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Radionuclides and Radiochemistry

According to the International Energy Outlook Part I: Their Role in 2004 of the OECD, the worldwide demand for energy will double by 2050, while the demand for electric- Society* ity will double by 2025. Large and densely inhabited by Mauro L. Bonardi and David S. developing countries such as China and India will place a particular burden on resources. Electricity produced Moore from nuclear power represents a sustainable solution nergy production is not the only use for the to the global energy problem that will result from energy of the . Nuclear and this demand, especially considering the very small Eradiochemistry and related sciences and tech- level of radioactive wastes produced annually by the nologies—like radioanalytical, radiopharmaceutical, global nuclear industry (i.e., 200 000 m3 of medium and radiation chemistry—are frequently applied in and intermediate level nuclear wastes and 10 000 m3 many branches of science and through technology for of high-level wastes). It is noteworthy that the global the betterment of people around the world. amount of energy presently consumed worldwide in one year—corresponding to an “equivalent” power of The Energy of the Atomic Nucleus 13 TW thermal—could be produced by the fission of merely 5 million kg of either 232Th (in thermal breeder The popular perception of the energy released by reactors), 235U or 239Pu. Compare this to the burden on

nuclear processes—such as induced fission of ecosystems of CO2 released by the combustion of fos- 235U, 239Pu (bred from natural U), or 233U (bred from sil fuels at a rate of 0.8 million kg.s-1. It should be noted natural 232Th) or of hydrogen — that 232Th is present in the Earth’s crust in amounts is that it is used for energy production (i.e., heat, and four to seven times greater than U. from that electricity and, in the future, nuclear-hydro- gen or hydricity) or nuclear weapons. Indeed, scientists Non-Energetic Applications of the knew as early as the that the energy release Energy of the Atomic Nucleus from 1 kg of 235U is equal to that of the combustion of either 2 000 tonne of oil equivalent or 3 000 tonne of Nuclear materials, however, are used for more than coal equivalent. In a , this energy cor- energy production. Non-energetic applications of the responds to the detonation of 20 000 tonne of TNT energy of the nucleus affect the biomedical field, the (1 tonne TNT = 4.184 GJ). During the environment, cultural heritage, research, advanced of this mass of 235U, a mass of roughly 1 g (less than technologies, security issues, and human wellbeing. 0.1 percent of the initial mass)—calculated through Nuclear processes, such as the decay of radioac- the equation ΔE = Δm c2—is converted into energy. tive species (i.e., radionuclides), are widely used for Therefore, nuclear fission has an enormous advantage combating human diseases (i.e., radiopharmaceutical as a clean source of energy and with the further advan- chemistry), foodstuff irradiation for sterilization and tage that there are no greenhouse gas emissions. preservation purposes (i.e., radiation chemistry), and Presently—in spite of the negative perception of the safeguarding of cultural heritage and the environ- nuclear technologies—only 441 nuclear power plants ment (i.e., radioanalytical and radiation chemistry). (NPPs) produce 16 percent of worldwide electricity They are also used for heating and lighting in difficult (33 percent in the 22 countries of the OECD, with environments and for an extensive range of other, maxima of 80 percent and 82 percent in France and often surprising, applications.1,2 The American Nuclear Lithuania). At the present time, 34 to 40 NPPs are Society recently estimated that the under construction in 12 countries, while around 30 number of employees and scientists engaged world- are planned in several countries . The environmentalist James Ephraim Lovelock, nucleus in research, industry, government, hospitals, creator of the Gaia hypothesis, says “opposition to transportation and safety, environmental protection, nuclear energy is based on irrational fear” . nologies, and space exploration is much larger than

* Part II will focus on issues related to terminology; it is sched- uled to appear in the Jan-Feb 2008 CI.

10 CHEMISTRY International November-December 2007 Table I—Milestones in Nuclear Science (C, P: leading to Nobel Prizes in Chemistry or ) 1895 P discovery of X-rays by Wilhelm Conrad Röntgen; atomic prelude to nuclear sci- ences, led to first human radiography 1896 P “activity” of U salts by ; Was it related to Röntgen’s X-rays? 1898, first radiochemical separation: Po and Ra from U ores by Marie Sklodowska 1911 C and : term radioactivity was “invented,” perspectives in life sciences 1908 C and properties of radioactive elements by 1920s, radiotracer technique by György von Hèvesy, first application of 32P in medicine 1943 C 1921C chemistry of radioactive substances and isotopes in nature by 1922C mass spectrometry of large number of isotopes by Francis Aston 1929 P, cyclotron by Lawrence, first by and Walter Zinn 1942 1934C heavy hydrogen (deuterium) by 1934P neutron thermalization and activation by Enrico Fermi and co. 1934 “hot ” nuclear recoil effect by and Thomas Chalmers 1932, neutron discovery by 1935 P 1935 C syntheses of new radioactive elements by Frédéric Joliot and Irène Joliot-Curie 1939 C, nuclear fission by Hahn, Strabmann, Meitner, Frisch and Petrzhak, Flerov 1940 1949 C 14C dating by James Arnold and Willard Libby 1951 P by accelerator by and 1951 C first 5 transuranium elements (Np, Pu, Am, Cm, Bk) by Glenn Seaborg and Co. 1956 first 99Mo/99mTc “generator” for radiodiagnostics by Walter Tucker* 1958 P radioanalytical applications of Pavel Chěrenkov – Sergei Vavilov effect 1960s gamma camera for radionuclide emission radiodiagnostics (Hal Anger camera) 1961 P Mössbauer effect and spectroscopy by Rudolph Mössbauer 1963 P nuclear shell structure by Maria Göppert-Mayer and Hans Jensen 1967 P nuclear energy production mechanisms in stars by 1970s thyroid cancer radiodiagnostic and radiotherapy by 131I; 123I for radiodiagnostics 1976, 2-[18F]-fluoro-2-deoxy-D-glucose (2-FDG) for brain studies, tumor seeking 1985 1980 tomographic radiodiagnostic techniques (SPET, PET, PET/CT, spiral PET) 1990 labelling of brain and tumor receptors, investigations on dementiae senilis 1994 P and spectroscopy by and 1997 polyphosphonates for bone metastases pain palliation labelled with 186gRe, 153Sm 1999 oligopeptides for metabolic radiotherapy labelled with 64Cu, 90Y, 177gLu 2001 alpha emitters for high-LET metabolic radioimmunotherapy: 211At, 225Ac///213Bi 2002 P cosmic X-rays by ; circle of Röntgen X-rays closed ? *10 million radiodiagnostic investigations in North America annually, same in Europe and Japan.

