Immunolocalisation of sodium/proton exchanger-like proteins in the gills of elasmobranchs

Na⁺/H⁺ exchangers are integral membrane proteins that exchange Na⁺ and H⁺ across cell membranes. The Na⁺/H⁺ exchangers 2 and 3 are epithelial isoforms in mammals and contribute to acid–base homeostasis. The gills of fishes, including elasmobranchs, are also associated with acid/base balance, and are probably the primary acid/base regulatory organ. This study examines the presence of Na⁺/H⁺ exchangers 2 and 3 using immunohistochemistry and immunoblotting in the gills of four species of elasmobranchs, the banjo ray (Trygonorrhina fasciata), southern eagle ray (Myliobatis australis), the gummy shark (Mustelus antarcticus) and the Australian angel shark (Squatina australis) using heterologous antibodies. Na⁺/H⁺ exchanger 2-like immunoreactivity was observed in the gills of the banjo ray, eagle ray and angel shark. In the banjo and eagle rays, this Na⁺/H⁺ exchanger-like immunoreactivity co-localised with immunoreactivity to Na⁺/K⁺-ATPase, a marker for the mitochondrial-rich cells of fishes. Na⁺/H⁺ exchanger 3-like immunoreactivity was only observed in the gills of the angel and gummy sharks, some Na⁺/H⁺ exchanger 3-like cells also showed Na⁺/K⁺-ATPase immunoreactivity. However, immunoblotting of banjo and eagle ray gill membranes demonstrated Na⁺/H⁺ exchanger 3-like immunoreactivity, which was not consistent with the immunohistochemical results. These data demonstrate the presence of epithelial Na⁺/H⁺ exchangers 2 and 3 in the gills of elasmobranchs and a link with acid/base regulation is suggested.

Monitoring a commercial fermentation with proton nuclear magnetic resonance spectroscopy with the aid of chemometrics

Proton nuclear magnetic resonance spectroscopy (NMR) has shown the potential for being a valuable tool in monitoring a commercial fermentation. In this preliminary study, a suite of organic analytes including ethanol, fructose, glucose, methanol, glycerol, malic acid, tartaric acid, succinic acid, acetic acid and lactic acid were simultaneously determined during the fermentation. Data collection and analysis using chemometric algorithms aided the understanding of key processes including the effects of seeding a wine with bacteria for malo-lactic fermentation.

A study of hydrogen bonding in concentrated diol/water solutions by proton NMR correlations with glass formation

Solute/water interactions in a series of diol solutions have been investigated by ¹H NMR. Strong hydrogen bonding between water and alcohols that are more basic than water is thought to result in lower chemical shifts of water protons compared to the case of pure water. This is attributed to a greater degree of covalent character in the hydrogen bonding between water and the more basic diols. The inductive effect of the methyl group and longer chain alkyls is observed to increase basicity in ethylene glycol, propylene glycol, and 2,3-butanediol solutions. A correlation between the glass-forming ability of the diol solutions and the stronger hydrogen-bonding solutes (i.e., stronger bases) is developed, with 2,3-butanediol best promoting glass formation at the lowest concentrations.

Characterization of a proton conductor based on silicotungstic acid

It was found in this work that silicotungstic acid hydrate could be mixed with phosphoric acid (H₃PO₄, 85%) to make a viscous paste material with high conductivity (10⁻² S/cm at room temperature). The STA/H₃PO₄ paste samples were stable at 80°C in the atmosphere, and at 100°C under constant humidity over 10 days. The conductivity behavior of the paste samples has been investigated under various conditions, and it was found to be dependent on temperature, paste composition, and environment humidity.

A new class of proton-conducting ionic plastic crystals based on organic cations and dihydrogen phosphate

Choline dihydrogen phosphate ([N_1.1.1.2OH]DHP) and 1-butyl-3-methylimidazolium dihydrogen phosphate ([C₄mim]DHP) were synthesized as a new class of proton-conducting ionic plastic crystals. Both [N_1.1.1.2OH]DHP and [C₄mim]DHP showed solid–solid phase transition(s) and showed a final entropy of fusion lower than 20 J K⁻¹ mol⁻¹ which is consistent with Timmerman’s criterion for molecular plastic crystals. The ionic conductivity of [N_1.1.1.2OH]DHP was in the range of 10⁻⁶ S cm⁻¹–10⁻³ S cm⁻¹ in the plastic crystalline phase. On the other hand, the ionic conductivity of [C₄mim]DHP showed about 10⁻⁵ S cm⁻¹ in the plastic crystalline phase. [N_1.1.1.2OH]DHP showed one order of magnitude higher ionic conductivity than [C₄mim]DHP in the temperature range where the plastic phase is stable.

