A new route to prepare multiresponsive organogels from a block ionomer via charge-driven assembly

We report a novel route to prepare multiresponsive organogels through charge-driven assembly between a block ionomer and a diblock copolymer. The ionic complex aggregates to form spherical cores, which are connected by the middle block of the block ionomer to form gels. The organogels are responsive to acids, amines and salts.

Nanofibrillar micelles and entrapped vesicles from biodegradable block copolymer/polyelectrolyte complexes in aqueous media

Here we report a viable route to fibrillar micelles and entrapped vesicles in aqueous solutions. Nanofibrillar micelles and entrapped vesicles were prepared from complexes of a biodegradable block copolymer poly(ethylene oxide)-block-poly(lactide) (PEO-b-PLA) and a polyelectrolyte poly(acrylic acid) (PAA) in aqueous media and directly visualized using cryogenic transmission electron microscopy (cryo-TEM). The self-assembly and the morphological changes in the complexes were induced by the addition of PAA/water solution into the PEO-b-PLA in tetrahydrofuran followed by dialysis against water. A variety of morphologies including spherical wormlike and fibrillar micelles, and both unilamellar and entrapped vesicles, were observed, depending on the composition, complementary binding sites of PAA and PEO, and the change in the interfacial energy. Increasing the water content in each [AA]/[EO] ratio led to a morphological transition from spheres to vesicles, displaying both the composition- and dilution-dependent micellar-to-vesicular morphological transitions.

Phase behavior and nanomechanical mapping of block ionomer complexes

Block ionomer complexes SSEBS-c-PCL were prepared, as a consequence of proton transfer from the sulfonic acid of sulfonated polystyrene-block- poly(ethylene-ran-butylene)-block-polystyrene (SSEBS) to the tertiary amine of a tertiary amine terminated poly(?-caprolactone) (APCL). The phase behavior of SSEBS-c-PCL was thoroughly investigated and the results showed that APCL in SSEBS-c-PCL displays unique crystallization behavior owing to the influence of interactions between the amine and sulfonic acid groups as well as the effects of confinement. Further, small-angle X-ray scattering study revealed that SSEBS-c-PCL displays a less ordered micro-phase structure compared to SSEBS. A quantitative mapping of mechanical properties at the nanoscale was achieved using peak force mode atomic force microscopy. It is found that the block ionomer complex possesses a higher average elastic modulus after complexation with crystallizable APCL. Additionally, the moduli for both hard and soft phases increase and the phase with higher modulus assignable to the hard SPS component shows much more pronounced changes after complexation, confirming that APCL interacts mainly with the SPS blocks. This provides an understanding of the composition and nanomechanical properties of these new block ionomer complexes and an alternative insight into the micro-phase structures of multi-phase materials.

Estimating the intensity of ward admission and its effect on emergency department access block

Emergency department access block is an urgent problem faced by many public hospitals today. When access block occurs, patients in need of acute care cannot access inpatient wards within an optimal time frame. A widely held belief is that access block is the end product of a long causal chain, which involves poor discharge planning, insufficient bed capacity, and inadequate admission intensity to the wards. This paper studies the last link of the causal chain-the effect of admission intensity on access block, using data from a metropolitan hospital in Australia. We applied several modern statistical methods to analyze the data. First, we modeled the admission events as a nonhomogeneous Poisson process and estimated time-varying admission intensity with penalized regression splines. Next, we established a functional linear model to investigate the effect of the time-varying admission intensity on emergency department access block. Finally, we used functional principal component analysis to explore the variation in the daily time-varying admission intensities. The analyses suggest that improving admission practice during off-peak hours may have most impact on reducing the number of ED access blocks.

Toughening epoxy thermosets with block ionomers : the role of phase domain size

Herein we report a novel approach to toughen epoxy thermosets using a block ionomer, i.e., sulfonated polystyrene-block-poly(ethylene-co-butylene)-block- polystyrene (SSEBS). SSEBS was synthesized by sulfonation of SEBS with 67 wt % polystyrene (PS). Phase morphology of the epoxy/SSEBS blends can be controlled at either nanometer or micrometer scale by simply adjusting the sulfonation degree of SSEBS. It has been found that there exists a critical degree of sulfonation (10.8 mol %) forming nanostructures in these epoxy/SSEBS blends. Above this critical value, macrophase separation can be avoided and only microphase separation occurs, yielding transparent nanostructured blends. All epoxy/SSEBS blends display increased fracture toughness compared to neat epoxy. But the toughening efficiency varies with the phase domain size, and their correlation has been established over a broad range of length scales from nanometers to a few micrometers. In the nanostructured blends with SSEBS of high sulfonation degrees, the fracture toughness decreases with decreasing size of the phase domains. In the macrophase-separated blends, only a slight improvement in toughness can be obtained with SSEBS of low sulfonation degrees. The epoxy blend with submicrometer phase domains in the range 0.05-1.0 μm containing SSEBS of a moderate degree of sulfonation (5.8 mol %) displays the maximum toughness. This study has clearly clarified the role of phase domain size on toughening efficiency in epoxy thermosets.

