Abstract:Three complexes with 2-[bis(2-pyridylmethyl)-amino] propanic acid (Adpa) were synthesized and characterized. The crystal structure of [(Adpa)CoCl] (1) shows that the cobalt(II) atom is coordinated by three N atoms, one oxygen atom from the Adpa ligand and one chloride, forming a distorted trigonal bipyramidal geometry. The fluorescence titration data indicate the interactions of ct-DNA with complexes [(Adpa)FeCl 2 ] (2) and [(Adpa)-Fe(H 2 O) 2 ] (3) are exothermic, but binding of complex (1) with ct-DNA is end… Show more
“…The observations also indicated that the 2-PA molecule-in the complex that was the unit of the polymer-might have been attached to Au surface through pyridine-N whereas aminomethyl-N participated in complexation. It is therefore plausible that 2-PA molecule acted as monodentate ligand in this complexation reaction that is different from the reported literature, [10,14,15,18] suggesting the flexidentate nature of the ligand.…”
Section: Chemistryselectcontrasting
confidence: 75%
“…In summary, literature reports [10,14,15,18] suggest that the reaction between Co(II) and 2‐PA leads to the formation of a chelate complex. However, the current work‐ based on SERRS and mass spectrometric studies‐ revealed that in basic media Co(II) reacted with 2‐PA to produce bridged polynuclear peroxo complex via sigmoidal kinetics, where 2‐PA molecule acted as a monodentate ligand even in the presence of the Au nanoparticles.…”
Section: Discussionmentioning
confidence: 84%
“…Among others, 2‐PA based cobalt complexes have received great recent interests in the synthesis of metal complexes having open coordination sites or to mimic non‐heme dioxygenase [10] . Cobalt complexes with 2‐PA moieties are deemed important for their potential antitumor activities [10,11] . In addition, they have been considered as hypoxia‐activated prodrugs [12] .…”
Section: Introductionmentioning
confidence: 99%
“…Thus, understanding of the structure and function of the central complexes is key to the knowledge of the workings of the co‐enzymes. Among others, 2‐PA based cobalt complexes have received great recent interests in the synthesis of metal complexes having open coordination sites or to mimic non‐heme dioxygenase [10] . Cobalt complexes with 2‐PA moieties are deemed important for their potential antitumor activities [10,11] .…”
Section: Introductionmentioning
confidence: 99%
“…[10] Cobalt complexes with 2-PA moieties are deemed important for their potential antitumor activities. [10,11] In addition, they have been considered as hypoxia-activated prodrugs. [12] Biological activities of Schiff-base complex between cobalt and 2-PA are extensively studied in coordination chemistry because of the enhanced activities as compared to non-Schiff-base complex.…”
We report the catalytic formation of bridged polynuclear peroxo complex of Co(II) and 2-picolylamine (2-PA) in aqueous alkaline medium on the surface of Au nanoparticle. The reaction followed sigmoidal kinetics both in absence and presence of the Au nanoparticle with an order of magnitude higher rate constant in the presence of nanoparticle. Importantly, using UV-Vis spectroscopy, mass spectrometry and surface enhance resonance Raman scattering (SERRS), we conclude the formation of peroxo complex with 2-PA acting as a monodentate ligand. The absorbance of the polynuclear complex at 595 nm and the extinction maximum of (agglomerated) the Au nanoparticles at 750 nm provided the right opportunity to pursue SERRS using 632.8 nm laser excitation. Density functional theoretical calculation indicated that the lowering of HOMO-LUMO energy gap of 2-PA bonded to the nanoparticle surface helped catalyze the reaction.
“…The observations also indicated that the 2-PA molecule-in the complex that was the unit of the polymer-might have been attached to Au surface through pyridine-N whereas aminomethyl-N participated in complexation. It is therefore plausible that 2-PA molecule acted as monodentate ligand in this complexation reaction that is different from the reported literature, [10,14,15,18] suggesting the flexidentate nature of the ligand.…”
Section: Chemistryselectcontrasting
confidence: 75%
“…In summary, literature reports [10,14,15,18] suggest that the reaction between Co(II) and 2‐PA leads to the formation of a chelate complex. However, the current work‐ based on SERRS and mass spectrometric studies‐ revealed that in basic media Co(II) reacted with 2‐PA to produce bridged polynuclear peroxo complex via sigmoidal kinetics, where 2‐PA molecule acted as a monodentate ligand even in the presence of the Au nanoparticles.…”
Section: Discussionmentioning
confidence: 84%
“…Among others, 2‐PA based cobalt complexes have received great recent interests in the synthesis of metal complexes having open coordination sites or to mimic non‐heme dioxygenase [10] . Cobalt complexes with 2‐PA moieties are deemed important for their potential antitumor activities [10,11] . In addition, they have been considered as hypoxia‐activated prodrugs [12] .…”
Section: Introductionmentioning
confidence: 99%
“…Thus, understanding of the structure and function of the central complexes is key to the knowledge of the workings of the co‐enzymes. Among others, 2‐PA based cobalt complexes have received great recent interests in the synthesis of metal complexes having open coordination sites or to mimic non‐heme dioxygenase [10] . Cobalt complexes with 2‐PA moieties are deemed important for their potential antitumor activities [10,11] .…”
Section: Introductionmentioning
confidence: 99%
“…[10] Cobalt complexes with 2-PA moieties are deemed important for their potential antitumor activities. [10,11] In addition, they have been considered as hypoxia-activated prodrugs. [12] Biological activities of Schiff-base complex between cobalt and 2-PA are extensively studied in coordination chemistry because of the enhanced activities as compared to non-Schiff-base complex.…”
We report the catalytic formation of bridged polynuclear peroxo complex of Co(II) and 2-picolylamine (2-PA) in aqueous alkaline medium on the surface of Au nanoparticle. The reaction followed sigmoidal kinetics both in absence and presence of the Au nanoparticle with an order of magnitude higher rate constant in the presence of nanoparticle. Importantly, using UV-Vis spectroscopy, mass spectrometry and surface enhance resonance Raman scattering (SERRS), we conclude the formation of peroxo complex with 2-PA acting as a monodentate ligand. The absorbance of the polynuclear complex at 595 nm and the extinction maximum of (agglomerated) the Au nanoparticles at 750 nm provided the right opportunity to pursue SERRS using 632.8 nm laser excitation. Density functional theoretical calculation indicated that the lowering of HOMO-LUMO energy gap of 2-PA bonded to the nanoparticle surface helped catalyze the reaction.
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