New fast SCFT algorithm applied to binary diblock copolymer/homopolymer blends

We present an efficient strategy for mapping out the classical phase behavior of block copolymer systems using self-consistent field theory (SCFT). With our new algorithm, the complete solution of a classical block copolymer phase can be evaluated typically in a fraction of a second on a single-processor computer, even for highly segregated melts. This is accomplished by implementing the standard unit-cell approximation (UCA) for the cylindrical and spherical phases, and solving the resulting equations using a Bessel function expansion. Here the method is used to investigate blends of AB diblock copolymer and A homopolymer, concentrating on the situation where the two molecules are of similar size.

Influence of a non-ionic amphiphilic copolymer on the self-assembly of a peptide amphiphile that forms nanotapes

The influence of a non-ionic polymeric surfactant on the self-assembly of a peptide amphiphile (PA) that forms nanotapes is investigated using a combination of microscopic, scattering and spectroscopic techniques. Mixtures of Pluronic copolymer P123 with the PA C16-KTTKS in aqueous solution were studied at a fixed concentration of the PA at which it is known to self-assemble into extended nanotapes, but varying P123 concentration. We find that P123 can disrupt the formation of C16- KTTKS nanotapes, leading instead to cylindrical nanofibril structures. The spherical micelles formed by P123 at room temperature are disrupted in the presence of the PA. There is a loss of cloudiness in the solutions as the large nanotape aggregates formed by C16-KTTKS are broken up, by P123 solubilization. At least locally, b-sheet structure is retained, as confirmed by XRD and FTIR spectroscopy, even for solutions containing 20 wt% P123. This indicates, unexpectedly, that peptide secondary structure can be retained in solutions with high concentration of non-ionic surfactant. Selfassembly in this system exhibits slow kinetics towards equilibrium, the initial self-assembly being dependent on the order of mixing. Heating above the lipid chain melting temperature assists in disrupting trapped non-equilibrium states.

Cyclic extrusion of a lava dome based on a stick-slip mechanism

Lava dome eruptions are sometimes characterised by large periodic fluctuations in extrusion rate over periods of hours that may be accompanied by Vulcanian explosions and pyroclastic flows. We consider a simple system of nonlinear equations describing a 1D flow of lava extrusion through a deep elastic dyke feeding a shallower cylindrical conduit in order to simulate this short-period cyclicity. Stick-slip conditions depending on a critical shear stress are assumed at the wall boundary of the cylindrical conduit. By analogy with the behaviour of industrial polymers in a plastic extruder, the elastic dyke acts like a barrel and the shallower cylindrical portion of the conduit as a die for the flow of magma acting as a polymer. When we applied the model to the Soufrière Hills Volcano, Montserrat, for which the key parameters have been evaluated from previous studies, cyclic extrusions with periods from 3 to 30 h were readily simulated, matching observations. The model also reproduces the reduced period of cycles observed when a major unloading event occurs due to lava dome collapse.

Development of biomimetic squid-inspired suckers

Biomechanical properties of squid suckers were studied to provide inspiration for the development of sucker artefacts for a robotic octopus. Mechanical support of the rings found inside squid suckers was studied by bending tests. Tensile tests were carried out to study the maximum possible sucking force produced by squid suckers based on the strength of sucker stalks, normalized by the sucking areas. The squid suckers were also directly tested to obtain sucking forces by a special testing arrangement. Inspired by the squid suckers, three types of sucker artefacts were developed for the arm skin of an octopus inspired robot. The first sucker artefact made of knitted nylon sheet reinforced silicone rubber has the same shape as the squid suckers. Like real squid suckers, this type of artefact also has a stalk that is connected to the arm skin and a ring to give radial support.The second design is a straight cylindrical structure with uniform wall thickness made of silicone rubber. One end of the cylinder is directly connected to the arm skin and the other end is open. The final design of the sucker has a cylindrical base and a concave meniscus top. The meniscus was formed naturally using the surface tension of silicone gel, which leads to a higher level of the liquid around the edge of a container. The wall thickness decreases towards the tip of the sucker opening. Sucking forces of all three types of sucker artefacts were measured. Advantages and isadvantages of each sucker type were discussed. The final design of suckers has been implemented to the arm skin prototypes.

