Mechanistic studies of the photochemical nitration of phenols, 1,2-dimethoxybenzene and anisoles with tetranitromethane by15N CIDNP

During the photochemical nitration of phenol, 3,5-dimethylphenol and 1,2-dimethoxybenzene (8) with¹⁵N-enriched tetranitromethane, the¹⁵N nuclear magnetic resonance (NMR) signals of the nitro products 2-nitrophenol, 4-nitrophenol, 2-nitro-3,5-dimethylphenol, 4-nitro-3,5-dimethylphenol and 1,2-dimethoxy-4-nitrobenzene (9) appear in emission. The nuclear polarizations are built up in radical pairs formed by radical cations or in case of the phenols by phenoxyl radicals and^?NO₂. They are generated by photoreactions from excited triplet states of the reactants or by free radical encounters. With8, 1,2-dimethoxy-4-trinitromethylbenzene is also formed which slowly converts to9. In contrast to this, the¹⁵N NMR signals of the nitration products of anisole (11) and 3,5-dimethylanisole (12), 2-nitroanisole, 4-nitroanisole, 3,5-dimethyl-2-nitroanisole and 3,5-dimethyl-4-nitroanisole appear in enhanced absorption indicating the appearance of singlet radical pairs [11 ^+?,^?NO₂]^S and [12 ^+? ,^?NO₂]^S in which the nuclear polarizations are built up. The singlet radical pairs are formed by decomposition of an unstable intermediate, most probably a nitro-trinitromethyl adduct.     

Detection and Quantitation Of Several Atomic Species By Intra-cavity Quenching Of Laser Emission

Until recently laser research has been the province of the physicist wherein lasers have been utilized extensively as sources of coherent, highly monochromatic energy. The thrust of this research has been to employ the organic solution laser output as an analytical signal from which information about a particular system may be extracted. Preliminary investigations in this laboratory showed that a great number of variables are active in the achievement of lasing from an organic solution. More significantly, concurrent work in this laboratory produced some anomalous results which were subsequently attributed to a cavity defect. This suggested that small energy losses at discrete wavelengths within the resonant cavity of an organic solution laser could result in quenching of broad band laser emission at those specific wavelengths. These considerations led to investigations in which atoms and mlecules were purposefully introduced into the resonant cavity of an organic solution laser.¹ A search of the literature revealed that investigators at The National Bureau of Standards had previously observed this phenomenon and had reported on the intra-cavity absorption of a pulsed rhodamine 6G laser emission by sodium vapor.² In a follow-up paper Keller and co-workers demonstrated the enhancement of absorption for Eu(NO₃)₃) when placed within the cavity of a rhodamine 6G laser. Concurrently absorption was observed from Ba and Sr in an air-acetylene flame within a dye laser cavity by, Thrash et al.⁴ Hansch and co-workers⁵ duplicated the intra-cavity absorption experiment with iodine vapor and compared the sensitivity of this result with measurements obtained from conventional absorption techniques. At about the same time Latz, Wyles, and Green¹ reported data which dennnstrated that the extent of intra-cavity absorption for nitrogen dioxide was linearly related to its concentration. Investigation into the use of a laminar flow burner with an air-acetylene flame within a dye laser cavity showed part per billion (ppb) detection limits for sodium as well as the detection of barium and mercury. The completion of these intracavity absorption studies in the visible region of the spectrum yielded the results which are reported here as well as quantitative intyacavity absorption data for Eu⁺³. In an independent study Konjevic also reported detection of sodium by intra-cavity absorption from an airnatural gas flame⁶.     

Narrow-band UV radiation (250–260 nm) from intracavity doubling a single-mode ring dye laser

Generation of continuous-wave, tunable UV radiation (250–260 nm) by intracavity doubling a coumarin-515 ring dye laser is described. A cooled (200–280 K) ADP crystal with end faces cut at Brester's angle is placed inside the laser ring cavity which has been compensated for astigmatism and coma. UV output powers at 254 nm of 120 μW and 60 μW are achieved with the laser operating multimode (bandwidth ? 20 GHz) and single-mode (bandwidth ? 50 MHz), respectively. Continuous single-mode scans over the 253.7 nm mercury profile demonstrate sub-Doppler resolution of the Hg 6s6p ³P^O₁ - 6s²¹S₀ transition.     

