Synthesis of Rhenium(I) Tricarbonyl Complexes with Carbohydrate‐Pendant Tridentate Ligands and Their Cellular Uptake

Mikata, Yuji; Takahashi, Kyôko; Noguchi, Yoshiyuki; Naemura, Masami; Ugai, Anna; Itami, Saori; Yasuda, Keiko; Tamotsu, Satoshi; Matsuo, Takashi; Storr, Tim

doi:10.1002/ejic.201100953

Cited by 13 publications

(8 citation statements)

References 39 publications

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“…Coordination of metal ions or metal complexes to carbohydrates and their derivatives in tridentate fashion has been described. 11,12,14,18,22,41,52,53 To obtain further evidence of the coordination mode of amidine 1 to S-3 via the hydroxyl group at C-3 (species I) or at C-6 (species II), the difference in the Gibbs's free energy of the both assemblies was computed in the gas phase and in aqueous solution using DFT methods and the COSMO model. 54,55 The resulting energies of the two putative assemblies derived from S-3 and 1 are by 25.2 kcal mol −1 (gas phase) and 28.3 kcal mol −1 (water) lower, when 1 coordinates over the hydroxyl group at C-3 (Chart 5, species I) instead of at C-6 (Chart 5, species II).…”

Section: Identifying Putative Binding Sites In Galactonoamidine Upon mentioning

confidence: 99%

Discrimination of chiral copper(ii) complexes upon binding of galactonoamidine ligands

Striegler

Pickens

2016

Dalton Trans.

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The coordination between N-p-methylbenzyl-d-galactonoamidine, a putative transition state analogue of the hydrolyis of glycosidic bonds, and symmetric and chiral binuclear copper(ii) complexes was characterized by spectroscopic titration, isothermal titration calorimetry, circular dichroism spectroscopy, and DFT calculations to elucidate the binding sites in the carbohydrate upon coordination to selected metal complexes. For the formation of metal complex-glyconoamidine assemblies, contributions of the amidine site and of the hydroxyl group at C-2 in the glycon of the amidine are noted. The chiral complexes S- and R-Cubpdbo are discriminated by a third binding site in the carbohydrate that leads to higher stability of complexes derived from S-Cubpdbo (4-5 kcal mol) compared to those formed from R-Cubpdbo.

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Section: Identifying Putative Binding Sites In Galactonoamidine Upon mentioning

confidence: 99%

Discrimination of chiral copper(ii) complexes upon binding of galactonoamidine ligands

Striegler

Pickens

2016

Dalton Trans.

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“…4). [26][27][28][29][30][31] This is possibly due to the inclusion of a six membered chelate ring instead of two five membered chelate rings seen in other complexes with the same donor atom set. In fac-[Re I (CO) 3 L 1 ], the remaining coordination sphere of the metal is completed by an NNO donor atom set provided by the pyridyl nitrogen, tertiary amine and carboxylate groups of the ligand.…”

Section: Synthesis and Characterisationmentioning

confidence: 99%

“…The Re-N1 bond length is within the range of similar fac-[Re I (CO) 3 NNO] complexes but bonds Re-O1 and Re-N2 are slightly longer, at 2.142(4) Å and 2.262(5) Å, compared to 2.107-2.132 Å and 2.232-2.255 Å respectively for similar complexes. [26][27][28][29][30][31] This is possibly due to the inclusion of a six membered chelate ring instead of two five membered chelate rings seen in other complexes with the same donor atom set.…”

Section: Synthesis and Characterisationmentioning

confidence: 99%

“…This is again likely due to the six membered chelate ring with the bond Re-N2 (2.251(4) Å) also being longer relative to similar complexes (Re-N amine 2.216-2.242 Å). 26,27,[32][33][34][35][36] Ligands HL 1-2 and L [3][4] are fluorescent due to the presence of the stilbene functional group. The methyl ester of L 1 and L 3 have similar absorbance spectra each displaying two maxima at λ max = 300 nm and λ max = 312 nm.…”

Section: Synthesis and Characterisationmentioning

confidence: 99%

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Rhenium and technetium complexes that bind to amyloid-β plaques

et al. 2015

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Alzheimer's disease is associated with the presence of insoluble protein deposits in the brain called amyloid plaques. The major constituent of these deposits is aggregated amyloid-β peptide. Technetium-99m complexes that bind to amyloid-β plaques could provide important diagnostic information on amyloid-β plaque burden using Single Photon Emission Computed Tomography (SPECT). Tridentate ligands with a stilbene functional group were used to form complexes with the fac-[M(I)(CO)3](+) (M = Re or (99m)Tc) core. The rhenium carbonyl complexes with tridentate co-ligands that included a stilbene functional group and a dimethylamino substituent bound to amyloid-β present in human frontal cortex brain tissue from subjects with Alzheimer's disease. This chemistry was extended to make the analogous [(99m)Tc(I)(CO)3](+) complexes and the complexes were sufficiently stable in human serum. Whilst the lipophilicity (log D7.4) of the technetium complexes appeared ideally suited for penetration of the blood-brain barrier, preliminary biodistribution studies in an AD mouse model (APP/PS1) revealed relatively low brain uptake (0.24% ID g(-1) at 2 min post injection).

