10102-43-9Relevant articles and documents
Photodissociation of NO2 Adsorbed on LiF(001)
Dixon-Warren, St. J.,Jackson, R. C.,Polanyi, J. C.,Rieley, H.,Shapter, J. G.,Weiss, H.
, p. 10983 - 10994 (1992)
The photochemistry of NO2 physisorbed on single-crystal LiF(001) at 100 K has been studied at λ1 = 248 nm.The adsorbate was examined by polarized FTIR in both the presence and absence of λ1 radiation.In the absence of UV irradiation the adlayer is composed of dimeric (NO2)2.In the presence of UV, FTIR shows that some N2O3 is formed.Photodissociations(PDIS) giving both NO(g) and molecular NO2(g) were the predominant mechanisms as determined by time-of-flight mass spectrometry (TOF-MS) and resonantly enhanced multiphoton ioniziation (REMPI).The main objective of this work was the characterization of the photoproduct, NO, internal state distribution by 1 + 1 REMPI.Vibrational levels from v = 0 to 9 were probed with rotational resolution using a tunable laser, λ2.The rotational distributions for each vibrational level could be described by one Boltzmann temperature.The spin-orbit states of NO(g) were equally populated in all vibrational levels.The lambda doublet states, Π(A') and Π(A ), were equally populated.The principal observation was that the vibrational distribution in NO(g) was inverted and bimodal with a peak in v = 0 and a second substantial peak in v = 3-4, qualitatively resembling but qualitatively different from that for photolysis of NO2(g).Time delays between the two lasers were used to probe the translational energy of the NO(g) photofragment in specified states of internal excitation.The transational energy distributions were invariant over all vibrational levels, except v = 0 for which much slower fragments were observed.This complete determination of the energy distribution in the degrees of freedom of the NO(g) from photodissociation of adsorbate has implications for the identity of the photolyzing species and the dynamics of photodissociation.Two mechanisms for photoformation of NO2(g) were found: one at low coverages and one at higher coverages, the former giving peak translational energies ca. 1.2 kcal/mol and the latter 0.4 kcal/mol.
A laser flash photolysis study of nitrous acid in the aqueous phase
Ouyang, Bin,Dong, Wenbo,Hou, Huiqi
, p. 306 - 311 (2005)
The OH quantum yield from the photolysis of nitrous acid in the aqueous phase by the 355 nm light was measured to be 0.25 ± 0.03. OH radical thus formed reacted readily with HNO2 to produce NO2, which sequentially reacted with HNO2 to form the HNO2-NO 2 adduct. The NO2 + HNO2 reaction was reversible with a forward rate constant of 3.76 × 107 dm 3 mol-1 s-1 and a backward rate constant of 1.06 × 105 s-1. Decay of the HNO2-NO 2 adduct would most likely generate HNO3 and NO at a rate constant of 3.0 × 103 s-1.
Photolysis of the (2-) Ion in Water and Poly(vinyl alcohol) Films: Evidence for Cyano Radical, Cyanide Ion and Nitric Oxide Loss and Redox Pathways
Oliveira, Marcelo G. de,Langley, G. John,Rest, Antony J.
, p. 2013 - 2020 (1995)
Ultraviolet-visible and IR spectroscopy and mass spectrometry have been used to investigate photolysis of the (2-) ion upon irradiation with UV/VIS light in aqueous solutions and in poly(vinyl alcohol) films at 12 and 298 K.Changes in the ν(CN) and ν(NO) bands in the IR and in the d-d and charge-transfer bands in the UV/VIS region were used to monitor the appearance and disappearance of complex ions as a function of photolysis time.Mass spectrometric analysis of the gaseous products released during the irradiation of aqueous solutions revealed NO, HCN, and (CN)2.The combined results showed that the (2-) ion undergoes photoaquation and photoreduction, producing aquacyanoferrate-(III) and -(II) species.The origin of the iron(II) species was shown to be mainly due to the photoreduction of the iron(III) species produced after primary loss of the nitrosyl ligand as molecular NO and not as NO(1+).Subsequent thermal reactions between the iron-(II) and -(III) species led to the formation of mixed-valence compounds, e.g.Prussian blue.A scheme for the photochemical and thermal reactions with CN(.), CN(1-) and NO loss pathways is proposed.The possible implications of the results for the use of (2-) as a vasodilator are discussed.
