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K Bannister, S Lockwood, L Goncalves, R Patel, A H Dickenson
BACKGROUND: Following neuropathy α2-adrenoceptor-mediated diffuse noxious inhibitory controls (DNIC), whereby a noxious conditioning stimulus inhibits the activity of spinal wide dynamic range (WDR) neurons, are abolished, and spinal 5-HT7 receptor densities are increased. Here, we manipulate spinal 5-HT content in spinal nerve ligated (SNL) animals and investigate which 5-HT receptor mediated actions predominate. METHODS: Using in vivo electrophysiology we recorded WDR neuronal responses to von frey filaments applied to the hind paw before, and concurrent to, a noxious ear pinch (the conditioning stimulus) in isoflurane-anaesthetised rats...
November 28, 2016: European Journal of Pain: EJP
Konstantin B Shumaev, Olga V Kosmachevskaya, Elvira I Nasybullina, Sergey V Gromov, Alexander A Novikov, Alexey F Topunov
Dinitrosyl iron complexes (DNICs) are physiological NO derivatives and account for many NO functions in biology. Polyfunctional dipeptide carnosine (beta-alanyl-L-histidine) is considered to be a very promising pharmacological agent. It was shown that in the system containing carnosine, iron ions and Angeli's salt, a new type of DNICs bound with carnosine as ligand {(carnosine)2-Fe-(NO)2}, was formed. We studied how the carbonyl compound methylglyoxal influenced this process. Carnosine-bound DNICs appear to be one of the cell's adaptation mechanisms when the amount of reactive carbonyl compounds increases at hyperglycemia...
November 22, 2016: Journal of Biological Inorganic Chemistry: JBIC
Hiu Chuen Lok, Sumit Sahni, Patric J Jansson, Zaklina Kovacevic, Clare L Hawkins, Des R Richardson
Nitric oxide (NO) is integral to macrophage cytotoxicity against tumors due to its ability to induce iron release from cancer cells. However, the mechanism how activated macrophages protect themselves from endogenous NO remains unknown. We previously demonstrated using tumor cells that glutathione S-transferase P1 (GSTP1) sequesters NO as dinitrosyl-dithiol iron complexes (DNICs) and inhibits NO-mediated iron release from cells via the transporter, multidrug resistance protein 1 (MRP1/ABCC1). These prior studies also showed that MRP1 and GSTP1 protect tumor cells against NO cytotoxicity, which parallels their roles in defending cancer cells from cytotoxic drugs...
November 19, 2016: Journal of Biological Chemistry
Anne A Fischer, Nuru Stracey, Sergey V Lindeman, Thomas C Brunold, Adam T Fiedler
Mononuclear non-heme iron complexes that serve as structural and functional mimics of the thiol dioxygenases (TDOs), cysteine dioxygenase (CDO) and cysteamine dioxygenase (ADO), have been prepared and characterized with crystallographic, spectroscopic, kinetic, and computational methods. The high-spin Fe(II) complexes feature the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine ((Ph2)TIP) ligand that replicates the three histidine (3His) triad of the TDO active sites. Further coordination with bidentate l-cysteine ethyl ester (CysOEt) or cysteamine (CysAm) anions yielded five-coordinate (5C) complexes that resemble the substrate-bound forms of CDO and ADO, respectively...
November 1, 2016: Inorganic Chemistry
Shou-Cheng Wu, Chung-Yen Lu, Yi-Lin Chen, Feng-Chun Lo, Ting-Yin Wang, Yu-Jen Chen, Shyng-Shiou Yuan, Wen-Feng Liaw, Yun-Ming Wang
Nitric oxide (NO) is an important cellular signaling molecule that modulates various physiological activities. Angiogenesis-promoting activities of NO-donor drugs have been explored in both experimental and clinical studies. In this study, a structurally well characterized and water-soluble neutral {Fe(NO)2}(9) DNIC [(S(CH2)2OH)(S(CH2)2NH3)Fe(NO)2] (DNIC 2) was synthesized to serve as a NO-donor species. The antitumor activity of DNIC 2 was determined by MTT assay, confocal imaging, and Annexin-V/PI staining...
