Molecular engineering of mechanophore activity for stress-responsive polymeric materials

© The Royal Society of Chemistry.Force reactive functional groups, or mechanophores, have emerged as the basis of a potential strategy for sensing and countering stress-induced material failure. The general utility of this strategy is limited, however, because the levels of mechanophore activation in the bulk are typically low and observed only under large, typically irreversible strains. Strategies that enhance activation are therefore quite useful. Molecular-level design principles by which to engineer enhanced mechanophore activity are reviewed, with an emphasis on quantitative structure-activity studies determined for a family of gem-dihalocyclopropane mechanophores. This journal is

Experimental Design to Optimize High-Volume Ash Grout in the Presence of Welan Gum and Superplasticizer

Applications such as soil, rock and oil-well grouting all require enormous amounts of cement and are good examples of areas where a high volume of fly ash could partially replace cement to produce low-cost, environmentally safe and durable concrete. There is an increasing need to identify the rheological properties of cement grout using a simple test to determine the fluidity, and other properties of underwater grouts such as washout resistance and compressive strength. This paper presents statistical models developed using a fractorial design which was carried out to model the influence of key parameters on properties affecting the performance of underwater grout. Such responses of fluidity included mini-slump and flow time measured by Marsh cone, washout resistance, unit weight and compressive strength. The models are valid for mixes with 0.40 to 0.60 water-to-cementitious materials ratio, 0.02 to 0.08% of anti-washout admixture, by mass of binder, and 0.6 to 1.8% of superplasticizer, by mass of cementitious materials. The grout was made with 50% of pulverized-fuel ash replacement, by mass ofcementitious materials. Also presented are the derived models that enable the identification of underlying primary factors and their interactions that influence the modelled responses of underwater cement grout. Such parameters can be useful to reduce the test protocol needed for proportioning of underwater cement grout. This paper highlighted the influence of W/CM and dosage of antiwashout admixture and superplasticizer on fluidity, washout resistance and compressive strength and attempted also to demonstrate the usefulness of the models to improve understanding of trade-offs between parameters.

An Analytical Study of Surplus Value using a Value Driven Design Methodology

People are now becoming more environmentally aware and as a consequence of this, industries such as the aviation industry are striving to design more environmentally friendly products. To achieve this, the current design methodologies must be modified to ensure these issues are considered from product conception through to disposal. This paper discusses the environmental problems in relation to the aviation industry and highlights some logic for making the change from the traditional Systems Engineering approach to the recent design paradigm known as Value Driven Design. Preliminary studies have been undertaken to aid in the understanding of this methodology and the existing surplus value objective function. The main results from the work demonstrate that surplus value works well bringing disparate issues such as manufacture and green taxes together to aid decision making. Further, to date studies on surplus value have used simple sensitivity analysis, but deeper consideration shows non-linear interactions between some of the variables and further work will be needed to fully account for complex issues such as environmental impact and taxes.

Climate change adaptation : a decision support framework to encourage environmentally responsible behaviour

Structured Abstract:
Purpose: Very few studies investigate environmentally responsible behaviour (ERB). This paper presents a new 'Awareness Behaviour Intervention Action' (ABIA) Decision Support Framework to sustain ERB.

Design/methodology/approach: Previous ERB programmes have failed to deliver lasting results; they have not appropriately understood and provided systems to address ERB (Costanzo et al., 1986). These programmes were based on assumptions (Moloney et al., 2010), which this paper addresses. The ABIA Framework has been developed through a case study of social housing tenants waiting for low or zero carbon homes.

Findings: The ABIA Framework enables a better understanding of current attitudes to environmental issues and provides support for ERB alongside technological interventions employed to promote and sustain carbon reduction.

Research limitations/implications: The ABIA Framework should be tested on individuals and communities in a variety of socio-economic, political and cultural contexts. This will help unpack how it can impact on the behaviours of individuals and communities including stakeholders.

Practical implications: This type of research and the ABIA Framework developed from it are crucial if the UK pledge to become the first country in the World where all new homes from 2016 are to be zero carbon.

Social implications: The Framework encourages both individual and community discussion and solving of sustainability issues.

Originality/value: There are few, if any, studies that have developed a framework which can be used to support behavioural change for adaptation to sustainable living in low or zero carbon homes.

