Mesoporous silica spheres from colloids

A novel method has been developed to synthesize mesoporous silica spheres using commercial silica colloids (SNOWTEX) as precursors and electrolytes (ammonium nitrate and sodium chloride) as destabilizers. Crosslinked polyacrylamide hydrogel was used as a temporary barrier to obtain dispersible spherical mesoporous silica particles. The influences of synthesis conditions including solution composition and calcination temperature on the formation of the mesoporous silica particles were systematically investigated. The structure and morphology of the mesoporous silica particles were characterized via scanning electron microscopy (SEM) and N2 sorption technique. Mesoporous silica particles with particle diameters ranging from 0.5 to 1.6 μm were produced whilst the BET surface area was in the range of 31-123 m2 g-1. Their pore size could be adjusted from 14.1 to 28.8 nm by increasing the starting particle diameter from 20-30 nm up to 70-100 nm. A simple and cost effective method is reported that should open up new opportunities for the synthesis of scalable host materials with controllable structures.

The Media as Political Actors

This chapter provides a history of the media as political actors and identifies key principles that have shaped their role in both democratic and authoritarian polities (i.e., information, interpretation, participation, critical scrutiny). In addition, the chapter explores recent trends impacting on the performance of that role, such as the emergence of the Internet and, as a consequence of that process, a globalized public sphere of transnational news media outlets. It is argued that to make the Internet truly valuable as a political resource, democratic societies continue to require the work of skilled, professional journalists and their sense making, interpretative functions. Because of that journalists and their organizations remain crucial to the translation of content into meaningful messages.

Reliability and reproducibility of a handheld videorefractor

PURPOSE To assess the performance of the 2Win eccentric videorefractor in relation to subjective refraction and table-mounted autorefraction. METHODS Eighty-six eyes of 86 adults (46 male and 40 female subjects) aged between 20 and 25 years were examined. Subjective refraction and autorefraction using the table-mounted Topcon KR8800 and the handheld 2Win videorefractor were carried out in a randomized fashion by three different masked examiners. Measurements were repeated about 1 week after to assess instrument reproducibility, and the intertest variability was compared between techniques. Agreement of the 2Win videorefractor with subjective refraction and autorefraction was assessed for sphere and for cylindrical vectors at 0 degrees (J0) and 45 degrees (J45). RESULTS Reproducibility coefficients for sphere values measured by subjective refraction, Topcon KR8800, and 2Win (±0.42, ±0.70, and ±1.18, respectively) were better than their corresponding J0 (±1.0, ±0.85, and ±1.66) and J45 (±1.01, ±0.87, and ±1.31) vector components. The Topcon KR8800 showed the most reproducible values for mean spherical equivalent refraction and the J0 and J45 vector components, whereas reproducibility of spherical component was best for subjective refraction. The 2Win videorefractor measurements were the least reproducible for all measures. All refractive components measured by the 2Win videorefractor did not differ significantly from those of subjective refraction, in both sessions (p > 0.05). The Topcon KR8800 autorefractometer and the 2Win videorefractor measured significantly more positive spheres and mean spherical equivalent refraction (p < 0.0001), but the J0 and J45 vector components were similar (p > 0.05), in both sessions. CONCLUSIONS The 2Win videorefractor compares well, on average, with subjective refraction. The reproducibility values for the 2Win videorefractor were considerably worse than either subjective refraction or autorefraction. The wide limits of reproducibility of the 2Win videorefractor probably limit its usefulness as a primary screening device.

Stimulation of osteogenesis and angiogenesis of hBMSCs by delivering Si ions and functional drug from mesoporous silica nanospheres

Multifunctional bioactive materials with the ability to stimulate osteogenesis and angiogenesis of stem cells play an important role in the regeneration of bone defects. However, how to develop such biomaterials remains a significant challenge. In this study, we prepared mesoporous silica nanospheres (MSNs) with uniform sphere size (∼90 nm) and mesopores (∼2.7 nm), which could release silicon ions (Si) to stimulate the osteogenic differentiation of human bone marrow stromal cells (hBMSCs) via activating their ALP activity, bone-related gene and protein (OCN, RUNX2 and OPN) expression. Hypoxia-inducing therapeutic drug, dimethyloxaloylglycine (DMOG), was effectively loaded in the mesopores of MSNs (D-MSNs). The sustained release of DMOG from D-MSNs could stabilize HIF-1α and further stimulated the angiogenic differentiation of hBMSCs as indicated by the enhanced VEGF secretion and protein expression. Our study revealed that D-MSNs could combine the stimulatory effect on both osteogenic and angiogenic activity of hBMSCs. The potential mechanism of D-MSN-stimulated osteogenesis and angiogenesis was further elucidated by the supplementation of cell culture medium with pure Si ions and DMOG. Considering the easy handling characteristics of nanospheres, the prepared D-MSNs may be applied in the forms of injectable spheres for minimally invasive surgery, or MSNs/polymer composite scaffolds for bone defect repair. The concept of delivering both stimulatory ions and functional drugs may offer a new strategy to construct a multifunctional biomaterial system for bone tissue regeneration.

