Effect of core cross-linking on the physical properties of poly(dimethylsiloxane)-based diblock copolymer worms prepared in silicone oil

A trithiocarbonate-capped poly(dimethylsiloxane) (PDMS) precursor is chain-extended via reversible addition–fragmentation chain transfer dispersion polymerization of 2-(dimethylamino)ethyl methacrylate (DMA) in decamethylcyclopentasiloxane (D5) silicone oil at 90 °C. For a fixed mean degree of polymerization (DP) of 66 for the PDMS steric stabilizer block, targeting core-forming PDMA block DPs of between 105 and 190 enables the preparation of either well-defined worms or vesicles at a copolymer concentration of 25% w/w. The as-synthesized linear PDMS66–PDMA100 worms exhibit thermoresponsive behavior in D5, undergoing a worm-to-sphere transition on heating to 100 °C. Variable temperature 1H NMR spectroscopy indicates that this thermal transition is driven by reversible solvent plasticization of the PDMA cores. This change in copolymer morphology is characterized by transmission electron microscopy (TEM) studies, variable temperature dynamic light scattering and small-angle X-ray scattering experiments. Oscillatory rheology studies indicate that degelation occurs at 32 °C, but shear-induced polarized light imaging measurements suggest that full conversion of worms into spheres requires significantly higher temperatures (∼110 °C). 1,2-Bis(2-iodoethoxy)ethane (BIEE) is evaluated as a cross-linker for PDMS66–PDMAx diblock copolymer nano-objects in D5. This bifunctional reagent quaternizes the tertiary amine groups on the DMA residues within the worm cores, introducing cross-links via the Menshutkin reaction. TEM studies confirm that such covalently-stabilized worms no longer undergo a worm-to-sphere transition when heated to 100 °C. Kinetic studies performed on PDMS66–PDMA176 vesicles suggest that cross-linking requires approximately 13 h at 20 °C to ensure that these nano-objects remain intact when dispersed in chloroform, which is a good solvent for both blocks. Oscillatory rheology studies of a PDMS66–PDMA100 worm gel indicated that covalent stabilization using a BIEE/DMA molar ratio of 0.15 increased its dynamic elastic modulus (G′) by almost two orders of magnitude. Furthermore, such cross-linked worms exhibit a much lower critical gelation concentration (∼2% w/w) compared to that of the linear precursor worms (∼12% w/w)

HadISDH: an updateable land surface specific humidity product for climate monitoring

HadISDH is a near-global land surface specific humidity monitoring product providing monthly means from 1973 onwards over large-scale grids. Presented herein to 2012, annual updates are anticipated. HadISDH is an update to the land component of HadCRUH, utilising the global high-resolution land surface station product HadISD as a basis. HadISD, in turn, uses an updated version of NOAA's Integrated Surface Database. Intensive automated quality control has been undertaken at the individual observation level, as part of HadISD processing. The data have been subsequently run through the pairwise homogenisation algorithm developed for NCDC's US Historical Climatology Network monthly temperature product. For the first time, uncertainty estimates are provided at the grid-box spatial scale and monthly timescale. HadISDH is in good agreement with existing land surface humidity products in periods of overlap, and with both land air and sea surface temperature estimates. Widespread moistening is shown over the 1973–2012 period. The largest moistening signals are over the tropics with drying over the subtropics, supporting other evidence of an intensified hydrological cycle over recent years. Moistening is detectable with high (95%) confidence over large-scale averages for the globe, Northern Hemisphere and tropics, with trends of 0.089 (0.080 to 0.098) g kg−1 per decade, 0.086 (0.075 to 0.097) g kg−1 per decade and 0.133 (0.119 to 0.148) g kg−1 per decade, respectively. These changes are outside the uncertainty range for the large-scale average which is dominated by the spatial coverage component; station and grid-box sampling uncertainty is essentially negligible on large scales. A very small moistening (0.013 (−0.005 to 0.031) g kg−1 per decade) is found in the Southern Hemisphere, but it is not significantly different from zero and uncertainty is large. When globally averaged, 1998 is the moistest year since monitoring began in 1973, closely followed by 2010, two strong El Niño years. The period in between is relatively flat, concurring with previous findings of decreasing relative humidity over land

