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Nitric Oxide in Transplant Rejection and Anti-Tumor Defense pp 49–82Cite as

EPR Detection and Biological Implications of Nitrosyl Nonheme Iron Complexes

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Abstract

The problem of unequivocal detection of nitric oxide (NO) and its derivatives in living systems remains a challenging task for investigators. In this regard, one of the most useful and promising approaches has proved to be technique(s) using electron paramagnetic resonance (EPR) spectroscopy (Henry et al., 1996). This chapter describes the advantages and the limitations of the approach based on studying paramagnetic nonheme iron-NO complexes with sulphur-containing ligands by EPR. Additionally, the biological activities of these complexes will be discussed. Emphasis will be given to the work done in our group during the last 30 years, which is not well known to Western scientists. First, we consider dinitrosyl iron complexes (DNIC) with endogenous thiol ligands having the general formula (RS−)2 Fe+(NO+)2, their physicochemical properties, mechanism of generation in cells and tissues, and the value of their EPR assessment as an indicator of NO formation. Then we show that introduction of exogenous ligands such as dithiocarbamate derivatives (alone or with iron) can stabilize Fe-NO complexes and thus sharply increase NO trapping capacity of the system. We also illustrate some successful applications of this approach. In the third part of the chapter we demonstrate that nitrosyl nonheme iron complexes can be considered not only production as indicative of NO but also that when applied exogenously as model complexes, may in themselves be very interesting and potential pharmacological tools, acting as NO donors and nitrosylating compounds.

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References

  • Akaike T, Noguchi Y, Ijiri S, Setoguchi K, Suga M, Zheng YM. Dietzschold B, Maeda H, Pathogenesis of influenza virus-induced pneumonia: involvement of both nitric oxide and oxygen radicals. Proc Natl Acad Sci USA 1996,93:2448–2453

    Article  PubMed  CAS  Google Scholar 

  • Aliev DI, Vanin AF. The reaction of nitroprusside with tissue preparations. Zhurn Phys Khim (Rus) 1982,56:2362–2364

    CAS  Google Scholar 

  • Andriambeloson E, Kleschyov AL, Muller B, Beretz A, Stockt J-C, Andriantsitohaina R. Nitric oxide production and endothelium-dependent vasorelaxation induced by wine polyphenols in rat aorta. Br J Pharmacol 1997;120:1053–1058

    Article  PubMed  CAS  Google Scholar 

  • Bashkatova VG, Mikoyan VD, Kosacheva ES, Kubrina LN, Vanin AF, Raevsky KS. Direct determination of nitric oxide by EPR method in rat brain at different seizurea. Dokl Rus Akad Nauk 1996;348:119–121

    CAS  Google Scholar 

  • Bassosi R, Gaggelli E, Tiezzi E, Valensi G. Nitrosyl iron complexes with mercapto-purines and-pyrimidines studied by nuclear magnetic and electron spin resonance spectroscopy. J Chem Soc Perkin Trans 2 1975;423–428

    Google Scholar 

  • Bastian NR, Xu S, Shao XL, Shelby J, Granger DL, Hibbs JB. Nw-monomethyl-L-arginine inhibits nitric oxide production in murine cardiac allografts but does not affect graft rejections. Biochim Biophys Acta 1994a;1226:225–231

    Google Scholar 

  • Bastian NR, Yim C-Y, Hibbs JB, Samlowski WE. Induction of iron-derived EPR signals in murine cancers by nitric oxide. J Biol Chem 1994b;269:5127–5131

    Google Scholar 

  • Bode H, Jusche J, Wahrhausen HF. Untersuchungen über substituirte dithiocarbamidate IX. Z Anal Chem 1962;190:48–60

    Article  CAS  Google Scholar 

  • Boese M, Mordvintcev PI, Vanin AF, Busse R, Mülsch A. S-Nitrosation of serum albumin by dinitrosyl-iron complex. J Biol Chem 1995;270:29224–29429

    Article  Google Scholar 

  • Bryar TR, Eaton DR. Electronic configuration and structure of paramagnetic iron dinitrosyl complexes. Can J Chem 1992;70:1917–1926

    Article  CAS  Google Scholar 

  • Bukrinsky MI, Nottet HSLM, Schmidtmayerova H, Dubrovsky L, Flanagan CR, Mullins ME, Lipton SA, Gendelman HE. Regulation of nitric oxide synthase activity in human immunodeficiency virus type 1 (HIV-l)-infected monocytes: implications for HIV-associated neurological disease. J Exp Med 1995;181:735–745

    Article  PubMed  CAS  Google Scholar 

  • Bune AJ, Shergill JK, Cammack R, Cook HT. L-arginine depletion by arginase induces nitric oxide production in endotoxic shock: an electron paramagnetic resonance study. FEBS Lett 1995;366:127–130

    Article  PubMed  CAS  Google Scholar 

  • Burbaev DS, Vanin AF. Reduced form of nitrosyl non-heme iron complexes. Dokl Akad Nauk SSSR (Rus) 1973;213:860–862

    CAS  Google Scholar 

  • Burbaev DS, Vanin AF, Blumenfeld LA. Electronic and spatial structures of paramagnetic dinitrosyl ferrous complexes. Zhurn Strukt Khim (Rus) 1971; 2:252–256

    Google Scholar 

  • Butler AR, Calsy-Harrison AM, Glidewell C. The pentacyanonitrosyl-ferrate ion-Y. The course of the reactions of nitroprusside with a range of thiols. Polyhedron 1988a;7:1197–1202

    Google Scholar 

  • Butler AR, Glidewell C, Li M-H. Nitrosyl complexes of iron-sulfur clusters. Adv Inorg Chem. 1988b;32:335–393