A uniformly valid far field asymptotic expansion of the green function for two-dimensional propagation above a homogeneous impedance plane

A generalized asymptotic expansion in the far field for the problem of cylindrical wave reflection at a homogeneous impedance plane is derived. The expansion is shown to be uniformly valid over all angles of incidence and values of surface impedance, including the limiting cases of zero and infinite impedance. The technique used is a rigorous application of the modified steepest descent method of Ot

Insights into the molecular architecture of a peptide nanotube using FTIR and solid-state NMR spectroscopic measurements on an aligned sample

The self-assembly of proteins and peptides into b-sheet-rich amyloid fibers is a process that has gained notoriety because of its association with human diseases and disorders. Spontaneous self-assembly of peptides into nonfibrillar supramolecular structures can also provide a versatile and convenient mechanism for the bottom-up design of biocompatible materials with functional properties favoring a wide range of practical applications.[1] One subset of these fascinating and potentially useful nanoscale constructions are the peptide nanotubes, elongated cylindrical structures with a hollow center bounded by a thin wall of peptide molecules.[2] A formidable challenge in optimizing and harnessing the properties of nanotube assemblies is to gain atomistic insight into their architecture, and to elucidate precisely how the tubular morphology is constructed from the peptide building blocks. Some of these fine details have been elucidated recently with the use of magic-angle-spinning (MAS) solidstate NMR (SSNMR) spectroscopy.[3] MAS SSNMR measurements of chemical shifts and through-space interatomic distances provide constraints on peptide conformation (e.g., b-strands and turns) and quaternary packing. We describe here a new application of a straightforward SSNMR technique which, when combined with FTIR spectroscopy, reports quantitatively on the orientation of the peptide molecules within the nanotube structure, thereby providing an additional structural constraint not accessible to MAS SSNMR.

Coupled subdaily and multiweek cycles during the lava dome erupt of Soufriere Hills Volcano, Montserrat

Observations of volcanoes extruding andesitic lava to produce lava domes often reveal cyclic behaviour. At Soufriere Hills Volcano, Montserrat, cycles with sub-daily and multi-week periods have been recognised on many occasions. These two types of cycle have been modelled separately as stick-slip magma flow at the junction between a dyke and an overlying cylindrical conduit (Costa et al. 2012), and as the filling and discharge of magma through the elastic-walled dyke (Costa et al., 2007a) respectively. Here, we couple these two models to simulate the behaviour over a period of well-observed multi-week cycles, with accompanying sub-daily cycles, from 13 May to 21 September 1997. The coupled model captures well the asymmetrical first-order behaviour: the first 40% of the multi-week cycle consists of high rates of lava extrusion during short period/high amplitude sub-daily cycles as the dyke reservoir discharges itself. The remainder of the cycle involves increasing pressurization as more magma is stored, and extrusion rate falls, followed by a gradual increase in the period of the sub-daily cycles.

Experimental evidence for proposed transformation pathway from the inverse hexagonal to inverse diamond cubic phase from oriented lipid samples

A macroscopically oriented inverse hexagonal phase (HII) of the lipid phytantriol in water is converted to an oriented inverse double diamond bicontinuous cubic phase (QIID). The initial HII phase is uniaxially oriented about the long axis of a capillary with the cylinders parallel to the capillary axis. The HII phase is converted by cooling to a QII D phase which is also highly oriented, where the cylindrical axis of the former phase has been converted to a ⟨110⟩ axis in the latter, as demonstrated by small-angle X-ray scattering. This epitaxial relationship allows us to discriminate between two competing proposed geometric pathways to convert HII to QIID. Our findings also suggest a new route to highly oriented cubic phase coatings, with applications as nanomaterial templates.