Oil-in-oil pickering emulsions stabilized by diblock copolymer nanoparticles

Hypothesis Diblock copolymer nanoparticles have been shown to be Pickering emulsifiers for both oil-in-water and water-in-oil emulsions. Recently, we reported the preparation of sterically-stabilized diblock copolymer spheres in a low-viscosity silicone oil (Macromolecules 53 (2020) 1785–1794). We hypothesized that such spheres could be used as a Pickering emulsifier for a range of oil-in-oil emulsions comprising droplets of a bio-sourced oil dispersed in silicone oil. Experiments Diblock copolymer spheres were prepared via reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate in silicone oil and characterized by dynamic light scattering and transmission electron microscopy. These spheres were evaluated as Pickering emulsifiers for a series of oil-in-oil Pickering emulsions. The influence of both sphere size and core-forming block composition was investigated. Findings \ud Optimization of the nanoparticle size and core-forming block composition enabled stable bio-sourced oil-in-silicone emulsions to be obtained for nine out of the ten bio-sourced oils investigated. These emulsions were characterized in terms of their mean droplet size by optical microscopy

RAFT dispersion polymerization of benzyl methacrylate in silicone oil using a silicone-based methacrylic stabilizer provides convenient access to spheres, worms, and vesicles

Reversible addition–fragmentation chain transfer (RAFT) solution polymerization of 3-[tris(trimethylsiloxy)silyl] propyl methacrylate (SiMA) was conducted in toluene to prepare three PSiMA precursors with mean degrees of polymerization (DP) of 12, 13, or 15. Each precursor was then chain-extended in turn via RAFT dispersion polymerization of benzyl methacrylate (BzMA) in a low-viscosity silicone oil (decamethylcyclopentasiloxane, D5). 1H NMR studies confirmed that such polymerizations were relatively fast, with more than 99% BzMA conversion being achieved within 100 min at 90 °C. Moreover, gel permeation chromatography analysis indicated that these polymerizations were well controlled, with dispersities remaining below 1.25 when targeting PBzMA DPs up to 200. A phase diagram was constructed at a constant copolymer concentration of 20% w/w. Only spherical micelles were accessible when the PSiMA15 stabilizer was utilized, as determined by transmission electron microscopy and small-angle X-ray scattering (SAXS) studies. Nevertheless, these spheres exhibited narrow size distributions and tunable z-average diameters ranging between 19 and 49 nm, as determined by dynamic light scattering. In contrast, spheres, worms, or vesicles could be prepared depending on the target PBzMA DP when utilizing the relatively short PSiMA12 precursor. Moreover, each of these nano-objects could be obtained at copolymer concentrations as low as 5% w/w. To obtain more detailed structural information, these spheres, worms and vesicles were further characterized by SAXS. PSiMA12-PBzMA55 worms formed reasonably transparent free-standing gels when prepared at copolymer concentrations as low as 5% w/w and exhibited an elastic modulus (G′) of 90 Pa at 25 °C, as judged by oscillatory rheology studies. Finally, broadening of the molecular weight distribution was observed during the long-term storage of PSiMA-PBzMA dispersions at ambient temperature. We tentatively suggest that this instability is related to hydroxyl impurities in the SiMA, which leads to cross-linking side reactions. This problem also causes incipient flocculation of the spheres and worms during the long-term storage of such dispersions at 20 °C

