ClNO Research Articles

Intensification of opening a thrust alloy based on platinum and rhodium

A high chemical resistance inherent in the alloys based on platinum group metals is one of the reasons for a number of difficulties that arise when dissolving such materials. Nowadays, the dissolution in aqua regia is one of the most effective methods for dissolving corrosion-resistant alloys. The main disadvantage of this method is a release of toxic gaseous substances such as nitrosyl chloride and nitrogen oxides. To decrease the volume of gases thus released without reducing the redox potential of the system, we proposed a method of dissolving a Pt – Rh alloy in HCl-HNO3 with a controlled dosed supply of HNO3 at a given value of the oxidation-reduction potential (ORP) of the system. The potential of the system has been chosen proceeding from the potential for HNO3 – HCl – Pt and HNO3 – HCl-Rh systems and amounted to 0.85 and 0.9 V. The impact of the dispersion and the inherent flaw of PtRh alloys on the dissolution indices of the alloy was also considered. It is shown that the dissolution of a Pt – Rh alloy with a rhodium content of 15 % in HCl – HNO3 at a constant value of ORP = 0.9 V compared to the use of the classic mixture (HCl:HNO3 = 1:3 vol.) provides a decrease in nitric acid consumption by 40%, reduction of the process time, increase in the recovery factor for both platinum and rhodium, and a two-fold reduction of the volume of released nitrogen oxides (theoretical calculation). It is also revealed that the process of mechanical activation of the alloy reduces the dissolution time and leads to almost quantitative dissolution of the sample.

High- dose nitric oxide gas inhalation for HIV infection

Therapeutic effect of high-dose nitric oxide gas inhalation (NO concentration was not less than than 1000 ppm) on two patients with HIV infection was shown. Inhaled NO therapy led to a rapid decrease in viral load to an undetectable level which was persistent even after analytical treatment interruption. It is suggested that HIV infection is controlled by nitrosonium (NO+) cations, the oxidized form of neutral NO molecules that enter the blood. Subsequent conversion of NO+ cations into nitrite anions due to a reaction with hydroxyl ions is inhibited by the binding of NO+ cations and chloride anions leading to the formation of nitrosyl chloride in the blood. Further entry of nitrosyl chloride into cells and tissues ensures NO+ transfer to them. Interaction between nitrosyl chloride and thiols requires the appearance of relevant S-nitrosothiols as NO donors in cells and tissues.

Critical Role of Trichloramine Interaction with Dichloramine for N-Nitrosamine Formation during Breakpoint Chlorination.

Breakpoint chlorination is prevalent in drinking water and potable reuse water treatment. Breakpoint chlorination enhances the formation of N-nitrosamines through reactions that form nitrosating agents. The most recent study suggests that nitroxyl (HNO) can react with free chlorine (HOCl) to form the nitrosyl chloride (ClNO) nitrosating agent but has not experimentally verified its importance in breakpoint chlorination. This study first assessed the formation of N-nitrosamines from model N-chloro-alkylamine precursors when they were added to a mixture of HOCl and HNO-derived nitrosating agents generated by chlorinating hydroxyurea. Results demonstrated negligible N-nitrosamine formation. Instead, we observed that the interaction of NCl3 with NHCl2 (total Cl2/total N molar ratio = 2.4-3:1) produced an intermediate capable of nitrosating N-chloro-alkylamines to N-nitrosamines at yields 8-fold higher to those observed in NHCl2 treatment alone, within a very short timescale (<3 min). We examined the stoichiometry of the reaction of NCl3 with NHCl2 using a UV-spectrum-based approach. Nitrosyl chloride was proposed as the key intermediate, likely formed alongside the reformation of NHCl2. Further isotopic experiments, byproduct measurements, and kinetic modeling supported the hypotheses. Modeling indicated that the reaction of NCl3 with NHCl2 explained ∼75% of NDMA formation during breakpoint chlorination. Because NCl3 is mainly derived from the reaction of HOCl with NHCl2, controlling NHCl2 (e.g., with additional treatment) is critical for minimizing nitrosamine formation in waters where breakpoint chlorination occurs.

Double Photoionization of Nitrosyl Chloride by Synchrotron Radiation in the 24-70 eV Photon Energy Range.