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“…Connection of either monoamino‐monoamide dithiol (MAMA) or mercaptoacetylglycylglycylglycine (MAG 3 ) to 2‐deoxy‐2‐aminoglucose (DG), galactose (Gal) or glucose (Glc) with different linking units and radiolabeling with 99m Tc yielded radiotracers with a sugar‐dependent biodistribution in vivo, displaying promising tumor‐to‐muscle ratios ( 99m Tc‐MAG 3 ‐DG in MA891 breast‐tumor‐bearing mice;22 99m Tc‐MAG 3 ‐Glc in Ehrlich‐tumor‐bearing mice23,24) or enrichment in the liver as potential imaging agent for hepatic function ( 99m Tc‐MAG 3 ‐Gal in healthy Swiss mice25). Moreover, additional binding functionalities such as 1,3‐diamines,26 3‐hydroxypyridone,27 2‐hydroxybenzyl,28 pyridyltriazole,29,30 2,2′‐dipycolylamine,31 bis(2‐pyridylmethyl)amine (DPA),32,33 bis(2‐quinolylmethyl)amine (DQA),32 N ‐(2‐pyridylmethyl)glycine (NPG),32 2,2′‐bipyridine,34 N ‐(2‐picolyl‐4‐hydroxy‐3amino)benzoic acid (PHAB),35 and tripodal amines,36 functionalized with sugar moieties (limited to specific monosaccharides), have been used as ligands and reported as promising chelators for Tc I and Re I cores.…”

Section: Introductionmentioning

confidence: 99%

Glycoconjugated Rhenium(I) and 99m‐Technetium(I) Carbonyl Complexes from Pyridyltriazole Ligands Obtained by “Click Chemistry”

et al. 2014

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A series of pyridyltriazole ligands containing sugar moieties have been prepared by copper(I)‐mediated 1,3‐dipolar cycloaddition (“click” reaction) of azides functionalized with D‐glucose, D‐galactose, D‐mannose, D‐xylose as well as D‐maltose residues, and 2‐ethynylpyridine as alkyne. The peracetylated saccharide residues as well as their water‐soluble deprotected derivatives were treated with Re(CO)5Cl to obtain the corresponding mononuclear rhenium(I) carbonyl complexes [LRe(CO)3Cl]. For comparison, one ReI complex bearing a tert‐butylbenzyl residue instead of a sugar moiety as well as two dinuclear rhenium complexes derived from a branched ligand containing two pyridyltriazole units were prepared. The structure and integrity of the ligands and complexes was established by NMR, IR, UV/Vis and fluorescence spectroscopy, mass spectrometry, and by elemental analysis. Coordination of the metal ion occurred by both the pyridyl nitrogen atoms and one of the triazole nitrogen atoms. Upon treatment with an excess of histidine, the ReI complexes were stable for only 2.5 h. After a longer period (24 h) ligand exchange was detected by HPLC measurements. In contrast, a complex labeled with 99mTc was found to be stable for up to 24 h against an excess of histidine. Cytotoxicity was screened for all ReI complexes against HepG2 cells using a concentration of 100 μM. All sugar‐functionalized complexes were found to be nontoxic, except for the complex derived from the pyridyl (tert‐butylbenzyl)‐triazole, which exhibited remarkable toxicity.

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Synthesis of Rhenium(I) Tricarbonyl Complexes with Carbohydrate‐Pendant Tridentate Ligands and Their Cellular Uptake

Cited by 13 publications

References 39 publications

Discrimination of chiral copper(ii) complexes upon binding of galactonoamidine ligands

Discrimination of chiral copper(ii) complexes upon binding of galactonoamidine ligands

Rhenium and technetium complexes that bind to amyloid-β plaques

Glycoconjugated Rhenium(I) and 99m‐Technetium(I) Carbonyl Complexes from Pyridyltriazole Ligands Obtained by “Click Chemistry”

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