Ray, P. C.
, p. 523 - 527 (1904)
Widely differing photochemical behavior in related octahedral {Ru-NO} 6 compounds: Intramolecular redox isomerism of the excited state controlling the photodelivery of NO
De Candia, Ariel G.,Marcolongo, Juan P.,Etchenique, Roberto,Slep, Leonardo D.
, p. 6925 - 6930 (2010)
trans-[(NC)Ru(py)4(μ-CN)Ru(py)4(NO)]3+ (py = pyridine) is a stable species in aqueous solution. It displays an intense absorption in the visible region of the spectrum (λmax = 518 nm; εmax = 6100 M-1 cm-1), which turns this compound into a promising agent for the photodelivery of NO. The quantum yield for the photodelivery process resulting from irradiation with 455 nm visible light was found experimentally to be (0.06 ± 0.01)×10 -3 mol einstein-1, almost 3 orders of magnitude smaller than that in the closely related cis-[RuL(NH3)4(μ-pz) Ru(bpy)2(NO)]5+ species (L = NH3 or pyridine, pz = pyrazine, bpy = 2,2′-bipyridine; φNO = 0.02-0.04 mol einstein-1 depending on L) and also much smaller than the one in the mononuclear compound trans-[ClRu(py)4(NO)]2+ (φNO = (1.63 ± 0.04)×10-3 mol einstein-1). DFT computations provide an electronic structure picture of the photoactive excited states that helps to understand this apparently abnormal behavior.
Randeniya, Lakshman K.,Zeng, Xiangkang,Smith, M. A.
, p. 346 - 352 (1988)
Scott, D. C.,Winterbottom, F.,Scholefield, M. R.,Goyal, S.,Reisler, H.
, p. 471 - 480 (1994)
State-resolved photofragmentation of [ClNO]n van der Waals clusters in a supersonic jet
Conde, Carlos,Maul, Christof,Quinones, Edwin
, p. 1929 - 1938 (1999)
The effects of the ultraviolet laser irradiation of [ClNO]2, weakly bound clusters, formed in a supersonic jet, are analyzed by considering three processes: the photofragmentation of bare ClNO, the Cl+ClNO reaction, and NO relaxation within the cluster. The photofragmentation of jet-cooled ClNO at 355 nm produces NO (υ″ = 1) with a kinetic energy of 2240 cm-1, a spin-orbit preference of F1/F2 = 1.2, and Λ-doublet state preferences of Π(A″)/Π±(A″) = 2.0 and 4.0 for the F1 and F2 manifolds, respectively. The NO distribution of rotational states was parametrized using a Gaussian function centered at N = 34, with a fwhm of 17. On the other hand, the Cl+ClNO reaction, studied at a collision energy of 2780 cm-1, gives NO(υ″ = 1) described by a Boltzmann rotational distribution with Trot = 950±100 K. The relative population of the NO spin-orbit states is F1/F2 = 2.5, with a Λ-doublet state preference of Π(A″)/Π(A′) = 1.2 and Etrans(NO) of 578 cm-1. It is found that 57% of available energy is disposed as Eint(Cl2). As a result of the irradiation of the [ClNO]n, clusters at 355 nm are observed: Boltzmann ensembles of NO(υ″ = 1) and NO(υ″ = 0) molecules described by Trot of 310±30 and 170±25 K, respectively, with no spin-orbit or Λ-doublet state preferences, overlapped with a Gaussian distribution already assigned to the NO photofragment. The relative contribution of the NO(υ″ = 1) photofragment to the spectra is drastically reduced upon increasing the backing pressure, as it undergoes translational and rotational relaxation within the clusters. Our high-resolution studies provide evidence that suggests that the reaction takes place within the [ClNO]n clusters.
