Main Contributions (see also Research Summary)
Following on from pioneering work on thioaldehydes and ketones the first Phosphaalkenes (which contain C=P moieties e.g. CH2=PH etc) were created and the general synthetic routes to this whole new family were developed in 1974/5. Secondly, the development of general methods of synthesising Phosphaalkynes (RC≡P species such as MeC≡P etc, which have triple bonds between carbon and phosphorus) when only HCP was known and had been around for nearly 15 years. Although some of these species had been conjectured to exist as intermediates it was these studies which led to their isolation and characterisation and in particular ushered in the new fields of Phosphaalkene and Phospahalkyne Chemistry. This work was carried out in collaboration with my Sussex colleague John Nixon.
An undergraduate (Anthony Alexander) research project aimed initially at understanding the dynamics of long carbon chain molecules (polyynes, initiated with my Sussex colleague David Walton) led to the detection by radioastronomy of the large (long) carbon chain molecules in interstellar space (with Takeshi Oka and Canadian Astronomers: Lorne Avery, Norman Broten and John McLeod as well as Colin Kirby at Sussex). Importantly they were subsequently detected in the outflows of stars.
Our long carbon chain molecules seemed to be too large to have been created by the slow 2-body processes in the general interstellar medium where they are detected (e.g. gas phase ion molecule reactions and surface grain surface catalysis) which at the time were the only processes considered capable of producing the observed species. When our chains were subsequently detected in the outflows of carbon stars it seemed to me that here was a possible solution to their abundance. It was this conjecture which led to an experiment to show that the molecules were most likely produced in the atmospheres of red giant carbon stars and perhaps somehow able to survive. This conjecture was confirmed by the experiments. However these studies serendipitously uncovered the amazing and totally unexpected existence of C60 Buckminsterfullerene. Interestingly this experiment was also carried out partly as a pilot for experiments to try to determine whether carbon chain species were responsible for the diffuse interstellar bands, DIBs. These experiments were carried out at Rice University together with Robert Curl, James Heath, Sean O’Brien, Yuan Liu and Richard Smalley. Buckminster Fuller Dome Expo67 Montreal . Origin of the name Buckminsterfullerene Applewhite Chemical Intelligencer
On a Monday five days prior to the Friday on which the manuscript of the beautiful work of Kraetschmer et. al., arrived on my desk for review, C60 and C70 were independently isolated as a red solution in benzene at Sussex. That Friday was a Bad Day at Brighton Rock! The 720 amu mass spectrum had also been detected a week or so before! The chromatographic separation of C60 and C70 was developed and the buckminsterfullerene structure of C60 confirmed by the detection of single line in the NMR spectrum.
I consider this single NMR line confirming that all the carbon atoms in C60 are equivalent one of my group’s and my personal most satisfying contributions. if not the most satisfying.
This work was carried out with Jon Hare, Roger Taylor, Ala’a Abdul Sada, Tony Avent and David Walton.
After the extraction in 1990 Roger Taylor, David Walton and I set up the Sussex Fullerene Centre. A lot was achieved here is Adam Darwish’s beautiful report on the separation of Fullerenes. Roger working mainly with Adam pioneered the chromatographic separation
In the period 1985 – 1990 follow-up work to confirm the conjecture that C60 had the buckminsterfullerene cage structure led to the development of the Isolated Pentagon Rule IPR which predicted that if C60 was indeed a truncated icosahedron as we had proposed, then C70 had to be the next special structure as there was no cage possible with non-abutting pentagons between C60 and C70. Although there might be more than one explanation of the special structure of C60 it is was clear to me that another explanation of C60 and C70 as special was essentially impossible. This conclusion was also reached independently and furthermore neatly proven by the Galveston group of Schmalz Klein Seitz and Hite.
An elaboration of the IPR to multiple abutting pentagon structures resulted in the prediction that C50 should be metastable and stabilised by adding say 10 hydrogen atoms and in particular the small fullerene C28 should be tetravalent and metastable. Interestingly C50Cl10 has been isolated.