September 19, 2016: Inorganic Chemistry
Yubin M Kwon, Mayra Delgado, Lev N Zakharov, Takele Seda, John D Gilbertson
The proton-responsive pyridinediimine ligand, (DEA)PDI (where (DEA)PDI = [(2,6-(i)PrC6H3)(N[double bond, length as m-dash]CMe)(N(Et)2C2H4)(N[double bond, length as m-dash]CMe)C5H3N]) was utilized for the reduction of NO2(-) to NO. Nitrite reduction is facilitated by the protonated secondary coordination sphere coupled with the ligand-based redox-active sites of [Fe(H(DEA)PDI)(CO)2](+) and results in the formation of the {Fe(NO)2}(9) DNIC, [Fe((DEA)PDI)(NO)2](+).
September 21, 2016: Chemical Communications: Chem Comm
F Wittkamp, C Nagel, P Lauterjung, B Mallick, U Schatzschneider, U-P Apfel
Here we present the syntheses and structural, spectroscopic, as well as electrochemical properties of four dinitrosyl iron complexes (DNICs) based on silicon- and carbon-derived di- and tripodal phosphines. Whereas CH3C(CH2PPh2)3 and Ph2Si(CH2PPh2)2 coordinate iron in a η(2) - binding mode, CH3Si(CH2PPh2)3 undergoes cleavage of one Si-C bond to afford [Fe(NO)2(P(CH3)Ph2)2] at elevated temperatures. The complexes were characterized by IR spectroelectrochemistry as well as UV-vis measurements. The oxidized {Fe(NO)2}(9) compounds were obtained by oxidation with (NH4)2[Ce(NO3)6] and their properties evaluated with Mössbauer and IR spectroscopy...
June 21, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
Amy L Speelman, Bo Zhang, Alexey Silakov, Kelsey M Skodje, E Ercan Alp, Jiyong Zhao, Michael Y Hu, Eunsuk Kim, Carsten Krebs, Nicolai Lehnert
Dinitrosyl iron complexes (DNICs) are among the most abundant NO-derived cellular species. Monomeric DNICs can exist in the {Fe(NO)2}(9) or {Fe(NO)2}(10) oxidation state (in the Enemark-Feltham notation). However, experimental studies of analogous DNICs in both oxidation states are rare, which prevents a thorough understanding of the differences in the electronic structures of these species. Here, the {Fe(NO)2}(9) DNIC [Fe(dmp)(NO)2](OTf) (1; dmp = 2,9-dimethyl-1,10-phenanthroline) is synthesized from a ferrous precursor via an unusual pathway, involving disproportionation of an {FeNO}(7) complex to yield the {Fe(NO)2}(9) DNIC and a ferric species, which is subsequently reduced by NO gas to generate a ferrous complex that re-enters the reaction cycle...
May 20, 2016: Inorganic Chemistry
Yasuo Itomi, Yasuhiro Tsukimi, Toru Kawamura
Fibromyalgia is characterized by chronic widespread musculoskeletal pain. A hypofunction in descending pain inhibitory systems is considered to be involved in the chronic pain of fibromyalgia. We examined functional changes in descending pain inhibitory systems in rats with specific alternation of rhythm in temperature (SART) stress, by measuring the strength of diffuse noxious inhibitory controls (DNIC). Hindpaw withdrawal thresholds to mechanical von Frey filament or fiber-specific electrical stimuli by the Neurometer system were used to measure the pain response...
August 5, 2016: European Journal of Pharmacology
Anatoly F Vanin
The material presented herein is an overview of the results obtained by our research team during the many years' study of biological activities and occurrence of dinitrosyl iron complexes (DNIC) with thiol-containing ligands in human and animal organisms. With regard to their dose dependence and vast diversity of biological activities, DNIC are similar to the system of endogenous NO, one of the most universal regulators of biological processes. The role of biologically active components in DNIC is played by their iron-dinitrosyl fragments, [Fe(NO)2], endowed with the ability to generate neutral NO molecules and nitrosonium ions (NO(+))...