Wu, Yue,Yu, Tao,Dou, Bo-Sheng,Wang, Cheng-Xian,Xie, Xiao-Fan,et al.
, p. 88 - 107 (1989)
Laser Photolysis Studies of Nitric Oxide Adducts of Cobalt(II) Porphyrins. Photoinduced Denitrosylation at the Temperature Range 160-300 K
Hoshino, Mikio,Arai, Shigeyoshi,Yamaji, Minoru,Hama, Yoshimasa
, p. 2109 - 2111 (1986)
Laser photolysis studies reveal that nitric oxide cobalt(II) porphyrins in 2-methyltetrahydrofuran solutions undergo facile photolytic dissociation to yield nitric oxide and cobalt(II) porphyrin.The quantum yields for the photodissociation of nitric oxide
Henry, L.
, p. 498 (1934)
Production of reactive oxygen and nitrogen species by light irradiation of a nitrosyl phthalocyanine ruthenium complex as a strategy for cancer treatment
Heinrich, Tassiele A.,Tedesco, Antonio Claudio,Fukuto, Jon M.,Da Silva, Roberto Santana
, p. 4021 - 4025 (2014)
Production of reactive oxygen species has been used in clinical therapy for cancer treatment in a technique known as Photodynamic Therapy (PDT). The success of this therapy depends on oxygen concentration since hypoxia limits the formation of reactive oxygen species with consequent clinical failure of PDT. Herein, a possible synergistic effect between singlet oxygen and nitric oxide (NO) is examined since this scenario may display increased tumoricidal activity. To this end, the trinuclear species [Ru(pc)(pz)2{Ru(bpy) 2(NO)}2](PF6)6(I) (pc = phthalocyanine; pz = pyrazine; bpy = bipyridine) was synthesized to be a combined NO and singlet oxygen photogenerator. Photobiological assays using (I) at 4 × 10-6 M in the B16F10 cell line result in the decrease of cell viability to 21.78 ± 0.29% of normal under light irradiation at 660 nm. However, in the dark and at the same concentration of compound (I), viability was 91.82 ± 0.37% of normal. The potential application of a system like (I) in clinical therapy against cancer may be as an upgrade to normal photodynamic therapy.
Two-photon spectroscopy of the low lying Rydberg states of NO. I. The 3p and 3d complexes
Meyer, Henning
, p. 7721 - 7731 (1997)
The rotational structure and polarization dependence of two-photon spectra of aligned ensembles of open shell diatomics is investigated in terms of the spherical tensor components of the two-photon absorption operator. The formalism allows the straightforward incorporation of state interactions and perturbations. It is applied to the two-photon spectroscopy of NO, in particular to the excitation of the Rydberg states derived from the 3p and 3d complexes. All states investigated show a nearly quadratic power dependence indicating the saturation of the ionization step. Transitions dominated by a zeroth rank tensor component (e.g., C 2Π-X 2Π or H 2Σ, H′ 2Π-X 2Π) are insensitive to a possible angular momentum alignment in the ensemble. These transitions are ideally suited to determine degeneracy averaged observables, e.g., collision cross sections in a molecular beam scattering experiment or product velocity anisotropies in a single color photodissociation experiment. Rotational alignment data must be determined using two-photon transitions which are carried by a second rank tensor component (e.g., D 2Σ-X 2Π or F 2Δ-X 2Π).
