With great structure comes great functionality: Understanding and emulating spider silk

The overarching aim of biomimetic approaches to materials synthesis is to mimic simultaneously the structure and function of a natural material, in such a way that these functional properties can be systematically tailored and optimized. In the case of synthetic spider silk fibers, to date functionalities have largely focused on mechanical properties. A rapidly expanding body of literature documents this work, building on the emerging knowledge of structure–function relationships in native spider silks, and the spinning processes used to create them. Here, we describe some of the benchmark achievements reported until now, with a focus on the last five years. Progress in protein synthesis, notably the expression on full-size spidroins, has driven substantial improvements in synthetic spider silk performance. Spinning technology, however, lags behind and is a major limiting factor in biomimetic production. We also discuss applications for synthetic silk that primarily capitalize on its nonmechanical attributes, and that exploit the remarkable range of structures that can be formed from a synthetic silk feedstock.

Spinning a sustainable yarn : environmental sustainability and brand story in the Australian fashion industry

In the Australian fashion industry, few fashion brands have intervened in the design of their products or the systems around their product to tackle environmental pollution and waste. Instead, support of charities (whether social or environmental) has become conflated with sustainability in the eyes of the public. Thus it is difficult to assess with any accuracy fashion brands’ response to sustainability. This article aims to address this through proposing a categorization system to structure the various interventions that a company may make. This system is applied to two case studies, analysing campaigns that respond to environmental sustainability by two established Australian brands, Country Road and Billabong. The case studies demonstrate how the interventions employed by a company, at least in the Australian context, are carefully developed to align with their brand story, revealing the interplay between the intangible aspects of a brand’s positioning and the tangible, measurable impacts of their garments.

Spinning in the NAPLAN ether: 'Postscript on the Control Societies' and the seduction of education in Australia

This paper applies concepts Deleuze developed in his ‘Postscript on the Societies of Control’, especially those relating to modulatory power, dividuation and control, to aspects of Australian schooling to explore how this transition is manifesting itself. Two modulatory machines of assessment, NAPLAN and My Schools, are examined as a means to better understand how the disciplinary institution is changing as a result of modulation. This transition from discipline to modulation is visible in the declining importance of the disciplinary teacher–student relationship as a measure of the success of the educative process. The transition occurs through seduction because that which purports to measure classroom quality is in fact a serpent of modulation that produces simulacra of the disciplinary classroom. The effect is to sever what happens in the disciplinary space from its representations in a luminiferous ether that overlays the classroom.

Electro-spinning of pure collagen nano-fibres – just an expensive way to make gelatin?

Scaffolds manufactured from biological materials promise better clinical functionality, providing that characteristic features are preserved. Collagen, a prominent biopolymer, is used extensively for tissue engineering applications, because its signature biological and physico-chemical properties are retained in vitro preparations. We show here for the first time that the very properties that have established collagen as the leading natural biomaterial are lost when it is electro-spun into nano-fibres out of fluoroalcohols such as 1,1,1,3,3,3-hexafluoro-2-propanol or 2,2,2-trifluoroethanol. We further identify the use of fluoroalcohols as the major culprit in the process. The resultant nano-scaffolds lack the unique ultra-structural axial periodicity that confirms quarter-staggered supramolecular assemblies and the capacity to generate second harmonic signals, representing the typical crystalline triple-helical structure. They were also characterised by low denaturation temperatures, similar to those obtained from gelatin preparations ( p > 0.05). Likewise, circular dichroism spectra revealed extensive denaturation of the electro-spun collagen. Using pepsin digestion in combination with quantitative SDS-PAGE, we corroborate great losses of up to 99% of triple-helical collagen. In conclusion, electro-spinning of collagen out of fluoroalcohols effectively denatures this biopolymer, and thus appears to defeat its purpose, namely to create biomimetic scaffolds emulating the collagen structure and function of the extracellular matrix.