Investigation of proton dynamics and the proton transport pathway in choline dihydrogen phosphate using solid-state NMR

Choline dihydrogen phosphate has previously been shown to be a good ionic conductor as well as an excellent host for acid doping, leading to high proton conductivities required for e.g., electrochemical devices including proton membrane fuel cells and sensors. A combination of variable-temperature ¹H solid-state NMR and 2D NMR pulse sequences, including ³¹P and ¹³C CODEX and ¹H BaBa, show that the proton conduction mechanism primarily involves assisted transport via a restricted three-site motion of the phosphate unit around the P–O bond that is hydrogen bonded to the choline and exchange of protons between these anions. In other words, proton transport at ambient temperatures appears to occur most favorably along the crystallographic b axis, from phosphate dimer to dimer. At elevated temperatures exchange between the protons of the hydroxyl group on the choline cation and the hydrogen-bonded dihydrogen phosphate groups also contributes to the structural diffusion of the protons in this solid state conductor.

Proton transport in choline dihydrogen phosphate/H3PO4 mixtures

Mixtures of the plastic crystal material choline dihydrogen phosphate [Choline][DHP] and phosphoric acid, from 4.5 mol% to 18 mol% H₃PO₄, were investigated and shown to have significantly higher proton conductivity compared to the pure [Choline][DHP]. This was particularly evident from the electrochemical hydrogen reduction reaction and the proton NMR diffusion measurements, in addition to ionic conductivity measured from the impedance spectroscopy. The ionic conductivity was observed to increase by more than an order of magnitude in phase I (i.e. the highest temperature solid phase in [Choline][DHP]) reaching up to 10⁻² S cm⁻¹. The multinuclear NMR spectroscopy data suggest that, at least on the timescale of the NMR measurement, the H⁺ cations and [DHP] anions are equivalent in both phases. The pulsed field gradient NMR diffusion measurements of the 18 mol% acid sample indicate that all three ions are mobile, however the H⁺ diffusion coefficient is an order of magnitude higher than for the [Choline] cation or the [DHP] anion, and therefore conduction in these materials is dominated by proton conductivity. The thermal stability, as measured by TGA, is unaffected with increasing acid additions and remains high; i.e. no significant mass loss below 200 °C.

Identification of a by-product of nitric oxide synthase activity in human acute brain injury with in vivo proton magnetic resonance spectroscopy

BACKGROUND AND PURPOSE: Laboratory studies have been used to identify nitric oxide as a notable mediator in neuronal death after acute brain injury. To our knowledge, this has not previously been confirmed with in vivo study in humans. Our purpose was to seek in vivo evidence for the induction of nitric oxide synthase (NOS) in human acute brain injury by using proton MR spectroscopy.

METHODS: In vitro proton MR spectra were obtained in neural extracts from 30 human cadavers, and in vivo spectra were obtained in 20 patients with acute brain injury and in a similar number of control subjects.

RESULTS: We identified a unique peak at 3.15 ppm by using in vivo proton MR spectroscopy in eight of 20 patients with acute brain injury but not in 20 healthy volunteers (P < .002). On the basis of in vitro data, we have tentatively assigned this peak to citrulline, a NOS by-product.

CONCLUSION: To our knowledge, our findings suggest, for the first time, that excitotoxicity may occur in human acute brain injury. Confirmation with the acquisition of spectra in very early acute cerebral injury would provide a rationale for the use of neuroprotective agents in these conditions, as well as a new noninvasive method for quantification.