    Google Scholar 

  • Cantilena LR, Irwin G, Preskorn S, Klaassen CD. The effect of diethyldithiocarbamate on brain uptake of cadmium. Toxicol Appl Pharmacol 1982,63:338–343

    Article  PubMed  CAS  Google Scholar 

  • Castro L, Rodriguez N, Radi R. Aconitase is readly inactivated by peroxynitrite, but not its precursor, nitric oxide. J Biol Chem 1994;269:29409–29415

    PubMed  CAS  Google Scholar 

  • Chamulitrat W, Jordan SJ, Mason RP, Litton AL, Wilson JG, Wood ER, Wolberg G, Molina Y, Vedia L. Targets of nitric oxide in a mouse model of liver inflammation by Corynebacterium parvum. Arch Biochem Biophys 1995;316:30–37

    Article  PubMed  CAS  Google Scholar 

  • Chetverikov AG, Ruuge EK, Burbaev DS, Vanin AF. The change of the shape of the EPR signal with gav 2.03 in biological objects depending on the conditions of the registration. Biofizika (Rus) 1969; 14:932–935

    CAS  Google Scholar 

  • Chiang RW, Woolum JC, Commoner B. Further study of the properties of the rat livers of carcinogen-treated rats. Biochim Biophys Acta 1972;257:452–460

    Article  PubMed  CAS  Google Scholar 

  • Commoner B, Woolum JC, Senturia BH, Ternberg JL. The effects of 2-acetylaminofluorene and nitrite on free radicals and carcinogenesis in rat liver. Cancer Res 1970;30:2091–2097

    PubMed  CAS  Google Scholar 

  • Connely NG, Gardner C. Simple halogen nitrosyl anions of iron. J Chem Soc Dalton Trans 1976; 1525–1527

    Google Scholar 

  • Cooper CE, Brown GC. The interaction between nitric oxide and brain nervee terminals as studied by electronic paramagnetic resonance. Biochem Biophys Res Commun 1995;212:404–412

    Article  PubMed  CAS  Google Scholar 

  • Corbett JA, Sweetland MA, Wang JL, Lancaster JR, McDaniel ML. Nitric oxide mediates cytokine-induced inhibition of insulin secretion by human islets of Langerhans. Proc Natl Acad Sci USA 1993;90:1731–1735

    Article  PubMed  CAS  Google Scholar 

  • Crow JP, Cullen WR, Herring FG, Sams JR, Tapping RL. Mössbauer and electron paramagnetic resonance studies of some iron nitrosyl complexes. Inorg Chem 1971;10:1616–1623

    Article  Google Scholar 

  • Doi K, Akaike T, Horie H, Noguchi Y, Fujii S, Beppu T, Ogawa M, Maeda H. Excessive production of nitric oxide in rat solid tumor and its implication in rapid tumor growth. Cancer 1996;77:1598–1604

    PubMed  CAS  Google Scholar 

  • Drapier J-C, Pellat C, Henry Y. Generation of EPR-detectable nitrosyl-iron complexes in tumor target cells cocultured with activated macrophages. J Biol Chem 1991;266:10162–10167

    PubMed  CAS  Google Scholar 

  • Enemark JH, Feltham RD. Principles of structure, binding, and reactivity for metal nitrosyl complexes. Coord Chem Rev 1974;13:339–406

    Article  CAS  Google Scholar 

  • Flitney FW, Megson IL, Flitney DE, Butler AR. Iron-sulphur cluster, a novel class of nitric oxide generator: mechanism of vasodilator action on rat isolated artery. Br J Pharmacol 1992; 107:842–848

    Article  PubMed  CAS  Google Scholar 

  • Foster MA, Hutchison JMS. The origin of an ESR signal at g=2.03 from normal rabbit liver and the effects of nitrites upon it. Phys Med Biol 1974;19:289–302

    Article  PubMed  CAS  Google Scholar 

  • Galagan ME, Oranovskaya EV, Mordvintcev PI, Medvedev OS, Vanin AF. Hypotensive effect of dinitrosyl iron complexes in conscious animals. Bull Kardiol Center SSSR (Rus) 1988;N2:75–80

    Google Scholar 

  • Geng Y-L, Petersson A-S, Wennmalm A, Hannson G. Cytokine-induced expression of nitric oxide synthase results in nitrosylation of heme and nonheme iron proteins in vascular smooth muscle cells. Exp Cell Res 1994;214:418–424

    Article  PubMed  CAS  Google Scholar 

  • Goodman BA, Raynor JB, Symons MCR. Electron spin resonance of bis(N’N-diethyldithiocarbamato)nitrosyl iron. J Chem Soc (A) 1969;2572–2575

    Google Scholar 

  • Hausladen A, Fridovich I. Superoxide and peroxynitrite inactivate aconitase, but nitric oxide does not. J Biol Chem 1994;269:29405–29408

    PubMed  CAS  Google Scholar 

  • Henry YA, Guissani A, Ducastel B. Nitric Oxide Research from Chemistry to Biology: EPR Spectroscopy of Nitrosylated Compounds. RG Landes, Austin, TX, USA, 1997

    Google Scholar 

  • Hooper DC, Ohnishi ST, Kean R, Numagami Y, Dietzschold B, Koprovski H. Local nitric oxide production in viral and autoimmune diseases of the central nervous system. Proc Natl Acad Sci USA 1995,92:5312–5316

    Article  PubMed  CAS  Google Scholar 

  • Ileperuma OA, Feltham RD. Iron-sulfur complexes of NO. 2. Synthesis and exchange studies of Fe(NO)(S2CN(CH3)2)2.Crystal and molecular structure of cys — Fe(NO)(S2 CN(C2H5)2)2. Inorg Chem 1977,16:1876–1883

    Article  CAS  Google Scholar 

  • Ischiropoulos H, Beers MF, Ohnishi ST, Fisher D, Garner SE, Thorn SR. Nitric oxide production and perivascular tyrosine nitration in brain after carbon monoxide poisoning in the rat. J Clin Invest 1996;97:2260–2267

    Article  PubMed  CAS  Google Scholar 

  • Khrapova NV, Malenkova IV, Vanin AF. S-Nitrosothiols and dinitrosyl iron complexes as a sources of nitric oxide in animal organisms. Biofizika (Rus) 1995;40:117–121

    CAS  Google Scholar 

  • Kim Y-M, Bergonia H, Lancaster JR. Nitrogen oxide-induced autoprotection in isolated rat hepatocytes. FEBS Lett 1995;374:228–232.

