Size Determination of Porosity Inclusions in an Organic Solid Material by (1)H NMR Diffusion and SEM-FIB Experiments: The TATB Case.

An original approach has been presented to characterize the local geometry of pores containing protonated small molecule impurities in organic materials. It was here applied in TATB (1,3,5-triamino-2,4,6-trinitrobenzene) powder material to investigate the porosity able to enclose water molecules. The presence of such defects may have a significant impact on TATB-based compositions mechanical properties, efficiency, and shock sensitivity. Apparent self-diffusion coefficients measured on the low water signal residue were consistent with highly mobile species experiencing restricted diffusion in confined porosities. Applying the methodology commonly used for the characterization of porous systems, we could demonstrate for the first time that pores, with an average size in the 3-5 µm range, were already present in the native TATB powder before any formulation and that these pores were closed and filled with water/NH4Cl solutions. The presence of such macrocavities was further confirmed by analyzing the TATB 3D porous structure using the SEM-FIB dual-beam technique at the scale of particle fractions. Calculation of the pore volumes was performed to deduce pore size distributions assuming spherical cavities. A volume-weighted average size was calculated showing a satisfactory agreement with NMR results and a suitable complementarity of the two approaches.

Electrochemical detection of nitromethane vapors combined with a solubilization device.

During the past decade, the number of terrorism acts has increased and the need for efficient explosive detectors has become an urgent worldwide necessity. A prototype, Nebulex™, was recently developed in our laboratory. Basically, it couples the solubilization of an analyte from the atmosphere by a nebulization process and in-situ detection. This article presents the development and integration of an electrochemical sensor for the detection of nitromethane, a common chemical product that can be used to make an improvised explosive device. A gold screen-printed electrode was used in a flow-cell and a detection limit of 4.5 µM was achieved by square wave voltammetry. The detection method was also determined to be selective toward nitromethane over a large panel of interfering compounds. Detection tests with the Nebulex™ were thus carried out using a custom-made calibrated nitromethane vapor generator. Detection times of less than one minute were obtained for nitromethane contents of 8 and 90 ppmv. Further measurements were performed in a room-measurement configuration leading to detection times in the range of 1-2 min, clearly demonstrating the system's efficiency under quasi-real conditions.

Sensitivity improvement of 1H-15N cross-polarization at high MAS frequency applied to NMR structural characterization of organic solids.

(15)N CP/MAS solid state NMR should be a method of choice to obtain essential structural information on organic materials containing nitrogen atoms. However, the technique is generally not selected for the characterization of non-labelled chemical compounds, which represents the most common situation encountered by chemists. Actually, due to the poor sensitivity of (15)N the method is time-consuming and a very fine calibration is often a prerequisite to reach a sufficient signal/noise. The main drawback comes from the weakness of (15)N-(1)H dipolar couplings which leads to a splitting of the static Hartman Hahn condition into very narrow sideband conditions under MAS. Practically, it is more difficult to obtain a high enough CP transfer level on (15)N for the entire spectrum than on other more conventional nuclei like (13)C. An experimental investigation of the CP efficiency using the ramp and adiabatic CP transfer experiments is here proposed. Preliminary adjustments of experimental settings were first made on an (15)N-labeled substituted heterocyclic model system, and then applied to several other organic compounds. Particular attention was paid to the detection of non-protonated nitrogen atoms with a significant chemical shift anisotropy, which represented the least favourable case. It was experimentally demonstrated that, for these atoms, the adiabatic passage provided a much higher transfer level than the more conventional ramp sequence leading to an enhancement factor of up to 3.5 at a MAS frequency of 30 kHz. The resulting sensitivity rendered possible the detection of non-protonated nitrogen atoms at natural abundance with 2.5-mm rotors at 9.4 T.

Design of interpenetrated networks of mesostructured hybrid silica and nonconductive poly(vinylidene fluoride)-cohexafluoropropylene (PVdF-HFP) polymer for proton exchange membrane fuel cell applications.

Organic-inorganic hybrid membranes of poly(vinylidene fluoride)-cohexafluoropropylene (PVdF-HFP) and mesostructured silica containing sulfonic acid groups were synthesized by using the sol-gel process. These hybrid membranes were prepared by in situ co-condensation of tetraethoxysilane and an organically modified silane (ormosil) by a self-assembly route using organic surfactants as templates for tuning the architecture of the hybrid organosilica component. In this paper, we describe the elaboration and characterization of hybrid membranes all the way from the precursor solution to the evaluation of the fuel cell performances. These hybrid materials were extensively characterized by using NMR and IR spectroscopy, electron microscopy, or impedance spectroscopy so as to determinate their physicochemical and electrochemical properties. Even though the ion-exchange capacity (IEC) was quite weak, the first fuel cell tests performed with these hybrid membranes show promising results relative to optimized Nafion 112 thanks to great water management of the silica inside the hydrophobic polymer.

