Technetium production

First, the batch size of products is often small, and in the case of a technetium product prepared in a hospital or clinic, may consist of only a single vial with a total volume of less than 10 ml. 

This makes it impossible to follow the European Pharmacopeia requirements for the number of containers to be tested (10% or 4, whichever is the greater), without preparing extra vials of the product specifically for the test, which is economically unrealistic and also imposes an additional radiation burden on to the operators. There are also problems with the volume of the product available for testing. The European Pharmacopeia states that if the quantity in the container is between 4 and 20 ml, which is common for technetium products, 2 ml should be used for each culture medium being tested. If followed strictly, this would mean a large reduction in the volume of material available for patient use. 

Synthesis by Substitution Routes. Many of the limitations inherent in the redox route described above can be avoided by preparation of technetium-99m radiopharmaeeutieals by a substitution route, i.e. the classical substitution of ligands onto a pre-reduced and isolated technetium center. Substitution routes allow control over the oxidation state and ligand environment of the technetium product, and permit the synthesis of complexes containing different ligands. By substitution routes it should be possible to prepare series of complexes in which some ligands are held fixed while others are varied in a systematic fashion to affect biological specificity. 

Gr. technetos, artificial) Element 43 was predicted on the basis of the periodic table, and was erroneously reported as having been discovered in 1925, at which time it was named masurium. The element was actually discovered by Perrier and Segre in Italy in 1937. It was found in a sample of molybdenum, which was bombarded by deuterons in the Berkeley cyclotron, and which E. Eawrence sent to these investigators. Technetium was the first element to be produced artificially. Since its discovery, searches for the element in terrestrial material have been made. Finally in 1962, technetium-99 was isolated and identified in African pitchblende (a uranium rich ore) in extremely minute quantities as a spontaneous fission product of uranium-238 by B.T. Kenna and P.K. Kuroda. If it does exist, the concentration must be very small. Technetium has been found in the spectrum of S-, M-, and N-type stars, and its presence in stellar matter is leading to new theories of the production of heavy elements in the stars. 

M. H. Campbell, Summay Report Eoading Technetium-99 on IRA-401 and Measurement of Product Purity, Atimtic Richfield Hmford Co., Richlmd, Wash., June 1967. 

Plutonium was the first element to be synthesized in weighable amounts (6,7). Technetium, discovered in 1937, was not isolated until 1946 and not named until 1947 (8). Since the discovery of plutonium in 1940, production has increased from submicrogram to metric ton quantities. Because of its great importance, more is known about plutonium and its chemistry than is known about many of the more common elements. The metallurgy and chemistry are complex. MetaUic plutonium exhibits seven aUotropic modifications. Five different oxidation states are known to exist in compounds and in solution. 

Technetium-9 9m sestamibi is used in myocardial perfusion imaging for the evaluation of ischemic heart disease. It is prepared from a lyophilized kit containing tetrakis(2-methoxy isobutyl isonittile) copper(I) tetrafluoroborate stored under nitrogen. Upon reconstitution with up to 5.6 GBq (150 mCi) of 99mTc pertechnetate, the product is formed by boiling for 10 minutes. 

Technetium-99m teboroxime is a myocardial imaging agent and is excreted primarily by the hepatobiliary system. It is rapidly taken up by the myocardium and mosdy washes out within 30 minutes. Imaging protocols are performed immediately after injection. The product is a lyopbili ed mixture of boronic acid, dioxine, and other excipients, and the agent is formed with a beating step. 

Technetium-99m gluceptate is used in brain and kidney imaging. Sodium gluceptate is the active ingredient. The product is formed by the addition... 

Technetium-99m disofenin is used for hepatobiliary imaging. Disofenin (2,6-diisopropylphenylcarbamoyhnethyliminodiacetic acid) is the active ingredient. Product formation is accompHshed by addition of up to 3.7 GBq (100 mCi) of Tc pertechnetate. 

Technetium-99m albumin coUoid is cleared by the reticuloendothehal (RE) cells and is used for visualization of the RE system of the Hver, spleen, and bone marrow. The product is formed by the addition of up to 2.8 GBq (75 mCi) of Tc pertechnetate. 

The +4 Oxidation state ls the only uae in which all three elements form stable oxides, but only m the c.ase of technetium is this the most stable oxide. TcOz is the hnal product wi n any Tc/O... 

Wildung RE, YA Gorby, KM Krupka, NJ Hess, SW LI, AE Plymale, JP McKinley, JK Fredrickson (2000) Effect of electron donor and solution chemistry on products of dissimilatory reduction of technetium by Shewanella putrefaciens. Appl Environ Microbiol 66 2451-2460. 

Technetium then became available in a weighable quantity because of uranium nuclear fission leading to the production of "Tc in nuclear reactors. The total amount of "Tc in the world at the end of 1993 is estimated to be 78 tons, more abundant than rhenium on the earth. 

Although the half-life of "Tc in steller interiors is remarkably decreased, a substantial amount of the isotope ean survive the s-process. Observations have revealed that more than 50 stars contain technetium in their outer envelope. According to other calculations, the production of neutrons in the competitive processes of neutron capture and / -decay is even more enhanced at such high temperatures, and this fact almost compensates for the depletion of "Tc [41]. 

The O-donor complexes of Tc(V) exhibit moderate and differential stability in aqueous solution. In the presence of reducing agents, such as stannous chloride, they are reduced to mainly undefined products of Tc in a lower oxidation state. However, at the low technetium concentration of "mTc that is used in nuclear medicine, the rate of the reduction process is very low. This makes it possible to prepare Tc(V) radiopharmaceuticals with O-donor ligands by the usual procedure, in which an excess of reducing agent over technetium is unavoidably used. The Tc(V) complexes also tend either to be easily oxidized or to disproportionate [23],... 

Complexation studies with bidentate phosphine ligands showed that stable cationic complexes of Tc(V), Tc(III), and Tc(I) are easily accessible. The influence of reaction conditions on reaction route and products is well demonstrated by the reaction of pertechnetate with the prototype 1,2-bis(dimethylphosphino)-ethane (dmpe) (Fig. 16). Careful control of reduction conditions allows the synthesis of [Tc02(dmpe)2]+, [TCl2(dmpe)2]+, and [Tc(dmpe)3]+, with the metal in the oxidation states V, III, and I [120,121]. This series illustrates the variety of oxidation states available to technetium and their successive generation by the action of a 2-electron reducing agent. 

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