Nanostructure toughening of epoxy thermosets with block Ionomer complexes

This thesis addresses an important issue in polymer materials science, the toughening of thermosetting polymers. A novel approach has been developed, i.e., the use of block ionomers/complexes to promote compatibilization with thermosetting epoxies. The morphology and mechanical properties of the resulting nanostructured epoxies were intensively studied to establish structure-property correlation.

Synthesis and self-assembly of hybrid amphiphilic block copolymers

This thesis focused on the synthesis and self-assembly of novel block copolymers for the purpose of drug delivery. The block copolymers achieved comprise of a synthetic block and a peptide block and self-assemble into nano sized particles which can act as drug containers.

Distinct disulfide isomers of μ-Conotoxins KIIIA and KIIIB block voltage-gated sodium channels

In the preparation of synthetic conotoxins containing multiple disulfide bonds, oxidative folding can produce numerous permutations of disulfide bond connectivities. Establishing the native disulfide connectivities thus presents a significant challenge when the venom-derived peptide is not available, as is increasingly the case when conotoxins are identified from cDNA sequences. Here, we investigate the disulfide connectivity of μ-conotoxin KIIIA, which was predicted originally to have a [C1–C9,C2–C15,C4–C16] disulfide pattern based on homology with closely related μ-conotoxins. The two major isomers of synthetic μ-KIIIA formed during oxidative folding were purified and their disulfide connectivities mapped by direct mass spectrometric collision-induced dissociation fragmentation of the disulfide-bonded polypeptides. Our results show that the major oxidative folding product adopts a [C1–C15,C2–C9,C4–C16] disulfide connectivity, while the minor product adopts a [C1–C16,C2–C9,C4–C15] connectivity. Both of these peptides were potent blockers of NaV1.2 (Kd values of 5 and 230 nM, respectively). The solution structure for μ-KIIIA based on nuclear magnetic resonance data was recalculated with the [C1–C15,C2–C9,C4–C16] disulfide pattern; its structure was very similar to the μ-KIIIA structure calculated with the incorrect [C1–C9,C2–C15,C4–C16] disulfide pattern, with an α-helix spanning residues 7–12. In addition, the major folding isomers of μ-KIIIB, an N-terminally extended isoform of μ-KIIIA identified from its cDNA sequence, were isolated. These folding products had the same disulfide connectivities as μ-KIIIA, and both blocked NaV1.2 (Kd values of 470 and 26 nM, respectively). Our results establish that the preferred disulfide pattern of synthetic μ-KIIIA and μ-KIIIB folded in vitro is 1–5/2–4/3–6 but that other disulfide isomers are also potent sodium channel blockers. These findings raise questions about the disulfide pattern(s) of μ-KIIIA in the venom of Conus kinoshitai; indeed, the presence of multiple disulfide isomers in the venom could provide a means of further expanding the snail’s repertoire of active peptides.

Permian fusuline fauna from the lower part of the lugu formation in the central qiangtang block and its geological implications

A Kubergandian (Kungurian) fusuline fauna from the lower part of the Lugu Formation in the Cuozheqiangma area, central Qiangtang Block is described. This fusuline fauna belongs to the Southern Transitional Zone in palaeobiogeography, and is characterised by the presence of the distinctive bi-temperate genus Monodiexodina and many genera common in lower latitude Tethyan areas such as Parafusulina and Pseudodoliolina. The occurrence of Monodiexodina in the fauna confirms that the seamount-type carbonates of the Lugu Formation did not originate from the Palaeotethys Ocean, but rather from a branch of the Neotethys Ocean after the rifting of the Qiangtang Block from the Tethys Himalaya area in the Artinskian. © 2014 Geological Society of China.

A block-aware hybrid data dissemination with hotspot elimination in wireless sensor network

As a significant milestone in the data dissemination of wireless sensor networks (WSNs), the comb-needle (CN) model was developed to dynamically balance the sensor data pushing and pulling during hybrid data dissemination. Unfortunately, the hybrid push-pull data dissemination strategy may overload some sensor nodes and form the hotspots that consume energy significantly. This usually leads to the collapse of the network at a very early stage. In the past decade, although many energy-aware dynamic data dissemination methods have been proposed to alleviate the hotspots issue, the block characteristic of sensor nodes has been overlooked and how to offload traffic from hot blocks with low energy through long-distance hybrid dissemination remains an open problem. In this paper, we developed a block-aware data dissemination model to balance the inter-block energy and eliminate the spreading of intra-block hotspots. Through the clustering mechanism based on geography and energy, "similar" large-scale sensor nodes can be efficiently grouped into specific blocks to form the global block information (GBI). Based on GBI, the long-distance block-cross hybrid algorithms are further developed by effectively aggregating inter-block and intra-block data disseminations. Extensive experimental results demonstrate the capability and the efficiency of the proposed approach. © 2014 Elsevier Ltd.