(1)H, (13)C and (15)N NMR spectral assignments for new triazapentalene derivatives.

Mesomeric heteropentalene betaines are conjugated fused polyheterocyclic structures that represent interesting intermediates for organic synthesis. Five such structures, containing at least four nitrogen atoms and various substituents, have been characterized by (1)H, (13)C and (15)N NMR. We report, apparently for the first time, nitrogen NMR data and coupling information on such systems. Inter-ring long-range correlations across five bonds with (15)N ((5)J(HN)) and up to seven bonds with (13)C ((6)J(HC) and (7)J(HC)) were observed in HSQC experiments. The incorporation of an electron-withdrawing substituent such as NO(2) was observed to cause an increase in the magnitude of the remote couplings and deshielding of nearby protons, carbons and on all nitrogen atoms of the structure, including remote ones situated on other cycles.

Restricted diffusion and exchange of water in porous media: average structure determination and size distribution resolved from the effect of local field gradients on the proton NMR spectrum.

NMR Pulsed field gradient measurements of the restrained diffusion of confined fluids constitute an efficient method to probe the local geometry in porous media. In most practical cases, the diffusion decay, when limited to its principal part, can be considered as Gaussian leading to an apparent diffusion coefficient. The evolution of the latter as a function of the diffusion interval yields average information on the surface/volume ratio of porosities and on the tortuosity of the network. In this paper, we investigate porous model systems of packed spheres (polystyrene and glass) with known mean diameter and polydispersity, and, in addition, a real porous polystyrene material. Applying an Inverse Laplace Transformation in the second dimension reveals an evolution of the apparent diffusion coefficient as a function of the resonance frequency. This evolution is related to a similar evolution of the transverse relaxation time T2. These results clearly show that each resonance frequency in the water proton spectrum corresponds to a particular magnetic environment produced by a given pore geometry in the porous media. This is due to the presence of local field gradients induced by magnetic susceptibility differences at the liquid/solid interface and to slow exchange rates between different pores as compared to the frequency differences in the spectrum. This interpretation is nicely confirmed by a series of two-dimensional exchange experiments.

Diffusive diffraction measurements in porous media: effect of structural disorder and internal magnetic field gradients.

Pulsed Field Gradient NMR (PFG-NMR) method used to measure the self-diffusion coefficient of liquids can also be exploited to probe the local geometry of porous media. In most practical cases, the measured diffusion attenuation is generally Gaussian and can be interpreted in terms of an apparent diffusion coefficient. Using well chosen experimental conditions, a so called "diffusive diffraction" phenomenon can be observed in the diffusion curve with a specific shape and maxima location characteristic of the system local dimensions. In this paper we investigate this phenomenon by presenting new experimental results obtained on several porous model systems of packed sphere particles. Using different experimental approaches, the diffusion pattern could be finely observed and interpreted in the context of the pore hopping model formalism. Different calibrated systems of polystyrene and glass spheres with known mean diameter and polydispersity were used to investigate specifically the influence of structural heterogeneity and local internal gradients. Structural data obtained in that way were found in close agreement with laser diffraction granulometry measurement and Scanning Emission Microscopy.

Spectral assignments for 1H, 13C and 15N solution and solid-state NMR spectra of s-tetrazine and dihydro-s-tetrazine derivatives.

Tetrazine-based organic species are interesting intermediates for organic synthesis and represent a source of new materials bearing specific properties with potential applications in biology and material science. 1H, 13C, 15N NMR measurements carried out in solution and in the solid-state have been used to characterize a series of 3,6-disubstituted 1,2,4,5-tetrazine/dihydrotetrazine new derivatives. Experimental results presented here provide data for the assignment of 15N chemical shifts including new organic small molecules; two polymers having the tetrazine ring in the main chain and several previously published compounds. We report apparently for the first time 15N experimental chemical shift data for tetrazine systems in the solid state.

Tautomerism and 1H, 13C and 15N NMR spectral assignments of some nitro derivatives of malonic acid diamide.

Because of its reactivity, malonic acid diamide (1) was initially identified as an alternative precursor for the development of a new class of high-density insensitive energetic materials possessing low sensitivity to thermal decomposition and detonation by impact. Nitration of 1 was studied under different conditions and led to three different tautomeric forms (2-4) of nitromalonic acid diamine. Using stronger oxidation conditions the oxadiazole 5 was generated in one step. We report the full 1H, 13C and 15N NMR structural characterization of these compounds in DMSO together with thermal, infrared, mass spectrometric and x-ray analysis. Experimental data obtained for 4 are compatible with an enol-imine form. Our interpretation is consistent with calculated 1H and 13C NMR spectra (ACD).