Photo-cross-linked poly(D,L-lactide)-based networks. Structural characterization by HR-MAS NMR spectroscopy and hydrolytic degradation behavior

To date, biodegradable networks and particularly their kinetic chain lengths have been characterized by analysis of their degradation products in solution. We characterize the network itself by NMR analysis in the solvent-swollen state under magic angle spinning conditions. The networks were prepared by photoinitiated cross-linking of poly(dl-lactide)−dimethacrylate macromers (5 kg/mol) in the presence of an unreactive diluent. Using diffusion filtering and 2D correlation spectroscopy techniques, all network components are identified. By quantification of network-bound photoinitiator fragments, an average kinetic chain length of 9 ± 2 methacrylate units is determined. The PDLLA macromer solution was also used with a dye to prepare computer-designed structures by stereolithography. For these networks structures, the average kinetic chain length is 24 ± 4 methacrylate units. In all cases the calculated molecular weights of the polymethacrylate chains after degradation are maximally 8.8 kg/mol, which is far below the threshold for renal clearance. Upon incubation in phosphate buffered saline at 37 °C, the networks show a similar mass loss profile in time as linear high-molecular-weight PDLLA (HMW PDLLA). The mechanical properties are preserved longer for the PDLLA networks than for HMW PDLLA. The initial tensile strength of 47 ± 2 MPa does not decrease significantly for the first 15 weeks, while HMW PDLLA lost 85 ± 5% of its strength within 5 weeks. The physical properties, kinetic chain length, and degradation profile of these photo-cross-linked PDLLA networks make them most suited materials for orthopedic applications and use in (bone) tissue engineering.

Sulfated fibrous ZrO2/Al2O3 core and shell nanocomposites : a novel strong acid catalyst with hierarchically macro-mesoporous nanostructure

A series of solid strong acid catalysts were synthesised from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2 % to 50 %. The ZrO2/Al2O3 nanocomposites and their solid strong acid counterparts were characterised by a variety of techniques including 27Al magic angle spinning nuclear magnetic resonance (MAS-NMR), scanned electronic microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), Nitrogen adsorption and infrared emission spectroscopy (IES). NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained solid acids was tested by using them as catalysts for the benzolyation of toluene. It was found that a sample with a 50 % zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia.

Collective equipments of power: The road and the city

A year ago, I became aware of the historical existence of the group CERFI— Le centre d’etudes, de recherches, et de formation institutionelles, or The Study Center for Institutional Research and Formation. CERFI emerged in 1967 under the hand of Lacanian psychiatrist and Trotskyite activist Félix Guattari, whose antonymous journal Recherches chronicled the group’s subversive experiences, experiments, and government-sponsored urban projects. It was a singularly bizarre meeting of the French bureaucracy with militant activist groups, the French intelligentsia, and architectural and planning practitioners at the close of the ‘60s. Nevertheless, CERFI’s analysis of the problems of society was undertaken precisely from the perspective of the state, and the Institute acknowledged a “deep complicity between the intellectual and statesman ... because the first critics of the State, are officials themselves!”1 CERFI developed out of FGERI (The Federation of Groups for Institutional Study and Research), started by Guattari two years earlier. While FGERI was created for the analysis of mental institutions stemming from Guattari’s work at La Borde, an experimental psychiatric clinic, CERFI marks the group’s shift toward urbanism—to the interrogation of the city itself. Not only a platform for radical debate on architecture and the city, CERFI was a direct agent in the development of urban planning schemata for new towns in France. 2 CERFI’s founding members were Guattari, the economist and urban theorist François Fourquet, feminist philosopher Liane Mozère, and urban planner and editor of Multitides Anne Querrien—Guattari’s close friend and collaborator. The architects Antoine Grumback, Alain Fabre, Macary, and Janine Joutel were also members, as well as urbanists Bruno Fortier, Rainier Hoddé, and Christian de Portzamparc. 3 CERFI was the quintessential social project of post-‘68 French urbanism. Located on the Far Left and openly opposed to the Communist Party, this Trotskyist cooperative was able to achieve what other institutions, according to Fourquet, with their “customary devices—the politburo, central committee, and the basic cells—had failed to do.”4 The decentralized institute recognized that any formal integration of the group was to “sign its own death warrant; so it embraced a skein of directors, entangled, forming knots, liquidating all at once, and spinning in an unknown direction, stopping short and returning back to another node.” Allergic to the very idea of “party,” CERFI was a creative project of free, hybrid-aesthetic blocs talking and acting together, whose goal was none other than the “transformation of the libidinal economy of the militant revolutionary.” The group believed that by recognizing and affirming a “group unconscious,” as well as their individual unconscious desires, they would be able to avoid the political stalemates and splinter groups of the traditional Left. CERFI thus situated itself “on the side of psychosis”—its confessed goal was to serve rather than repress the utter madness of the urban malaise, because it was only from this mad perspective on the ground that a properly social discourse on the city could be forged.

