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Annaraj, J.,Kim, S.,Seo, M.S.,Lee, Y.M.,Kim, Y.,Kim, S.J.,Choi, Y.S.,Jang, H.G.,Nam, W. Elsevier Sequoia [etc.] 2009 Inorganica chimica acta Vol.362 No.3
A new iron(II) complex bearing an N3S2 thioether ligand was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear nonheme iron(IV)-oxo intermediate was generated in the reaction of the iron(II) complex with various terminal oxidants. The iron(IV)-oxo species show a capability of epoxidizing olefins, and the olefin epoxidation occurs via an electrophilic oxidation mechanism.
Annaraj, Jamespandi,Cho, Jaeheung,Lee, Yong-Min,Kim, Sung Yeon,Latifi, Reza,de Visser, Sam P.,Nam, Wonwoo WILEY-VCH Verlag 2009 Angewandte Chemie Vol.48 No.23
<P>The dark side of the Mn: A manganese(III) complex bearing a 13-membered macrocyclic ligand (1, see picture) binds a peroxo ligand in a side-on η<SUP>2</SUP> fashion. The reactivity of 1 is influenced by the introduction of anionic ligands trans to the peroxo group. Electronic and structural changes upon trans-ligand binding explain the increased nucleophilicity of the resulting complexes 1-X. <img src='wiley_img/14337851-2009-48-23-ANIE200900118-content.gif' alt='wiley_img/14337851-2009-48-23-ANIE200900118-content'> </P> <B>Graphic Abstract</B> <P>The dark side of the Mn: A manganese(III) complex bearing a 13-membered macrocyclic ligand (1, see picture) binds a peroxo ligand in a side-on η<SUP>2</SUP> fashion. The reactivity of 1 is influenced by the introduction of anionic ligands trans to the peroxo group. Electronic and structural changes upon trans-ligand binding explain the increased nucleophilicity of the resulting complexes 1-X. <img src='wiley_img/14337851-2009-48-23-ANIE200900118-content.gif' alt='wiley_img/14337851-2009-48-23-ANIE200900118-content'> </P>
Cho, Jaeheung,Sarangi, Ritimukta,Annaraj, Jamespandi,Kim, Sung Yeon,Kubo, Minoru,Ogura, Takashi,Solomon, Edward I.,Nam, Wonwoo Nature Publishing Group 2009 Nature chemistry Vol.1 No.7
Metal-dioxygen adducts, such as metal-superoxo and -peroxo species, are key intermediates often detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. The synthesis and spectroscopic characterization of an end-on nickel(II)-superoxo complex with a 14-membered macrocyclic ligand was reported previously. Here we report the isolation, spectroscopic characterization, and high-resolution crystal structure of a mononuclear side-on nickel(III)-peroxo complex with a 12-membered macrocyclic ligand, [Ni(12-TMC)(O<SUB>2</SUB>)]<SUP>+</SUP> (1) (12-TMC = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). In contrast to the end-on nickel(II)-superoxo complex, the nickel(III)-peroxo complex is not reactive in electrophilic reactions, but is capable of conducting nucleophilic reactions. The nickel(III)-peroxo complex transfers the bound dioxygen to manganese(II) complexes, thus affording the corresponding nickel(II) and manganese(III)-peroxo complexes. Our results demonstrate the significance of supporting ligands in tuning the geometric and electronic structures and reactivities of metal–O<SUB>2</SUB> intermediates that have been shown to have biological as well as synthetic usefulness in biomimetic reactions.
Xavier, S. Stanly John,Siva, G.,Annaraj, J.,Kim, Ae Rhan,Yoo, Dong Jin,kumar, G. Gnana Elsevier 2018 Sensors and actuators. B Chemical Vol.259 No.-
<P><B>Abstract</B></P> <P>An environmentally benign and cost efficient cysteine fluorescence sensor is constructed on the basis of nitrogen doped carbon nanodots (NCNDs) prepared by using citron fruit extract and human urine waste as carbon and nitrogen sources, respectively. The turn-off-on fluorescence technique is exploited for the sensing of cysteine, in which the initial fluorescence of NCNDs is quenched with Hg<SUP>2+</SUP> <I>via</I> an electron transfer process. Owing to the competitive binding of Hg<SUP>2+</SUP> with cysteine, the ‘turn-off’ fluorescence sensor is switched to the ‘turn-on’ state. Under optimized conditions, NCNDs-Hg<SUP>2+</SUP> assembly demonstrates a lower detection limit and a wide linear range toward cysteine detection. Furthermore, NCNDs display the discriminative detection of cysteine from the similar bioactive molecules and the co-existence of interference species does not influence the detection of NCNDs toward the interest of an analyte. Furthermore, the practical application of NCNDs based fluorescence sensor is validated with the good recovery in human urine samples, which explores the new avenues in the fluorescence sensing of biomolecules.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Environmentally benign NCNDs are prepared from citron and human urine. </LI> <LI> Turn-off-on fluorescence technique is exploited for the cysteine sensing. </LI> <LI> Fluorescence behavior of NCNDs is quenched with Hg<SUP>2+</SUP> and is regenerated with cysteine. </LI> <LI> NCNDs exhibit rapid fluorometric response with a LOD of 40 nM toward cysteine. </LI> <LI> NCNDs demonstrate selective cysteine detection and real sample analysis. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>