Electromechanical behaviour of Nafion-based soft actuators.

Soft actuators based on Ionic Polymer-Metal Composites (IPMCs) are of considerable interest for applications in biomedical devices and robotics. In this work, thin commercial and thick laboratory-prepared Nafion membranes were made into model IPMC actuator devices by incorporation of Pt electrode layers. In extensive electromechanical tests the maximum average tip displacement and maximum force generated were recorded. The effect of amplitude and frequency of the applied voltage on both displacement and force was examined as were the effects of the origin of the Nafion membrane, the Pt loading, the structure of the electrode and the presence or absence of an Au overlayer. The cast samples generated much smaller displacements but much larger forces than the commercial Nafion samples. For all samples, displacement and force increased with increasing applied voltage, with increased number of Pt plating cycles and when an Au overlayer was present but decreased with increasing applied voltage frequency. Waveform analysis of applied voltage, current and force was performed by considering the capacitive nature of the IPMC actuators.

NMR studies of cooperative effects in adsorption.

The conversion of gas adsorption isotherms into pore size distributions generally relies upon the assumption of thermodynamically independent pores. Hence, pore-pore cooperative adsorption effects, which might result in a significantly skewed pore size distribution, are neglected. In this work, cooperative adsorption effects in water adsorption on a real, amorphous, mesoporous silica material have been studied using magnetic resonance imaging (MRI) and pulsed-gradient stimulated-echo (PGSE) NMR techniques. Evidence for advanced adsorption can be seen directly using relaxation time weighted MRI. The number and spatial distributions of pixels containing pores of different sizes filled with condensate have been analyzed. The spatial distribution of filled pores has been found to be highly nonrandom. Pixels containing the largest pores present in the material have been observed to fill in conjunction with pixels containing much smaller pores. PGSE NMR has confirmed the spatially extensive nature of the adsorbed ganglia. Thus, long-range (≥40 µm) cooperative adsorption effects, between larger pores associated with smaller pores, occur within mesoporous materials. The NMR findings have also suggested particular types of pore filling mechanisms occur within the porous solid studied.

Time-resolved mapping of water diffusion coefficients in a working soft actuator device.

Diffusion-weighted imaging was employed to spatially map the distribution of the diffusion coefficient of water, D, in bare, water-soaked, Li(+)-exchanged, cast Nafion and in an ionic polymer-metal composite (IPMC) soft actuator element, prepared from this bare Nafion by impregnation with Pt electrodes. D was evaluated in two orthogonal directions: along one of the long dimensions of the sample (Dx) and through its thickness (Dz). D-maps of the IPMC element were obtained both in the absence of an applied potential and in situ during the application of a 3 V dc potential across the thickness of the sample. In the bare Nafion, D-maps showed uniform values of both Dx and Dz of about 6 x 10 (-10) m(2) s(-1). In the IPMC two effects were observed: (i) D at the electroded surfaces of the IPMC was higher than at the center of the sample; (ii) this difference was much greater in Dz than in Dx . Both effects were explained by the influence of the impregnated Pt electrodes on polymer structure. The D-maps in the electrochemical measurements showed high values of D (up to 8 x 10(-10) m(2) s(-1)) at the cathode and low values (from 1 x 10(-10) m(2) s(-1)) at the anode. This was explained in terms of the effect on the Nafion nanostructure of the forced electro-migration of Li(H2O)x(+) species toward the cathode.

Ascorbic acid conjugates isolated from the phloem of Cucurbitaceae.

