Structural characterization of conducting polypyrrole using 13C cross-polarization/magic-angle spinning solid-state nuclear magnetic resonance spectroscopy

¹³C nuclear magnetic resonance (n.m.r.) has been used to study polypyrrole and N-substituted polypyrrole in the solid state. The extent of oxidation appears to be counterion-dependent; in particular, the quinoid structure appears favoured in the films prepared with dodecyl sulfate. Resonances associated with the quinoid unit are lost upon reduction of the polypyrrole film, which supports the idea that the quinoid structure is associated with the oxidized form of polypyrrole. N-substituted polypyrroles have a more distinct resonance at 110 ppm, which is linked to lower degrees of oxidation or charge delocalization in these systems. The decrease in conductivity of polypyrrole upon thermal ageing in air is associated with both the loss of counterion (‘thermal dedoping’) and the decomposition of the quinoid structure in the polymer backbone. There is no indication of carbonyl formation in the solid-state n.m.r. spectra obtained in the present study.

A potential novel rapid screening NMR approach to boundary film formation at solid interfaces in contact with ionic liquids

The boundary films generated on a series of inorganic compounds, typical of native films on metal and ceramic surfaces, when exposed to various ionic liquids (ILs) based on the trihexyl(tetradecyl)phosphonium cation have been characterized using multinuclear solid-state NMR. The NMR results indicate that SiO₂ and Mg(OH)₂ interact strongly with the anion and cation of each IL through a mechanism of adsorption of the anion and subsequent close proximity of the cation in a surface double layer (as observed through ¹H−²⁹Si cross polarization experiments). In contrast, Al₂O₃, MgO, ZnO, and ZrO₂ appear less active, strongly suggesting the necessity of hydroxylated surface groups in order to enhance the generation of these interfacial films. Using solid-state NMR to characterize such interfaces not only has the potential to elucidate mechanisms of wear resistance and corrosion protection via ILs, but is also likely to allow their rapid screening for such durability applications.

Quantifying rubber degradation using NMR

Ageing can lead to the degradation of the tensile properties of natural rubber. The ageing process causes changes in the polymer segmental motion as well as the chemical structure, both of which can be monitored using nuclear magnetic resonance (NMR) spectroscopy. This work demonstrates that NMR can quantify rubber degradation due to ageing, and also that relatively simple NMR equipment can be used. This simpler equipment can be made portable and so could give a simple and fast indication of the condition of rubber in service. The 1H NMR transverse relaxation time, T2, and the 13C NMR spectrum using cross polarization and magic angle spinning (CP MAS) for samples taken at various levels of a degraded natural rubber liner were compared. These experiments showed that, as the level of degradation increased, the 1H NMR transverse relaxation time decreased. The 13C spectra showed considerable peak broadening, indicative of decreased mobility with increased level of degradation as well as the presence of degradation products. Further investigations using lower powered NMR equipment to measure the 1H NMR transverse relaxation times of two different series of natural rubbers were also performed. This work has shown that this simpler method is also sensitive to structural and mechanical property changes in the rubber. This method of monitoring rubber degradation could lead to the non-destructive use of NMR to determine the condition of a part in service.

Dynamic nuclear polarisation enhanced (14)N overtone MAS NMR spectroscopy.

Dynamic nuclear polarisation (DNP) has been used to obtain magic angle spinning (14)N(OT) (nitrogen-14 overtone) solid-state NMR spectra from several model amino acids, with both direct and indirect observation of the (14)N(OT) signal. The crystalline solids were impregnated with biradical solutions of organic liquids that do not dissolve the crystalline phase. The bulk phase was then polarized via(1)H spin diffusion from the highly-polarized surface (1)H nuclei, resulting in (1)H DNP signal enhancements of around two orders of magnitude. Cross polarisation from (1)H nuclei directly to the (14)N overtone transition is demonstrated under magic angle spinning, using a standard pulse sequence with a relatively short contact time (on the order of 100 μs). This method can be used to acquire (14)N overtone MAS powder patterns that match closely with simulated line shapes, allowing isotropic chemical shifts and quadrupolar parameters to be measured. DNP enhancement also allows the rapid acquisition of 2D (14)N(OT) heteronuclear correlation spectra from natural abundance powder samples. (1)H-(14)N(OT) HETCOR and (13)C-(14)N(OT) HMQC pulse sequences were used to observe all single-bond H-N and C-N correlations in histidine hydrochloride monohydrate, with the spectra obtained in a matter of hours. Due to the high natural abundance of the (14)N isotope (99.6%) and the advantages of observing the overtone transition, these methods provide an attractive route to the observation of C-N correlations from samples at natural isotopic abundance and enable the high resolution measurement of (14)N chemical shifts and quadrupolar interaction parameters.

Ultra-wideline 14N solid-state NMR as a method for differentiating polymorphs: glycine as a case study

Nitrogen-14 solid-state NMR (SSNMR) is utilized to differentiate three polymorphic forms and a hydrochloride (HCl) salt of the amino acid glycine. Frequency-swept Wideband, Uniform Rate, Smooth Truncated (WURST) pulses were used in conjunction with Carr-Purcell Meiboom-Gill refocusing, in the form of the WURST-CPMG pulse sequence, for all spectral acquisitions. The ¹⁴N quadrupolar interaction is shown to be very sensitive to variations in the local electric field gradients (EFGs) about the ¹⁴N nucleus; hence, differentiation of the samples is accomplished through determination of the quadrupolar parameters CQ and ηQ, which are obtained from analytical simulations of the ¹⁴N SSNMR powder patterns of stationary samples (i.e., static NMR spectra). Additionally, differentiation of the polymorphs is also possible via the measurement of ¹⁴N effective transverse relaxation time constants, T^eff2(¹⁴N). Plane-wave density functional theory (DFT) calculations, which exploit the periodicity of crystal lattices, are utilized to confirm the experimentally determined quadrupolar parameters as well as to determine the orientation of the ¹⁴N EFG tensors in the molecular frames. Several signal-enhancement techniques are also discussed to help improve the sensitivity of the ¹⁴N SSNMR acquisition method, including the use of selective deuteration, the application of the BRoadband Adiabatic INversion Cross-Polarization (BRAIN-CP) technique, and the use of variable-temperature (VT) experiments. Finally, we examine several cases where ¹⁴N VT experiments employing Carr-Purcell-Meiboom-Gill (CPMG) refocusing are used to approximate the rotational energy barriers for RNH3⁺ groups.