Chromium-51 (51Cr) is an attractive radionuclide for diagnosis, which is usually applied for red cells and platelet radiolabeling. However, commercially available 51Cr produced in nuclear reactors via neutron activation requires long irradiation times and complex separation methods. In this work, five metal–organic frameworks (MIL-100 (Cr), MIL-100 (Fe), MIL-100 (Al), MIL-101 (Cr) and aluminium fumarate MOF (FuAl)) were synthesized and the effect of gamma ray irradiation with a high dose rate and a maximum dose of 6 MGy was investigated. The two chromium-based MOFs, MIL-100 (Cr) and MIL-101 (Cr), were selected as radiation targets to produce high specific activity 51Cr by the Szilard-Chalmers effect. A solid–liquid extraction was applied to extract the produced 51Cr under different conditions, including different extractants, extraction times and pH. The most promising results were achieved when using irradiated MIL-101 (Cr) and EDTA as extracting agent, reaching an enrichment factor of 1132 ± 50.@en

Two porphyrinic metal-organic frameworks (PCN-222 and PCN-224) were prepared and their potential as molybdenum adsorbents for the ⁹⁹Mo/^99mTc generator was explored. The molybdenum adsorption properties of the two adsorbents, including adsorption kinetics and equilibrium isotherms, were evaluated at different molybdenum concentrations and pH. The maximum adsorption capacity of PCN-222 and PCN-224 was evaluated to be 525 mg g⁻¹ and 455 mg g⁻¹, respectively. The possible adsorption mechanism was investigated by X-ray Photoelectron Spectra and Fourier-Transform Infrared Spectroscopy. The results demonstrated that molybdenum species were adsorbed on the two MOFs through electrostatic attraction and hydrogen bonds. In the case of PCN-222, the Mo-O-Zr coordination interaction also played an important role. Additionally, the elution performance of two ⁹⁹Mo/^99mTc generators developed by using PCN-222 and PCN-224 as adsorbents was measured to assess possible clinical applications. The PCN-222-based ⁹⁹Mo/^99mTc generator exhibited better elution performance and showed that around 56% of ^99mTc could be obtained without zirconium breakthrough when relatively high pH solutions were used (pH = 9.6).

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Temperature sensors that can operate in high-temperature and harsh environments are highly desired. However, this is a great challenge for sensing materials to operate under extreme working conditions because of oxidation and/or corrosion at high temperature. In this study, polymer-derived SiAlCN ceramics were prepared as sensing materials to overcome the abovementioned issues. A SiAlCN ceramic temperature sensor was designed and fabricated, and it performed excellent temperature-sensing properties with high accuracy, high stability, and high repeatability up to 1000 °C. Compared with traditional thermocouples, the SiAlCN ceramic sensor exhibited a faster response rate (a shorter response time). These results showed that SiAlCN ceramic is a promising sensor material for temperature measurement in high-temperature and harsh environments.

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The cerium-based metal–organic framework UiO-66 (Ce) was examined as a potential adsorbent for the ⁹⁹Mo/^99mTc generator. The results showed that the adsorbent had an outstanding adsorption performance, reaching up to 475 mg/g adsorption capacity at pH 3. An adsorption mechanism was proposed, where the adsorption was governed by hydrogen bonds, Ce-O-Mo coordination, π-anions and electrostatic interaction. Additionally, the adsorbent exhibited excellent radiation stability and good adsorption performance when radioactive ⁹⁹Mo was applied. A ⁹⁹Mo/^99mTc generator was fabricated with UiO-66 (Ce) as adsorbent and its performance was evaluated over two weeks. The elution results showed that 92 ± 3% of ^99mTc elution efficiency could be obtained with negligible cerium breakthrough, showing the great potential of UiO-66 (Ce) as adsorbent for ⁹⁹Mo/^99mTc generators.

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Four different MOFs were exposed to γrays by a cobalt-60 source reaching a maximum dose of 5 MGy. The results showed that the MIL-100 (Cr) and MIL-100 (Fe) did not exhibit obvious structural damage, suggesting their excellent radiation stability. MIL-101 (Cr) showed good radiation stability up to 4 MGy, but its structure started degrading with increasing radiation dose. Furthermore, the results showed that the structure of AlFu MOFs started to decompose at a gamma dose of 1 MGy, exhibiting a much lower tolerance to γradiation. At this radiation energy, the dominant interaction of the gamma-ray with MOFs is the Compton effect and the radiation stability of MOFs can be improved by prolific aromatic linkers, high linker connectivity, and good crystallinity. The results of this study indicate that MIL-100 and MIL-101 MOFs have a good potential to be employed in nuclear applications, where relatively high radiation doses play a role, for example, nuclear waste treatment and radionuclides production.

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Radionuclides are essential in nuclear medicine and therefore new and improved production methods continue to play an important role in ensuring sustainable availability. This thesis focuses on the production of two radionuclides (99mTc and 51Cr) using metal-organic frameworks (MOFs). MOFs are novel porous materials and their potential to be utilized in radionuclide production has been explored for the first time in this thesis. Chapter 1 gives a general introduction to the current production of 99mTc and 51Cr, and emphasizes the role that metal-organic frameworks can play based on their attractive properties.@en

The potential of the metal–organic framework UiO-66 and its functionalized derivatives for their utilization in the ⁹⁹Mo/^99mTc generator was assessed. Molybdenum adsorption experiments, structure characterization, molecular simulations and column experiments with molybdenum-99 were carried out. The results showed that the maximum molybdenum adsorption capacity achieved for UiO-66 was 335 mg g⁻¹. Adsorption on the surface of the UiO-66 occurs via electrostatic interaction and DFT calculations verified the enhanced affinity between the adsorbents and the molybdenum ions by Zr-O-Mo coordination, anion-π as well as hydrogen bonds. In addition, the performance of a ⁹⁹Mo/^99mTc generator fabricated with Form-UiO-66 was evaluated. The results showed that adsorption was comparable with the experiments using non-active molybdenum and that the ^99mTc elution efficiency of around 70% could be achieved without zirconium breakthrough.

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