Exploiting thermally-reversible chemistry for controlling the crosslinking of polymer networks

High explosives are highly sensitive to accidental detonation by impact, fire, shrapnel and small arms fire. This sensitivity can be reduced by storing the energetic material within a rubbery polymer matrix and are known as plastic bonded explosives (PBX). The current procedure used to manufacture PBX involves mixing the energetic material with a hydroxy-functionalised aliphatic polymer. Upon the addition of an isocyanate crosslinker an immediate polymerisation occurs and thus the rapidly curing mixture must be used to fill the missile or shells, referred to as ‘stores’. This process can lead to poor distribution of the crosslinker resulting in the formation of an inhomogeneously crosslinked matrix and the formation of voids. One solution to this problem involves containing the crosslinker within polyurethane microcapsules that are uniformly dispersed in the explosive-polymer mixture. Upon the application of a stimulus the crosslinker can be released from the microcapsules and the formation of a uniformly crosslinked PBX achieved. Herein is reported the design and synthesis of polyurethane microcapsules that release isocyanate crosslinkers when desired using a thermal stimulus. This has been achieved by exploiting the thermally-reversible nature of oxime-urethane and Diels-Alder adducts that have been incorporated into the shell wall of the microcapsules. An alternative approach to controlling the polymerisation of PBX materials has also been achieved using thermally-reversible blocked isocyanates that regenerate the isocyanate crosslinker when exposed to heat.

Equilibrium behavior of symmetric ABA triblock copolymer melts

Melts of ABA triblock copolymer molecules with identical end blocks are examined using self-consistent field theory (SCFT). Phase diagrams are calculated and compared with those of homologous AB diblock copolymers formed by snipping the triblocks in half. This creates additional end segments which decreases the degree of segregation. Consequently, triblock melts remain ordered to higher temperatures than their diblock counterparts. We also find that middle-block domains are easier to stretch than end-block domains. As a result, domain spacings are slightly larger, the complex phase regions are shifted towards smaller A-segment compositions, and the perforated-lamellar phase becomes more metastable in triblock melts as compared to diblock melts. Although triblock and diblock melts exhibit very similar phase behavior, their mechanical properties can differ substantially due to triblock copolymers that bridge between otherwise disconnected A domains. We evaluate the bridging fraction for lamellar, cylindrical, and spherical morphologies to be about 40%–45%, 60%–65%, and 75%–80%, respectively. These fractions only depend weakly on the degree of segregation and the copolymer composition.

Hard tissue formation adjacent to implants of various size and configuration immediately placed into extraction sockets: an experimental study in dogs

Objectives To evaluate the influence of implant size and configuration on osseointegration in implants immediately placed into extraction sockets. Material and methods Implants were installed immediately into extraction sockets in the mandibles of six Labrador dogs. In the control sites, cylindrical transmucosal implants (3.3 mm diameter) were installed, while in the test sites, larger and conical (root formed, 5 mm diameter) implants were installed. After 4 months of healing, the resorptive patterns of the alveolar crest were evaluated histomorphometrically. Results With one exception, all implants were integrated in mineralized bone, mainly composed of mature lamellar bone. The alveolar crest underwent resorption at the control as well as at the test implants. This resorption was more pronounced at the buccal aspects and significantly greater at the test (2.7 +/- 0.4 mm) than at the control implants (1.5 +/- 0.6 mm). However, the control implants were associated with residual defects that were deeper at the lingual than at the buccal aspects, while these defects were virtually absent at test implants. Conclusions The installment of root formed wide implants immediately into extraction sockets will not prevent the resorption of the alveolar crest. In contrast, this resorption is more marked both at the buccal and lingual aspects of root formed wide than at standard cylindrical implants. To cite this article:Caneva M, Salata LA, de Souza SS, Bressan E, Botticelli D, Lang NP. Hard tissue formation adjacent to implants of various size and configuration immediately placed into extraction sockets: an experimental study in dogs.Clin. Oral Impl. Res. 21, 2010; 885-895.doi: 10.1111/j.1600-0501.2010.01931.x.