    Article  PubMed  CAS  Google Scholar 

  • Kleschyov AL. Nitric oxide is a common and hypotensive-active metabolite of some nitrogen-containing vasodilators and activators of soluble guanylyl cyclase in vivo. MD Thesis, Pirogov State Medical University, Moscow, 1986

    Google Scholar 

  • Kleschyov AL, Mordvintcev PI, Shabarchina MM, Vanin AF. Reduction of sodium nitroprusside followed by elimination of nitric oxide in animal organisms. Zhum Phys Khim (Rus) 1985a;59:462–467

    Google Scholar 

  • Kleschyov AL, Mordvintcev PI, Vanin AF. Role of nitric oxide and iron in hypotensive action of nitrosyl iron complexes with various anion ligands. Studia Biophys 1985b; 105:93–102

    Google Scholar 

  • Kleschyov AL, Mordvintcev PI, Vanin AF, Sedov KR. Creation of physiologically active deposite of nitric oxide in organism of animals. Bull Sib Otd AMN SSSR (Rus) 1988;N2:41–44

    Google Scholar 

  • Kleschyov AL, Muller B, Stoclet J-C. Nitric oxide store as dinitrosyl-iron complexes in lipopolysaccharide-treated vessels: localization and mechanism of formation. Br J Pharmacol (Suppl) 1997;120–90P

    Google Scholar 

  • Kleschyov AL, Sedov KR, Mordvintcev PI, Vanin AF. Biotransformation of sodium nitroprusside into dinitrosyl iron complexes in tissue of ascites tumors of mice. Biochem Biophys Res Commun 1994;202:168–173

    Article  PubMed  CAS  Google Scholar 

  • Komarov A, Lai C-S. Detection of nitric oxide production in mice by spin-trapping electron paramagnetic resonance spectroscopy. Biochim Biophys Acta 1995,1272:29–36

    Article  PubMed  Google Scholar 

  • Komarov A, Mattson D, Jones MM, Singh PK, Lai C-S. In vivo spin trapping of nitric oxide in mice. Biochem Biophys Res Commun 1993;195:1191–1198

    Article  PubMed  CAS  Google Scholar 

  • Kotake Y, Tanigawa T, Tanigawa M, Ueno I. Evaluation of nitric oxide spin traps: solubility in water, trapping efficiency and spin adduct stability. Magn Res Med 1995a;6:106–108

    Google Scholar 

  • Kotake Y, Tanigawa T, Tanigawa M, Ueno I. Spin trapping isotopically-labelled nitric oxide produced from (15N)L-arginine and (17O)dioxygen by activated macrophages using water soluble Fe++− dithiocarbamate spin trap. Free Rad Res 1995b;23:287–295

    Google Scholar 

  • Kotake Y, Tanigawa T, Tanigawa M, Ueno I, Allen DR, Lai C-S. Continuous monitoring of cellular nitric oxide generation by spin trapping with an iron-dithiocarbamate complex. Biochim Biophys Acta 1996;1289:362–368

    Article  PubMed  Google Scholar 

  • Kozlov AV, Yegorov DY, Vladimirov YV, Azizova OA. Intracellular free iron in liver tissue and liver homogenate: studies with EPR on the formation of paramagnetic complexes with desferal and nitric oxide. Free Rad Biol Med 1992;13:9–16

    Article  PubMed  CAS  Google Scholar 

  • Kubrina LN, Caldwell WS, Mordvintcev PI, Malenkova IV, Vanin AF. EPR evidence for nitric oxide production from guanidino nitrogen of L-arginine in animal tissues in vivo. Biochim Biophys Acta 1992,1099:233–237

    Article  PubMed  CAS  Google Scholar 

  • Kubrina LN, Mikoyan VD, Mordvintcev PI, Vanin AF. Iron potentiates lipopolysaccharide-induced nitric oxide formation in animal organs. Biochim Biophys Acta 1993;1176:240–244

    Article  PubMed  CAS  Google Scholar 

  • Kubrina LN, Mordvintcev PI, Vanin AF. Nitric oxide production in animal tissues under inflammation. Bull Exp Biol Med (Rus) 1989;113:31–36

    Google Scholar 

  • Kuppusamy P, Ohnishi ST, Numagami Y, Ohnishi T, Zweier J. Three dimensional imaging of nitric oxide production in the rat brain subjected to ischemia-hypoxia. J Cerebral Blood Flow Metab 1995; 15:899–903

    Article  CAS  Google Scholar 

  • Kuznetcov VA, Mordvintcev PI, Dank EK, Yurkiv VA, Vanin AF. Low molecular weight and protein dinitrosyl non-heme iron complexes as inhibitors of platelet aggregation. Vopr Med Khim (Rus) 1988;N5:43–46

    Google Scholar 

  • Lai C-S, Komarov A. Spin trapping of nitric oxide produced in vivo in septic-shock mice. FEBS Lett 1994;345:120–124