Spinning a sustainable yarn: assessing the claims of Australian companies’ eco-initiatives

In Australia, few fashion brands have intervened in the design of their products or the systems around their product to tackle environmental pollution and waste. Instead, support of charities (whether social or environmental) has become conflated with sustainability in the eyes of the public.However, three established Australian brands recently put forward initiatives which explicitly tackle the pre-consumer or post-consumer waste associated with their products. In 2011, Billabong, one of the largest surfwear companies in the world, developed a collection of board shorts made from recycled bottles that are also recyclable at end of life. The initiative has been promoted in partnership with Bob Marley’s son Rohan Marley, and the graphics of the board shorts reference the Rastafarian colours and make use of Marley’s song lyrics. In this way, the company has tapped into an aspect of surf culture linked to environmental activism, in which the natural world is venerated. Two mid-market initiatives, by Metalicus and Country Road, each have a social outcome that arguably aligns to the values of their middle-class consumer base. Metalicus is spear-heading a campaign for Australian garment manufacturers to donate their pre consumer waste – fabric off-cuts – to charity Open Family Australia to be manufactured into quilts for the homeless. Country Road has partnered with the Australian Red Cross to implement a recycling scheme in which consumers donate their old Country Road garments in exchange for a Country Road gift voucher. Both strategies, while tackling waste, tell an altruistic story in which the disadvantaged can benefit from the consumption habits of the middle-class. To varying degrees, the initiative chosen by each company feeds into the stories they tell about themselves and about the consumers who purchase their clothing. However, how can we assess the impact of these schemes on waste management in real terms, or indeed the worth of each scheme in the wider context of the fashion system? This paper will assess the claims made by the companies and analyse their efficacy, suggesting that a more nuanced assessment of green claims is required, in which ‘green’ comes in many tonal variations.

Zeta-potential and morphology of electrospun nano- and microfibers from biopolymers and their blends used as scaffolds in tissue engineering

Electrostatic spinning or electrospinning is a fiber spinning technique driven by a high-voltage electric field that produces fibers with diameters in a submicrometer to nanometer range.1 Nanofibers are typical one-dimensional colloidal objects with an increased tensile strength, whose length can achieve a few kilometers and the specific surface area can be 100 m2 g–1 or higher.2 Nano- and microfibers from biocompatible polymers and biopolymers have received much attention in medical applications3 including biomedical structural elements (scaffolding used in tissue engineering,2,4–6 wound dressing,7 artificial organs and vascular grafts8), drug and vaccine delivery,9–11 protective shields in speciality fabrics, multifunctional membranes, etc. Other applications concern superhydrophobic coatings,12 encapsulation of solid materials,13 filter media for submicron particles in separation industry, composite reinforcement and structures for nano-electronic machines.