Nitric Oxide Reacts Very Fast with Hydrogen Sulfide, Alcohols, and Thiols to Produce HNO: Revised Rate Constants
Neuman, Nicolas I.,Venancio, Mateus F.,Rocha, Willian R.,Bikiel, Damian E.,Suárez, Sebastián A.,Doctorovich, Fabio
, p. 15997 - 16007 (2021)
The chemical reactivity of NO and its role in several biological processes seem well established. Despite this, the chemical reduction of ?NO toward HNO has been historically discarded, mainly because of the negative reduction potential of NO. However, this value and its implications are nowadays under revision. The last reported redox potential, E′(NO,H+/HNO), at micromolar and picomolar concentrations of ?NO and HNO, respectively, is between -0.3 and 0 V at pH 7.4. This potential implies that the one-electron-reduction process for NO is feasible under biological conditions and could be promoted by well-known biological reductants with reduction potentials of around -0.3 to -0.5 V. Moreover, the biologically compatible chemical reduction of ?NO (nonenzymatic), like direct routes to HNO by alkylamines, aromatic and pseudoaromatic alcohols, thiols, and hydrogen sulfide, has been extensively explored by our group during the past decade. The aim of this work is to use a kinetic modeling approach to analyze electrochemical HNO measurements and to report for the first-time direct reaction rate constants between ?NO and moderate reducing agents, producing HNO. These values are between 5 and 30 times higher than the previously reported keff values. On the other hand, we also showed that reaction through successive attack by two NO molecules to biologically compatible compounds could produce HNO. After over 3 decades of intense research, the ?NO chemistry is still there, ready to be discovered.
Ashmore, P. G.,Burnett, M. G.
, p. 1315 - 1324 (1961)
Kinetic Study of the Equilibrium HO2 + NO OH + NO2 and the Thermochemistry of HO2
Howard, Carleton J.
, p. 6937 - 6941 (1980)
Rate constants for the reactions HO2 + NO -> NO2 (kF) and OH + NO2 -> HO2 + NO (kR) have been measured at high temperatures by using laser magnetic resonance ddtection of HO2 and OH reactants in a flow tube reactor.The results are kF(T) = (3.51 +/- 0.35) * 10-12 exp cm3 molecule-1 s-1 for 232 R(T) = (3.03 +/- 0.60) * 10-11 exp cm3 molecule-1 s-1 for 452 = 2.5 +/- 0.6 kcal mol-1.Other measurements of this quantity and the thermochemistry of HO2 are discussed.
Divers, E.,Haga, T.
, p. 48 (1887)
Synthesis, characterization and photochemical properties of some ruthenium nitrosyl complexes
Kumar, Amit,Pandey, Rampal,Gupta, Rakesh Kumar,Ghosh, Kaushik,Pandey, Daya Shankar
, p. 837 - 843 (2013)
Synthesis of new nitrosyl complexes [RuCl3(CNPy) 2(NO)] (1), [RuCl3(AMPy)2(NO)] (2), [RuCl 3(CPI)2(NO)] (3), [RuCl3(NOPI)2(NO)] (4), and [RuCl3(HPI)2/
Black, G.,Sharpless, R. L.,Slanger, T. G.
, p. 55 - 58 (1982)
Ogai, A.,Qian, C. X. W.,Iwata,L.,Reisler, H.
, p. 367 - 374 (1988)
Selective Catalytic Reduction of Nitric Oxide with Ammonia on MFI-Type Ferrisilicate
Uddin, Md. Azhar,Komatsu, Takayuki,Yashima, Tatsuaki
, p. 3275 - 3280 (1995)
The catalytic properties of framework Fe(3+) in MFI-type H-ferrisilicate for the selective reduction of nitric oxide with ammonia in the presence of oxygen have been investigated and compared with those of Fe-exchanged ZSM-5, iron oxide supported on silicalite and HZSM-5.H-ferrisilicate exhibited a high activity and selectivity for the reduction of nitric oxide into nitrogen.A side reaction, i.e. the oxidation of ammonia with oxygen into nitrogen, occured only above 773 K.The activity and selectivity of Fe-exchanged ZSM-5 for the reduction of nitric oxide were comparable to those of H-ferrisilicate, while iron oxide supported on silicalite catalysed the oxidation of ammonia with oxygen into nitric oxide preferentially under the same reaction conditions.The catalytic activity of HZSM-5 for this reaction was much lower than that of H-ferrisilicate.Therefore, the framework Fe(3+) ions in H-ferrisilicate are the active sites for the selective catalytic reduction of nitric oxide.