Quadrupole relaxation enhancement and polarisation transfer in DMSO solution of [Bi(NO3)3(H2O)3]*18-crown-6 in solid state

ABSTRACT

¹H spin-lattice relaxation studies have been performed for pure [Bi(NO₃)₃(H₂O)₃]*18-crown-6 in powder and its solution in dimethyl sulfoxide (DMSO). The experiments have been carried out in the frequency range of 10?kHz–30?MHz and the temperature range of 240–277?K; at 277?K the solution is already frozen. The ¹H relaxation of pure [Bi(NO₃)₃(H₂O)₃]*18-crown-6 has been interpreted in terms of three dynamical processes. Quadrupole Relaxation Enhancement effects have been observed in the frozen DMSO solution of [Bi(NO₃)₃(H₂O)₃]*18-crown-6. The specific mechanisms of the ¹H spin-lattice relaxation enhancement have been discussed distinguishing between effects caused by time independent (residual) and fluctuating ¹H-²⁰⁹Bi dipole-dipole interactions.     

Radiolysis of ferrous ammonium sulphate in alkali nitrate and alkali halide matrices

Radiolysis of ferrous ammonium sulphate (FAS) dispersed in (a) alkali nitrates [KNO₃, NaNO₃, Ba(NO₃)₂, CO(NH₃)₆(NO₃)₃] (b) alkali halides [KCl, KBr] and (c) binary mixtures of above [KNO₃ + KCl, Ba(NO³)₂ + BaCl₂) has been extensively investigated. FAS becomes oxidized and Fe³⁺ formation seems to depend upon the nitrate concentration and gamma dose but is independent of halide concentration. Mossbauer studies confirm these findings and it appears that basic ferric sulphate may be formed during the oxidation process.     

A study of the uptake of NO3 on film coatings of natural sea salt

A comparative analysis of the uptake NO₃ on natural sea salt (NSS) and Dead Sea salt (DSS) is performed using a coated-insert flow reactor coupled to an electron impact ionization mass spectrometer for detecting gas-phase reactants and products. The uptake coefficients are determined by measuring both reactant consumption and gaseous products formation at various concentrations of NO₃, from 8 · 10¹² to 4 · 10¹³ cm^?3, and water vapor, from 8 · 10¹² to 1.6 · 10¹⁵ cm^?3. It has been established that the uptake on a fresh coating is time-dependent, with the uptake coefficient exponentially varying with time, γ(t) = γ _a exp(?t/τ) + γ _s , from an initial value to a steady-state value, both of which depends on the type of salt and the concentration of the gaseous reactant but do not depend on [H₂O] in this range of water vapor concentrations. The dependence of the coefficient of steady-state uptake of the gaseous reactant is determined as 1/γ _s = a + b[NO₃]. It is shown that the main primary products of the NO₃ uptake on NSS are HCl and Cl _ad formed with branching ratios of 1 : 1 and 1 : 2 in the initial and steady-state uptake stages, respectively. For the uptake of NO₃ on DSS, the primary products are HCl and Br, formed in proportions of 1 : 0.1 and 1 : 0.006 for the respective uptake stages. Chemical reactions leading to the formation of these products are proposed.     

Theoretical studies on 2‐(5‐amino‐3‐nitro‐1,2,4‐triazolyl)‐3,5‐dinitropyridine (PRAN) and its derivatives