A Systematic Review of HIV Interventions for Young Women in Sub-Saharan Africa

Adolescent girls and young women (AGYW) ages (15–24 years old) in Southern and Eastern Africa account for nearly 30% of all new HIV infections. We conducted a systematic review of studies examining the effectiveness of behavioral, structural, and combined (behavioral + structural) interventions on HIV incidence and risky sexual behaviors among AGYW. Following PRISMA guidelines, we searched PubMed, CINAHL, Web of Science, and Global Health. Twenty-two studies met inclusion criteria conducted in Eastern and Southern Africa and comprised behavioral, structural, or combined (behavioral and structural) interventions. All findings are based on 22 studies. HIV incidence was significantly reduced by one structural intervention. All three types of interventions improved condom use among AGYW. Evidence suggests that structural interventions can reduce HIV incidence, while behavioral and combined interventions require further investigation

Synthesis of crystallizable poly(behenyl methacrylate)-based block and statistical copolymers and their performance as wax crystal modifiers

Two series of behenyl methacrylate-based diblock and statistical copolymers have been prepared by reversible addition–fragmentation chain transfer (RAFT) solution polymerization in n-dodecane and evaluated as additives for the crystal habit modification of a model wax (n-octacosane). DSC studies indicated that each statistical copolymer exhibited a significantly lower crystallization temperature (Tc) and melting temperature (Tm) for the semi-crystalline behenyl methacrylate component than the corresponding diblock copolymer of almost identical overall composition. Temperature-dependent turbidimetry studies were conducted for each copolymer using a series of solutions of 5.0% w/w n-octacosane dissolved in n-dodecane to determine Tcool, which is the temperature at which zero transmittance is first observed owing to wax crystallization. At a constant molar copolymer concentration of 0.26 mM, each of the eight copolymers produced a reduction in Tcool of approximately 3–5 °C. Scanning electron microscopy (SEM) studies confirmed that the presence of such copolymers led to a reduction in the overall size and/or a higher crystal aspect ratio. The diblock and statistical copolymers were similar in their performance as potential wax crystal modifiers. However, the statistical copolymers were easier to prepare and did not suffer from any homopolymer contamination. Moreover, optical microscopy and SEM studies revealed that needle-like crystals were formed instead of platelets when employing behenyl methacrylate-rich statistical copolymers

Quantum transport in double-gated graphene devices

Double-gated graphene devices provide an important platform for understanding electrical and optical properties of graphene. Here we present transport measurements of single layer, bilayer and trilayer graphene devices with suspended top gates. In zero magnetic fields, we observe formation of pnp junctions with tunable polarity and charge densities, as well as a tunable band gap in bilayer graphene and a tunable band overlap in trilayer graphene. In high magnetic fields, the devices' conductance are quantized at integer and fractional values of conductance quantum, and the data are in good agreement with a model based on edge state equilibration at pn interfaces

Half-metallicity and Slater-Pauling behavior in the ferromagnetic Heusler alloys

Introductory chapter for the book "Halfmetallic Alloys - Fundamentals and Applications" to be published in the series Springer Lecture Notes on Physics, P. H. Dederichs and I. Galanakis (eds). It contains a review of the theoretical work on the half-metallic Heusler alloys.Comment: Introductory chapter for the book "Halfmetallic Alloys - Fundamentals and Applications" to be published in the series Springer Lecture Notes on Physics, P. H. Dederichs and I. Galanakis (eds

Regularization-independent study of renormalized non-perturbative quenched QED

A recently proposed regularization-independent method is used for the first time to solve the renormalized fermion Schwinger-Dyson equation numerically in quenched QED$_4$. The Curtis-Pennington vertex is used to illustrate the technique and to facilitate comparison with previous calculations which used the alternative regularization schemes of modified ultraviolet cut-off and dimensional regularization. Our new results are in excellent numerical agreement with these, and so we can now conclude with confidence that there is no residual regularization dependence in these results. Moreover, from a computational point of view the regularization independent method has enormous advantages, since all integrals are absolutely convergent by construction, and so do not mix small and arbitrarily large momentum scales. We analytically predict power law behaviour in the asymptotic region, which is confirmed numerically with high precision. The successful demonstration of this efficient new technique opens the way for studies of unquenched QED to be undertaken in the near future.Comment: 20 pages,5 figure