    Article  PubMed  CAS  Google Scholar 

  • Lancaster JR, Hibbs JB. EPR demonstration of iron-nitrosyl complex formation by cytotoxic activated macrophages. Proc Natl Acad Sci. USA 1990;87:1223–1227

    Article  PubMed  CAS  Google Scholar 

  • Lancaster JR, Langrehr JM, Bergonia HA, Murase N, Simmons RL, Hoffman RA. EPR detection of heme and nonheme iron-contauning protein nitrosylation by nitric oxide during rejection of rat heart allograft. J Biol Chem 1992;267:10994–10998

    PubMed  CAS  Google Scholar 

  • Lancaster JR, Werner-Felmayer G, Wachter H. Coinduction of nitric oxide synthesis and intracellular nonheme iron-nitrosyl complexes in murine cytokine-treated fibroblasts. Free Rad Biol Med 1994; 16:869–870

    Article  PubMed  CAS  Google Scholar 

  • Laskin DL, DelValle MR, Heck DE, Hwang SM, Durham SK, Ohnishi ST, Goller NL, Laskin JD. Hepatic nitric oxide production following acute endotoxemia in rats is mediated by increase inducible nitric oxide synthase expression. Hepatology 1995,22:223–234

    PubMed  CAS  Google Scholar 

  • Lepoivre M, Flaman J-M, Henry Y. Early loss of the tyrosyl radical in ribonucleotide reductase of adenocarcinoma cells producing nitric oxide. J Biol Chem 1992,267:22994–23000

    PubMed  CAS  Google Scholar 

  • Malyshev IY, Malugin AV, Golubeva LY, Zenina TA, Manukhina EB, Mikoyan VD, Vanin AF. Nitric oxide donor induces HSP70 accumulation in the heart and in cultured cells. FEBS Lett 1996;391:21–23

    Article  PubMed  CAS  Google Scholar 

  • Malyshev IY, Manukhina EB, Mikoyan VD, Kubrina LN, Vanin AF. Nitric oxide is involved in heat-induced HSP70 accumulation. FEBS Lett 1995;370:159–162

    Article  PubMed  CAS  Google Scholar 

  • Martin V, Kleschyov AL, Klein J-P, Beretz A Induction of NO production by polyosides from the cell walls of Streptococcus mutans OMZ 175, a Gram positive bacteria, in the rat aorta. Adv Exp Med Biol 1997;418:669–672

    PubMed  CAS  Google Scholar 

  • Martini G, Tiezzi E. Equilibria between iron-dinitrosyl paramagnetic species in aqueous and alcoholic solutions studied by magnetic resonance spectroscopy. Trans Farad Soc 1971;67:2538–2547

    Article  CAS  Google Scholar 

  • Matthews EK, Seaton ED, Forsyth MJ, Humphrey PPA Photon pharmacology of an iron-sulphur cluster compound acting on smooth muscle. Br J Pharmacol 1994;113:87–94

    Article  PubMed  CAS  Google Scholar 

  • McCleverty JA. Reactions of nitric oxide coordinated to transition metals. Chem Rev 1979;79:53–76

    Article  CAS  Google Scholar 

  • McDonald CC, Phillips WD, Mower HF. An electron spin resonance study of some complexes of iron, nitric oxide and anionic ligands. J Am Chem Soc 1965,87:3319–3326

    Article  CAS  Google Scholar 

  • Meerson FZ, Lapshin AV, Mordvintcev PI, Mikoyan VD, Manukhina EB, Kubrina LN, Vanin AF. Increased production of nitric oxide in tissues of rats following their adaptation to short-time stress. Bull Exr Biol Med (Rus) 1994; 117:242–244

    CAS  Google Scholar 

  • Mian KB, Martin W. Differential sensitivity of basal and acetylcholine-stimulated activity of nitric oxide to destruction by superoxide anion in rat aorta. Br J Pharmacol 1995;115:993–1000

    Article  PubMed  CAS  Google Scholar 

  • Miki E, Motonaga M, Mizumachi K, Ishimori T, Katada M. Nitrosyliron complexes containing 8-quinoline or its derivatives. Bull Chem Soc Jpn 1982;55: 2858–2862

    Article  CAS  Google Scholar 

  • Mikoyan VD, Kubrina LN, Serezhenkov VA, Stukan RA, Vanin AF. Complexes of Fe2+ with diethyldithiocarbamate or N-methyl-D-glucamine dithiocarbamate as traps of nitric oxide in animal tissues: comparative investigations. Biochim Biophys Acta 1997;1336(2):225–234

    Article  PubMed  CAS  Google Scholar 

  • Mikoyan VD, Kubrina LN, Vanin AF. EPR evidence for nitric oxide formation via L-arginine-dependent way in stomach of mice in vivo. Biochem Mol Biol Int 1994,32:1157–1160

    PubMed  CAS  Google Scholar 

  • Mikoyan VD, Voevodskaya NV, Kubrina LN, Malenkova IV, Vanin AF. The influence of antioxidants and cycloheximide on the level of nitric oxide in the livers of mice in vivo. Biochim Biophys Acta 1995;1269:19–24

    Article  PubMed  Google Scholar 

  • Miyajima T, Kotake Y. Spin trapping agent, phenyl N-tert-butyl nitrone, inhibits induction of nitric oxide synthase on endotoxin-induced shock in mice. Biochem Biophys Res Comm 1995;215:114–121

    Article  PubMed  CAS  Google Scholar 

  • Mordvintcev PI, Kubrina LN, Kleschyov AL, Vanin AF. On the origin of structural differences between nitrosyl non-heme iron complexes formed in animal tissues in vivo or in vitro. Studia Biophys 1984; 103:63–70