Kinetics of SH with NO2, O3, O2, and H2O2
Friedl, Randall R.,Brune, William H.,Anderson, James G.
, p. 5505 - 5510 (1985)
A low pressure (1-8 torr of He) discharge flow reactor with (a) LIF detection of SH using a high repetition rate (20 kHz) metal atom laser to circumvent severe predissociation of the A2Σ+ state and (b) resonance fluorescence detection of OH has been used to examine the kinetics of the title reactions at 298 K: SH + NO2 -> HSO + NO, k1=(3.0+/-0.8)x10-11 cm3s-1; SH + O3 -> HSO + O2,k2 = (3.2+/- 1.0)x10-12cm3s-1;SH + O2 -> SO + OH,k3 -17 cm3s-1;SH + H2O2 -> H2S + HO2,k4a;SH + H2O2 -> HSOH + OH,k4b;SH + H2O2 -> HSO + H2O,k4c. k4=k4a+k4b+k4c-15 cm3s-1.Regeneration of SH in reaction 2 by HSO + O3 is observed and is used to infer a rate constant for HSO + O3 -> products of (1.0+/-0.4)x10-13cm3s-1.Absence of OH production in that reaction implies that the primary products are SH + 2O2.Isotope experiments with H2S replaced by D2S substantiate that conclusion and yield a reaction rate constant for DSO + O3 -> SD + 2O2 of 9x10-14 cm3s-1.Brief discussions of SH reactivity compared with OH and Br are offered, as well as a summary of the atmospheric chemistry of SH.
Photochemical and pharmacological aspects of nitric oxide release from some nitrosyl ruthenium complexes entrapped in sol-gel and silicone matrices
de Lima, Renata Galv?o,Sauaia, Marilia Gama,Ferezin, Camila,Pepe, Iuri Muniz,José, Nádia Mamede,Bendhack, Lusiane M.,da Rocha, Zênis Novais,da Silva, Roberto Santana
, p. 4620 - 4624 (2007)
The entrapped [Ru(terpy)(L)NO](PF6)3, where terpy = 2,2′:6′,2″-terpyridine and L = 2,2′-bipyridine (bpy) and 3,4-diiminebenzoic acid (NH · NHq) complexes into sol-gel processed polysiloxane and silicone matrices, shows NO release characteristics when submitted to light irradiation at 355 and 532 nm, as judged by NO measurement using a NO-sensor electrode. The pharmacological properties of doped matrix showed vasodilator characteristics by visible light irradiation, which is of great interest because the target delivery system can avoid the occurrence of side effects possibly by the aquo ruthenium species. All matrices obtained showed to be amorphous materials. The scanning electron micrographs of the matrices showed irregularly shaped particles, with a broad size of 1000 μm for both matrices and homogeneous distribution.
O-Atom Yields from Microwave Discharges in N2O/Ar Mixtures
Piper, Lawrence G.,Rawlins, Wilson T.
, p. 320 - 325 (1986)
We have studied the products of Ar/N2O microwave discharges to determine their fitness as sources of atomic oxygen in discharge-flow reactors.For N2O feed rates below 10 to 20 μmol s-1, the discharge converts about 75percent of the N2O to atomic oxygen and, in addition, prduces small quantities of atomic nitrogen, generally less than 10percent of the O-atom product.At higher N2O feed rates the O-atom production efficiency decreases, and some nitric oxide accompanies the O atoms out of the discharge.At intermediate N2O feed rates, only atomic oxygen is observed, and neither N nor NO leaves the discharge.The exact point at which this occurs is a function of the discharge power and the Ar/N2O mixing ratio.Adding molecular nitrogen to the discharge eliminates any NO product, but at the penalty of a slightly reduced O-atom production efficiency.Atomic oxygen flows in excess of 20 μmol s-1 are produced at pressures near 1 torr and dicharge powers of only 30 W.In kinetic modeling of the discharge chemistry, we can account for the experimental observations only if the electron-impact dissociation of the N2O in the discharge proceeds through a spin-forbidden channel to produce O(3P).In addition, the model indicates that about 10-20percent of the N2O dissociations resuts from collisions between metastable argon atoms in the discharge and N2O.