Proton transport properties in zwitterion blends with brønsted acids

We describe zwitterion, 3-(1-butyl-1H-imidazol-3-ium-3-yl)propane-1-sulfonate (Bimps), mixtures with 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfoneamide (HN(Tf)₂) as new proton transport electrolytes. We report proton transport mechanisms in the mixtures based on results from several methods including thermal analyses, the complex-impedance method, and the pulsed field gradient spin echo NMR (pfg-NMR) method. The glass transition temperature (Tg) of the mixtures decreased with increasing HN(Tf)₂ concentration up to 50 mol %. The Tg remained constant at −55 °C with further acid doping. The ionic conductivity of HN(Tf)₂ mixtures increased with the HN(Tf)₂ content up to 50 mol %. Beyond that ratio, the mixtures showed no increase in ionic conductivity (10⁻⁴ S cm⁻¹ at room temperature). This tendency agrees well with that of Tg. However, the self-diffusion coefficients obtained from the pfg-NMR method increased with HN(Tf)₂ content even above 50 mol % for all component ions. At HN(Tf)₂ 50 mol %, the proton diffusion of HN(Tf)₂ was the fastest in the mixture. These results suggest that Bimps cannot dissociate excess HN(Tf)₂, that is, the excess HN(Tf)₂ exists as molecular HN(Tf)₂ in the mixtures. The zwitterion, Bimps, forms a 1:1 complex with HN(Tf)₂ and the proton transport property in this mixture is superior to those of other mixing ratios. Furthermore, CH₃SO₃H and CF₃SO₃H were mixed with Bimps for comparison. Both systems showed a similar tendency, which differed from that of the HN(Tf)₂ system. The Tg decreased linearly with increasing acid content for every mixing ratio, while the ionic conductivity increased linearly. Proton transport properties in zwitterion/acid mixtures were strongly affected by the acid species added.

Proton conductive composite membranes

In this work we investigated the synthesis of composite organic and inorganic membranes for proton conduction. Particles derived from metal alkoxides (M(OR)n) sol-gel processes (Ti, Zr, W with phosphoric acid) were embedded in polymeric matrices of poly-vinyl alcohol, (3-glycidoxypropyl)-trimethoxysilane and ethylene glycol. The structure of the composite membranes was complex as several IR peaks were convoluted, indicating the assignment of several functional groups. However, the peaks assigned to OH groups reduced in intensity in the composite membranes, indicating that cross-linking of hydroxyl groups in the organic and inorganic phases of the membrane may have occurred. The particles allowed for re-arrangement of the polymer matrix, as crystallinity was reduced compared to a polymer blank membrane. The composite membrane process resulted in homogeneous dispersion of nanoparticles into the polymer film. Proton conduction of the inorganic phase was mainly dominated by titania. Binary mixtures of titania phosphate (sample name TiP) resulted in proton conduction of 7.15 × 10−2 S.cm−1, one order of magnitude higher than zirconia phosphate (ZrP). The addition of Zr and W to TiP forming ternary or quaternary phases also led to lower proton conduction as compared to TiP. Similar trends were also observed for the composite membranes, though the TiP composite membrane proton conduction reduced after several hours of testing at 50°C, which was mainly attributed to acid leaching.

An organic ionic plastic crystal electrolyte based on the triflate anion exhibiting high proton transport

A novel organic ionic plastic crystal (OIPC) electrolyte based on a quaternary ammonium cation and the triflate anion has been synthesized, which shows fast proton transport and high thermal stability in the solid state when doped with triflic acid.

Characterization and evaluation of BaCo0.7Fe0.2Nb0.1O3−δ as a cathode for proton-conducting solid oxide fuel cells

This study characterizes BaCo0.7Fe0.2Nb0.1O3−δ (BCFN) perovskite oxide and evaluates it as a potential cathode material for proton-conducting SOFCs with a BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte. A four-probe DC conductivity measurement demonstrated that BCFN has a modest electrical conductivity of 2–15 S cm−1 in air with p-type semiconducting behavior. An electrical conductivity relaxation test showed that BCFN has higher Dchem and Kchem than the well-known Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxide. In addition, it has relatively low thermal expansion coefficients (TECs) with values of 18.2 × 10−6 K−1 and 14.4 × 10−6 K−1 at temperature ranges of 30–900 °C and 30–500 °C, respectively. The phase reaction between BCFN and BZCY was investigated using powder and pellet reactions. EDX and XRD characterizations demonstrated that BCFN had lower reactivity with the BZCY electrolyte than strontium-containing perovskite oxides such as SrCo0.9Nb0.1O3-δ and Ba0.6Sr0.4Co0.9Nb0.1O3−δ. The impedance of BCFN was oxygen partial pressure dependent. Introducing water into the cathode atmosphere reduced the size of both the high-frequency and low-frequency arcs of the impedance spectra due to facilitated proton hopping. The cathode polarization resistance and overpotential at a current density of 100 mA cm−2 were 0.85 Ω cm−2 and 110 mV in dry air, which decreased to 0.43 Ω cm−2 and 52 mV, respectively, in wet air (∼3% H2O) at 650 °C. A decrease in impedance was also observed with polarization time; this was possibly caused by polarization-induced microstructure optimization. A promising peak power density of ∼585 mW cm−2 was demonstrated by an anode-supported cell with a BCFN cathode at 700 °C.