Poly(styrene-b-isobutylene-b-styrene) block copolymer ionomers (BCPI) and BCPI/silicate nanocomposites. 2. NaBCPI sol-gel polymerization templates

Polystyrene (PS) blocks in poly(styrene-b-isobutylene-b-styrene) (PS-PIB-PS) block copolymers were partially sulfonated and the acid groups converted to Na⁺SO₃⁻ groups to create ionomers. Then, dimethylacetamide was used to selectively swell the ionic PS domains and the swollen films were exposed to sol-gel reactive tetraethylorthosilicate solutions. (EtO)_4−xSi(OH)_x monomers then permeated films so that sol-gel reactions occurred within/around the ionic PS domains. Environmental scanning electron microscopy/energy dispersive X-ray spectroscopy investigations showed that silicate structures can be incorporated within the interior of the ionomer films. Differential scanning calorimetry studies indicated that there is no variance in the PIB block T_g with respect to ionomer formation, or with respect to silicate loading of the ionomer at low levels, which suggests that the silicate component does not reside in the PIB phase. ²³Na solid state NMR spectroscopy detected isolated Na⁺SO₃⁻ groups as well as aggregated SO₃⁻Na⁺ ion pairs for ‘as cast’ and ‘dry’ non-silicate containing ionomer samples. In a hydrated sample, almost all Na⁺ ions were solvent-separated. AFM analysis showed that phase separation exists, but that the degree of order is significantly less than that for hybrids based on the corresponding benzyltrimethylammonium ionomer. This frustrated morphology was also seen in the results of small angle X-ray scattering experiments. Given the scale of organic/inorganic heterogeneity, these hybrids are properly classified as nanocomposites.     

Fluorine-free binders for Carbon Black based Electrochemical Supercapacitors

Industrially manufactured carbon blacks (CBs) provide highly dispersed carbon materials with a specific surface of up to 1700 m² g^–1. Precompaction at p > 10 MPa in the presence of 3–10 wt% PTFE (provided as a dispersion) is known to lead to stable electrodes for electrochemical supercapacitors. Specific capacitances for single electrodes (C_s,1) were measured by constant current cycling (CCC) at 34 mA cm^–2 to be up to 250 F g^–1. It is shown that substitution of PTFE by fluorine-free binders, such as aqueous dispersions of polystyrene, styrene/butadien-copolymer and ethylene/acrylic acid copolymer is possible. Optimum systems were with 3–10 wt% binders of butadiene/styrene copolymers. They allowed stable results within hundreds of cycles. No shedding of the CB particles was observed, and swelling of the electrode was minimum.     

Electrochemical supercapacitors based on industrial carbon blacks in aqueous H2SO4

It is shown that industrial carbon blacks (CBs) are interesting materials for electrochemical supercapacitors (ECSCs). The specific areas A _s ranged from 28 to 1690 m² g^–1. The highest values were realized through activation in CO₂ at 1100 °C. Precompacted carbon black electrodes with 5–10 wt% PTFE as a binder in the pellet in 10–12 M H₂SO₄ were characterized by constant current cycling, CCC, j = 20–50 mA cm^–2. Voltage–time curves showed nearly pure capacitive behaviour. Specific capacitance of single electrodes, C _s,1, could be derived therefrom. A plot of C _s,1 against A _s shows a linear behavior according to C _s,1 = C _A,DL A _s, where C _A,DL is the Helmholtz double layer capacitance per atomic surface area. Best fit was obtained with C _A,DL = 16 F cm^–2. The highest experimental values, C _s,1 = 250 F g^–1, are due to 60% of the theoretical maximum, which corresponds to an A _s calculated from both faces of isolated graphene layers. Only marginal pseudocapacitances are observed. Model cells for ECSCs (with microporous Celgard^TM separators) could be extensively cycled (CCC). A monopolar cell endured Z > 2000 cycles. Bipolar cells (5 units) allowed 700 cycles. Practical problems such as the development of electrode holders and of carbon black filled polypropylene composites for current collectors are discussed. It is concluded that entirely metal-free ECSCs with low cost can be produced.     

On the Limited Selectivity of Silica-Based Epoxidation Catalysts

Epoxidation of 2-cyclohexen-1-ol with TBHP and TiO₂–SiO₂, Fe₂O₃–SiO₂ and SiO₂ aerogels has been studied. The influence of surface silanol groups and transition metal impurities in titania–silica on the product distribution has been analyzed. The results, supported by literature data, indicate that high surface area silica cannot generally be regarded as an inert matrix in epoxidation catalysts. Contribution of Ti-free silica limits the selectivity of Ti- and Si-containing catalysts in demanding epoxidation reactions. The activity of silica – together with the background oxidation of the olefin – may lead to overestimated intrinsic activities when the reaction rate is related to the Ti content of the catalyst.     

Salivary defense proteins: their network and role in innate and acquired oral immunity

There are numerous defense proteins present in the saliva. Although some of these molecules are present in rather low concentrations, their effects are additive and/or synergistic, resulting in an efficient molecular defense network of the oral cavity. Moreover, local concentrations of these proteins near the mucosal surfaces (mucosal transudate), periodontal sulcus (gingival crevicular fluid) and oral wounds and ulcers (transudate) may be much greater, and in many cases reinforced by immune and/or inflammatory reactions of the oral mucosa. Some defense proteins, like salivary immunoglobulins and salivary chaperokine HSP70/HSPAs (70 kDa heat shock proteins), are involved in both innate and acquired immunity. Cationic peptides and other defense proteins like lysozyme, bactericidal/permeability increasing protein (BPI), BPI-like proteins, PLUNC (palate lung and nasal epithelial clone) proteins, salivary amylase, cystatins, prolin-rich proteins, mucins, peroxidases, statherin and others are primarily responsible for innate immunity. In this paper, this complex system and function of the salivary defense proteins will be reviewed.     

The effect of beta-alanine supplementation on neuromuscular fatigue in elderly (55–92 Years): a double-blind randomized study

Background

Ageing is associated with a significant reduction in skeletal muscle carnosine which has been linked with a reduction in the buffering capacity of muscle and in theory, may increase the rate of fatigue during exercise. Supplementing beta-alanine has been shown to significantly increase skeletal muscle carnosine. The purpose of this study, therefore, was to examine the effects of ninety days of beta-alanine supplementation on the physical working capacity at the fatigue threshold (PWC_FT) in elderly men and women.

Methods

Using a double-blind placebo controlled design, twenty-six men (n = 9) and women (n = 17) (age ± SD = 72.8 ± 11.1 yrs) were randomly assigned to either beta-alanine (BA: 800 mg × 3 per day; n = 12; CarnoSyn?) or Placebo (PL; n = 14) group. Before (pre) and after (post) the supplementation period, participants performed a discontinuous cycle ergometry test to determine the PWC_FT.

Results

Significant increases in PWC_FT (28.6%) from pre- to post-supplementation were found for the BA treatment group (p < 0.05), but no change was observed with PL treatment. These findings suggest that ninety days of BA supplementation may increase physical working capacity by delaying the onset of neuromuscular fatigue in elderly men and women.

Conclusion

We suggest that BA supplementation, by improving intracellular pH control, improves muscle endurance in the elderly. This, we believe, could have importance in the prevention of falls, and the maintenance of health and independent living in elderly men and women.