DIODE LASER KINETIC STUDIES OD RADICAL REACTIONS. 1. REACTION OF CF3 RADICALS WITH NO2
Sugawara, Ko-ichi,Nakanaga, Taisuke,Takeo, Harutoshi,Matsumura, Chi
, p. 1894 - 1898 (1989)
The reaction of CF3 radicals with NO2 has been studied over the pressure range 4-20 Torr at 300 K.CF3 radicals were produced by infrared multiphoton dissociation of CF3I.The subsequent decay of the radicals was monitored by using time-resolved diode laser
Ceria Nanoparticles as an Unexpected Catalyst to Generate Nitric Oxide from S-Nitrosoglutathione
Chandrawati, Rona,Gao, Yuan,Kumar, Priyank,Luo, Zijie,Yang, Tao,Zhou, Yingzhu
, (2022/01/24)
Ceria nanoparticles (NPs) are widely reported to scavenge nitric oxide (NO) radicals. This study reveals evidence that an opposite effect of ceria NPs exists, that is, to induce NO generation. Herein, S-nitrosoglutathione (GSNO), one of the most biologically abundant NO donors, is catalytically decomposed by ceria NPs to produce NO. Ceria NPs maintain a high NO release recovery rate and retain their crystalline structure for at least 4 weeks. Importantly, the mechanism of this newly discovered NO generation capability of ceria NPs from GSNO is deciphered to be attributed to the oxidation of Ce3+ to Ce4+ on their surface, which is supported by X-ray photoelectron spectroscopy and density functional theory analysis. The prospective therapeutic effect of NO-generating ceria NPs is evaluated by the suppression of cancer cells, displaying a significant reduction of 93% in cell viability. Overall, this report is, to the authors’ knowledge, the first study to identify the capability of ceria NPs to induce NO generation from GSNO, which overturns the conventional concept of them acting solely as a NO-scavenging agent. This study will deepen our knowledge about the therapeutic effects of ceria NPs and open a new route toward the NO-generating systems for biomedical applications.
Nitric oxide generation study of unsymmetrical β-diketiminato copper(ii) nitrite complexes
Chand, Kuldeep,Chu, Yu-Cheng,Hsu, Sodio C. N.,Kao, Chai-Lin,Lin, Ya-Fan,Tsai, Ming-Li,Wang, Tzai-Wei
supporting information, p. 3485 - 3496 (2022/03/14)
β-Diketiminato copper(ii) L1CuCl-L4CuCl and their nitrite complexes L1Cu(O2N) and L2Cu(O2N) have been synthesized and characterized. X-ray analysis of the L1CuCl-L4CuCl complexes clearly reveals their mononuclear structure with a four-coordinated Cu(ii) center bound by one chloride and three nitrogen atoms of unsymmetrical β-diketiminato ligands. Cyclic voltametric analysis of the Cu(ii) complexes shows that the length of the pyridyl arm controls the Cu(ii)/Cu(i) redox process. DFT and EPR results confirm that the geometry of the Cu(ii) complexes is also controlled by the length of the chelating pyridyl arm. The oxygen atom transfer nitrite reduction of the Cu(ii) nitrite complexes leads to the formation of copper(i)-PPh3 and OPPh3 which were confirmed by 1H and 31P NMR. The length of the pyridyl arm of the copper(ii) nitrite complexes governs the NO-releasing ability. These findings illustrate the important bioinspired behaviour and NO generation from nitrite via oxygen atom transfer of the unsymmetrical β-diketiminato copper(ii) complexes as compared to symmetrical β-diketiminato copper(ii) complexes.