CHEMISTRY International November-December 2007 11 Radionuclides and Radiochemistry

the number of people working in the nuclear power investigation for selective irradiation of DNA inside industry. cell nuclei, after internalization of properly labelled species through cellular and nuclear membranes.2,3 Radionuclides, Labelled Table II shows the primary specifications of a labelled Compounds, and compound to be used on living organisms, humans, animals, and cells. Radiopharmaceuticals Table I shows a select list of relevant discoveries and Table II—Analytical and Radioanalytical QC/QA of a Labelled related Nobel Prizes in Chemistry and Physics associ- Compound (e.g., radiopharmaceutical) ated with the nuclear sciences, emphasizing those with Symbol or significant applications in the diagnosis and treatment Measurand: quantity or parameter acronym Typical range of illness. Since the discovery of radioactivity in 1896, chemical purity CP sub-ppm traces just after the discovery of X-rays in 1895 by Wilhelm C. Röntgen, there has been a wide range of beneficial radiochemical purity RCP % applications of nuclear technology to human health. radionuclidic purity (isotopic, non- RNP % Even excluding all the radiodiagnostic and radio- isotopic) therapeutic techniques based on the use of X- and activity (i.e., radio-activity) a SI A MBq to GBq gamma rays (radiography, CT, cobaltotherapy, gamma- derived quantity knife), or accelerated particle beams that irradiate -1 specific activity AS or a GBq.μg pathological tissues (electron beams, IMRT, and dilution factor IDF dimensionless heavy ion hadrontherapy), there are many techniques -1 based on the use of both sealed and unsealed internal activity concentration CA or cA MBq.g radioactive sources. Among these are endocavitary biological purity BIOP radiotherapy and brachytherapy of tumors and other stability with time (all previous tissues, which have been in use for half a century. parameters) More recently, brachytherapy of prostate cancer has involved using Ti or stainless steel seeds containing 125I—or 103Pd—that are inserted permanently into a Since the discovery of X-rays a century ago, the patient’s body, and cause minimal discomfort. application of radionuclides and labeled compounds More relevant for the nuclear and radiochemistry in many branches of nuclear science and technology community are the applications of radiopharmaceu- has led to a vast array of improvements in both energy tical compounds labelled with radioactive production and quality of life. The role of different produced either by a nuclear reactor or an accelera- branches of nuclear and radiochemistry proved funda- tor. The first are obtained by neutron capture or fis- mental to this purpose.2 sion and are neutron rich and in general decay by beta minus (negatron) emission; they are suitable for References metabolic radiotherapy after being administered to 1. Radiation and Modern Life, Fulfilling ’s Dream, humans (and animals) as labelled chemical species. Waltar A.E., Prometheus Book, New York, USA, 2004. The latter are normally neutron poor and decay by 2. Handbook on Nuclear Chemistry, 5 Vols, Vértes A., Nagy S., Klencsár Z., Eds., Kluwer Academic, Amsterdam, The electron capture and/or ; these are Netherlands, 2003. used for radiodiagnostic and molecular imaging in 3. Handbook of Radiopharmaceuticals: Radiochemistry and 2D by gamma-camera, and more recently by SPET, Applications, Welch M.J., Redvalny C.S., Eds., Wiley, New PET, PET/CT, and spiral-PET tomographic equipment York, USA, 2003. with 3D capability. In addition, a number of novel alpha emitters recently have been proposed for high- Mauro L. Bonardi is a professor at the Universita degli LET radionuclide targeted radioimmunotherapy, while Studi di Milano, Accelerators and Applied Superconductivity Laboratory, in Segrate, applications of a range of low energy monoenergetic Italy. David S. Moore is at the Los Alamos National Lab, in Los Auger and IC emitters (64Cu, 111In, 117mSn) are under Alamos, New Mexico, USA.

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