Cancer risk from 'third-hand smoke' by Lewis Brindley

Nicotine residues on indoor surfaces can react with ambient gases to generate cancer-causing
compounds, researchers in the US have found. The research is hoped to shed new light on the
possible danger of 'third-hand smoke' - where toxins from tobacco fumes can linger on household
surfaces.
'Certain compounds - such as ambient nitrous acid or nitrogen dioxide - are present in higher
quantities indoors rather than outdoors,' explains Hugo Destaillats, who led the research at
Lawrence Berkeley National Laboratory in California, US. This is because they are generated by
combustion from indoor gas supplies, fireplaces or the use of electronic equipment.
Destaillats and his team used cellulose as a model indoor material, and placed a block of it inside
a truck belonging to a smoker for three days. They then analysed the block and compared the
results with lab-based tests based on cellulose exposed to vaporised nicotine in a tubular-flow
reactor. 'We found that ambient gases [in the truck] reacted with residual nicotine to generate
tobacco-specific nitrosamines that are known to be carcinogenic.'
Two of the compounds - N-nitroso nornicotine (NNN) and 4-(methylnitrosamino)-1-(3-pyridil)-1-
butanone (NNK) are also found in tobacco smoke, so have been well-studied in the past. But a
third compound was identified that is not usually present in tobacco smoke: 1-(N-methyl-N-
nitrosamino)-1-(3-pyridinyl)-4-butanal), termed NNA. Since it is absent from smoke, NNA has not
been investigated in detail, but the team is hopeful that toxicologists will now undertake studies.
Unlike second-hand smoke, inhaled unintentionally in public places, the hazards of third-hand
smoke are not so clear-cut. Many factors are involved, from size and ventilation of the indoor
environment to the different materials used - microlayers of toxins can accumulate in upholstery,
wallpaper, clothing and hair.
'One group that is particularly at risk from this type of smoke are children,' says Jonathan
Winickoff, an assistant professor of paediatrics who has studied the danger of third-hand smoke
at Harvard Medical School. 'Children interact with their environment in a very different way, so
their exposure could be twenty times higher than adults.'
'I think this is important work that will set the stage for many further studies on residual tobacco
smoke contamination,' Winickoff adds. 'The implication of third-hand smoke is that there is no way
for a person to smoke indoors without contaminating that environment.'
Ketene comes in from the cold by Simon Hadlington
Researchers in the US and Korea have shown how an unusual functional group, which has been
largely neglected in materials chemistry, can be incorporated into polymers to give the polymer
both a reactive handle for attaching other molecules and a route to cross-linking adjacent polymer
chains.
The ketene group, -C=C=O, is capable of rich and diverse chemistry, says Craig Hawker of the
University of California, Santa Barbara, who led the research with Bongjin Moon of Sogang
University in Seoul, but has not been widely exploited in polymer chemistry. 'We speculate that
polymer chemists have always viewed ketenes as simply too reactive to handle and too difficult to
generate,' says Hawker.Now, however, Hawker and Moon have shown how ketenes can be
incorporated into a range of polymer backbones where their chemistry can be harnessed. A
compound called Meldrum's acid, consisting of a heterocyclic oxygen-containing ring and two
carbonyl groups, can be heated to produce a ketene. In addition, the molecule contains a highly
reactive CH2 group, allowing a range of other groups to be attached to the Meldrum's acid.

Meldrum's acid decomposes when heated through the

loss of acetone and carbon dioxide to form the ketene,
which has two paths of reactivity: dimerisation to the
cyclobutanedione, or addition in the presence of a
nucleophile to afford the corresponding ester or amide
The researchers demonstrated that various monomers, such as styrene, can be fixed to the
Meldrum's acid and subsequently polymerised. This gives polymer chains with Meldrum's acid
groups dangling from the backbone chains, which produce ketenes when the materials
are heated. 'We have presented polymers based on polystyrene and polynorbornene, but we
envision many different structures to be developed in the future,' says Hawker. 'Also, it is very
easy to tune the amount of Meldrum's acid which is contained in these polymers. For example, we
made polymers which were 98 per cent polystyrene with only 2 per cent reactive Meldrum's acid
monomer, or 100 per cent Meldrum's acid monomer.'
Adjacent polymer chains can be cross-linked via the ketene groups, while leaving some ketenes
remaining which are available for further chemistry.Rachel O'Reilly, a polymer scientist at
the University of Warwick in the UK, says that the new research represents a real breakthrough
for polymer functionalisation and has the potential to be a transformative technology in materials
science. 'The work described will be an excellent addition to the 'click' family of reactions and from
a seemingly forgotten reagent,' O'Reilly says.Hawker adds a neat historical footnote to the work.
'Diphenyl ketene was first discovered in 1905 by Hermann Staudinger, who spent the next ten
years of his career establishing the scope of ketene chemistry as we know it today,' he says.
'Around 1920, Staudinger diverted his focus to polymer chemistry, and was awarded the Nobel
prize in 1953. Incorporating ketenes into polymer systems brings together two of the pinnacles of
Staudinger's career and brings a satisfying degree of historical closure.'