    Google Scholar 

  • Mordvintcev P, Mülsch A, Busse R, Vanin A. On-line detection of nitric oxide formation in liquid aqueous phase by electron paramagnetic resonance spectroscopy. Anal Biochem 1991;199:142–146

    Article  PubMed  CAS  Google Scholar 

  • Mordvintcev PI, Putintcev MD, Galagan ME, Oranovskaya EV, Medvedev OS, Vanin AF. Hypotensive activity of dinitrosyl iron complexes with proteins in narcotized animals. Bull Kardiol Center SSSR (Rus) 1988;N1:46–51

    Google Scholar 

  • Mordvintcev PI, Rudneva VG, Vanin AF, Shimkevich LL, Khodorov BI. Inhibiting effect of dinitrosyl iron complexes with low molecular weight ligands on platelet aggregation. Biokhimiya (Rus) 1986;51:1851–1857

    Google Scholar 

  • Mordvintcev PI, Vanin AF. Dinitrosyl non-heme iron complexes in animal or human blood plasma. Izv Akad Nauk SSSR. Ser Biol (Rus) 1988;5:942–946

    Google Scholar 

  • Muller B, Kleschyov AL, Stoclet J-C. Evidence for N-acetylcysteine-sensitive nitric oxide storage as dinitrosyl-iron complexes in lipopolysaccharide-treated rat aorta. Br J Pharmacol 1996;119:1281–1285

    Article  PubMed  CAS  Google Scholar 

  • Mülsch A, Mordvintcev P, Vanin AF, Busse R. The potent vasodilating and guanylyl cyclase activating dinitrosyl-iron(II) complex is stored in a protein-bound form in vascular tissue and is released by thiols. FEBS Lett 1991;294:252–256

    Article  PubMed  Google Scholar 

  • Mulsch A, Mordvintcev P, Vanin A. Quantification of nitric oxide in biological samples by electron spin resonance spectroscopy. Neuroprotocols 1992a;1:165–173

    Google Scholar 

  • Mülsch A, Vanin A, Mordvintcev P, Hauschildt S; Busse R. NO accounts completely for oxygenated nitrogen species generated by enzymic L-arginine oxygenation. Biochem J 1992b;288:597–603

    Google Scholar 

  • Mülsch A, Mordvintcev PI, Vanin AF, Busse R. Formation and release of dinitrosyl iron complexes by endothelial cells. Biochem Biophys Res Commun 1993a;196:1303–1308

    Google Scholar 

  • Mülsch A, Schray-Utz B, Mordvintcev PI, Hauschildt S, Busse R. Diethyldithiocarbamate inhibits induction of macrophage NO synthase. FEBS Lett 1993b;321:215–218

    Google Scholar 

  • Mülsch A, Busse R, Mordvintcev PI, Vanin AF, Nielsen EO, Scheel-Kruger J, Olesen S-P. Nitric oxide promotes seizure activity in kainate-treated rats. NeuroRep 1994,5:2325–2328

    Article  Google Scholar 

  • Mülsch A, Bara A, Mordvintcev P, Vanin A, Busse R. Specificity of different organic nitrates to elicit NO formation in rabbit vascular tissues and organs in vivo. Br J Pharmacol 1995a;116:2743–2749

    Google Scholar 

  • Mülsch A, Morvintcev P, Bassenge E, Jung F, Clement B, Busse R. In vivo spin trapping of glyceryl trinitrate-derived nitric oxide in rabbit blood vessels and organs. Circulation 1995b; 92:1876–1882

    Google Scholar 

  • Nogata C, Joki Y, Kodama M, Tagashira Y, Nakadata M. Free radicals, induced in rat liver by a chemical carcinogen, N-methyl-N’-nitro-N-nitrosoguanidine. Ann NY Acad Sci 1973;222:1031–1042

    Article  Google Scholar 

  • Norby SW, Weyhenmeyer JA, Clarkson RB. Stimulation and inhibition of nitric oxide production in macrophages and neural cells as observed by spin trapping. Free Rad Biol Med 1997;22:1–9

    Article  PubMed  CAS  Google Scholar 

  • Nüssler AK, Geller DA, Sweetland MA, DiSilvio M, Billiar TR, Madariaga JB, Simmons RL, Lancaster JR. Induction of nitric oxide synthesis and its reactions in cultured human and rat hepatocytes stimulated with cytokines plus LPS. Biochem Biophys Res Commun 1993,194:826–835

    Article  PubMed  Google Scholar 

  • Obolenskaya MY, Vanin AF, Mordvintcev PI, Mülsch A, Dekker K. EPR evidence for nitric oxide production by the regenerating rat liver. Biochem Biophys Res Commun 1994;202:571–576

    Article  PubMed  CAS  Google Scholar 

  • Paschenko SV, Khramtsov VV, Scatchkov MP, Plyusnin VF, Bassenge E. EPR and laser flash photolysis studies of the reaction of nitric oxide with water soluble NO trap Fe(II)-proline-dithiocarbamate complex. Biochem Biophys Res Commun 1996;225:577–584

    Article  PubMed  CAS  Google Scholar 

  • Payne MJ, Woods LFJ, Gibbs P, Cammack R. Electron paramagnetic resonance spectroscopic investigatioas of the inhibition of the phosphoroclastic system of Clostridium sporogenesis by nitrite. J Gen Microbiol 1990;136:2067–2076

    Article  PubMed  CAS  Google Scholar 

  • Pearsall KA, Bonner FT. Aqueous nitrosyl iron(II) chemistry. 2. Kinetics and mechanism of nitric oxide reduction. The dinitrosyl complex. Inorg Chem 1982;21:1978–1985

