Sulfate-based anionic diblock copolymer nanoparticles for efficient occlusion within zinc oxide

Occlusion of copolymer particles within inorganic crystalline hosts not only provides a model for understanding the crystallisation process, but also may offer a direct route for the preparation of novel nanocomposite materials with emergent properties. In the present paper, a series of new well-defined anionic diblock copolymer nanoparticles are synthesised by polymerisation-induced self-assembly (PISA) via reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerisation and then evaluated as crystal habit modifiers for the in situ formation of ZnO in aqueous solution. Systematic studies indicate that both the chemical nature (i.e. whether sulfate-based or carboxylate-based) and the mean degree of polymerisation (DP) of the anionic stabiliser block play vital roles in determining the crystal morphology. In particular, sulfate-functionalised nanoparticles are efficiently incorporated within the ZnO crystals whereas carboxylate-functionalised nanoparticles are excluded, thus anionic character is a necessary but not sufficient condition for successful occlusion. Moreover, the extent of nanoparticle occlusion within the ZnO phase can be as high as 23% by mass depending on the sulfate-based nanoparticle concentration. The optical properties, chemical composition and crystal structure of the resulting nanocomposite crystals are evaluated and an occlusion mechanism is proposed based on the observed evolution of the ZnO morphology in the presence of sulfate-based anionic nanoparticles. Finally, controlled deposition of a 5 nm gold sol onto porous ZnO particles (produced after calcination of the organic nanoparticles) significantly enhances the rate of photocatalytic decomposition of a model rhodamine B dye on exposure to a relatively weak UV source

Star Diblock Copolymer Concentration Dictates the Degree of Dispersion of Carbon Black Particles in Nonpolar Media: Bridging Flocculation versus Steric Stabilization

The solution behavior of a polystyrene–hydrogenated polyisoprene star diblock copolymer (Mn ∼ 384 K; 6 mol % polystyrene) is examined in nonpolar media. Variable temperature 1H NMR studies using deuterated n-dodecane confirm that the outer polystyrene blocks are only partially solvated in n-dodecane at 25 °C: the apparent polystyrene content of 3.2 ± 0.2 mol % remains essentially constant on heating up to 100 °C. Physical adsorption of this star diblock copolymer onto carbon black particles is examined, with particular attention being paid to the effect of copolymer concentration on colloidal stability. An isotherm is constructed for copolymer adsorption onto carbon black from n-dodecane at 20 °C using a supernatant depletion assay based on UV spectroscopy analysis of the aromatic chromophore in the polystyrene block. Langmuir-type adsorption is observed with a maximum adsorbed amount, Γ, of ∼2.2 ± 0.1 mg m–2. In addition, thermogravimetric analysis is used to directly determine the amount of adsorbed copolymer on the carbon black particles, which are essentially incombustible under an inert atmosphere. Analytical centrifugation, optical microscopy, and transmission electron microscopy studies indicate that the star diblock copolymer acts as an effective flocculant at low concentration, with steric stabilization only being observed above a certain critical copolymer concentration (∼5.5% w/w based on carbon black). This is attributed to the spatial location of the polystyrene block and the star copolymer architecture, which enables copolymer adsorption onto multiple carbon black particles at low coverage, leading to bridging flocculation. Above 5.5% w/w copolymer, the surface coverage is sufficiently high that all of the polystyrene “stickers” adsorb onto single carbon black particles, resulting in colloidally stable, sterically stabilized carbon black dispersions. Small-angle X-ray scattering (SAXS) is also used to characterize the copolymer-coated carbon black particles: this technique provides useful complementary insights regarding the rather subtle changes in the fractal morphology that occur with increasing copolymer concentration. Moreover, SAXS also provides direct evidence for the presence of the copolymer chains at the particle surface