Piñatex, the design development of a new sustainable material

This is a research project by practice, which firstly develops a new material invention derived from natural fibres extracted from waste pineapple leaves; secondly it articulates the contemporary designer’s role in facilitating sustainable solutions through: Insights from my own material invention, PiñatexTM, which integrates the materiality of design with the immateriality of concepts and values Developing a visual model of mapping I began with these questions: ‘What are the challenges in seeking to make a new and sustainable material from the waste products of pineapple agriculture in the Philippines?’ and ‘How can a design practice link elements of materiality (artifacts) with immaterial elements (value systems) in order to improve sustainable social and economic development?’ Significant influences have been the work of Papanek1 (2003), Hawken2 (1999) and Abouleish3 (2008) and in particular the ethical business model initiated by McDonough and Braungart in Cradle to Cradle®4 (2002). My own research project is inspired by the Cradle to Cradle® model. It proposes the development of a new material, PiñatexTM which is derived from natural fibres extracted from waste pineapple leaves and could be used in a wide variety of products that are currently fabricated in leather or petroleum-based materials. The methods have comprised: Contextual reviews; case studies (SEKEM, Cradle to Cradle® and Gawad Kalinga); practical experiments in the field of natural fibres, chemistry, product development, manufacturing and prototyping, leading to an invention and a theoretical model of mapping. In addition, collaboration has taken place across scientific, technological, social, ecological, academic and business fields. The outcome is a new material based on the synchronicity between the pineapple fibres, polymers, resins and coatings specially formulated. The invention of the new material that I developed as a central part of this research by practice has a patent in the national phase (PCT/GB 2011/000802) and is in the first stages of manufacturing, commercial testing and further design input (Summer 2014). The contribution to knowledge is firstly the material, PiñatexTM, which exhibits certain key qualities, namely environmentally non-toxic, biodegradable, income-generating potential and marketability. This is alongside its intrinsic qualities as a textile product: aesthetic potential, durability and stability, which will make it suitable for the accessories, interiors and furnishing markets. The theoretical mapping system Upstream and Downstream forms a secondary contribution.

Strategy-proofness makes the difference: deferred-acceptance with responsive priorities

In college admissions and student placements at public schools, the admission decision can be thought of as assigning indivisible objects with capacity constraints to a set of students such that each student receives at most one object and monetary compensations are not allowed. In these important market design problems, the agent-proposing deferred-acceptance (DA-)mechanism with responsive strict priorities performs well and economists have successfully implemented DA-mechanisms or slight variants thereof. We show that almost all real-life mechanisms used in such environments - including the large classes of priority mechanisms and linear programming mechanisms - satisfy a set of simple and intuitive properties. Once we add strategy-proofness to these properties, DA-mechanisms are the only ones surviving. In market design problems that are based on weak priorities (like school choice), generally multiple tie-breaking (MTB)procedures are used and then a mechanism is implemented with the obtained strict priorities. By adding stability with respect to the weak priorities, we establish the first normative foundation for MTB-DA-mechanisms that are used in NYC.

Design, synthèse et application en catalyse verte d’un ligand alkyl imidazolium β-cyclodextrine

Le 21e siècle est le berceau d’une conscientisation grandissante sur les impacts environnementaux des processus utilisés pour synthétiser des molécules cibles. Parmi les avancées qui ont marqué ces dernières décennies, il est également question de réduction de déchets, de conservation de l’énergie et de durabilité des innovations. Ces aspects constituent les lignes directrices de la chimie verte. De ce fait, il est impératif de développer des stratégies de synthèse dont les impacts environnementaux sont bénins. Dans ce mémoire nous présentons la synthèse, la caractérisation et l’étude des propriétés catalytiques en milieu aqueux d’un ligand composé d’une unité -cyclodextrine native, d’une unité imidazolium et d’une chaine alkyle à 12 carbones. Ce ligand hybride s’auto-assemble dans l’eau sous forme de micelles, permettant ainsi d’effectuer en sa présence des couplages de Suzuki-Miyaura dans l’eau, avec de bons rendements. La fonctionnalisation de la face primaire de la -cyclodextrine par un noyau alkyl-imidazolium, précurseur de ligand de type carbène N-hétérocyclique, a permis le développement d’un système catalytique vert et hautement recyclable. Dans un deuxième temps, nous présentons l’utilisation du même ligand hybride dans des couplages de Heck dans l’eau, démontrant ainsi la versatilité du ligand.

Formation of vesicles through solvent assisted self-assembly of hydrophobic pentapeptides: encapsulation and pH responsive release of dyes by the vesicles

In the biomimetic design two hydrophobic pentapetides Boc-Ile-Aib-Leu-Phe-Ala-OMe ( I) and Boc-Gly-Ile-Aib-Leu-Phe-OMe (II) (Aib: alpha-aminoisobutyric acid) containing one Aib each are found to undergo solvent assisted self-assembly in methanol/water to form vesicular structures, which can be disrupted by simple addition of acid. The nanovesicles are found to encapsulate dye molecules that can be released by the addition of acid as confirmed by fluorescence microscopy and UV studies. The influence of solvent polarity on the morphology of the materials generated from the peptides has been examined systematically, and shows that fibrillar structures are formed in less polar chloroform/petroleum ether mixture and vesicular structures are formed in more polar methanol/water. Single crystal X-ray diffraction studies reveal that while beta-sheet mediated self-assembly leads to the formation of fibrillar structures, the solvated beta-sheet structure leads to the formation of vesicular structures. The results demonstrate that even hydrophobic peptides can generate vesicular structures from polar solvent which may be employed in model studies of complex biological phenomena.