In this work, a set of derivatives of 2‐(5‐amino‐3‐nitro‐1,2,4‐triazolyl)‐3,5‐dinitropyridine (PRAN) with different energetic substituents (?N₃, –NO₂, –NH₂, –NF₂) have been studied at the Becke, three‐parameter, Lee–Yang–Parr/aug‐cc‐pvdz, Becke, three‐parameter, Lee–Yang–Parr/6‐31G(d), Becke, three‐parameter, Perdew 86/6‐31G(d), and Becke three‐parameter, Perdew–Wang 91/6‐31G(d,p) levels of density functional theory. The gas‐phase heats of formation were predicted with isodesmic reactions and the condensed‐phase HOFs were estimated with the Politzer approach. The effects of different functionals and basis sets were analyzed. –N₃ and –NO₂ greatly increase while –NH₂ and –NF₂ slightly decrease heats of formation. An analysis of the bond dissociation energies and impact sensitivity shows that all compounds have good stability. The crystal densities (1.82–2.00 g/cm³) computed from molecular packing calculations are big for all compounds and that of the –NF₂ derivative is the largest. All derivatives have higher detonation velocity and detonation pressure than PRAN. Compounds 3 and 4 (R = NO₂ and NF₂) have better performance than hexahydro‐1,3,5‐trinitro‐1,3,5‐trizine and the performance of 4 is quite close to that of 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane, they are promising candidates of high energy compounds and worth further investigations. Copyright © 2012 John Wiley & Sons, Ltd.     

An improved method for selective catalytic reduction of nitrogen oxides in exhaust gases

The selective catalytic reduction (SCR) of nitrogen dioxide in an air flow modeling the exhaust gas from an internal combustion engine is studied. Granulated V₂O₅ (13.5%)–MnO₂ (0.7–1.0%)/Al₂O₃ powder (AVK-10M catalyst) and ammonia injected into a SCR catalytic cell are used as a heterogeneous catalyst of NO₂ reduction and a reducing agent, respectively. If the efficiency of NO₂ removal is high enough and satisfies the requirements of the State Sanitary Standards for the maximum permissible concentrations of substances emitted into the atmosphere (\(MP{C_{N{O_2}}}\) = 0.085 mg/m³), the reducing agent (ammonia) is not completely consumed during SCR, so a considerable amount of NH₃ can be released into the atmosphere. Therefore, a strict control of both NO₂ and unreacted ammonia emissions is needed. The dependences of the concentrations of [NH₃] and [NO₂] on the [NH₃]/[NO₂] ratio for the model air flow passed through the AVK-10M granular heterogeneous catalyst are measured. It is found that the maximum degree of removal of NO₂ from the air takes place at [NH₃]/[NO₂] = 1.3. In the conventional process, the concentration of [NO₂] drop from 530.00 to 0.07 mg/m³, i.e., below the \(MP{C_{N{O_2}}}\). At the same time, the ammonia concentration increases to [NH₃] = 3.4 mg/m³, which becomes 85 times the \(MP{C_{N{O_2}}}\), 0.04 mg/m³. To remove unreacted ammonia from air flows, we developed [P–(SO₃ ^-)₂ · Me²⁺] sulfocationites, where Me are the Cu and/or Ca ions, P is a styrene–divinylbenzene copolymer. It is shown that the concentration of ammonia passed through the adsorption cell filled with a freshly sulfocationite drops below \(MP{C_{N{H_3}}}\) = 0.04 mg/m³. The dependences of the dynamic exchange capacity (DEC) before ammonia breakthrough for the [P–(SO₃ ^-)₂ · Cu²⁺] delta-sulfocationite on the air flow rate, [NH₃] concentration, and humidity are measured. The maximum value of the DEC, δ = 59.5 mg/cm³, is observed at an air flow velocity of 2.171 m/s, [NH₃] = 0.0035 mg/L, and 75% humidity. To illustrate practical applications of the proposed improved SCR method, it is shown that a 3-L replaceable [P–(SO₃ ^-)₂ · Cu²⁺] sorbent cartridge in a SCR exhaust gas purifier for a car internal combustion engine does not need replacement more frequently than every 50000 km.     

Unexpected Features of the Intramolecular Spin Exchange in Imidazoline Nitroxide Biradicals Dissolved in Ionic Liquids