The behavior of nitrosyl chloride (ClNO) exposed to ionizing radiation was studied by direct probing valence-shell electrons in temporal coincidence with ions originating from the fragmentation process of the transient ClNO2+. Such a molecular dication was produced by double photoionization with synchrotron radiation in the 24-70 eV photon energy range. The experiment has been conducted at the Elettra Synchrotron Facility of Basovizza (Trieste, Italy) using a light beam linearly polarized with the direction of the polarization vector parallel to the ClNO molecular beam axis. ClNO molecules crossing the photon beam at right angles in the scattering region are generated by effusive expansion and randomly oriented. The threshold energy for the double ionization of ClNO (30.1 ± 0.1 eV) and six dissociation channels producing NO+/Cl+, N+/Cl+, N+/O+, O+/Cl+, ClN+/O+, NO+/Cl2+ ion pairs, with their relative abundance and threshold energies, have been measured.

Modulation of Uptake and Reactivity of Nitrogen Dioxide in Metal-Organic Framework Materials.

We report the modulation of reactivity of nitrogen dioxide (NO2 ) in a charged metal-organic framework (MOF) material, MFM-305-CH3 in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl- ions in the pores. Uptake of NO2 into MFM-305-CH3 leads to reaction between NO2 and Cl- to give nitrosyl chloride (NOCl) and NO3 - anions. A high dynamic uptake of 6.58 mmol g-1 at 298 K is observed for MFM-305-CH3 as measured using a flow of 500 ppm NO2 in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g-1 . The binding domains and reactivity of adsorbed NO2 molecules within MFM-305-CH3 and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.

Modulation of Uptake and Reactivity of Nitrogen Dioxide in Metal‐Organic Framework Materials

AbstractWe report the modulation of reactivity of nitrogen dioxide (NO2) in a charged metal–organic framework (MOF) material, MFM‐305‐CH3 in which unbound N‐centres are methylated and the cationic charge counter‐balanced by Cl− ions in the pores. Uptake of NO2 into MFM‐305‐CH3 leads to reaction between NO2 and Cl− to give nitrosyl chloride (NOCl) and NO3− anions. A high dynamic uptake of 6.58 mmol g−1 at 298 K is observed for MFM‐305‐CH3 as measured using a flow of 500 ppm NO2 in He. In contrast, the analogous neutral material, MFM‐305, shows a much lower uptake of 2.38 mmol g−1. The binding domains and reactivity of adsorbed NO2 molecules within MFM‐305‐CH3 and MFM‐305 have been probed using in situ synchrotron X‐ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high‐field solid‐state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.

Reduction and Photoreduction of NO2 in Humic Acid Films as a Source of HONO, ClNO, N2O, NO X , and Organic Nitrogen.

Atmospheric nitrous acid (HONO), a trace atmospheric gas, is often underestimated in global atmospheric models due to the poor understanding of its daytime sources and sinks. HONO is known to accumulate during nighttime and undergo rapid photodissociation during the day to form NO and highly reactive OH radical, making it important to have accurate atmospheric HONO estimations. Despite its rapid photolysis, recent field observations have found quasi-steady-state concentrations of HONO at midday, suggesting photolytic HONO formation pathways to replenish daytime atmospheric HONO. Recent studies suggest that the presence of complex organic photosensitizers in atmospheric aerosols converts atmospheric NO2 into HONO. To better understand the effect of environmental photosensitizers in daytime mechanisms of HONO formation, we present here laboratory studies on the heterogeneous photolytic reduction of NO2 by humic acid films, a proxy for organic chromophoric compounds. The effect of pH and Cl- in the photosensitized formation of HONO and other nitrogen-containing gases is also investigated. A dual Fourier transform infrared (FTIR) system is utilized to simultaneously perform in situ analysis of condensed-phase reactants and gas-phase products. We find that the rate of HONO formation is faster at lower pHs. Nitrogen incorporation in the complex organic chromophore is observed, suggesting a competing pathway that results in suppressed daytime formation of nitrogenous gases. Significantly, the presence of chloride ions also leads to the organic-mediated photolytic formation of nitrosyl chloride (ClNO), a known precursor of HONO. Overall, this work shows that organic acid photosensitizers can reduce adsorbed NO2 to form HONO, ClNO, and NO while simultaneously incorporating nitrogen into the organic chromophores present in aerosol.