Gracilariopsis mclachlanii sp nov and Gracilariopsis persica sp nov of the Gracilariaceae (Gracilariales, Rhodophyceae) from the Indian Ocean

Two new species of Gracilariopsis from the Indian Ocean are proposed-Gracilariopsis (Gp.) mclachlanii Buriyo, Bellorin et M. C. Oliveira sp. nov. from Tanzania and Gracilariopsis persica Bellorin, Sohrabipour et E. C. Oliveira sp. nov. from Iran-based on morphology and DNA sequence data (rbcL gene and SSU rDNA). Both species fit the typical features of Gracilariopsis: axes cylindrical throughout, freely and loosely ramified up to four orders, with an abrupt transition in cell size from medulla to cortex, cystocarps lacking tubular nutritive cells and superficial spermatangia. Nucleotide sequence comparisons of rbcL and SSU rDNA placed both species into the Gracilariopsis clade as distinct species from all the accepted species for this genus, forming a deeply divergent lineage together with some species from the Pacific. The new species are very difficult to distinguish on morphological grounds from other species of Gracilariopsis, stressing the importance of homologous molecular marker comparisons for the species recognition in this character-poor genus.

Cladistic analysis of the Stygninae and description of a new species of Protimesius Roewer, 1913 (Opiliones: Stygnidae)

A new species of Stygnidae is described from the state of Bahia, Brazil. Protimesius bahiensis sp. nov. can be distinguished from the remaining species of the genus by the combination of: male femur IV unarmed and cylindrical; male patella IV with a row of large dorsal acute tubercles, increasing in size distally and male tibia IV with one mesodistal tubercle; ventral plate of the penis with three pairs of distal curved setae and one pair of intermediate setae, smaller than the rest. A cladistic analysis of the subfamily is presented. Stygninae is divided in two groups of genera: (Ricstygnus, Stygnus, Sickesia), with a wide distribution and (Pickeliana (Protimesius (Phareus (Stenophareus (Auranus (Verrucastygnus, Stenostygnoides)))))), associated to the Guiana Shield, Amazon basin and Northeastern Brazil. The monophyly of Protimesius is supported by the apex of pedipalpal tibia sockets bifid (homoplastically present in Verrucastygnus and Stenostygnoides) and by the presence of scopulae with non-spatulated hairs.

Phylogenetic relationships of the Neotropical spider genus Itatiaya (Araneae)

A cladistic analysis using parsimony under equal weights is applied to test the phylogenetic relationships of Itatiaya Mello-Leitao, previously described in Ctenidae. The data matrix comprised 25 taxa scored for a total of 47 characters. The cladistic analysis yielded two equally parsimonious trees of 124 steps. The consensus of the two most parsimonious trees is used to discuss the phylogenetic relationships and justify taxonomic modifications. The results indicate that this genus is a representative of Zoropsidae, which is newly recorded from the Neotropical region. The monophyly of Itatiaya is supported by three non-ambiguous synapomorphies and three homoplastic synapomorphies. A new diagnosis is provided for Itatiaya. Itatiaya pucupucu is placed as sister species to the remaining species of the genus. A polytomic clade composed of Itatiaya modesta, Itatiaya iuba, Itatiaya apipema and the clade formed by Itatiaya tacamby + Itatiaya pykyyra is supported by the presence of modified cylindrical gland spigots. Additionally, the male of I. pykyyra Polotow & Brescovit is described for the first time.

Histomorphologic evaluation of Ti-13Nb-13Zr alloys processed via powder metallurgy. A study in rabbits

This study presents the in-vivo evaluation of Ti-13Nb-13Zr alloy implants obtained by the hydride route via powder metallurgy. The cylindrical implants were processed at different sintering and holding times. The implants` were characterized for density, microstructure (SEM), crystalline phases (XRD), and bulk (EDS) and surface composition (XPS). The implants were then sterilized and surgically placed in the central region of the rabbit`s tibiae. Two double fluorescent markers were applied at 2 and 3 weeks, and 6 and 7 weeks after implantation. After an 8-week healing period, the implants were retrieved, non-decalcified section processed, and evaluated by electron, UV light (fluorescent labeling), and light microscopy (toluidine blue). BSE-SEM showed close contact between bone and implants. Fluorescent labeling assessment showed high bone activity levels at regions close to the implant surface. Toluidine blue staining revealed regions comprising osteoblasts at regions of newly forming/formed bone close to the implant surface. The results obtained in this study support biocompatible and osseoconductive properties of Ti-13Nb-13Zr processed through the hydride powder route. (c) 2007 Published by Elsevier B.V.