Three imidazoline-type nitroxide biradicals of the similar composition R ₅ ^NO –CH=N–N=CH–R ₅ ^N , B1, R ₅ ^NO –CH=N–N=C(CH₃)–R ₅ ^N , B2, and R ₅ ^N –C(CH₃)=N–N=C(CH₃)–R ₅ ^N , B3, with R ₅ ^N and R ₅ ^NO denoting, respectively, the nitroxide rings 1-oxyl-2,2,5,5-tetramethyl-3-imidazoline and 1-oxyl-2,2,5,5-tetramethyl-3-N–oxide imidazoline, have been studied by X-band electron paramagnetic resonance (EPR) spectroscopy. Variations of the intramolecular electron spin exchange in these biradicals dissolved in ethanol and the room temperature ionic liquid bmimBF₄ were characterized as a function of temperature by means of the analysis of the EPR lines shape. Thermodynamic parameters of the conformational rearrangements in ethanol were calculated. Analyzing the EPR spectra of these biradicals in bmimBF₄, it was revealed that the two-conformational model does not describe their conformational transitions. Moreover, the observed EPR spectra are not central symmetric especially at low temperatures that cannot be described and explained in the framework of the current theory of the intramolecular spin exchange. Probable reasons of this “strange” behavior are discussed.     

Radiative lifetimes of superradiant populated Ba Rydberg levels

Radiative lifetimes of 6s7f¹F₃, as8f¹F₃, and 6s9d¹D₂ Ba Rydberg levels were measured in an atomic beam by time resolved recording of the exponential decay of the fluorescence. The excitation was performed by use of two pulsed dye lasers and a superradiant emission or a superradiant cascade controlled by a cavity.     

Influence of Pressure on the Intramolecular Spin Exchange in a Short Imidazolium-Nitroxide Biradical

A short-chain imidazoline-type nitroxide biradical R ₅ ^NO –CH=N–N=C(CH₃)–R ₅ ^N , B2, with nitroxide rings R ₅ ^N and R ₅ ^NO as 1-oxyl-2,2,5,5-tetramethyl-3-imidazoline and 1-oxyl-2,2,5,5-tetramethyl-3-N-oxide imidazoline, respectively, has been studied using X-band electron paramagnetic resonance (EPR) spectroscopy in CH₃CN solutions at variable temperature T and pressure P. Changes of the solution viscosity on the intramolecular electron spin exchange in B2 is characterized by calculating the value of the exchange integral |J/a|, where a denotes the ¹⁴N hyperfine splitting (hfs) constant. It is revealed that the intramolecular dynamics in B2 do not follow the Debye–Stokes–Einstein law, while the Arrhenius dependence is fulfilled. Probable reasons of such behavior are discussed.     

Rotational and vibrational relaxation of the NO3 - ion in molten binary systems (M,Ag)NO3 (M = Li,Na and K) by Raman spectroscopy

Polarized and depolarized Raman scattering spectra for the totally symmetric stretching υ₁ mode of nitrate ions (D_3h symmetry) in the molten binary systems (M1,Ag)NO₃(M1= Li, Na, and K) have been measured. Vibrational and rotational autocorrelation³ functions, C_v(t) and C_r(t), respectively, have been evaluated from Fourier transformation of the spectra. The shifts in the peak frequencies are deeply correlated with the polarizability of silver in these mixtures. The vibrational relaxation rate increases with increasing mole fraction of silver nitrate in (K,Ag)NO₃, but does not vary so much in (Li,Ag)NO₃ and (Na,Ag)NO₃. The vibrational relaxation time negatively deviates from additivity on the order of (Na,Ag)NO₃< (Li,Ag)NO₃< (K,Ag)NO₃. In the systems (Na,Ag)NO₃ and (K,Ag)NO₃ rotational relaxation time becomes slower with increasing concentration of AgNO₃. The Ag⁺ coordinating to several nitrate ions in these mixtures appreciably restricts the rotational motion of the nitrate ions. On the other hand, rotational motion becomes easier in the mixture system (Li,Ag)NO₃ mainly because the different preferential sites of the two cations coordinating to an NO₃ ^-ion, and partly because the exchange rates of these cations around the NO_-3 ^-ion are high.     

Detailed I.R. Study of the Phase Transition in the System AgNO3-Fe(NO3)3

A complete infrared study of the mixed crystal system of AgNO₃ and Fe(NO₃)₃ is carried out in the region 400–4000 cm^?1. The study includes internal fundamental normal vibrations of the NO₃^? ion in the ordered and disordered phases of AgNO₃ at different values of the ferric concentration, I.R. spectra, spectral band shape intensities, and frequencies of the internal modes as functions of the ferric ion concentration. Special attention is paid to bending mode, combination mode, asymmetric stretching mode, and over-tone. The rotational energy barrier is determined at different concentration of the ferric ions in the system of AgNO₃-Fe(NO₃)₃.     