April 1, 2016: Nitric Oxide: Biology and Chemistry
A K Martusevich, A G Soloveval, A V Davydyuk, S P Peretyagin
We have studied the effect of dinitrosyl iron complexes (DNIC) on blood lipid peroxidation and antioxidant system under experimental thermal trauma (burn) conditions in three groups of rats, each containing 10 animals. Group 1 was intact control, groups 2 and 3 were subjected to model thermal trauma, and group 3 were daily intraperitoneally injected with 3 ml of 0.3 mM of aqueous DNIC solution for 10 days. In addition, the DNIC solution action was studied in vitro on isolated human blood with oxidative stress conditions induced by high doses of ozone...
2015: Eksperimental'naia i Klinicheskaia Farmakologiia
Tzung-Wen Chiou, Tsai-Te Lu, Ying-Hao Wu, Yi-Ju Yu, Li-Kang Chu, Wen-Feng Liaw
Despite extensive efforts, the electrocatalytic reduction of water using homogeneous/heterogeneous Fe, Co, Ni, Cu, W, and Mo complexes remains challenging because of issues involving the development of efficient, recyclable, stable, and aqueous-compatible catalysts. In this study, evolution of the de novo designed dinitrosyl iron complex DNIC-PMDTA from a molecular catalyst into a solid-state hydrogen evolution cathode, considering all the parameters to fulfill the electronic and structural requirements of each step of the catalytic cycle, is demonstrated...
December 1, 2015: Angewandte Chemie
Yu-Ting Tseng, Chien-Hong Chen, Jing-Yu Lin, Bing-Han Li, Yu-Huan Lu, Chia-Her Lin, Hsin-Tsung Chen, Tsu-Chien Weng, Dimosthenes Sokaras, Huang-Yeh Chen, Yun-Liang Soo, Tsai-Te Lu
A positive myocardial inotropic effect achieved using HNO/NO(-) , compared with NO⋅, triggered attempts to explore novel nitroxyl donors for use in clinical applications in vascular and myocardial pharmacology. To develop M-NO complexes for nitroxyl chemistry and biology, modulation of direct nitroxyl-transfer reactivity of dinitrosyl iron complexes (DNICs) is investigated in this study using a Fe(III) -porphyrin complex and proteins as a specific probe. Stable dinuclear {Fe(NO)2 }(9) DNIC [Fe(μ-(Me) Pyr)(NO)2 ]2 was discovered as a potent nitroxyl donor for nitroxylation of Fe(III) -heme centers through an associative mechanism...
December 1, 2015: Chemistry: a European Journal
Peter Dungel, Martin Perlinger, Adelheid Weidinger, Heinz Redl, Andrey V Kozlov
Nitrite protects various organs from ischemia-reperfusion injury by ameliorating mitochondrial dysfunction. Here we provide evidence that this protection is due to the inhibition of iron-mediated oxidative reactions caused by the release of iron ions upon hypoxia. We show in a model of isolated rat liver mitochondria that upon hypoxia, mitochondria reduce nitrite to nitric oxide (NO) in amounts sufficient to inactivate redox-active iron ions by formation of inactive dinitrosyl iron complexes (DNIC). The scavenging of iron ions in turn prevents the oxidative modification of the outer mitochondrial membrane and the release of cytochrome c during reoxygenation...