Ranitidine: A Proposed Mechanistic Rationale for NDMA Formation and a Potential Control Strategy

The formation of N-nitrosodimethylamine (NDMA) in ranitidine hydrochloride drug substance (DS) and drug products has attracted considerable attention over the last few years. The drug structure is unusual in that it contains a vinyl nitro moiety. Although a variety of studies have been carried out to understand how NDMA is formed in the DS solids, a mechanistic description of NDMA formation has remained elusive. A new mechanistic view of NDMA formation is detailed here. Autoxidation of ranitidine can rationalize nitrite ion and dimethylamine liberation from ranitidine. The subsequent nitrosation is argued to be due to conversion of nitrite ion to the gas phase nitrosating agent nitrosyl chloride, NOCl. Oxygen scavenging packaging systems should be able to stop the autoxidation, and thus shut down the nitrite release from ranitidine. Without nitrite release NDMA cannot form. This may provide a practical means to stabilize ranitidine DS and solid dosage formulations against NDMA formation.

Electronic state influence on selective bond breaking of core-excited nitrosyl chloride (ClNO).

The potential for selective bond breaking of a small molecule was investigated with electron spectroscopy and electron-ion coincidence experiments on ClNO. The electron spectra were measured upon direct valence photoionization and resonant core excitation at the N 1s- and O 1s-edges, followed by the emission of resonant-Auger (RA) electrons. The RA spectra were analyzed with particular emphasis on the assignment of the participator and spectator states. The states are of special relevance for investigating how distinct electronic configurations influence selective bond breaking. The electron-ion coincidence measurements provided branching fractions of the produced ion fragments as a function of electron binding energy. They explicitly demonstrate how the final electronic states created after photoionization and RA decay influence fragmentation. In particular, we observed a significantly different branching fraction for spectator states compared with participator states. In addition, it was also observed that the bonds broken for the spectator states correlate with the antibonding nature of the spectator-electron orbital.

Search for compounds with antioxidant and antiradical activity among N9-substituted 2-(biphenyl-4-yl)imidazo[1,2-a]benzimidazoles

Introduction: Biphenyl and imidazobenzimidazole derivatives attract ongoing attention as a combination of these two privileged substructures with promising pharmacological activities. The aim of this study was to synthesize and inves­tigate in vitro antioxidant activity of promising novel compounds: 2-(biphenyl-4-yl)imidazo[1,2-a]benzimidazoles.&#x0D; Materials and methods: The newly synthesized compounds were characterized by IR, 1H NMR and CHBr(Cl)NO analyses. All newly synthesized compounds were screened for their in vitro antioxidant activity: inhibition of lipid per­oxidation (LPO), 2,2’-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS•+) radical cation decolorization and inhibition of hemoglobin (Hb)-H2O2-induced luminol chemiluminescence.&#x0D; Results and discussion: 2-Amino-3-[(2-biphenyl-4-yl)-2-oxo-ethyl)]-1-R-1Н-benzimidazolium bromides were synthesized, and their cyclization into functionalized imidazo[1,2-a]benzimidazole derivatives was studied. The resulting compounds showed LPO inhibitory activity comparable to that of dibunol. Compounds 1a and 1d (see graphical abstract), containing a methyl or dimethylaminoethyl substituent in the N9 position also proved to be equally highly active in the Hb-H2O2-induced luminol chemiluminescence model, while compound 1a was somewhat more active than 1d in the ABTS• radical scavenging assay.&#x0D; Conclusion: The study showed that compounds 1a and 1d have the highest antioxidant activity. Thus, this new class of 2-(biphenyl-4-yl)imidazo[1,2-a]benzimidazole derivatives represents a valuable leading series with great potential for use as antioxidants and as promising candidates for further efficacy evaluation.&#x0D; Graphical abstract:

Photolytic insertion of carbon monoxide into nitrosyl chloride: formation of nitrosoformyl chloride.

