Luke A. O'Dell

Controlled delivery of antimicrobial gallium ions from phosphate-based glasses

Gallium-doped phosphate-based glasses (PBGs) have been recently shown to have antibacterial activity. However, the delivery of gallium ions from these glasses can be improved by altering the calcium ion concentration to control the degradation rate of the glasses. In the present study, the effect of increasing calcium content in novel gallium (Ga2O3)-doped PBGs on the susceptibility of Pseudomonas aeruginosa is examined. The lack of new antibiotics in development makes gallium-doped PBG potentially a highly promising new therapeutic agent. The results show that an increase in calcium content (14, 15 and 16 mol.% CaO) cause a decrease in degradation rate (17.6, 13.5 and 7.3 microg mm(-2) h(-1)), gallium ion release and antimicrobial activity against planktonic P. aeruginosa. The most potent glass composition (containing 14 mol.% CaO) was then evaluated for its ability to prevent the growth of biofilms of P. aeruginosa. Gallium release was found to reduce biofilm growth of P. aeruginosa with a maximum effect (0.86 log(10) CFU reduction compared to Ga2O3-free glasses) after 48 h. Analysis of the biofilms by confocal microscopy confirmed the anti-biofilm effect of these glasses as it showed both viable and non-viable bacteria on the glass surface. Results of the solubility and ion release studies show that this glass system is suitable for controlled delivery of Ga3+. 71Ga NMR and Ga K-edge XANES measurements indicate that the gallium is octahedrally coordinated by oxygen atoms in all samples. The results presented here suggest that PBGs may be useful in controlled drug delivery applications, to deliver gallium ions in order to prevent infections due to P. aeruginosa biofilms.

Fast and simple acquisition of solid-state 14N NMR spectra with signal enhancement via population transfer.

A new approach for the acquisition of static, wideline (14)N NMR powder patterns is outlined. The method involves the use of frequency-swept pulses which serve two simultaneous functions: (1) broad-band excitation of magnetization and (2) signal enhancement via population transfer. The signal enhancement mechanism is described using numerical simulations and confirmed experimentally. This approach, which we call DEISM (Direct Enhancement of Integer Spin Magnetization), allows high-quality (14)N spectra to be acquired at intermediate field strengths in an uncomplicated way and in a fraction of the time required for previously reported methods.

The WURST kind of pulses in solid-state NMR

WURST pulses (wideband, uniform rate, smooth truncation) were first introduced two decades ago by Kupče and Freeman as a means of achieving broadband adiabatic inversion of magnetisation for solution-state (13)C decoupling at high magnetic field strengths. In more recent years these pulses have found use in an increasingly diverse range of applications in solid-state NMR. This article reviews a number of recent developments that take advantage of WURST pulses, including broadband excitation, refocusing and cross polarisation for the acquisition of ultra-wideline powder patterns, signal enhancement for half-integer and integer spin quadrupolar nuclei, spectral editing, direct and indirectly observed (14)N overtone MAS, and symmetry-based homonuclear recoupling. Simple mathematical descriptions of WURST pulses and some brief theory behind their operation in the adiabatic and non-adiabatic regimes are provided, and various practical considerations for their use are also discussed.

Variable-temperature 17O NMR studies allow quantitative evaluation of molecular dynamics in organic solids