Incoherent broad-band cavity-enhanced absorption spectroscopy for simultaneous trace measurements of NO2 and NO3 with a LED source

In the past decade, due to a growing awareness of the importance of air quality and air pollution control, many diagnostic tools and techniques have been developed to detect and quantify the concentration of pollutants such as NO _x , SO _x , CO, and CO₂. We present here an Incoherent Broad-Band Cavity-Enhanced Spectroscopy (IBB-CEAS) set-up which uses a LED emitting around 625 nm for the simultaneous detection of NO₂ and NO₃. The LED light transmitted through a high-finesse optical cavity filled with a gas sample is detected by a low resolution spectrometer. After calibration of the spectrometer with a NO₂ reference sample, a linear multicomponent fit analysis of the absorption spectra allows for simultaneous measurements of NO₂ and NO₃ concentrations in a flow of ambient air. The optimal averaging time is found to be on the order of 400 s and appears to be limited by the drift of the spectrometer. At this averaging time the smallest detectable absorption is 2×10⁻¹⁰ cm⁻¹, which corresponds to detection limits of 600 pptv for NO₂ and 2 pptv for NO₃. This compact and low cost instrument is a promising diagnostic tool for air quality control in urban environments.     

Affinement d'une raie de fluorescence de Pr3+: LaAlO3 par excitation laser

A cw dye laser has been used for fluorescence line narrowing experiments by resonant excitation on Pr³⁺ ions in LaAlO₃. Scanning the excitation radiation through the absorption line width corresponding to the transition ³H₄ (0 cm^-1) → ¹D₂ (16 694 cm^-1) while fluorescence was observed, has put into evidence a deformation of the symmetry around Pr³⁺ ions, different for every site.This experiment shows the power of cw dye laser spectroscopy for investigating optical spectra in crystals.     

Preparation of Zn2+–Ni2+–Fe3+–CO32−LDHs and study of photocatalytic activities for decomposition of Methyl Orange solution

New type photocatalytic materials of Zn²⁺–Ni²⁺–Fe³⁺–CO₃^2?LDHs were prepared by complexing agent-assisted homogeneous precipitation technique and Zn(NO₃)₂·6H₂O, Ni(NO₃)·6H₂O, Fe(NO₃)₃·9H₂O used as raw materials in the case of molar ratio of Zn²⁺/Ni²⁺/Fe³⁺ = 1:6:2. Zn²⁺–Ni²⁺–Fe³⁺–CO₃^2?LDHs having a specific surface area of 96.5 m²/g. The structure and catalytic properties of the material were systematically studied. The experimental results show that the Zn²⁺–Ni²⁺–Fe³⁺–CO₃^2?LDHs has a higher adsorption performance and lower band gap which make it an excellent catalyst for reducing the degradation of the methyl orange. Study on the process of photocatalytic reaction shows that Methyl Orange was adsorbed to the layer of Zn²⁺–Ni²⁺–Fe³⁺–CO₃^2?LDHs, and then it was photodecomposed to inorganic molecules and ions by Zn²⁺, Ni²⁺, and Fe³⁺ on the surface of Zn²⁺–Ni²⁺–Fe³⁺–CO₃^2?LDHs.     

Inelastic intermolecular exchange of vibrational quanta and relaxation of vibrationally excited states in binary solid systems

The processes of molecular relaxation in the binary nitrate–perchlorate solid systems LiNO₃–LiClO₄, NaNO₃–NaClO₄, and KNO₃–KClO₄ have been investigated using Raman spectroscopy. It has been found that the relaxation time of the ν₁(A) vibration of the NO₃ ^- anion in the binary solid system is shorter than that in the pure metal nitrates. It has been shown that an increase in the relaxation rate is caused by the existence of an additional mechanism of relaxation of vibrationally excited states of the nitrate ion in the system. This mechanism is associated with the excitation of a vibration of another anion (ClO₄ ^-), as well as with the “creation” of a lattice phonon. It has been established that the condition for the realization of the relaxation mechanism is that the difference between the frequencies of the aforementioned vibrations should correspond to the range of sufficiently high densities of states of the phonon spectrum.     

