A novel strategy for the design of 8-hydroxyquinolinate-based lanthanide bioprobes that emit in the near infrared range.
A new polydentate tripodal ligand T2soxMe was synthesized to take advantage of the chelating effect of tridentate 8-hydroxyquinolinate subunits. Potentiometric and spectrophotometric titrations reveal seven pK(a) values of between 3.7 and 10.2. In water, the use of T2soxMe leads to thermodynamically stable and soluble Ln(III) complexes at physiological pH, with conditional stability constants in the range log beta(11)=7.8-8.6. The chelates are resistant toward hydrolysis and show interesting photophysical properties, particularly in the near infrared (NIR) range. The emission lifetimes of the Nd(III) and Yb(III) complexes recorded in D(2)O and H(2)O suggest the absence of water molecules in the first coordination sphere of the metal ions. Moreover, the low energy of the triplet state allows efficient energy transfer from the ligand to the metal ions: in water at pH 7.4, the sensitization efficacy of the NIR luminescence reaches 75 and approximately 100 % for Nd(III) and Yb(III), respectively, leading to overall quantum yields of 0.027 and 0.13 %; Er(III) luminescence is also detected. According to the WST-1 test, the Yb(III) podate at concentrations of up to 250 microM does not display sizeable cytotoxicity for Jurkat cells after 24 h of incubation. Finally, the same podate is shown to couple to human serum albumin, leading to an increase of 50 % in the NIR-luminescence intensity.
Comby
Steve
S
Laboratory of Lanthanide Supramolecular Chemistry, Ecole Polytechnique Fédérale de Lausanne (EPFL), BCH 1402, 1015 Lausanne, Switzerland.
Imbert
Daniel
D
Vandevyver
Caroline
C
Bünzli
Jean-Claude G
JC
D015374:Biosensing Techniques / Q000379:methods*; D002470:Cell Survival / Q000187:drug effects; D002614:Chelating Agents / Q000138:chemical synthesis / Q000737:chemistry* / Q000494:pharmacology; D006801:Humans; D006863:Hydrogen-Ion Concentration; D007259:Infrared Rays; D019169:Jurkat Cells; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000494:pharmacology; D015125:Oxyquinoline / Q000031:analogs & derivatives / Q000737:chemistry*; D011199:Potentiometry; D011789:Quantum Theory; D012015:Reference Standards; D012680:Sensitivity and Specificity; D012709:Serum Albumin / Q000187:drug effects; D013053:Spectrophotometry; D019265:Spectroscopy, Near-Infrared / Q000379:methods*; D013329:Structure-Activity Relationship
D002614:Chelating Agents; D028581:Lanthanoid Series Elements; D008024:Ligands; D009942:Organometallic Compounds; D012709:Serum Albumin; D015125:Oxyquinoline