Mesenchymal stem cells as mediators of the neuronal cell niche

This study examined the role of heparan sulfate proteoglycans (HSPGs) in neural lineage differentiation of human mesenchymal stem cells (hMSCs). Several HSPGs were identified as potential new targets controlling neural fate specification and may be applied to the development of improved models to examine and repair brain damage. hMSCs were characterised throughout extended in vitro expansion for neural lineage potential (neurons, astrocytes, oligodendrocytes) and differentiated using terminal differentiation and intermediate sphere formation. Brain damage and neurological disorders caused by injury or disease affect a large number of people often resulting in lifelong disabilities. Multipotent mesenchymal stem cells have a large capacity for self-renewal and provide an excellent model to examine the regulation and contribution of both stem cells and their surrounding microenvironment to the repair of neural tissue damage.

Striving for a better world: Lessons from Freire in Grenada, Jamaica and Australia

The author of this paper considers the influence of Paulo Freire’s pedagogical philosophy on educational practice in three different geographical/political settings. She begins with reflections on her experience as a facilitator at Freire’s seminar, held in Grenada in 1980 for teachers and community educators, on the integration of work and study. This case demonstrates how Freire’s method of dialogic education achieved outcomes for the group of thoughtful collaboration leading to conscientisation in terms of deep reflection on their lives as teachers in Grenada and strategies for decolonising education and society. The second case under consideration is the arts-based pedagogy shaping the work of the Area Youth Foundation (AYF) in Kingston, Jamaica. Young participants, many of them from tough socio-economic backgrounds, are empowered by learning how to articulate their own experiences and relate these to social change. They express this conscientisation by creating stage performances, murals, photo-novella booklets and other artistic products. The third case study describes and evaluates the Honey Ant Reader project in Alice Springs, Australia. Aboriginal children, as well as the adults in their community, learn to read in their local language as well as Australian Standard English, using booklets created from indigenous stories told by community Elders, featuring local customs and traditions. The author analyses how the “Freirean” pedagogy in all three cases exemplifies the process of encouraging the creation of knowledge for progressive social change, rather than teaching preconceived knowledge. This supports her discussion of the extent to which this is authentic to the spirit of the scholar/teacher Paulo Freire, who maintained that in our search for a better society, the world has to be made and remade. Her second, related aim is to raise questions about how education aligned with Freirean pedagogy can contribute to moving social change from the culture circle to the public sphere.

The structures of the isomorphous potassium and rubidium salts of 4-nitrobenzoic acid and an overview of the metal complex stereochemistries of the alkali metal salt series with this ligand

The structures of the isomorphous potassium and rubidium polymeric coordination complexes with 4-nitrobenzoic acid, poly[mu2-aqua-aqua-mu3-(4-nitrobenzoato)-potassium], [K(C7H4N2O2)(H2O)2]n, (I) and poly[mu3-aqua-aqua-mu5-(4-nitrobenzoato)-rubidium], [Rb(C7H4N2O2)(H2O)2]n, (II) have been determined. In (I) the very distorted KO6 coordination sphere about the K+ centres in the repeat unit comprise two bridging nitro O-atom donors, a single bridging carboxyl O-atom donor and two water molecules, one of which is bridging. In the the Rb complex (II), the same basic MO6 coordination is found in the repeat unit but is expanded to RbO9 through a slight increase in the accepted Rb-O bond length range and includes an additional Rb-O(carboxyl) bond, completing a bidentate O,O'-chelate interaction, and additional bridging Rb-Onitro) and Rb-O(water) bonds. The comparative K-O and Rb-O bond length ranges are 2.738(3)-3.002(3)Ang. (I) and 2.884(2)-3.182(2)Ang. (II). The structure of (II) is also isomorphous as well as isostructural with the known structure of the nine-coordinate caesium 4-nitrobenzoate analogue, [Cs(C7H4N2O~2~)(H~2~O)2]n, (III) in which the Cs---O range is 3.047(4)-3.338(4)Ang. In all three complexes, common basic polymeric extensions are found, including two different centrosymmetric bridging interactions through both water and nitro groups as well as extensions along c through the p-related carboxyl group, giving a two-dimensional structure in (I). In (II) and (III), three-dimensional structures are generated through additional bridges through the nitro and water O-atoms. In all structures, both water molecules are involved in similar intra-polymer O-H...O hydrogen-bonding interactions to both carboxyl as well as water O-atom acceptors. A comparison of the varied coordination behaviour of the full set of Li-Cs salts with 4-nitrobenzoic acid is also made.