We report a comprehensive variable-temperature solid-state (17)O NMR study of three (17)O-labeled crystalline sulfonic acids: 2-aminoethane-1-sulfonic acid (taurine, T), 3-aminopropane-1-sulfonic acid (homotaurine, HT), and 4-aminobutane-1-sulfonic acid (ABSA). In the solid state, all three compounds exist as zwitterionic structures, NH(3)(+)-R-SO(3)(-), in which the SO(3)(-) group is involved in various degrees of O···H-N hydrogen bonding. High-quality (17)O NMR spectra have been obtained for all three compounds under both static and magic angle spinning (MAS) conditions at 21.1 T, allowing the complete set of (17)O NMR tensor parameters to be measured. Assignment of the observed (17)O NMR parameters to the correct oxygen sites in the crystal lattice was achieved with the aid of DFT calculations. By modeling the temperature dependence of (17)O NMR powder line shapes, we have not only confirmed that the SO(3)(-) groups in these compounds undergo a 3-fold rotational jump mechanism but also extracted the corresponding jump rates (10(2)-10(5) s(-1)) and the associated activation energies (E(a)) for this process (E(a) = 48 ± 7, 42 ± 3, and 45 ± 1 kJ mol(-1) for T, HT, and ABSA, respectively). This is the first time that SO(3)(-) rotational dynamics have been directly probed by solid-state (17)O NMR. Using the experimental activation energies for SO(3)(-) rotation, we were able to evaluate quantitatively the total hydrogen bond energy that each SO(3)(-) group is involved in within the crystal lattice. The activation energies also correlate with calculated rotational energy barriers. This work provides a clear illustration of the utility of solid-state (17)O NMR in quantifying dynamic processes occurring in organic solids. Similar studies applied to selectively (17)O-labeled biomolecules would appear to be very feasible.

Identifying H–N proximities in solid-state NMR using 14N overtone irradiation under fast MAS

Two NMR methods for the identification of 1H–14N proximities in solid powder samples are considered. Both approaches involve the irradiation of the 14N overtone transition (Δm = 2) and observation of 1H signals under fast MAS and at an intermediate magnetic field strength (11.7 T). First, the recently reported 1H–14NOT HMQC experiment is developed into a generally-applicable, broadband version using frequency-swept WURST pulses capable of exciting the full range of 14NOT signals. We demonstrate the validity of this approach on various samples, also showing that standard pulses can be used to selectively excite individual nitrogen sites and provide more accurate indirect 14NOT powder patterns from which 14N NMR parameters can be extracted if required. As a second approach, we present some preliminary results demonstrating the feasibility of 1H–14NOT overtone rotary recoupling (ORR) under fast MAS. Dephasing fractions of up to 0.3 have been obtained using a basic TRAPDOR-style pulse sequence, a simple approach that shows much potential for optimisation. WURST pulses are also shown to provide improvements in the recoupling bandwidth. Crucially, for both of these methods our experimental results and exact numerical simulations confirm that the +2ωr overtone sideband should be irradiated for optimal experimental efficiency.

Ultra-wideline 14N NMR spectroscopy as a probe of molecular dynamics

We show that ultra-wideline solid-state (14)N NMR can be used as a quantitative probe of molecular dynamics. Jump rates for the molecular flipping mechanism in crystalline urea are determined at various temperatures and are shown to be in good agreement with other NMR techniques.

Proton transport behaviour and molecular dynamics in the guanidinium triflate solid and its mixtures with triflic acid

Knowledge of the proton transport behaviour in electrolyte materials is crucial for designing and developing novel solid electrolytes for electrochemical device applications such as fuel cells or batteries. In the present work, high proton conductivity (approximately 10−3 S cm−1) was observed in the triflic acid (HTf) containing guanidinium triflate (GTf) composites. The proton transport mechanism in the composite was elucidated by comparing the diffusion coefficients obtained from NMR and conductivity measurements. Several orders of magnitude enhancement of conductivity is observed upon addition of HTf to the organic solid, and this appears to follow percolation behaviour with a percolation threshold of approximately 2% HTf. The data support a structural diffusion (or Grotthuss) mechanism of proton transport with a calculated Haven ratio significantly less than unity. 13C SUPER and 14N overtone NMR experiments were used to study the mobility and symmetry of the triflate anion and guanidinium cation respectively at a molecular level. The former experiment shows that the CF3 group in the anion displays fast and isotropic motion at room temperature. In contrast to the high mobility of the anion group, the 14N overtone experiments indicate that the guanidinium cation is static in both the pure and the acid-containing GTf samples at room temperature. It is anticipated that these solid-state NMR techniques may be also applied to other organic solid state electrolyte materials to achieve a better understanding of their transport mechanisms and molecular dynamics.