Further follow-up studies indicated that large spheroidal carbon particles would have onion-like concentric fullerene structures with quasi-icosahedral overall shapes. This is the only example I know of an arts project, in this case to create a sculpture, which has resulted in a scientific breakthrough.
In 1987 this prediction was made:
Comment (on Youtube “They are wrong”) at end of BBC Horizon Programme video re C60 and analogues such as C60+ as carriers of DIBs: They’re Wrong
The apparent coincidence that C60 was produced under conditions in which our carbon chains were also formed suggested that it and other fullerene analogues might be in space and possibly responsible for the diffuse interstellar bands DIBs. The ambient radiation field in space is such that the neutral C60 molecule is unlikely be present in the general interstellar medium but the positive ion C60+ is highly likely. This led to the suggestion that this ion and other fullerene analogues such as the endohedral species M@C60 as well as M…C60 (where various M species are attached to the outside of the cage) were strong contenders for the carriers of the DIB’s. The C60 cage was likely to survive longer in space than any other molecule because of its geodetic stability to photoionisation and the probability that species such as C60… M+ would be able to get rid of any excitation due to photons or collisions by dissociation into say C60+ and M without destruction of the fullerene cage which has no particular low-energy pathway to destruction; it is a sort of molecular super atom! People who looked for neutral C60 did not appear to realise that where the DIB carriers are present the UV starlight radiation flux would ensure that C60 and any analogues would be almost completely ionised.
The above 1987/88 etc conclusion that C60+ was the best candidate for a DIB carrier was confirmed by John Maier’s group in Basel in July 2015 when they unequivocally showed that it was responsible for two DIBs…the first time in nearly 100 years that any DIB carrier has been conclusively identified.
Molecular Rotation Spectra Monograph
Since arriving at FSU in 2004 research has been carried out on metal organic framework systems with Naresh Dalal, Tony Cheetham and Prashant Jain, nanoscience and nanotechnology with Steve Acquah and carbon cluster dynamics with Paul Dunk using the FT ICR MS high-resolution technology developed by Alan Marshall at the National High Magnetic Field Lab at FSU.
Efforts to support Humanity, Skepticism, Humanism, Anti-antiscience etc
The Vega Science Trust website (www.vega.org.uk) now an archive was set up to give the scientists who are experts in their fields a broadcasting platform to inform students, teachers and the public directly about scientific matters that are exciting and also are of concern. The Trust which was managed by Gill Watson 1991-2004 has produced over 300 programmes for the Internet of which some 50 have been shown on the BBC2.
Whereas almost all educational programmes focus on a particular student cohort, the GEOSET initiative’s paradigmshifting strategy is to turn the focus of the educational process round by 180 degrees to target our best teachers and students to capture Specific Educational Objects or Concept Modules which they have devised to infuse real enthusiasm and passion for intellectual knowledge. Although the GEOSET site streams many outstanding lectures and courses, as indicated above, the primary aim is the creation of an easily accessed cache of recordings by students as well as specific Teaching Tricks Of The Trade i.e. TTOTTs which outstanding educators have found by experience work. Steve Acquah manages the FSU site and Colin Byfleet the gateway geoset.info site.
2001 UK Stamp design
Graphic designs mainly for scientific institutions organisations and events as well as individuals: Logos, book jackets, posters, brochures etc. cf Graphics
Set of eight lectures on Intersellar Chemistry
14 Children’s Science Workshops
Workshops carried out all over the world: UK US, Australia, Sweden, Germany, Malaysia, Chile, China, Japan, Brazil, Mexico, Italy, Spain, Iceland (Internet), Venezuela (Internet). At BA meeting for 10 year morning and afternoon each day of the BA week.
15 Lecture Presentations etc
Many of my short powerpoint snippet focused sub-presentations are here