    Article  CAS  Google Scholar 

  • Pellat C, Henry Y, Drapier J-C. IFN-activated macrophages: detection by electron paramagnetic resonance of complexes between L-arginine-derived nitric oxide and non-heme iron proteins. Biochem Biophys Res Commun 1990;166:119–125

    Article  PubMed  CAS  Google Scholar 

  • Quaresima V, Takehara H, Tsushima K, Ferrari M; Utsumi H. In vivo detection of mouse liver nitric oxide generation by spin trapping electron paramagnetic resonance spectroscopy. Biochem Biophys Res Commun 1996;221:729–734

    Article  PubMed  CAS  Google Scholar 

  • Rao DNR, Cederbaum AI. Production of nitric oxide and other iron-containing metabolites during the reductive metabolism of nitroprusside by microsomes and by thiols. Arch Biochem Biophys. 1995;321:363–371

    Article  PubMed  CAS  Google Scholar 

  • Reddy D, Lancaster JR, Cornforth DP. Nitrite inhibition of Clostridium botulinum: electron spin resonance detection of iron-nitric oxide complexes. Science 1983;221:769–770

    Article  PubMed  CAS  Google Scholar 

  • Reinke LA, Moore DR, Kotake Y. Hepatic nitric oxide formation: spin trapping detection in biliary efflux. Anal Biochem 1996,243:8–14

    Article  PubMed  CAS  Google Scholar 

  • Rochelle LG, Kruszyna H, Kruszyna R. Bioactivation of nitroprusside by porcine endothelial cells. Toxicol Appl Pharmacol 1994;128:123–128

    Article  PubMed  CAS  Google Scholar 

  • Sato S, Tominaga T, Ohnishi ST, Ohnishi T. Electron paramagnetic resonance study on nitric oxide production during brain local ischemia and reperfusion in the rat. Brain Res 1994;647:91–96

    Article  PubMed  CAS  Google Scholar 

  • Schwarz MA, Lazo JS, Yalowich JC, Allen WP, Whitmore M, Bergonia HA, Tzeng E, Billiar TR, Robbins PD, Lancaster JR, Pitt BR. Metallothioneine protects against the cytotoxic and DNA-damaging effects of nitric oxide. Proc Natl Acad Sci USA 1995,92:4452–4456

    Article  PubMed  CAS  Google Scholar 

  • Sergent O, Griffon B, Morel I, Chevanne M, Dubos M-P, Cillard P, Cillard J. Effect of nitric oxide on iron-mediated oxidative stress in primary hepatocyte culture. Hepatology 1997,25:122–127

    Article  PubMed  CAS  Google Scholar 

  • Servent D, Ducrocq, C, Henry Y, Guissani A, Lenfant M. Nitroglycerin metabolism by Phanerochaete chrysosporum: evidence for nitric oxide and nitrite formation. Biochim Biophys Acta 1991;1074:320–325

    Article  PubMed  CAS  Google Scholar 

  • Shinobu LA, Jones SG, Jones MM. Sodium N-methyl-D-glucamine dithiocarbamate and cadmium intoxication. Acta Pharmacol Toxicol 1984;54:189–194

    Article  CAS  Google Scholar 

  • Stadler J, Bergonia HA, DiSilvio M, Sweetland MA, Billiar TR, Simmons RL, Lancaster JR. Nonheme nitrosyl-iron complex formation in rat hepatocytes: detection by EPR spectroscopy. Arch Biochem Biophys 1993;302:4–11

    Article  PubMed  CAS  Google Scholar 

  • Stamler JS. Redox signalling: nitrosylation and related target interactions of nitric oxide. Cell 1994;78:931–936

    Article  PubMed  CAS  Google Scholar 

  • Tarasova NI, Kovalenko OA, Vanin AF. Mechanism of iron incorporation into animal tissues. Biofizika (Rus) 1981;26:678–682

    CAS  Google Scholar 

  • Tominaga T, Sato S, Ohnishi T, Ohnishi ST. Potentiation of nitric oxide formation following bilateral carotid occlusion and local cerebral ischemia in the rat: in vivo detection of the nitric oxide radical by electron paramagnetic resonance spin trapping. Brain Res 1993,614:342–346

    Article  PubMed  CAS  Google Scholar 

  • Vanin AF, Nalbandyan RM. Free radicals of a new type in yeast cells. Biofizika (Rus) 1965;11:167–168

    Google Scholar 

  • Vanin AF. Identification of divalent iron complexes with cysteine in biological systems by the EPR method. Biokhimia (Rus) 1967;32:228–232

    Google Scholar 

  • Vanin AF, Blumenfeld LA, Chetverikov AG. The investigation of nonheme iron complexes in cells and tissues by EPR method. Biofizika (Rus) 1967;12:829–841

    CAS  Google Scholar 

  • Vanin A.F., Chetverikov AG. Paramagnetic nitrosyl complexes of heme and non-heme iron. Biofizika (Rus) 1968;13:608–616

    CAS  Google Scholar 

  • Vanin AF, Blumenfeld LA, Burbaev DS, Lisovskaya IL, Chetverikov AG. The investigation of some iron complexes in biological objects. Proceedings of the International Jubilee EPR Conference; 1969 June 15-June 20; Kazan State University Publishers, Kazan. 1970a

    Google Scholar 

  • Vanin AF, Vakhnina LV, Chetverikov AG. Nature of the EPR signals of a new type found in cancer tissues. Biofizika (Rus) 1970b;l5:1044–1051

    Google Scholar 

  • Vanin AF, Kubrina LN, Lisovskaya IL, Malenkova IV, Chetverikov AG. Endogenous heme and nonheme nitrosyl iron complexes in cells and tissues. Biofizika (Rus) 1971;16:650–658