Analysis of phloem exudates from the fruit of Cucurbitaceae revealed the presence of several compounds with UV-visible absorption spectra identical to that of l-ascorbic acid. In Cucurbita pepo L. (zucchini), the compounds could be isolated from phloem exudates collected from aerial parts of the plant but were not detected in whole tissue homogenates. The compounds isolated from the phloem exudates of C. pepo fruit were eluted from strong anion exchange resin in the same fraction as l-ascorbic acid and were oxidised by ascorbate oxidase (E.C. 1.10.3.3). The major compound purified from C. pepo fruit exudates demonstrated similar redox properties to l-ascorbic acid and synthetic 6-O-glucosyl-l-ascorbic acid (6-GlcAsA) but differed from those of 2-O-glucosyl-l-ascorbic acid (2-GlcAsA) isolated from the fruit of Lycium barbarum L. Parent and fragment ion masses of the compound were consistent with hexosyl-ascorbate in which the hexose moiety was attached to C5 or C6 of AsA. Acid hydrolysis of the major C. pepo compound resulted in the formation of l-ascorbic acid and glucose. The purified compound yielded a proton NMR spectrum that was almost identical to that of synthetic 6-GlcAsA. A series of l-ascorbic acid conjugates have, therefore, been identified in the phloem of Cucurbitaceae and the most abundant conjugate has been identified as 6-GlcAsA. The potential role of such conjugates in the long-distance transport of l-ascorbic acid is discussed.

Mutation of the PDK1 PH domain inhibits protein kinase B/Akt, leading to small size and insulin resistance.

PDK1 activates a group of kinases, including protein kinase B (PKB)/Akt, p70 ribosomal S6 kinase (S6K), and serum and glucocorticoid-induced protein kinase (SGK), that mediate many of the effects of insulin as well as other agonists. PDK1 interacts with phosphoinositides through a pleckstrin homology (PH) domain. To study the role of this interaction, we generated knock-in mice expressing a mutant of PDK1 incapable of binding phosphoinositides. The knock-in mice are significantly small, insulin resistant, and hyperinsulinemic. Activation of PKB is markedly reduced in knock-in mice as a result of lower phosphorylation of PKB at Thr308, the residue phosphorylated by PDK1. This results in the inhibition of the downstream mTOR complex 1 and S6K1 signaling pathways. In contrast, activation of SGK1 or p90 ribosomal S6 kinase or stimulation of S6K1 induced by feeding is unaffected by the PDK1 PH domain mutation. These observations establish the importance of the PDK1-phosphoinositide interaction in enabling PKB to be efficiently activated with an animal model. Our findings reveal how reduced activation of PKB isoforms impinges on downstream signaling pathways, causing diminution of size as well as insulin resistance.

The observation and quantification of oil migration and binding in sediments using T2 magnetic resonance imaging.

Magnetic resonance imaging (MRI) makes use of the interactions between atomic nuclei and an external, strong, magnetic field to image the distribution of these nuclei through a substance. In this study, proton MRI has been used to indicate the presence of oil in sediment. Using a multiecho spin-echo acquisition sequence, images of relative oil density, and hence concentration, and of the magnetic resonance relaxation rate, T2, were produced. T2, which is greatly influenced by molecular motion, was equated to binding between the oil and the sediment, thus, providing an almost real-time "description" of all aspects of the oil-sediment interaction including motion of the oil. The interactions among three sediments from the Tay Estuary (East Coast of Scotland) and three crude oils (Fulmar, Forties and Venezuelan) are discussed. Observation of changes in images of oil density and changes in T2, using spread sheets, allow both rates of diffusion of the oil into the sediment and changes in the binding of the oil to the sediment to be calculated. Both the Forties and Fulmar oils move more rapidly than the Venezuelan oil in all of the sediments examined, while the strength of binding is sediment dependent. Thus, the ability of MRI to distinguish between the rates of flow of the oils into the sediment and the strengths of interaction between the various sediments and oils is demonstrated.

The determination of phosphorus containing compounds in dental casting investment products by 31P solid-state MAS-NMR spectroscopy.