Nitrosocarbonyls are exotic intermediates that remain scarcely characterized. By UV photolysis (365 nm) of nitrosyl chloride (ClNO) embedded in solid CO ice at 20 K, the elusive nitrosoformyl chloride (ClC(O)NO) has been synthesized via CO-insertion into the Cl-N bond in ClNO. The characterization of ClC(O)NO with matrix-isolation IR spectroscopy is supported by 13C and 15N isotope labeling and quantum chemical calculations at the B3LYP/6-311+G(3df) level of theory. Upon subsequent laser irradiation at 266 nm, CO-elimination in ClC(O)NO occurs by reformation of ClNO. In line with the calculated potential energy surface for ClC(O)NO at the CCSD(T)-F12a/aug-cc-pVTZ//B3LYP/6-311+G(3df) level, the observed IR frequencies and the corresponding isotopic shifts coincide with the calculated values for the lowest-energy planar conformer, in which the CO and NO moities adopt trans configuration with respect to the C-N bond. Furthermore, the CO-insertion in ClNO involves a stepwise pathway by first homolytic cleavage of the Cl-N bond in ClNO (→ Cl˙ + ˙NO), followed by successive CO-trapping (CO + Cl˙ → ClCO˙) and radical combination (ClCO˙ + ˙NO → ClC(O)NO) inside the solid CO-matrix cages.

IMPACT OF THE SUBLETHAL CONCENTRATIONS OF CYPERMETHRIN TOXICITY ON NITROGEN METABOLISM IN FRESH WATER FISH HETEROPNEUSTES FOSSILIS

Cypermethrin is a synthetic pyrethroid pesticide (C H Cl NO ) that has shown effective impact of strong pesticidal 22 19 2 3 activity observed in Heteropneustes Fossils, a fresh water fish exposed to sublethal concentrations of cypermethrin in different tissues liver, gill, and muscle for 4 and 7 seven days. The enzyme activity of Glutamate Dehydrogenase (GDH) was increased all the tissues especially in liver and gill. Significant change might be attributed to tissue change under toxic stress in Heteropneustes fossils. The increased levels of Urea and Ammonia also noticed indicate remarkably the role as biomarkers of cypermethrin toxicity. And the raise in Ammonia as well as urea levels indicates the concentration and tissue dependent which in turn helps to assess the impact of synthetic pyrethroids on the fish. The changes in Ammonia and Urea levels is often be reflected in nitrogen metabolism and interdependent biochemical reactions.

A compact, high-purity source of HONO validated by Fourier transform infrared and thermal-dissociation cavity ring-down spectroscopy

Abstract. A well-characterized source of nitrous acid vapour (HONO) is essential for accurate ambient air measurements by instruments requiring external calibration. In this work, a compact HONO source is described in which gas streams containing dilute concentrations of HONO are generated by flowing hydrochloric acid (HCl) vapour emanating from a permeation tube over continuously agitated dry sodium nitrite (NaNO2) heated to 50 ∘C. Mixing ratios of HONO and potential by-products including NO, NO2, and nitrosyl chloride (ClNO) were quantified by Fourier transform infrared (FTIR) and thermal-dissociation cavity ring-down spectroscopy (TD-CRDS). A key parameter is the concentration of HCl, which needs to be kept small (&lt;4 ppmv) to avoid ClNO formation. The source produces gas streams containing HONO in air in &gt;95 % purity relative to other nitrogen oxides. The source output is rapidly tuneable and stabilizes within 90 min. Combined with its small size and portability, this source is highly suitable for calibration of HONO instruments in the field.

High-resolution spectroscopy and analysis of the ν3 bands of ClNO (nitrosyl chloride) around 30 µm

The ν3 fundamental bands of 35ClNO and 37ClNO and the 2ν3-ν3 band of 35ClNO around 30 µm have been recorded using a high-resolution Fourier-transform spectrometer. The line-by-line analysis of the spectrum provides improved rotational and centrifugal distortion constants for the ν3 fundamental band of 35ClNO, and the first determination of these constants together with accurate band centers for the ν3 band of 37ClNO and for the 2ν3-ν3 band of 35ClNO. The band centers are 331.970996(28) cm−1 for the ν3 fundamental band of 35ClNO, 327.944735(78) cm−1 for the ν3 fundamental band of 37ClNO, and 329.962453(92) cm−1 for the 2ν3-ν3 band of 35ClNO.