    CAS  Google Scholar 

  • Vanin AF, Burbaev DS, Mardanyan SS, Nalbandyan RM, Mutuskin AA, Pshonova KV. On the coordination of iron in iron-sulphur proteins with thiol groups. Proceedings of The International Biophysics Congress; 1972 July 5-July 12; Pushchino Biophysical Institute Publishers, Moscow. 1973a

    Google Scholar 

  • Vanin AF, Mardanyan SS, Nalbandyan RM. Nitrosyl non-heme iron complexes in denaturated adrenodoxin. Studia Biophys. 1973b;38:13–18

    Google Scholar 

  • Vanin AF, Kiladze SV, Kubrina LN. On including of low molecular weight SH containing compounds in nitrosyl non-heme iron complexes in non-cellular and cellular preparations. Biofizika (Rus) 1975a;20:1068–1072

    Google Scholar 

  • Vanin AF, Osipov AN, Kubrina LN, Burbaev DS, Nalbandyan RM. On the origin of paramagnetic centers with g 2.03 in animal tissues and microorganisms. Studia Biophys 1975b;49:13–25

    Google Scholar 

  • Vanin AF, Kalamkarov GR, Kiladze SV, Ostrovsky MA. On two closely located SH-groups in rhodopsin molecule. Biofizika (Rus) 1977a;22:397–402

    Google Scholar 

  • Vanin AF, Kiladze SV, Kubrina LN. Factors influencing the formation of the dinitrosyl complexes of non-heme iron in animals organs in vivo. Biofizika (Rus) 1977b;22:850–857

    Google Scholar 

  • Vanin AF, Kubrina LN, Kiladze SV, Burbaev DS. Factors influencing formation of dinitrosyl non-heme iron complexes in the preparation of mouse liver or yeast in vitro. Biofizika (Rus) 1977c;22:646–674

    Google Scholar 

  • Vanin AF, Kiladze SV, Kubrina LN. On including non-heme iron into dfinitrosyl complexes in the livers of mice in vivo. Biofizika (Rus) 1978;23:474–479

    CAS  Google Scholar 

  • Vanin AF, Aliev DI, Varich VJ, Kubrina LN. On the shape of the EPR signal of a nitrosyl-nonheme iron complexes from animal tissues. Biofizika (Rus) 1979;956

    Google Scholar 

  • Vanin AF. Nitrosyl non-heme iron complexes in animal tissues and microorganisms. D. Sc. Thesis, Inst Chem Phys, Moscow, 1980

    Google Scholar 

  • Vanin AF, Varich VJ. Nitrosyl non-heme iron complexes in animal tissues. Studia Biophys 1981;86:175–185

    Google Scholar 

  • Vanin AF, Aliev DI. ESR signal shape of nitrosyl non-heme iron complexes as an indicator of proteins components in these complexes. Studia Biophys 1983;97:223–229

    CAS  Google Scholar 

  • Vanin AF, Mordvintcev PI, Kleschyov AL. Appearance of nitric oxide in animal tissues in vivo. Studia Biophys 1984;102:135–143

    CAS  Google Scholar 

  • Vanin AF, Kurbanov IS, Mordvintcev PI, Aliev DI. Influence of the intracellular medium on the structure of dinitrosyl complexes of non-heme iron in the liver of animals. Studia Biophys 1987;120:145–154

    Google Scholar 

  • Vanin AF. On the origin of non-heme iron including into dinitrosyl iron complexes in animal tissues. Biofizika (Rus)1987;31:128–132

    Google Scholar 

  • Vanin AF, Kubrina LN, Mordvintcev PI. Carbachol as an inducer of nitric oxide formation in animal livers in vivo. Dokl Akad Nauk SSSR (Rus) 1988;301:490–492

    CAS  Google Scholar 

  • Vanin AF, Kubrina LN, Malenkova IV, Mordvintcev PI. L-Arginine is an endogenous source of nitric oxide in animal tissues in vivo. Biokhimiya (Rus) 1991a;56:935–939

    Google Scholar 

  • Vanin AF, Vedernikov YP, Galagan ME, Ignatov SM, Kubrina LN, Malenkova Mordvintcev PI, Kostyanovskii RG. Supercarcinogenic and supermutagenic nitrosoalcoxyalkylamines as efficient producers of nitric oxide in vivo. Izv Akad Nauk SSSR, Ser Biol (Rus) 1991b;Nl:136–141

    Google Scholar 

  • Vanin AF, Men’shikov GB, Mordvintcev PI, Repin VS. Nitric oxide formation in activated macrophages. Bull Exp Biol Med (Rus) 1991c;N2:588–590

    Google Scholar 

  • Vanin AF. Endothelium-derived relaxing factor is a nitrosyl iron complex with thiol ligands (Hypothesis). FEBS Lett 1991d;289:l–3

    Google Scholar 

  • Vanin AF, Men’shikov GV, Moroz IA, Mordvintcev PI, Serezhenkov VA, Burbaev DS. The source of non-heme iron that binds nitric oxide in cultivated macrophages. Biochim Biophys Acta 1992;1135:275–279

    Article  PubMed  CAS  Google Scholar 

  • Vanin AF, Malenkova IV, Mordvintcev PI, Mulsch A. Dinitrosyl iron complexes with thiol-containing ligands and their reversible conversion into nitrosothiols. Biokhimiya (Rus) 1993a;58:1094–1103

    Google Scholar 

  • Vanin AF, Mordvintcev PI, Hauschildt S, Mülsch A. The relationship between L-arginine-dependent nitric oxide synthesis, nitrite release and dinitrosyl-iron complex formation by activated macrophages. Biochim Biophys Acta 1993b;1177:37–42