OBJECTIVES: To use (31)P solid-state MAS-NMR to determine the phosphorus compounds that occur in dental casting investment material: (a) as-received, (b) after setting and (c) after burn-out and discover whether such compounds are the same in each material across a product range. METHODS: [(1)H] High powered decoupling (HPDC) and [(1)H] cross-polarization (CP) (31)P solid-state MAS-NMR spectroscopy at a resonance frequency of 121.4 MHz were used. Six commercial products were examined. Manufacturer's instructions were followed and a special liquid was used without dilution. RESULTS: All products contain ammonium dihydrogen phosphate as the acid phosphate required for the setting reaction. All set by the formation of struvite and significant amounts of amorphous magnesium orthophosphate. In three products, lesser amounts of newberyite were present and in another the equivalent amorphous compound was formed. When burnt-out, magnesium metaphosphate or pyrophosphate was the dominant matrix compound. A higher burn-out temperature favoured pyrophosphate formation. Farringtonite was present to a lesser extent with the metaphosphate. SIGNIFICANCE: Compounds that were not detected in earlier X-ray powder diffraction spectroscopy studies were detected by NMR, notably amorphous and glassy compounds (magnesium orthophosphate in set investment and magnesium metaphosphate in burnt-out material). The variation between products was significant and far greater than expected from the published scientific literature. Since the formation of compounds is affected by technical procedure and ambient conditions, these findings could offer some insight into the cause of the unpredictability of expansion measurements between laboratories. Further research is being undertaken.

(31)P solid-state MAS-NMR spectroscopy of the compounds that form in phosphate-bonded dental casting investment materials during setting.

OBJECTIVES: To use (31)P solid-state MAS-NMR to determine which compounds form in phosphate-bonded dental casting investment material during setting, when the ambient temperature is altered. To determine whether they differ in material originating at the center of the mix from material that adheres to the mixing bowl wall. METHODS: (1)H high powered decoupled (HPDC) and (1)H cross polarized (CP) (31)P solid-state MAS-NMR spectroscopy were used at a resonance frequency of 121.4MHz to determine molecular structure. Four commercial products were examined. Manufacturer's instructions were followed and special liquid used without dilution. Ambient temperature was between 18 and 37 degrees C. RESULTS: Molecular structures change with ambient temperature and product. Amorphous Mg(3)(PO(4))(2) or struvite dominate with newberyite, cattiite, amorphous Mg(2)P(2)O(7) and amorphous MgHPO(4) present as minor phases. Exceptionally, amorphous MgHPO(4) dominates. Differences in structure were found in material taken from the center of the mix compared with that scraped from the bowl wall, but the incidence may be specific to the product/mixer combination and not a general effect. SIGNIFICANCE: The formation of compounds in phosphate-bonded investment can be affected by ambient temperature. This effect and the use of material adhering to the bowl wall (instead of that from the center of the mix) are possible causes for the unpredictability of setting expansion measurements between laboratories. There is variation between products. When phosphate-bonded investment is required for casting, a consistent ambient temperature must be used and it would be wise to mix sufficient material to avoid scraping the bowl.

Simulation of nonwetting phase entrapment within porous media using magnetic resonance imaging.

Models representing the pore structures of amorphous, mesoporous silica pellets have been constructed using magnetic resonance images of the materials. Using magnetic resonance imaging (MRI), maps of the macroscopic (approximately 0.01-1 mm) spatial distribution of porosity and pore size were obtained. The nature and key parameters of the physical mechanism for mercury retraction, during porosimetry experiments on the silica materials, were determined using integrated gas sorption experiments. Subsequent simulations of mercury porosimetry within the structural models derived from MRI have been used to successfully predict, a priori, the point of the onset of structural hysteresis and the final levels of mercury entrapment for the silicas. Hence, a firm understanding of the physical processes of mercury retraction and entrapment in these amorphous silica materials has been established.

In situ magnetic resonance imaging of electrically-induced water diffusion in a nafion ionic polymer film.

By deploying a functioning electrochemical cell inside a Magnetic Resonance Imaging (MRI) instrument, images of the electrically-induced diffusion of water through a Li+ ion-exchanged Nafion ionic polymer film in the form of two-dimensional maps of proton density and transverse relaxation time, T2, were generated and changes in these images over time and with respect to changes made to the applied potential were followed.