Effect of dangling chains on the structure and physical properties of a tightly crosslinked poly(ethylene glycol) network

Major imperfections in crosslinked polymers include loose or dangling chain ends that lower the crosslink d., thereby reducing elastic recovery and increasing the solvent swelling. These imperfections are hard to detect, quantify and control when the network is initiated by free radical reactions. As an alternative approach, the sol-​gel synthesis of a model poly(ethylene glycol) (PEG-​2000) network is described using controlled amts. of bis- and mono-​triethoxy silyl Pr urethane PEG precursors to give silsesquioxane (SSQ, R-​SiO1.5) structures as crosslink junctions with a controlled no. of dangling chains. The effect of the no. of dangling chains on the structure and connectivity of the dried SSQ networks has been detd. by step-​crystn. differential scanning calorimetry. The role that micelle formation plays in controlling the sol-​gel PEG network connectivity has been studied by dynamic light scattering of the bis- and mono-​triethoxy silyl precursors and the networks have been characterized by 29Si solid state NMR, sol fraction and swelling measurements. These show that the dangling chains will increase the mesh size and water uptake. Compared to other end-​linked PEG hydrogels, the SSQ-​crosslinked networks show a low sol fraction and high connectivity, which reduces solvent swelling, degree of crystallinity and the crystal transition temp. The increased degree of freedom in segment movement on the addn. of dangling chains in the SSQ-​crosslinked network facilitates the packing process in crystn. of the dry network and, in the hydrogel, helps to accommodate more water mols. before reaching equil.

‘Click’ functionalised polymer resins : a new approach to the synthesis of surface attached bipyridinium and naphthalene diimide [2]rotaxanes

Herein we describe the design and synthesis of a series of solid-tethered [2]rotaxanes utilising crown ether-naphthalene diimide or crown ether- bipyridinium host guest interactions. TentaGel polystyrene resins were initially modified in a two-stage procedure to azide functionalised beads before the target supramolecular architectures were attached using a copper catalysed “click” procedure. The final assembly was examined using IR spectroscopy and gel-phase 1H High Resolution Magic Angle Spinning (HR MAS) NMR spectroscopy. The HR MAS technique enabled a direct comparison between the solid-tethered architectures and the synthesis and characterisation of analogous solution-based [2]rotaxanes to be made.

Insight into morphology and structure of different particle sized kaolinites with same origin

The particle size, morphology, crystallinity order and structural defects of four kaolinite samples are characterized by the techniques including particle size analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). The particle size of four kaolinite samples gradually increases. Four samples all belong to the ordered kaolinite and show a decrease in structural order with the increase of kaolinite particle size. The changes of structural defect are proved by the increase of the band splitting in Raman spectroscopy, the decrease of the intensity of absorption bands in infrared spectroscopy, and the decrease of equivalent silicon atom and the increase of nonequivalent aluminum atom in MAS NMR spectroscopy. The differences in morphology and structural defect are attributed to the broken bonds of Al–O–Si, Al–O–Al and Si–O–Si and the Al substitution for Si in tetrahedral sheets.

Imaging intracellular protein dynamics by spinning disk confocal microscopy

The palette of fluorescent proteins (FPs) has grown exponentially over the past decade, and as a result, live imaging of cells expressing fluorescently tagged proteins is becoming more and more mainstream. Spinning disk confocal (SDC) microscopy is a high-speed optical sectioning technique and a method of choice to observe and analyze intracellular FP dynamics at high spatial and temporal resolution. In an SDC system, a rapidly rotating pinhole disk generates thousands of points of light that scan the specimen simultaneously, which allows direct capture of the confocal image with low-noise scientific grade-cooled charge-coupled device cameras, and can achieve frame rates of up to 1000 frames per second. In this chapter, we describe important components of a state-of-the-art spinning disk system optimized for live cell microscopy and provide a rationale for specific design choices. We also give guidelines of how other imaging techniques such as total internal reflection microscopy or spatially controlled photoactivation can be coupled with SDC imaging and provide a short protocol on how to generate cell lines stably expressing fluorescently tagged proteins by lentivirus-mediated transduction.