    Google Scholar 

  • Vanin AF. On the stability of the dinitrosyl-iron complex, a candidate for the endothelium-derived relaxing factor. Biochemistry (Moscow) 1995a;60:225–230

    Google Scholar 

  • Vanin AF. Roles of iron and cysteine in formation and decomposition of S-nitrosocysteine and S-nitrosoglutathione. Biochemistry (Moscow) 1995b;60: 441–447

    Google Scholar 

  • Vanin AF, Stukan RA, Manukhina EB. Physical properties of dinitrosyl iron complexes with thiol-containing ligands in relation with their vasodilator activity. Biochim Biophys Acta 1996;1295:5–12

    Article  PubMed  Google Scholar 

  • Vanin AF, Malenkova IV. Iron is a catalyst of cysteine and glutathione S-nitrosation on contact with nitric oxide in aqueous solutions at neutral pH. Biochemistry (Moscow) 1996;61.505–513

    CAS  Google Scholar 

  • Vanin AF, Malenkova IV, Serezhenkov VA. Iron catalyzes both decomposition and synthesis of S-nitrosothiols. Nitric Oxide Biol Chem 1997;l(3):191–203

    Article  Google Scholar 

  • Varich VJ, Vanin AF. On the formation mechanism of nitrosyl non-heme iron complexes in animal tissues in vivo. Biofizika (Rus) 1983;28:1055–1060

    CAS  Google Scholar 

  • Varich VJ, Vanin AF, Ovsyannikova LM. Discovery of endogenous nitric oxide in animal organism. Biofizika (Rus) 1987;32:1064–1067

    Google Scholar 

  • Vedernikov YP, Mordvintcev PI, Malenkova IV, Vanin AF. Effect of diethyldithiocarbamate on the activity of nitric oxide-releasing vasodilators. Eur J Pharmacol 1992;212:125–128

    Article  PubMed  CAS  Google Scholar 

  • Vedernikov YP, Mordvintcev PI, Malenkova IV, Vanin AF. Similarity between the vasorelaxing activity of dinitrosyl iron complexes and endothelium-derived relaxing factor. Eur J Pharmacol 1992;211:313–317

    Article  PubMed  CAS  Google Scholar 

  • Vetrovsky P, Kleschyov AL, Entlicher G, Poindron P, Stoclet J-C. Nitric oxide generation from extracellularly applied NG-hydroxy-Larginine in LPS activated RAW 264 macrophages. Biochim Biophys Acta 1997;1334:51–56

    Article  PubMed  CAS  Google Scholar 

  • Vithaythil AJ, Ternberg JL, Commoner B. Changes in electron spin resonance signals of rat liver during chemical carcinogenesis. Nature 1965,207:1246–1249

    Article  Google Scholar 

  • Voevodskaya NV, Vanin AF. Gamma-irradiation potentiates L-arginine-dependent nitric oxide formation in mice. Biochem Biophys Res Commun 1992;186:1423–1428

    Article  PubMed  CAS  Google Scholar 

  • Wang P, Zweier JL. Measurement of nitric oxide and peroxynitrite generation in the post ischemic heart. Evidence for peroxynitrite-mediated reperfusion injury. J Biol Chem 1996;271:29223–29230

    Article  PubMed  CAS  Google Scholar 

  • Wizeman TM, Gardner CR, Laskin JD. Production of nitric oxide and peroxynitrite in the lung during acute endotoxemia. J Leuk Biol 1994,56:759–768

    Google Scholar 

  • Woolum JC, Tiezzi E, Commoner B. Electron spin resonance of iron-nitric oxide complexes with amino acids, peptides and proteins. Biochim Biophys Acta 1968; 160:311–320

    Article  PubMed  CAS  Google Scholar 

  • Woolum JC, Commoner B. Isolation and identification of a paramagnetic comple from the livers of carcinogen-treated rats. Biochim Biophys Acta 1970;201:131–140

    Article  PubMed  CAS  Google Scholar 

  • Yoshimura T, Fujii S, Yokoyama H, Kamada H. In vivo electron paramagnetic resonance imaging of NO-bound iron complex in a rat head. Chem Lett 1995;309–310

    Google Scholar 

  • Yoshimura T, Yokoyama H, Fujii S, Takayama F, Oikawa K, Kamada H. In vivo EPR detection and imaging of endogenous NO in LPS-treated mice. Nature Biotechnology 1996;14:992–994

    Article  PubMed  CAS  Google Scholar 

  • Zweier J, Wang P, Kuppusamy P. Direct measurment of nitric oxide generation in the ischemic heart using electron paramagnetic resonance spectroscopy. J Biol Chem 1995a;270:304–307

    Google Scholar 

  • Zweier JL, Wang P, Samouilov A, Kuppusamy P. Enzyme-independent formation of nitric oxide in biological tissues. Nature Medicine 1995b;1:804–809

    Google Scholar 

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Authors and Affiliations

  1. Institute of Chemical Physics, Russian Academy of Science, Kosygin Str 4, Moscow, 117977, Russia

    Anatoly F. Vanin

  2. CNRS URA 600, Université Louis Pasteur de Strasbourg, 67401, Illkirch, France

    Andrei L. Kleschyov

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  1. Anatoly F. Vanin
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  2. Andrei L. Kleschyov
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  1. The Jagiellonian University, Poland

    Stanislaw Lukiewicz

  2. Johns Hopkins University School of Medicine, USA

    Jay L. Zweier

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Vanin, A.F., Kleschyov, A.L. (1998). EPR Detection and Biological Implications of Nitrosyl Nonheme Iron Complexes. In: Lukiewicz, S., Zweier, J.L. (eds) Nitric Oxide in Transplant Rejection and Anti-Tumor Defense. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-5081-5_3

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