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Browsing by Subject "Spectrum Analysis, Raman"

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    • Article  

      Coupling of helix E-F motion with the O-nitrito and 2-nitrovinyl coordination in myoglobin 

      Ioannou, Androulla; Lambrou, Alexandra; Daskalakis, Vangelis; Pinakoulaki, Eftychia (2017)
      Myoglobin (Mb) is known to react slowly with nitirite to form the green pigment by NO2 − cordination to the heme Fe in the O-binding nitrito (O1[sbnd]N[dbnd]O2) mode and to the heme 2-vinyl position. Nitrite is a powerful ...

    • Article  

      Detection of the His-heme Fe2+-NO species in the reduction of NO to N2O by ba3-oxidase from thermus thermophilus 

      Pinakoulaki, Eftychia; Ohta, T.; Soulimane, T.; Kitagawa, T.; Varotsis, Constantinos (2005)
      Reaction pathways in the enzymatic formation and cleavage of the N-N and N-O bonds, respectively, are difficult to verify without the structure of the intermediates, but we now have such information on the heme a3 2+-NO ...

    • Article  

      Direct detection of Fe(IV)=O intermediates in the cytochrome aa3 oxidase from Paracoccus denitrificans[H2O2 reaction 

      Pinakoulaki, Eftychia; Pfitzner, U.; Ludwig, B.; Varotsis, Constantinos (2003)
      We report the first evidence for the formation of the "607- and 580-nm forms" in the cytochrome oxidase aa3/H2O2 reaction without the involvement of tyrosine 280. The pKa of the 607-580-nm transition is 7.5. The 607-nm ...

    • Article  

      New antimony(III) halide complexes with dithiocarbamate ligands derived from thiuram degradation: The effect of the molecule's close contacts on in vitro cytotoxic activity 

      Urgut, O. S.; Ozturk, I. I.; Banti, Christina N.; Kourkoumelis, Nikolaos; Manoli, Maria; Tasiopoulos, Anastasios J.; Hadjikakou, Sotiris K. (2016)
      Antimony(III) halide complexes of the formulae {[SbBr(Me2DTC)2]n} (1), {[SbI(Me2DTC)2]n} (2) and {[(Me2DTC)2Sb(μ2-I)Sb(Me2DTC)2]+.I3-} (3) (Me2DTC = dimethyldithiocarbomate) were synthesized from SbX3, (X = Br or I) and ...

    • Article  

      Nitric oxide activation and reduction by heme-copper oxidoreductases and nitric oxide reductase 

      Pinakoulaki, Eftychia; Varotsis, Constantinos (2008)
      The understanding of the dynamics and conformational control involved in the interplay between structure and function of nitric oxide reductase (Nor) and heme-copper oxidoreductases in their function to convert nitric oxide ...

    • Article  

      Nitric-oxide reductase: Structure and properties of the catalytic site from resonance Raman scattering 

      Pinakoulaki, Eftychia; Gemeinhardt, S.; Saraste, M.; Varotsis, Constantinos (2002)
      We have applied resonance Raman spectroscopy to investigate the properties of the dinuclear center of oxidized, reduced, and NO-bound nitric-oxide reductase from Paracoccus denitrificans. The spectra of the oxidized enzyme ...

    • Article  

      The origin of the Fe IV = O intermediates in cytochrome aa 3 oxidase 

      Pinakoulaki, Eftychia; Daskalakis, Vangelis; Varotsis, Constantinos (2012)
      The dioxygen reduction mechanism in cytochrome oxidases relies on proton control of the electron transfer events that drive the process. Proton delivery and proton channels in the protein that are relevant to substrate ...

    • Article  

      Probing nitrite coordination in horseradish peroxidase by resonance Raman spectroscopy: Detection of two binding sites 

      Ioannou, Androulla; Pinakoulaki, Eftychia (2017)
      Nitrite is a powerful oxidant that affects the activity of peroxidases towards various substrates and leads to heme macrocycle modifications in members of the peroxidase family, such as the horseradish peroxidase (HRP). ...

    • Article  

      Probing the nitrite and nitric oxide reductase activity of cbb3 oxidase: Resonance Raman detection of a six-coordinate ferrous heme-nitrosyl species in the binuclear b3/CuB center 

      Loullis, Andreas; Pinakoulaki, Eftychia (2015)
      In this work we report the first spectroscopic evidence demonstrating that cbb3 oxidase catalyzes the reduction of nitrite to nitrous oxide under reducing anaerobic conditions. The reaction proceeds through the formation ...