Gamma tocotrienol targets tyrosine phosphatase SHP2 in mammospheres resulting in cell death through RAS/ERK pathway

Background There is increasing evidence supporting the concept of cancer stem cells (CSCs), which are responsible for the initiation, growth and metastasis of tumors. CSCs are thus considered the target for future cancer therapies. To achieve this goal, identifying potential therapeutic targets for CSCs is essential. Methods We used a natural product of vitamin E, gamma tocotrienol (gamma-T3), to treat mammospheres and spheres from colon and cervical cancers. Western blotting and real-time RT-PCR were employed to identify the gene and protein targets of gamma-T3 in mammospheres. Results We found that mammosphere growth was inhibited in a dose dependent manner, with total inhibition at high doses. Gamma-T3 also inhibited sphere growth in two other human epithelial cancers, colon and cervix. Our results suggested that both Src homology 2 domain-containing phosphatase 1 (SHP1) and 2 (SHP2) were affected by gamma-T3 which was accompanied by a decrease in K- and H-Ras gene expression and phosphorylated ERK protein levels in a dose dependent way. In contrast, expression of self-renewal genes TGF-beta and LIF, as well as ESR signal pathways were not affected by the treatment. These results suggest that gamma-T3 specifically targets SHP2 and the RAS/ERK signaling pathway. Conclusions SHP1 and SHP2 are potential therapeutic targets for breast CSCs and gamma-T3 is a promising natural drug for future breast cancer therapy.

Designing 'other' citizens into the city: Investigating perceptions of architectural opportunities for wildlife habitat in the Brisbane CBD

Traditional perceptions of the human-animal relationship in the urban context typically see the spatial rejection of wildlife from the built environment and limiting of biodiversity conservation programs to areas of natural reserve. As urban growth places further spatial demands on natural habitat and contributes to continued global biodiversity loss, the recently introduced conservation approach of reconciliation ecology makes a call promoting ecological stewardship through embedding wildlife habitat within human dominated areas. Coinciding with this, the architectural sphere has seen a recent trend of design investigation addressing artificial animal habitat as features of the built environment. Although these precedents are currently a niche and scattered trend they show potential to address the human-animal dualism challenging the framework of reconciliation ecology. This research explores the role design plays in influencing perceptions of urban wildlife habitat, particularly considering the need to create and communicate value around wildlife biodiversity as a component of urban cultural place-making and ecological literacy. The study purpose sets out to establish a set of approaches and cultural preferences with which to direct further classification and development of this architectural trend. Brisbane is utilised as a case study city, as a locale containing proximities of relatively high wildlife and human populations in an urban setting and an established legislative biodiversity heritage and ethic. Through use of a qualitative and quantitative questionnaire targeting Brisbane residents, the research methodology established that although respondents perceptions generally aligned with traditional prejudice against wildlife around human buildings, artificial habitat intervention would be supported within the CBD provided it allowed for adequate distancing of humans from wildlife and conformed with contextual surroundings, or otherwise addressed habitat through redevelopment at an urban scale. As such further research directions for artificial habitat should focus on integration of artificial habitat as a component of façade design or green infrastructure programs.

Information-theoretic analysis of brain white matter fiber orientation distribution functions

We propose a new information-theoretic metric, the symmetric Kullback-Leibler divergence (sKL-divergence), to measure the difference between two water diffusivity profiles in high angular resolution diffusion imaging (HARDI). Water diffusivity profiles are modeled as probability density functions on the unit sphere, and the sKL-divergence is computed from a spherical harmonic series, which greatly reduces computational complexity. Adjustment of the orientation of diffusivity functions is essential when the image is being warped, so we propose a fast algorithm to determine the principal direction of diffusivity functions using principal component analysis (PCA). We compare sKL-divergence with other inner-product based cost functions using synthetic samples and real HARDI data, and show that the sKL-divergence is highly sensitive in detecting small differences between two diffusivity profiles and therefore shows promise for applications in the nonlinear registration and multisubject statistical analysis of HARDI data.