Shear yielding of amorphous glassy solids: Effect of temperature and strain rate

We study shear yielding and steady state flow of glassy materials with molecular dynamics simulations of two standard models: amorphous polymers and bidisperse Lennard-Jones glasses. For a fixed strain rate, the maximum shear yield stress and the steady state flow stress in simple shear both drop linearly with increasing temperature. The dependence on strain rate can be described by a either a logarithm or a power-law added to a constant. In marked contrast to predictions of traditional thermal activation models, the rate dependence is nearly independent of temperature. The relation to more recent models of plastic deformation and glassy rheology is discussed, and the dynamics of particles and stress in small regions is examined in light of these findings

Impact of the calcium form of β-hydroxy-β-methylbutyrate upon human skeletal muscle protein metabolism

Background & aims: β-hydroxy-β-methylbutyrate (HMB) is purported as a key nutritional supplement for the preservation of muscle mass in health, disease and as an ergogenic aid in exercise. Of the two available forms of HMB (calcium (Ca-HMB) salt or free acid (FA-HMB)) – differences in plasma bioavailability have been reported. We previously reported that ∼3 g oral FA-HMB increased muscle protein synthesis (MPS) and reduced muscle protein breakdown (MPB). The objective of the present study was to quantify muscle protein metabolism responses to oral Ca-HMB. Methods: Eight healthy young males received a primed constant infusion of 1,2 13C2 leucine and 2H5 phenylalanine to assess MPS (by tracer incorporation in myofibrils) and MPB (via arterio-venous (A-V) dilution) at baseline and following provision of ∼3 g of Ca-HMB; muscle anabolic (MPS) and catabolic (MPB) signalling was assessed via immunoblotting. Results: Ca-HMB led a significant and rapid (<60 min) peak in plasma HMB concentrations (483.6 ± 14.2 μM, p < 0.0001). This rise in plasma HMB was accompanied by increases in MPS (PA: 0.046 ± 0.004%/h, CaHMB: 0.072 ± 0.004%/h, p < 0001) and suppressions in MPB (PA: 7.6 ± 1.2 μmol Phe per leg min−1, Ca-HMB: 5.2 ± 0.8 μmol Phe per leg min−1, p < 0.01). Increases in the phosphorylation of mTORc1 substrates i.e. p70S6K1 and RPS6 were also observed, with no changes detected in the MPB targets measured. Conclusions: These findings support the pro-anabolic properties of HMB via mTORc1, and show that despite proposed differences in bioavailability, Ca-HMB provides a comparable stimulation to MPS and suppression of MPB, to FA-HMB, further supporting its use as a pharmaconutrient in the modulation of muscle mass

Track D Social Science, Human Rights and Political Science

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/138414/1/jia218442.pd

Dimethyl fumarate in patients admitted to hospital with COVID-19 (RECOVERY): a randomised, controlled, open-label, platform trial

Dimethyl fumarate (DMF) inhibits inflammasome-mediated inflammation and has been proposed as a treatment for patients hospitalised with COVID-19. This randomised, controlled, open-label platform trial (Randomised Evaluation of COVID-19 Therapy [RECOVERY]), is assessing multiple treatments in patients hospitalised for COVID-19 (NCT04381936, ISRCTN50189673). In this assessment of DMF performed at 27 UK hospitals, adults were randomly allocated (1:1) to either usual standard of care alone or usual standard of care plus DMF. The primary outcome was clinical status on day 5 measured on a seven-point ordinal scale. Secondary outcomes were time to sustained improvement in clinical status, time to discharge, day 5 peripheral blood oxygenation, day 5 C-reactive protein, and improvement in day 10 clinical status. Between 2 March 2021 and 18 November 2021, 713 patients were enroled in the DMF evaluation, of whom 356 were randomly allocated to receive usual care plus DMF, and 357 to usual care alone. 95% of patients received corticosteroids as part of routine care. There was no evidence of a beneficial effect of DMF on clinical status at day 5 (common odds ratio of unfavourable outcome 1.12; 95% CI 0.86-1.47; p = 0.40). There was no significant effect of DMF on any secondary outcome

On a generalization of the Laplace approximation

10.1016/j.spl.2009.03.006Statistics and Probability Letters79111397-1403SPLT