Nitroolefins – The Crying Game

(This post was written for the ‘Toxic Chemicals’ carnival, over at ScienceGeist)

Let me tell you about the time I broke down crying in lab. No, it wasn’t an epic breakup, or even a death in the family. It was…a nitroolefin.

Many summers ago, I worked as a pharma intern, a small flywheel in a then-huge drugmaking machine. My supervisor, a kind, safety-conscious scientist, begged me to come straight to him if I had any questions about my reactions.

We were synthesizing a small nitroolefin – 2-nitropropene, to be exact – for some nitro-Michael additions. If you look at the Org. Syn. prep, it warns, right at the top in red letters, that the compound is a potent lachrymator. The term, from the Latin word for “teardrop,” describes compounds that irritate the eyes to such an extent that tears freely flow.

I carefully piloted the reaction, distilled the greenish-yellow product, and then watched it run up my TLC plate. Beautiful! Now, I just needed an NMR sample.

Gingerly, I dissolved a drop into some chloroform. Forgetting for an instant, I pulled the NMR tube out of the hood to cap it, and within seconds crumpled to the bench. It felt as if someone had stabbed smoldering iron toothpicks into my eyes. I stumbled around until my labmates dragged me over to the eyewash; later, I became well acquainted with our local safety officer. My eyes remained bloodshot for the rest of the day. Lesson learned: Lachrymators are not to be taken lightly! (I’ve experienced similar, though milder, reactions to benzyl bromide and thionyl chloride).

For those younger chemists thinking about summer lab work, take a few minutes to find out if your reagents might cause uncontrollable crying. Cautious handling, and a well-fit respirator, can go a long way towards your future safety and comfort.

Science for the future

A campaign group, calling itself ‘Science for the future’ is, today, delivering a coffin to Number 10 Downing street in London as a protest against what they claim to be the death of British science.

Their concern is that the UK state funded research councils,  (particularly the Engineering and physical sciences research council, (EPRSC) that funds most of the chemistry research in the UK) are giving priority to research that will deliver good economic outcomes over blue sky research.

This group isn’t just a rag tag bunch of disgruntled scientist who are peeved that their projects don’t get funded. Its backed by a heady list of Nobel Laureates and heavily honoured scientists who published their views on the matter in a letter to todays Daily Telegraph.

Between the press coverage in the Telegraph, the BBC etc. and twitter (#science4thefuture) things are being pretty well covered. So I thought I’d focus on one aspect of the group’s issues with the EPSRC.

Any grant proposal submitted to the EPSRC has to include a section addressing the ‘National Importance‘ of the research. The guidelines on how to construct this section of the proposal states:

National Importance is the extent, over the long term, for example 10-50 years, to which the research proposed;

  • contributes to, or helps maintain the health of other research disciplines contributes to addressing key UK societal challenges, contributes to current or future UK economic success and/or enables future development of key emerging industry(s)


Predicting the impact of our work 50 years into the future seems pretty incredible. There are plenty  that think completing this section of the grant proposal requires the employment of a soothsayer.


I too wonder about at it usefulness. Under this regime would lasers have been funded given that they were perceived to be little more than physicists’ toys?

But lets suppose for a moment that in 1958 Townes and  Schawlow had 20:20 foresight when they wrote a ‘National Importance’ statement for an EPSRC grant proposal. It may have gone something like this.

Over the next 50 years we envisage that lasers will have a extraordinary impact on research, technology and the everyday lives of people worldwide. Lasers will prove to be useful in every conceivable scientific discipline. For example, we expect them to be used as a viable means of inducing nuclear fission, eye surgens will correct abnormalities in the eyes by cutting into the cornea with lasers and so saving people the bother of wearing glasses, and we expect lasers to be used to manipulate single molecules with a technique that may become known as optical tweezers.

However lasers will not be restricted to the laboratory or trained medics. They  will become ubiquitous, every home will have a device that uses lasers to play their music, so replacing vinyl disks. In fact we expect lasers to become so cheap and readily available that they will even replace the pointy stick used to highlight the important parts of slide presentations.

Would anyone really have believed that?


By May 15, 2012 2 comments opinion, science news, science policy

5 million gallons and 2 years later…

If I were to walk outside right now and ask the next person I see what the words “Deepwater Horizon” brought to mind, I wouldn’t be surprised if he/she simply stared at me with a puzzled look. Yet exactly two years ago, we all watched the news as the story of the Deepwater Horizon oil rig explosion developed. It would ultimately become the worst man-made ecological disaster in history as the uncapped well poured nearly 5 million gallons of oil into the Gulf of Mexico. Many of us chastised the oil companies, BP in particular, for being too concerned with profits and expected the government to take action to prevent future spills. Now, two years later, the storm has quieted down but how much has things really changed? Here are some facts/figures I collected:

BP has paid out just 7.8 billion dollars for economic losses/medical bills to affected people, though it claims a total of 37.2 billion spent in response to the disaster. By comparison, BP had a total revenue of 386 billion dollars in 2011 alone.