Investigating preferences for dynamic electricity tariffs: the effect of environmental and system benefit disclosure

Dynamic electricity pricing can produce efficiency gains in the electricity sector and help achieve energy policy goals such as increasing electric system reliability and supporting renewable energy deployment. Retail electric companies can offer dynamic pricing to residential electricity customers via smart meter-enabled tariffs that proxy the cost to procure electricity on the wholesale market. Current investments in the smart metering necessary to implement dynamic tariffs show policy makers’ resolve for enabling responsive demand and realizing its benefits. However, despite these benefits and the potential bill savings these tariffs can offer, adoption among residential customers remains at low levels. Using a choice experiment approach, this paper seeks to determine whether disclosing the environmental and system benefits of dynamic tariffs to residential customers can increase adoption. Although sampling and design issues preclude wide generalization, we found that our environmentally conscious respondents reduced their required discount to switch to dynamic tariffs around 10% in response to higher awareness of environmental and system benefits. The perception that shifting usage is easy to do also had a significant impact, indicating the potential importance of enabling technology. Perhaps the targeted communication strategy employed by this study is one way to increase adoption and achieve policy goals.

Enzymatically-triggered, isothermally responsive polymers: re-programming poly(oligoethylene glycols) to respond to phosphatase

Polymers which can respond to externally applied stimuli have found much application in the biomedical field due to their (reversible) coil–globule transitions. Polymers displaying a lower critical solution temperature are the most commonly used, but for blood-borne (i.e., soluble) biomedical applications the application of heat is not always possible, nor practical. Here we report the design and synthesis of poly(oligoethylene glycol methacrylate)-based polymers whose cloud points are easily varied by alkaline phosphatase-mediated dephosphorylation. By fine-tuning the density of phosphate groups on the backbone, it was possible to induce an isothermal transition: A change in solubility triggered by removal of a small number of phosphate esters from the side chains activating the LCST-type response. As there was no temperature change involved, this serves as a model of a cell-instructed polymer response. Finally, it was found that both polymers were non cytotoxic against MCF-7 cells (at 1 mg·mL–1), which confirms promise for biomedical applications.

Equal Couples in Equal Houses : Cultural perspectives on Swedish solar and bio-pellet heating design

Knowing how to design a heating system that will work mechanically is quite different from knowling how to design a system that users perceive as responsive to their domestic practices and values. In this chapter, social anthropologist Henning argues that the challenge for designers involved in the development or marketing of green buildings with heating systems that are based on renewable sources of energy is to see things from the perspective of those who are supposed to live in these buildings. The chapter focuses on three culture-specific aspects of Swedish households and single-family houses: perceptions of house and home, of private and public space, and of male and female space. Through these three angles, some clues are given as to how design, performance and location of solar and bio-pellet heating systems could be made to resonate with predominant experiences, habits and ways of thinking among both men and women.

Signal transduction-related responses to phytohormones and environmental challenges in sugarcane

Background: Sugarcane is an increasingly economically and environmentally important C4 grass, used for the production of sugar and bioethanol, a low-carbon emission fuel. Sugarcane originated from crosses of Saccharum species and is noted for its unique capacity to accumulate high amounts of sucrose in its stems. Environmental stresses limit enormously sugarcane productivity worldwide. To investigate transcriptome changes in response to environmental inputs that alter yield we used cDNA microarrays to profile expression of 1,545 genes in plants submitted to drought, phosphate starvation, herbivory and N-2-fixing endophytic bacteria. We also investigated the response to phytohormones (abscisic acid and methyl jasmonate). The arrayed elements correspond mostly to genes involved in signal transduction, hormone biosynthesis, transcription factors, novel genes and genes corresponding to unknown proteins.Results: Adopting an outliers searching method 179 genes with strikingly different expression levels were identified as differentially expressed in at least one of the treatments analysed. Self Organizing Maps were used to cluster the expression profiles of 695 genes that showed a highly correlated expression pattern among replicates. The expression data for 22 genes was evaluated for 36 experimental data points by quantitative RT-PCR indicating a validation rate of 80.5% using three biological experimental replicates. The SUCAST Database was created that provides public access to the data described in this work, linked to tissue expression profiling and the SUCAST gene category and sequence analysis. The SUCAST database also includes a categorization of the sugarcane kinome based on a phylogenetic grouping that included 182 undefined kinases.Conclusion: An extensive study on the sugarcane transcriptome was performed. Sugarcane genes responsive to phytohormones and to challenges sugarcane commonly deals with in the field were identified. Additionally, the protein kinases were annotated based on a phylogenetic approach. The experimental design and statistical analysis applied proved robust to unravel genes associated with a diverse array of conditions attributing novel functions to previously unknown or undefined genes. The data consolidated in the SUCAST database resource can guide further studies and be useful for the development of improved sugarcane varieties.

Women with TT genotype for eNOS gene are more responsive in lowering blood pressure in response to exercise

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

An environmentally friendly reflectometric method for ranitidine determination in pharmaceuticals and human urine

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

An Environmentally Friendly Reflectometric Method for Bumetanide Determination in Pharmaceuticals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)