Control of surface free energy in titanium doped phosphate based glasses by co‐doping with zinc

To significantly improve the biocompatibility of titanium doped phosphate based glasses, codoping with zinc has been attempted. This study investigated the effect of doping a quaternary 15Na(2)O:30CaO:5TiO(2):50P(2)O(5) glass with zinc oxide (1, 3, and 5 mol %) on bulk, structural, surface, and biological properties; the results were compared with glasses free from ZnO and/or TiO(2). ZnO as adjunct to TiO(2) was effective in changing density, interchain bond forces, degradation behavior, and ions released from the degrading glasses. Incorporation of both TiO(2) and ZnO in T5Z1, T5Z3, and T5Z5 glasses reduced the level of Zn(2+) release by two to three orders of magnitude compared with glasses containing ZnO only (Z5). (31)P NMR results for T5Z1, T5Z3, and T5Z5 glasses showed the presence of Q(3) species suggesting that the TiO(2) is acting as a network former, and the phosphate network becomes slightly more connected with increasing ZnO incorporation. Regardless of their relative lower hydrophilicity and surface reactivity compared with the control glass free from TiO(2) and ZnO (T0Z0), these glasses have significantly higher surface reactivity compared with Thermanox. This has been also reflected in the maintenance of >98% viable Osteoblasts, proliferation rate, and expression level of osteoblastic marker genes in a comparable manner to Thermanox and T5 glasses, particularly T5Z1 and T5Z3 glasses. However, T0Z0 and Z5 glasses showed significantly reduced viability compared to Thermanox. Therefore, it can be concluded that ZnO doped titanium phosphate glasses, T5Z1 and T5Z3 in particular, can be promising substrates for bone tissue engineering applications.

Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres

The incorporation of polyvinylidene difluoride (PVDF) electrospun nanofibres within N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF4] was investigated with a view to fabricating self-standing membranes for various electrochemical device applications, in particular lithium metal batteries. Significant improvement in mechanical properties and ionic conduction was demonstrated in a previous study, which also demonstrated the remarkably high performance of the lithium-doped composite material in a device. We now seek a fundamental understanding of the role of fibres within the matrix of the plastic crystal, which is essential for optimizing device performance through fine-tuning of the composite material properties. The focus of the current study is therefore a thorough investigation of the phase behaviour and conduction behaviour of the pure and the lithium-doped (as LiBF4) plastic crystal, with and without incorporation of polymer nanofibres. Analysis of the structure of the plastic crystal, including the effects of lithium ions and the incorporation of PVDF fibres, was conducted by means of synchrotron XRD. Ion dynamics were evaluated using VT solid-state NMR spectroscopy. ATR-FTIR spectroscopy was employed to gain insights into the molecular interactions of doped lithium ions and/or the PVDF nanofibres in the matrix of the [C2mpyr][BF4] composites. Preliminary measurements using PALS were conducted to probe structural defects within the pure materials. It was found that ion transport within the plastic crystal was significantly altered by doping with lithium ions due to the precipitation of a second phase in the structure. The incorporation of the fibres activated more mobile sites in the systems, but restricted ion mobility with different trends being observed for each ion species in each crystalline phase. In the presence of the fibres a strong interaction observed between the Li ion and the pyrrolidinium ring disappeared and formation of the second phase was prevented. As a result, an increased number of mobile lithium ions are released into the solid solution structure of the matrix, simultaneously removing the blocking effect of the second phase. Thus, ion conduction was remarkably improved within the Li-doped composite compared to the neat Li-doped plastic crystal.

Rapid surface functionalization of carbon fibres using microwave irradiation in an ionic liquid

The modification of carbon fibre surfaces has been achieved using a novel combination of low power microwave irradiation (20 W) in both an ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and an organic solvent (1,2-dichlorobenzene). The use of the ionic liquid was superior to the organic solvent in this application, resulting in a higher density of surface grafted material. As a consequence, carbon fibres treated in the ionic liquid displayed improved interfacial adhesion in the composite material (+28% relative to untreated fibres) compared to those treated in organic solvent (+18%). The methodology presented herein can be easily scaled up to industrially relevant quantities and represent a drastic reduction in both reaction time (30 min from 24 h) and energy consumption, compared to previously reported procedures. This work opens the door to potential energy and time saving strategies which can be applied to carbon fibre manufacture for high performance carbon fibre reinforced composites.