Binding of rare earth metal complexes with an ofloxacin derivative to bovine serum albumin and its effect on the conformation of protein

The water-soluble Pr (Ⅲ) and Nd (Ⅲ) complexes with an ofloxacin derivative have been prepared and characterized. The single-crystal X-ray diffraction showed that the Pr (III) and Nd (III) complexes have the similar molecular structure. Under physiological pH condition, the effects of [PrL(NO₃)₂(CH₃OH)](NO₃) and [NdL(NO₃)₂(CH₃OH)](NO₃) on bovine serum albumin (BSA) were examined using fluorescence spectroscopy in combination with UV-vis absorbance and circular dichroism (CD) spectra. The result reveals that the quenching mechanism of fluorescence of BSA by two complexes is a static quenching process and the number of binding sites is about 1 for both. The thermodynamic parameters (ΔH=−14.52 kJ mol⁻¹, ΔS=56.54 J mol⁻¹ K⁻¹ for [PrL(NO₃)₂(CH₃OH)](NO₃) and ΔH=−24.63 kJ mol⁻¹, ΔS=22.07 J mol⁻¹ K⁻¹ for [NdL(NO₃)₂(CH₃OH)](NO₃)) indicate that hydrophobic and electrostatic interactions are the main binding force in the complexes-BSA system. The binding average distance between complexes and BSA was obtained on the basis of Förster's theory. In addition, it was proved by the CD spectra that the BSA secondary structure was changed in the presence of complexes in an aqueous solution.     

89Yttrium nuclear magnetic resonance studies

With a Fourier-transform spectrometer, especially developed for nuclei with weak NMR signals, the lines of⁸⁹Y have been investigated in aqueous solutions of Y(NO₃)₃, YCl₃, and Y(ClO₄)₃. The concentration dependence of the chemical shifts of the⁸⁹Y resonance frequencies in these solutions were measured. Using this dependence, the Larmor frequency of the⁸⁹Y³⁺ ion solely surrounded by water was determined by extrapolation. The Larmor frequency of⁸⁹Y was referred to those of²H,³⁹K, and⁷³Ge with high accuracy. The magnetic moment of the⁸⁹Y³⁺ ion purely surrounded by H₂O molecules is μ(⁸⁹Y³⁺) = ?0.1368523(4) μ_N. The concentration dependence of Y(NO₃)₃ solutions in D₂O yields the solvent isotope effect δ(⁸⁹Y³⁺ in D₂O)?δ(⁸⁹Y³⁺ in H₂O)= ?(4.3±0.5)ppm. The⁸⁹Y relaxation times T₁ and T₂ of a 3 molal aqueous Y(NO₃)₃ solution were determined in the pH range ?0.5...+1.25. T₁ 190...90 s is nearly constant in this range, whereas the transverse relaxation rate T₂ ^?1 increases strongly with increasing pH; this effect seems to be due to the chemical exchange of the hydrated Y³⁺ ion between a monomer and a polymer site.     

Conductivity studies of starch-based polymer electrolytes

A proton-conducting polymer electrolyte based on starch and ammonium nitrate (NH₄NO₃) has been prepared through solution casting method. Ionic conductivity for the system was conducted over a wide range of frequency between 50 Hz and 1 MHz and at temperatures between 303 K and 373 K. Impedance analysis shows that sample with 25 wt.% NH₄NO₃ has a smaller bulk resistance (R _b) compared to that of the pure sample. The amount of NH₄NO₃ was found to influence the proton conduction; the highest obtainable room temperature conductivity was 2.83 × 10⁻⁵ S cm⁻¹, while at 100 °C, the conductivity in found to be 2.09 × 10⁻⁴ S cm⁻¹. The dielectric analysis demonstrates a non-Debye behavior. Transport parameters of the samples were calculated using the Rice and Roth model and thus shows that the increase in conductivity is due to the increase in the number of mobile ions.