    • Article  

      The protein effect in the structure of two ferryl-oxo intermediates at the same oxidation level in the heme copper binuclear center of cytochrome c oxidase 

      Pinakoulaki, Eftychia; Daskalakis, Vangelis; Ohta, T.; Richter, O. -M H.; Budiman, K.; Kitagawa, T.; Ludwig, B.; Varotsis, Constantinos (2013)
      Identification of the intermediates and determination of their structures in the reduction of dioxygen to water by cytochrome c oxidase (CcO) are particularly important to understanding both O2 activation and proton pumping ...

    • Article  

      Resonance Raman detection of a ferrous five-coordinate nitrosylheme b3 complex in cytochrome cbb3 oxidase from Pseudomonas stutzeri 

      Pinakoulaki, Eftychia; Stavrakis, Stavros; Urbani, A.; Varotsis, Constantinos (2002)
      Understanding the chemical nature of the nitric oxide (NO) moiety of nitrosylheme copper oxidases is crucial for elucidation of the NO activation process. In the present work, direct resonance Raman spectroscopic observation ...

    • Article  

      Resonance Raman detection of the Fe2+-C-N modes in heme-copper oxidases: A probe of the active site 

      Pinakoulaki, Eftychia; Vamvouka, M.; Varotsis, Constantinos (2004)
      Resonance Raman spectroscopy has been employed to investigate the reduced cyano complexes of cytochrome aa3 from bovine heart and Rhodobacter sphaeroides and of cytochrome bo3 from E. coli. In the aa 3-type oxidases, the ...

    • Article  

      Resonance Raman detection of the myoglobin nitrito heme Fe-O-N=O/2-nitrovinyl species: Implications for helix E-helix F interactions 

      Lambrou, Alexandra; Pinakoulaki, Eftychia (2015)
      The description of biological activity in heme proteins responsible for activating small molecules requires identification of ligand movement into the metal and non-metal binding sites. Mechanisms of nitrite reductase ...

    • Article  

      The role of the cross-link His-Tyr in the functional properties of the binuclear center in cytochrome c oxidase 

      Pinakoulaki, Eftychia; Pfitzner, U.; Ludwig, B.; Varotsis, Constantinos (2002)
      Resonance Raman and Fourier transform infrared spectroscopies have been used to study the aa3-type cytochrome c oxidase and the Y280H mutant from Paracoccus denitrificans. The stability of the binuclear center in the absence ...

    • Article  

      Simultaneous resonance Raman detection of the heme a3-Fe-CO and CuB-CO species in CO-bound ba3-cytochrome c oxidase from Thermus thermophilus: Evidence for a charge transfer CuB-CO transition 

      Pinakoulaki, Eftychia; Ohta, T.; Soulimane, T.; Kitagawa, T.; Varotsis, Constantinos (2004)
      Understanding of the chemical nature of the dioxygen and nitric oxide moiety of ba3-cytochrome c oxidase from Thermus thermophilus is crucial for elucidation of its physiological function. In the present work, direct ...

    • Article  

      The structure of a ferrous heme-nitro species in the binuclear heme a3/CuB center of ba3-cytochrome c oxidase as determined by resonance Raman spectroscopy 

      Loullis, Andreas; Noor, M. R.; Soulimane, T.; Pinakoulaki, Eftychia (2015)
      Members of the cytochrome c oxidase family exhibit nitrite reductase activity. In this work, we have characterized a ferrous heme a3-nitro species in ba3-oxidase by resonance Raman spectroscopy. This provides the first ...

    • Article  

      The structure of the hyponitrite species in a heme Fe-Cu binuclear center 

      Varotsis, Constantinos; Ohta, T.; Kitagawa, T.; Soulimane, T.; Pinakoulaki, Eftychia (2007)
      NO laughing matter: The enzymatic production of laughing gas (N 2O) from two molecules of NO requires the formation of the N-N bond and the subsequent cleavage of the N-OH bond. Resonance Raman spectroscopic studies have ...

    • Article  

      Time-Resolved Resonance Raman and Time-Resolved Step-Scan FTIR Studies of Nitric Oxide Reductase from Paracoccus denitrificans: Comparison of the Heme b3-FeB Site to That of the Heme-CuB in Oxidases 

      Pinakoulaki, Eftychia; Varotsis, Constantinos (2003)
      Time-resolved resonance Raman (TR3) and time-resolved step-scan (TRS2) FTIR spectroscopies have been used to probe the structural dynamics at the heme b3 proximal and distal sites after carbon monoxide photolysis from fully ...

    • Article  

      UV resonance Raman spectroscopy of TTR(105-115): Determination of the pKa of tyrosine 

      Pieridou, Galatia K.; Hayes, Sophia C. (2009)
      The 11-residue peptide fragment from transthyretin (TTR(105-115)) has been investigated using UV resonance Raman spectroscopy. Excitation at 239.5 nm reveals selective enhancement of scattering from two Tyr residues. The ...

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