December 2015: Free Radical Biology & Medicine
Shih-Wey Yeh, Chih-Wei Lin, Bai-Heng Liu, Chih-Chin Tsou, Ming-Li Tsai, Wen-Feng Liaw
As opposed to the reversible redox reaction ({Fe(NO)2 }(10) reduced-form DNIC [(NO)2 Fe(S(CH2 )3 S)](2-) (1)⇌{Fe(NO)2 }(9) oxidized-form [(NO)2 Fe(S(CH2 )3 S)](-) ), the chemical oxidation of the {Fe(NO)2 }(10) DNIC [(NO)2 Fe(S(CH2 )2 S)](2-) (2) generates the dinuclear {Fe(NO)2 }(9) -{Fe(NO)2 }(9) complex [(NO)2 Fe(μ-SC2 H4 S)2 Fe(NO)2 ](2-) (3) bridged by two terminal [SC2 H4 S](2-) ligands. On the basis of the Fe K-edge pre-edge energy and S K-edge XAS, the oxidation of complex 1 yielding [(NO)2 Fe(S(CH2 )3 S)](-) is predominantly a metal-based oxidation...
November 2, 2015: Chemistry: a European Journal
Alexander А Тimoshin, Vladimir L Lakomkin, Alexander А Аbramov, Enno K Ruuge, Valery I Kapel'ko, Evgeny I Chazov, Anatoly F Vanin
Earlier it has been found that the hypotensive drug Oxacom containing binuclear dinitrosyl iron complexes (B-DNIC) with glutathione can effectively decrease, as a nitric monooxide (NO) donor, the mean arterial pressure (МАР) in rats upon intravenous bolus injection in the form of an aqueous solution (Chazov et al., 2012). The aim of this study was to investigate the hypotensive effects of Oxacom administered to experimental rats by intravenous, intramuscular, subcutaneous, intraperitoneal, intragastric, rectal routes...
October 15, 2015: European Journal of Pharmacology
Diana M Torta, Maxim V Churyukanov, Leon Plaghki, André Mouraux
Human studies have shown that heterotopic nociceptive conditioning stimulation (HNCS) applied to a given body location reduces the percept and brain responses elicited by noxious test stimuli delivered at a remote body location. It remains unclear to what extent this effect of HNCS relies on the spinal-bulbar-spinal loop mediating the effect of diffuse noxious inhibitory controls (DNICs) described in animals, and/or on top-down cortical mechanisms modulating nociception. Importantly, some studies have examined the effects of HNCS on the brain responses to nociceptive input conveyed by Aδ-fibres...
November 2015: European Journal of Neuroscience
Yasuo Itomi, Toru Kawamura, Yasuhiro Tsukimi
It is known that specific alteration of rhythm in temperature (SART) stress produces somatic pain. However, it remains to be investigated whether SART stress induces visceral pain. In this study, we investigated the visceral hypersensitivity in the SART stress model by pharmacological tools and heterotopical nociception. Four-week-old Sprague-Dawley rats were exposed to repeated cold stress. Visceral pain was measured by visceromotor response to colorectal distension, and the effects of alosetron and duloxetine on visceral pain were investigated in SART rats...
September 2015: Journal of Pharmacological Sciences
Jessica Fitzpatrick, Eunsuk Kim
Nitric oxide (NO) is an important signaling molecule that is involved in many physiological and pathological functions. Iron-sulfur proteins are one of the main reaction targets for NO, and the [Fe-S] clusters within these proteins are converted to various iron nitrosyl species upon reaction with NO, of which dinitrosyl iron complexes (DNICs) are the most prevalent. Much progress has been made in identifying the origin of cellular DNIC generation. However, it is not well-understood which other products besides DNICs may form during [Fe-S] cluster degradation nor what effects DNICs and other degradation products can have once they are generated in cells...
August 18, 2015: Accounts of Chemical Research
Randara Pulukkody, Marcetta Y Darensbourg
Resulting from biochemical iron-NO interactions, dinitrosyl iron complexes (DNICs) are small organometallic-like molecules, considered to serve as vehicles for NO transport and storage in vivo. Formed by the interaction of NO with cellular iron sulfur clusters or with the cellular labile iron pool, DNICs have been documented to be the largest NO-derived adduct in cells, even surpassing the well-known nitrosothiols (RSNOs). Continuing efforts in biological chemistry are aimed at understanding the movement of DNICs in and out of cells, and their important role in NO-induced iron efflux leading to apoptosis in cells...
July 21, 2015: Accounts of Chemical Research
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