Effect of trans(NO, OH)-[RuFT(Cl)(OH)NO](PF6) ruthenium nitrosyl complex on methicillin-resistant Staphylococcus epidermidis

Antibiotic resistance is becoming a global scourge with 700,000 deaths each year and could cause up to 10 million deaths by 2050. As an example, Staphylococcus epidermidis has emerged as a causative agent of infections often associated with implanted medical devices. S. epidermidis can form biofilms, which contribute to its pathogenicity when present in intravascular devices. These staphylococci, embedded in the biofilm matrix, are resistant to methicillin, which had long been the recommended therapy and which has nowadays been replaced by less toxic and more stable therapeutic agents. Moreover, current reports indicate that 75 to 90% of Staphylococcus epidermidis isolates from nosocomial infections are methicillin-resistant strains. The challenge of successfully combating antibiotics resistance in biofilms requires the use of compounds with a controlled mode of action that can act in combination with antibiotics. Ruthenium nitrosyl complexes are potential systems for NO release triggered by light. The influence of trans(NO, OH)-[RuFT(Cl)(OH)NO](PF6) on Staphylococcus epidermidis resistant to methicillin is described. The results show a 50% decrease in cell viability in bacteria treated with low concentrations of NO. When combined with methicillin, this low dose of NO dramatically decreases bacterial resistance and makes bacteria 100-fold more sensitive to methicillin.

Continuous generation, in-line quantification and utilization of nitrosyl chloride in photonitrosation reactions

The reagent is prepared from stable, inexpensive and readily available starting materials. In-line UV/vis monitoring enables determination of the reagent's concentration after a continuous extraction and liquid–liquid separation sequence.

Convenient Synthesis of Ethyl 5-Oxohomoadamantane-4-carboxylate: A Useful Precursor of Polyfunctional Homoadamantanes

A facile and convenient synthesis of ethyl 5-oxohomoadamantane-4-carboxylate is reported, and its chemical properties as a cage analogue of acetoacetic ester are investigated. Various derivatives of homoadamantane were synthesized through the reaction of 5-oxohomoadamantane-4-carboxylate with electrophilic agents, binucleophiles, and hydrazoic acid. Some new unusual products were obtained by the reaction of that β-keto ester with nitric acid and nitrosyl chloride. Cage compounds synthesized could be used as precursors for the diverse condensed heterocyclic compounds with potential viral ion channel abrogating activity that possess conformationally rigid lipophilic moieties.

Investigating core-excited states of nitrosyl chloride (ClNO) and their break-up dynamics following Auger decay.

The fragmentation of ClNO upon resonant core-electron excitation to the LUMO and LUMO+1 orbitals at the N and O K-edges is investigated. The produced fragment ions were detected in coincidence with a position sensitive ion time-of-flight detector which enables deduction of the angular distribution of the ions. This facilitates a comparison between the two resonances and the two K-edges with respect to fragmentation time, transition dipole moment orientation, fragment yield of single-ion and ion-pair channels, and fragmentation mechanisms. We observe significant correlations between the core-excited site and the location of the bonds that are broken, as well as the dissociation time. Moreover, we observe preferential cleavage of specific bonds upon excitation to the LUMO and LUMO+1 states which can be attributed to their orbital character.

Impact of electronegative character on ultrafast nonlinear optical absorption of azine derivatives

Two azine derivatives (NO(Cl) and NS(Cl)) with different electronegative central core were prepared and spectroscopically characterized. Their ultrafast third-order nonlinear optical (NLO) responses were investigated using open aperture Z-scan and optical limiting method with 190 fs laser pulses at 515 nm. The frontier molecular orbitals and energy gaps of samples were obtained through quantum chemical calculation. Transient absorption spectra demonstrated that the origin of strong NLO absorption of two molecules was attributed to excited-state absorption. A simplified three-energy-level model was used to determine their photo-physical parameters. Our results show that the stronger the electronegative cationic groups is, the stronger the NLO absorption performs. The azine compounds have large excited-state lifetime and large ratio of singlet excited-state absorption cross-section to that of ground state cross-section (∼20.2), indicating it is a candidate material for future ultrafast optical limiters.

Anhydrous Dinitrogen Trioxide Solutions for Brønsted Acid Free Nitrous Acid Chemistry

Dinitrogen trioxide, N2O3, is readily prepared and stabilized in high concentrations in dry organic solvents at normal working temperatures. These conditions allow for facile acid and water free nitrosation and nitration reactions for which three examples are given here: the preparation of benzenediazonium nitrite, [PhN2][NO2]; nitrosyl chloride, NOCl, and nitrosylsulfuric acid, (ONOSO3H).