Chemically significant interactions between ruthenium ions in oxo-bridged complexes of ruthenium(III)

Weaver, Tom Ray; Meyer, Thomas J.; Adeyemi, S. Ajao; Brown, Gilbert M.; Eckberg, Richard P.; Hatfield, William E.; Johnson, Eugene C.; Murray, Royce W.; Untereker, Darrel F.

doi:10.1021/ja00844a020

Cited by 149 publications

(116 citation statements)

References 8 publications

(11 reference statements)

Supporting

Mentioning

106

Contrasting

Unclassified

Order By: Relevance

“…A qualitative MO diagram for π -system of the RuORu type of complexes 31,32 is shown in Figure 2 and sheds some light into the orbitals involved in this type of bonding for the RuORu moiety Table 1. The same effect has been also found in the III,IV form of the blue dimer 35 .…”

Section: Ruoru Structure and Electronic Propertiesmentioning

confidence: 99%

Oxo-Bridge Scenario behind Single-Site Water-Oxidation Catalysts

et al. 2014

View full text Add to dashboard Cite

show abstract

Section: Ruoru Structure and Electronic Propertiesmentioning

confidence: 99%

Oxo-Bridge Scenario behind Single-Site Water-Oxidation Catalysts

et al. 2014

View full text Add to dashboard Cite

show abstract

“…In this method, we take advantage of the fact that two different reduced mediators, i.e., a reduced Ru complex and oxygen reduced to H 2 O 2 , are detected oxidatively on the electrodes of the 'first-' and 'second-generation' biosensors. Our method is based on a significant difference between electro-oxidation potentials of H 2 O 2 on Pt and glassy carbon (GC) electrodes [50,51,52,53,54,55,56], and the independence of the electro-oxidation potentials of the Ru complex on the nature of these electrode materials. Therefore, the selection of the electrode material, i.e., Pt or GC, often neglected in fabrication of glucose biosensors, is important in the present work.…”

Section: Edyta Kosela · Hanna Elzanowska · Wlodzimierz Kutnermentioning

confidence: 99%

Charge mediation by ruthenium poly(pyridine) complexes in 'second-generation' glucose biosensors based on carboxymethylated β-cyclodextrin polymer membranes

2002

View full text Add to dashboard Cite

Four different poly(pyridine) complexes of ruthenium, viz. Ru(II)(trpy)(phen)(OH(2))](2+) (1), trans-[Ru(III)(2,2'bpy)(2)(OH(2))(OH)](2+) (2), [(2,2'bpy)(2)(OH)Ru(III)ORu(III)(OH)(2,2'bpy)(2)](4+) (3), and [Ru(II)(4,4'bpy)(NH(3))(5)](2+) (4) (2,2'bpy=2,2'-bipyridine, 4,4'bpy=4,4'-bipyridine, trpy=2,2',2"-terpyridine, phen=1,10-phenanthroline), were tested as non-physiological charge mediators of 'second-generation' glucose biosensors. The membranes for these biosensors were prepared by casting anionic carboxymethylated beta-cyclodextrin polymer films (beta-CDPA) directly onto the Pt or glassy carbon (GC) disk electrodes. Simultaneously, glucose oxidase (GOD) was immobilized in the films by covalent bonding and the Ru complexes were incorporated both by inclusion in the beta-CD molecular cavities and by ion exchange at the fixed carboxymethyl cation-exchange sites. The leakage of the mediator from the polymer has been minimized by adopting a suitable pre-treatment procedure. The biosensors catalytic activities increased in the order 1<2<3<4, as established by linear sweep voltammetry. In case of complexes 2-4, the enzymatic glucose oxidation was mediated by the Ru complexes at their redox potentials. However, this oxidation was mediated by oxygen in case of complex 1 where H(2)O(2) was detected as the reaction product. The effectiveness of the mediators used in the presence of oxygen has been estimated using Pt and GC supports. The redox potential of the mediator does not depend on the support used, while the oxidation of H(2)O(2) proceeds on GC at much higher positive potentials than on Pt. The sensitivity and the linear concentration range of the biosensor studied varied significantly. For complex 4, which forms stable inclusion complex with beta-CD, the biosensor sensitivity was the highest and equal to 7.2 micro A mM(-1) cm(-2), detectability was as low as 1 mM, but the linear concentration range was limited only to 4 mM. In contrast, for complexes 2 and 3 the sensitivity was 0.4 and 3.2 micro A mM(-1) cm(-2), while the linear concentration range extended up to at least 24 and 14 mM glucose, respectively. Even though some common interfering substances, such as ascorbate, paracetamol or urea, are oxidized at potentials close to those of the Ru complex redox couples, their electro-oxidation currents at physiological concentrations are insignificant compared to those due to the biocatalytic oxidation of glucose. The biosensor response to glucose is reversible as demonstrated by the inhibition of GOD activity by Cu(II). That is, the Cu(II) concentration required to inhibit by half the response to glucose of the biosensor containing complex 2 was 1.0 mM. This inhibitory effect was fully reversed by addition of citrate, a ligand forming sufficiently stable complex with Cu(II).

show abstract

“…However, no oxo-bridged dimers have been detected by using the 2,2'-bipyridine test [11]. Hence, we propose a mechanism based on the catalytic process by the monomeric species Ru(H20)5OH 2+ …”

Section: Group [81mentioning

confidence: 79%

Kinetics and mechanism of the ruthernium(III) catalyzed oxidation of propane-1,3-diol by alkaline hexacyanoferrate(III)

Mucientes

Poblete

Santiago

et al. 1997

React Kinet Catal Lett

View full text Add to dashboard Cite

The kinetics of oxidation of propane-l,3-diol by alkaline hexacyanoferrate (IH) catalyzed by ruthenium trichloride has been studied spectrophotometricaUy. A reaction mechanism involving the formation of an intermediate complex between the substrate and the catalyst is proposed. In the rate-determining step this complex is attacked by hexacyanoferrate(llI) forming a fi'ee radical which is further oxidized.

show abstract

Chemically significant interactions between ruthenium ions in oxo-bridged complexes of ruthenium(III)

Cited by 149 publications

References 8 publications

Oxo-Bridge Scenario behind Single-Site Water-Oxidation Catalysts

Oxo-Bridge Scenario behind Single-Site Water-Oxidation Catalysts

Charge mediation by ruthenium poly(pyridine) complexes in 'second-generation' glucose biosensors based on carboxymethylated β-cyclodextrin polymer membranes

Kinetics and mechanism of the ruthernium(III) catalyzed oxidation of propane-1,3-diol by alkaline hexacyanoferrate(III)

Contact Info

Product

Resources

About