A theoretical framework for designing and evaluating strategies to identify cases of serious child abuse and neglect

A central dimension of the State’s responsibility in a liberal democracy and any just society is the protection of individuals’ central rights and freedoms, and the creation of the minimum conditions under which each individual has an opportunity to lead a life of sufficient equality, dignity and value. A special subset of this responsibility is to protect those who are unable to protect themselves from genuine harm. Substantial numbers of children suffer serious physical, emotional and sexual abuse, and neglect at the hands of their parents and caregivers or by other known parties. Child abuse and neglect occurs in a situation of extreme power asymmetry. The physical, social, behavioural and economic costs to the individual, and the social and economic costs to communities, are vast. Children are not generally able to protect themselves from serious abuse and neglect. This enlivens both the State’s responsibility to protect the child, and the debate about how that responsibility can and should be discharged. A core question arises for all societies, given that most serious child maltreatment occurs in the family sphere, is unlikely to be disclosed, causes substantial harm to both individual and community, and infringes fundamental individual rights and freedoms. The question is: how can society identify these situations so that the maltreatment can be interrupted, the child’s needs for security and safety, and health and other rehabilitation can be met, and the family’s needs can be addressed to reduce the likelihood of recurrence? This chapter proposes a theoretical framework applicable for any society that is considering justifiable and effective policy approaches to identify and respond to cases of serious child abuse and neglect. The core of the theoretical framework is based on major principles from both classical liberal political philosophy (Locke and Mill), and leading political philosophers from the twentieth century and the first part of the new millennium (Rawls, Rorty, Okin, Nussbaum), and is further situated within fundamental frameworks of civil and criminal law, and health and economics.

Alteration of the C-terminal ligand specificity of the Erbin PDZ domain by allosteric mutational effects

Modulation of protein binding specificity is important for basic biology and for applied science. Here we explore how binding specificity is conveyed in PDZ (postsynaptic density protein-95/discs large/zonula occludens-1) domains, small interaction modules that recognize various proteins by binding to an extended C terminus. Our goal was to engineer variants of the Erbin PDZ domain with altered specificity for the most C-terminal position (position 0) where a Val is strongly preferred by the wild-type domain. We constructed a library of PDZ domains by randomizing residues in direct contact with position 0 and in a loop that is close to but does not contact position 0. We used phage display to select for PDZ variants that bind to 19 peptide ligands differing only at position 0. To verify that each obtained PDZ domain exhibited the correct binding specificity, we selected peptide ligands for each domain. Despite intensive efforts, we were only able to evolve Erbin PDZ domain variants with selectivity for the aliphatic C-terminal side chains Val, Ile and Leu. Interestingly, many PDZ domains with these three distinct specificities contained identical amino acids at positions that directly contact position 0 but differed in the loop that does not contact position 0. Computational modeling of the selected PDZ domains shows how slight conformational changes in the loop region propagate to the binding site and result in different binding specificities. Our results demonstrate that second-sphere residues could be crucial in determining protein binding specificity.

From users to citizens: Some thoughts on designing for polity and civics

This paper presents an essay aimed at prompting broad discussion crucial in keeping the interaction design discourse fresh, critical, and in motion. We trace the changing role of people who have advanced from consumers to producers, from stationary office workers to mobile urban nomads, from passive members of the plebs to active instigators of change. Yet, interaction designers often still refer to them only as ‘users.’ We follow some of the historic developments from the information superhighway to the smart city in order to provide the backdrop in front of which we critically analyse three core areas. First, the issue of echo chambers and filter bubbles in social media results in a political polarisation that jeopardises the formation of a functioning public sphere. Second, pretty lights and colourful façades in media architecture are increasingly making way for situated installations and interventions fostering community engagement. And third, civic activism is often reduced to forms of slacktivism. We synthesise our discussion to propose ‘citizen-ability’ as an alternative goal for interaction designers to aspire to in order to create new polities and civics for a better quality of life.

A comment on the consistency of truncated nonlinear integral equation based theories of freezing

We report the results of two studies of aspects of the consistency of truncated nonlinear integral equation based theories of freezing: (i) We show that the self-consistent solutions to these nonlinear equations are unfortunately sensitive to the level of truncation. For the hard sphere system, if the Wertheim–Thiele representation of the pair direct correlation function is used, the inclusion of part but not all of the triplet direct correlation function contribution, as has been common, worsens the predictions considerably. We also show that the convergence of the solutions found, with respect to number of reciprocal lattice vectors kept in the Fourier expansion of the crystal singlet density, is slow. These conclusions imply great sensitivity to the quality of the pair direct correlation function employed in the theory. (ii) We show the direct correlation function based and the pair correlation function based theories of freezing can be cast into a form which requires solution of isomorphous nonlinear integral equations. However, in the pair correlation function theory the usual neglect of the influence of inhomogeneity of the density distribution on the pair correlation function is shown to be inconsistent to the lowest order in the change of density on freezing, and to lead to erroneous predictions. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.

Algebraic and geometric intersection numbers for free groups

We show that the algebraic intersection number of Scott and Swarup for splittings of free groups Coincides With the geometric intersection number for the sphere complex of the connected sum of copies of S-2 x S-1. (C) 2009 Elsevier B.V. All rights reserved.