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@INPROCEEDINGS{Hoffmann:1026490,
author = {Hoffmann, Chris and Strecker, Jonas and Mittelstedt, Rik
and Spahn, Ingo and Neumaier, Bernd},
title = {2,6-{B}is-({N}-hydroxylamino)-1,3,5-triazines as ligands
for 45{T}i-chelation},
reportid = {FZJ-2024-03434},
year = {2023},
abstract = {Objectives: 45Ti (T½ = 3.1 h) is a promising PET
radionuclide thatcan be produced by proton irradiation of
nat Sc targets. While fasthydrolysis of most Ti(IV)
complexes has hampered their application forthe preparation
of 45Ti-labeled PET tracers[1] , some recently
reportedbis(hydroxyamino)triazine (BHT) complexes[2,3] are
hydrolyticallystable for several hours. Therefore, in this
study differently substitutedBHT ligands including a bridged
one were prepared and evaluated withregard to their
potential to form stable complexes with 45Ti.Additionally, a
novel procedure for the separation of 45Ti from the45 Sc
target material by cation exchange chromatography was
devel-oped[4]. Finally, a conjugate of a BHT-ligand with a
prostate-specificmembrane antigen (PSMA)-binding moiety
potentially suitable for thepreparation of 45 Ti-labeled
probes for imaging of prostate carcinomawas
synthesized.Methods: BHT ligands were prepared by
substitution of chlorinesubstituents in cyanuric chloride
first with secondary amines (R 3-NH-C 2 H4C(O)R4 ) followed
by hydroxylamines (R1-NH-OH, R2 -NH-OH)(Fig. 1)[2].Two
PSMA-selective probes were synthesized starting from
methyl3{-[(4,6-bis(chloro)-1,3,5-triazin-2-yl](R3
)amino}propanoate by sub-stitution of the chlorine atoms
with benzyl protected hydroxylamines,NaOH hydrolysis of CO
2Me to CO 2 H, conversion of the carboxylic groupinto a
succinimidyl ester, its reaction with t-butyl-protected
Lys-C(O)-Glu and, finally, two step deprotection of the
resulting intermediatewith HCl and H2 .For preparation of
the non-radioactive BHT-type complexes, asolution of the
corresponding BHT ligand, DIPEA and TiCl4 inanhydrous THF
was stirred for 30 min at room temperature.Subsequent
evaporation of the solvent provided the complexes asred
powders.For radiochemical separation of 45Ti the scandium
target was firstdissolved in 10 m HCl. The 45Ti-containing
solution was loaded onto aZR hydroxamate resin column
(Triskem, France). The column waswashed with 10 m HCl and
water to remove Sc and 45 Ti was eluted with 0.1 m oxalic
acid in phosphate buffer (pH = 8). Separation took
30minutes. For radiometal complex formation, the respective
ligand wasadded to the 45Ti-solution and the mixture was
stirred at roomtemperature for 45 min. Stability tests were
performed by incubationin phosphate-buffered saline (PBS, pH
= 7.4) at 36 °C followed by radio-TLC analysis.Results: The
separation and preparation protocols developed in thiswork
enabled the synthesis of 45Ti-labeled BHT complexes
inradiochemical conversions of $55\%$ - $90\%,$ as
determined by HPLC andradio-TLC analysis of the reaction
mixtures. The radiolabeled com-plexes including
PSMA-targeting conjugate showed a high stability inPBS (t
1/2 > 250 h). Conclusions: Easily accessible BHT ligands,
which form hydro-lytically stable Ti(IV) complexes, are
valuable tools for the develop-ment of 45Ti-labeled
PET-probes.References[1] Chaple F., et al. Appl. Radiat.
2020, 166, 109398.[2] Ekeltchik I. et al. Dalton Trans.
2006, 10, 1285–1293.[3] Peri D., et al. Dalton Trans.
2006, 34, 4169–4172.[4] Radchenko V. et al. J. Chromatogr.
A. 2016, 1477, 39–46},
month = {May},
date = {2023-05-22},
organization = {25th International Symposium on
Radiopharmaceutical Sciences, Honolulu,
USA (USA), 22 May 2023 - 26 May 2023},
subtyp = {After Call},
cin = {INM-5},
cid = {I:(DE-Juel1)INM-5-20090406},
pnm = {5253 - Neuroimaging (POF4-525)},
pid = {G:(DE-HGF)POF4-5253},
typ = {PUB:(DE-HGF)6},
url = {https://juser.fz-juelich.de/record/1026490},
}