Preparation and Biological Evaluation of Di‐Hetero‐Organometallic‐Containing PNA Bioconjugates

Abstract

Two peptide nucleic acid (PNA) oligomers containing two different organometallic moieties, namely derivatives of azidoferrocene (Fc-N 3 ) and ferrocene carboxylic acid (Fc-COOH) for PNA5 and derivatives of β-cymantrenoylpropionic acid [Cym-CO(CH 2 ) 2 COOH] and the rhenium bisquinoline tricarbonyl complex [Re(BQ-N 3 )(CO) 3 ]Br for PNA6, have been prepared on a solid support by using two different synthetic methods: Peptide coupling and click chemistry. PNA5 and PNA6 were unambiguously characterized by ESI-MS or MALDI-TOF MS and their purity checked by LC-MS. As expected, the bioconjugate PNA6 presents two broad and strong absorption bands at 1933 and 2032 cm -1 in its IR spectrum due to the presence of six metal-carbonyl bonds. It has

Underestimated Potential of Organometallic Rhenium Complexes as Anticancer Agents

“…39 A non-negligible percentage of endosomal accumulation (about 20%) has also been detected for compound 7i 39 As a note of caution, although fluorescent microscopy imaging is an important tool in the investigation of the cellular behavior of Re organometallic complexes, their luminescence can sometimes be quenched in cells. 39,44,47 Due to this problem, direct measurements of Re content by inductively coupled plasma mass spectrometry (ICP-MS) or atomic absorption spectroscopy (AAS) 60 can be a more accurate method to quantify the cellular uptake and distribution of Re complexes.…”

Synthesis, characterisation and bioimaging of a fluorescent rhenium-containing PNA bioconjugate

“…5 Herein, we present the preparation and in-depth characterization, including X-ray crystallography, of Tc congeners, were already used for the (radio-)labeling of biomolecules by Zubieta, Valliant, Babich and our groups for both in vitro and in vivo imaging purposes. [18][19][20][21][22][23][24][25][26][27][28][29][30] We then report on 31 with triphenyl phosphine, diisopropyl azodicarboxylate and diphenylphosphoryl azide in THF following a similar procedure described by our groups (Scheme 1). 32 The presence of L-N 3 Figure S2 in the SI).…”

“…9 In this work, we capitalize on our recent discoveries to efficiently attach organometallic complexes to peptides and PNA oligomers using the copper(I)-catalysed Huisgen 1,3-dipolar cycloaddition reaction, often referred to as "Click Chemistry". 29,40,[44][45][46][47][48] In order to label the PNA oligomer with Table S1 and Figures S11-12 in the SI for IR spectra and analytical HPL chromatograms). Thermal stability studies.…”

Metal–Carbon Bonds in Biopolymer Conjugates: Bioorganometallic Nucleic Acid Chemistry

“…35 Recently, this approach was extended to allow functionalization with different and multiple organometallic moieties 7, potentially giving the resulting oligomer a variety of electrochemical and spectroscopic properties. 31,36 The main application of ferrocene-functionalized oligonucleotides is electrochemical sensing, with a common approach being immobilization on gold electrodes using terminal thiol groups. 15,17,18,37 Such systems typically monitor the changes in current (arising from oxidation of the tag) between singlestranded and duplex DNA, with the unbound probe strand sometimes formed into a hairpin (Figure 3).…”