The Gulf spill is not the only oil disaster in the last two years. Lost in the media coverage and the aftermath are spills in Utah (June 2010, 33000 gallons), Michigan (July 2010, 1.1 million gallons), Montana (July 2011, 63000 gallons), and countless other spills in foreign countries but from American companies.

Though the Oil Spill Commission ultimately concluded that BP did not sacrifice safety for profits, it also noted that a number of decisions made by BP to speed up construction of the oil rig increased the risks of a disaster. A recent report from former commission members noted that Congress has done very little to improve regulations on offshore drilling. For example, the current liability cap for an offshore oil spill is still a mere 75 million dollars.

I’m sure that decisions are made every day that have significant ecological impact but are necessary for the benefit of society. However, I certainly had hoped that the environmental impacts would remain minor. If something like the Deepwater Horizon disaster can’t galvanize the public into demanding long term changes, then what will it take? What can we do to reach a so-called “tipping point” when we as a society realize that environmental problems need to be solved now?

By April 21, 2012 5 comments opinion, science policy

Homeopathy: Science or Sympathetic Magic?

As a new contributor to Chemistry Blog, I’ve decided to ‘break myself in’ by tackling the somewhat controversial and thought-provoking topic of homeopathy.  As I write, we find ourselves part way through ‘World Homeopathy Awareness Week’, so the subject is enjoying quite a high profile and twitter seems to be alive with discussion on the matter.


Before I go further, I feel I should declare myself to be a sceptic.  I’m doubtful as to whether any other point of view on this subject would be published on Chemistry Blog –so that will come as no surprise.  After completing my chemistry studies, I chose a career in the pharmaceutical industry –to make a difference.  I also rely on daily medication to manage my own condition.  I’m therefore very aware of the difference proven chemistry can make to the quality of people’s lives.  The science of drug development is founded on proven facts; a great deal of money, effort, time and hard evidence is required for just one new drug to reach the market –I will return to this subject in a later article.


What are the principles of homeopathy?


Homeopathy is an alternative medicine, based on the principle of treating like with like.  Patients are treated with highly dilute preparations believed to cause symptoms in a healthy person, similar to those being experienced in the patient.  Commonly used dilutions are 10C and 30C.


To achieve a 30C dilution, the ‘active’ ingredient is diluted 1 part in 100 –and then a drop of this solution would be diluted to 1 part in 100 and so on for 30 repetitions.  The resulting final solution would be 1 part active in 1 followed by 60 zeroes.  To put this number in perspective; one molecule of ‘active’ in a volume the size of the entire observable universe would be 40C.  Homeopaths claim a process called ‘succussion’, the act of striking the vessel containing the solution against an elastic surface 10 times at each stage of the dilution process, activates the ‘vital energy’ of the diluted substance and they talk, not in terms of dilution, but in terms of ‘dynamisation’ or ‘potentisation’.


As chemists we know there is a limit to any dilution that can be made without losing the original substance entirely.  This limit is related to Avogadro’s number and in homeopathic terms roughly 1 part in 1024 –equivalent to a 12C preparation.  A 30C preparation would require giving 2 billion doses per second to 6 billion people for 4 billion years to deliver a single molecule of the original material to any patient.  It is worth pointing out here that homeopathy dates from a time predating the discovery of atoms and molecules, so it was a widely held belief that a substance could be diluted ‘ad infinitum’.


Homeopaths believe the more dilute a preparation is the more effective it is. They believe the diluent used (usually water) has a memory of the active molecule it once contained.  My professional life as an analytical chemist would be a living nightmare if this were the case and carefully prepared diluents were ‘remembering’ the properties of the all the compounds they had contained.  Just imagine what the HPLC chromatograms would look like!  There would simply be no point in trying to keep the equipment free from contamination.  The notion of ‘molecular memory’ is at best implausible; it suggests the shape of a molecule is more important than its chemistry. Putting reason aside for a moment and accepting that water has memory –how would it emulate the chemistry of that molecule?  That very notion would require our current understanding of chemistry to be re-written and that understanding has provided us with thousands of medications which have been proven to be effective.


Clearly, if homeopathy achieves a successful clinical outcome, there is something else at work here. There is likely to be a significant ‘placebo effect’ and there is anecdotal evidence to support this idea. Also, the act of consulting the homeopath and the attention and sympathy the practitioner gives the patient –is believed to support the healing process. This, however, can be dangerous when the practitioner advises the patient against engaging with conventional medicine –this can, and has, resulted in tragic consequences.


As a complementary therapy, homeopathy appears to benefit some and as such it has its place in modern medicine. It isn’t sensible to use it as the only course of treatment for any condition, especially not a serious disease. The ‘science’ doesn’t stack up -it’s just sympathetic magic.

By April 12, 2012 15 comments general chemistry, opinion