that while it does not fall foul of the USA pornography law (It does have scientific, artistic or cultural merit) it is not an item, which is suitable to be shown to all.

I would like to know what makes Dylan Evans qualified to have a learned opinion on “bat sex”. It is possible to have a reasoned and learned opinion on a subject outside your original field.

I hold the view that study in one area to PhD level gives (or at least should give) a person a set of critical thinking abilities which can be applied to other areas. The PhD outside his/her field needs to take the trouble to obtain a working knowledge of the subject and to learn about the methods used in a new field before they can offer a learned opinion on the new subject. So while the PhD does not convert a person into a polymath, the process of obtaining a PhD does make a person more able to become able to make an informed comment on another field.

As Dylan appears to be outside his own area when it comes to “bat sex”, I would dearly like to know what self training efforts he has made to make himself competent to work on the subject of “bat sex”. I am not going to say it is impossible through self training to learn a new area.

Ferdinand von Prondzynski (http://universitydiary.wordpress.com/2010/05/27/the-complexity-of-academic-freedom/) made a wise remark on the case we wrote

If my field is organic chemistry, are my views on corporate banking protected by academic freedom? If they are, why should my views on this be given greater standing than the views of non-academic members of the public?

I would argue that the academic who strays outside their area and does not make all reasonable efforts to develop a competence in the new area should not be afforded any special protection.

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