scholarly journals Electron-spin-resonance studies of the NADH-dependent nitrite reductase from Escherichia coli K12

1982 ◽  
Vol 207 (2) ◽  
pp. 333-339 ◽  
Author(s):  
R Cammack ◽  
R H Jackson ◽  
A Cornish-Bowden ◽  
J A Cole
Keyword(s):  
Escherichia Coli ◽  
Electron Spin Resonance ◽  
Low Temperature ◽  
Nitrite Reductase ◽  
Hyperfine Splitting ◽  
Midpoint Potential ◽  
Spin Resonance ◽  
Nitrite Reductases ◽  
Haem Iron ◽  
Nitrosyl Derivative

The NADH-dependent nitrite reductase of Escherichia coli, which contains sirohaem, flavin, non-haem iron and labile sulphide, was examined by low-temperature e.s.r. spectroscopy. The enzyme, stored in the presence of nitrite and ascorbate, gave the spectrum of a nitrosyl derivative, with hyperfine splitting due to the nitrosyl nitrogen. On removal of these reagents, a series of signals centred around g = 6 was observed, typical of high-spin ferric haem. Cyanide converted this into a low-spin form. On reduction of the enzyme with NADH, an axial spectrum at g = 1.92, 2.01 was observed. The temperature-dependence of this signal is indicative of a [2Fe-2S] iron-sulphur cluster. The midpoint potential of this cluster was estimated to be −230 +/- 15 mV by two independent methods. Reduction of the enzyme with dithionite yielded further signals, which are at present unidentified, at g = 2.1-2.28. No signals were observed that could be assigned to a [4Fe-4S] cluster, such as is found in other sulphite reductases and nitrite reductases that contain sirohaem.

Light-induced reversible ionization of tetramethylphenylenediamine in an inorganic polymer of n-butyl orthotitanate

1988 ◽  
Vol 66 (8) ◽  
pp. 1931-1935
Author(s):  
Hisashi Ueda ◽  
Masahiro Kaise
Keyword(s):  
Relaxation Time ◽  
Electron Spin Resonance ◽  
Visible Light ◽  
Relative Intensity ◽  
Hyperfine Splitting ◽  
Resonance Absorption ◽  
Spin Quantum ◽  
Spin Quantum Number ◽  
Spin Resonance ◽  
Intensity Ratios

n-Butyl orthotitanate, BT, polymerized in tetrahydrofuran, if irradiated by visible light, gives a new electron spin resonance absorption that is not found before irradiation. In the present work, three different polymers of BT were synthesized by adding tetramethyl phenylenediamine (TMPD), dimethyl phenylenediamine (DMPD), or phenylenediamine (PD), to the solution of BT. The polymers thus prepared were tested to see if they give a new esr signal when irradiated by visible light. The polymer to which 1 mol% of TMPD was added gave TMPD•+ when irradiated by visible light, but the TMPD•+ signal decayed after the irradiation was discontinued. This change, therefore, is reversible. The resonant position of every hyperfine splitting line of the TMPD•+ found in this polymer coincided with that of TMPD•+ in solution, but the relative intensity ratios and the line width of each line depended on the nuclear spin quantum number of the coupling nuclei. This can be interpreted by the restricted rotational motion of TMPD•+ in the polymer matrix. The contribution of the non-diagonal term to the spin relaxation time would explain this phenomenon. In the case of the polymer to which DMPD was added, a small amount of DMPD•+ seemed to be formed, but no radical was detected in the case of the polymer to which PD was added.

Applications of ESR to Carbonaceous Materials

1982 ◽  
Vol 36 (1) ◽  
pp. 52-57 ◽  
Author(s):  
L. S. Singer ◽  
I. C. Lewis
Keyword(s):  
Free Radicals ◽  
Electron Spin Resonance ◽  
Low Temperature ◽  
Electron Spin ◽  
Paramagnetic Species ◽  
Carbonaceous Materials ◽  
Conduction Electrons ◽  
Spin Resonance ◽  
Higher Temperature ◽  
Low Temperature Pyrolysis

The applications of electron spin resonance (ESR) to carbonaceous materials are reviewed. The stable paramagnetic species observed in the products of low-temperature pyrolysis are odd-alternate neutral free radicals, whereas the unpaired spins of higher temperature carbons and graphites are primarily conduction electrons. The variety of ESR properties and phenomena requires special attention to techniques of measurement and interpretations of results. The relevance to the carbonization process of the free radicals observed by ESR is also discussed.

New insights into the activity of Pseudomonas aeruginosa cd1 nitrite reductase

2008 ◽  
Vol 36 (6) ◽  
pp. 1155-1159 ◽  
Author(s):  
Serena Rinaldo ◽  
Alessandro Arcovito ◽  
Giorgio Giardina ◽  
Nicoletta Castiglione ◽  
Maurizio Brunori ◽  
...  
Keyword(s):  
Nitric Oxide ◽  
Pseudomonas Aeruginosa ◽  
Nitrite Reductase ◽  
Nitrite Reduction ◽  
Nitrite Reductases ◽  
Cytochrome Cd1 ◽  
Haem Iron ◽  
Shed Light ◽  
Denitrification Process

The cytochrome cd1 nitrite reductases are enzymes that catalyse the reduction of nitrite to nitric oxide (NO) in the bacterial energy conversion denitrification process. These enzymes contain two different redox centres: one covalently bound c-haem, which is reduced by external donors, and one peculiar d1-haem, where catalysis occurs. In the present paper, we summarize the current understanding of the reaction of nitrite reduction in the light of the most recent results on the enzyme from Pseudomonas aeruginosa and discuss the differences between enzymes from different organisms. We have evidence that release of NO from the ferrous d1-haem occurs rapidly enough to be fully compatible with the turnover, in contrast with previous hypotheses, and that the substrate nitrite is able to displace NO from the d1-haem iron. These results shed light on the mechanistic details of the activity of cd1 nitrite reductases and on the biological role of the d1-haem, whose presence in this class of enzymes has to date been unexplained.

Correlation of optical and electron spin resonance spectra for alkali metal solutions in ethylamine and tetrahydrofuran

1976 ◽  
Vol 54 (19) ◽  
pp. 3110-3113 ◽  
Author(s):  
R. Catterall ◽  
J. Slater ◽  
W. A. Seddon ◽  
J. W. Fletcher
Keyword(s):  
Electron Spin Resonance ◽  
Optical Absorption ◽  
Alkali Metal ◽  
Electron Spin ◽  
Hyperfine Splitting ◽  
Pulse Radiolysis ◽  
Optical Absorption Spectra ◽  
Monomeric Species ◽  
Spin Resonance ◽  
Sodium Tetraphenylboron

The band maxima of transient optical absorption spectra observed by pulse radiolysis in ethylamine (EA)/tetrahydrofuran (THF) mixtures containing sodium tetraphenylboron are correlated with electron spin resonance (esr) hyperfine splitting constants obtained in potassium/EA/THF solutions. The data suggest that the optical spectra can be attributed to the same 'monomeric' species as observed by esr in alkali metal solutions.

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