Co3O4 nanostructures with a high rate performance as anode materials for lithium-ion batteries, prepared via book-like cobalt-organic frameworks

The self-assembly of cobalt coordination frameworks (Co-CPs) with a two-dimensional morphology is demonstrated by a solvothermal method. The morphology of the Co-CPs has been controlled by various solvothermal conditions. The two-dimensional nanostructures agglomerated by Co3O4 nanoparticles remained after the pyrolysis of the Co-CPs. The as-synthesized Co3O4 anode material is characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge measurements. The morphology of Co3O4 plays a crucial role in the high performance anode materials for lithium batteries. The Co3O4 nanoparticles with opened-book morphology deliver a high capacity of 597 mA h g-1 after 50 cycles at a current rate of 800 mA g-1. The opened-book morphology of Co3O4 provides efficient lithium ion diffusion tunnels and increases the electrolyte/Co3O4 contact/interfacial area. At a relatively high current rate of 1200 mA g-1, Co3O4 with opened-book morphology delivers an excellent rate capability of 574 mA h g-1.

Approaches to Organization of Teaching for Creating Digital Learning Materials

Report published in the Proceedings of the National Conference on "Education in the Information Society", Plovdiv, May, 2013

Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300°C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400°C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.

Silica promoted self-assembled mesoporous aluminas. Impact of the silica precursor on the structural, textural and acidic properties

This paper investigates the effect of silica addition on the structural, textural and acidic properties of an evaporation induced self-assembled (EISA) mesoporous alumina. Two silica addition protocols were applied while maintaining the EISA synthesis route. The first route is based on the addition of a Na-free colloidal silica suspension (Ludox®), and the second method consists of the co-hydrolysis of tetraethyl orthosilicate (TEOS) with aluminium tri-sec-butoxide, to favour a more intimate mixing of the Al- and Si-hydrolysed species. The properties of the so derived materials were compared to the SiO2-free counterpart. The SiO2 addition was always beneficial from a structural and textural standpoint. TEOS appears to have a truly promoting effect; the ordering, surface area and pore volume are all improved. For Ludox®, the enhancement comes from the formation of smaller pores by a densification of the structure. The crystallization of γ-alumina depends on the interaction between the Al- and Si-species in the mesophase. Ludox®-based materials achieved crystallization at 750 °C but the intimate mixing in the TEOS-based mesophases shows a suppression of the phase transformation by 50-100 °C, with respect to the SiO2-free counterpart. This reduces the textural features substantially. For all SiO2-modified materials, the enhancement in the surface area is not accompanied by a concomitant improvement of total acidity, and the formation of weak Lewis acid sites was promoted. These effects were ascribed to SiO2 migration to the surface that blocks part of the acidity.

Condensation-enhanced self-assembly as a route to high surface area α-aluminas

High surface area nanosized α-alumina has been obtained by thermally treating a sol-gel-derived mesophase at 1200 C; the mesophase was synthesized by a sol-gel route involving evaporation induced self-assembly (EISA) of a hydrolyzed gel from Al-tri-sec-butoxide in s-BuOH in the presence of a nonionic surfactant (EO20PO70EO20), HCl as catalyst, and water (H2O/Al = 6). The activated material renders moderate surface areas of about 8.4-10 m2 g-1, associated with significant crystallite coarsening. The key aspect to produce smaller crystallites is making the mesophase more resistant to coarsening. This was achieved by enhancing the condensation step by treating the hydrolyzed gel with tetrabutyl ammonium hydroxide (TBAOH) before evaporation. The characteristics of the mesophase indicate condensation of the primary particles with less AlO5 unsaturated sites, at the expense of a lower solid yield due to small crystallites dissolution. The activated TBAOH condensed EISA material is composed of α-alumina aggregated crystallites of about 60-100 nm, and the material possesses surface areas ranging from 16 to 24 m2 g -1 due to the improved resistance to coarsening. At least two aspects are suggested to play a role in this. The worm-hole morphology of the mesophase aggregates yields high particle coordination, which favors densification rather than coarsening. Furthermore, the decrease of the AlO5 defect sites by the TBAOH condensation makes the mesophase less reactive and consequently more resistant to coarsening. © 2013 American Chemical Society.

Stabilization of self-assembled alumina mesophases

An efficient route to stabilize alumina mesophases derived from evaporation-induced self-assembly is reported after investigating various aspects in-depth: influence of the solvent (EtOH, s-BuOH, and t-BuOH) on the textural and structural properties of the mesophases based on aluminum tri-sec-butoxide (ATSB), synthesis reproducibility, role of nonvolatile acids, and the crystallization and thermal stability of the crystalline counterparts. Mesophase specific surface area and pore uniformity depend notably on the solvent; s-BuOH yields the highest surface area and pore uniformity. The optimal mesophase synthesis is reproducible with standard deviations in the textural parameters below 5%. The most pore-uniform mesophases from the three solvents were thermally activated at 1023 K to crystallize them into γ-alumina. The s-BuOH mesophase is remarkably thermally stable, retaining the mesoscopic wormhole order with 300 m2/g (0.45 cm3/g) and an increased acidic site density. These features are not obtained with EtOH or t-BuOH, where agglomerated γ-Al2O3 crystallites are formed with lower surface areas and broader pore size distributions. This was rationalized by the increase of the hydrolysis rate using EtOH and t-BuOH. t-BuOH dehydrates under the synthesis conditions or reacts with HCl, situations that increase the water concentration and rate of hydrolysis. It was found that EtOH exchanges rapidly, producing a highly reactive Al-ethoxide, thus enhancing the hydrolysis rate as well. Particle heterogeneity with random packing of fibrous and wormhole morphologies, attributed to the high hydrolysis rate, was observed for mesophases derived from both solvents. Such a low particle coordination favors coarsening with enlargement of the pore size distribution upon thermal treatment, explaining the lower thermal stability. Controlled hydrolysis and formation of low-polymerized Al species in s-BuOH are possibly responsible for the adequate assembly onto the surfactant. This was verified by the formation of a regular distribution of relatively size-uniform nanoparticles in the mesophase; high particle coordination prevents coarsening, favors densification, and maintains a relatively uniform pore size distribution upon thermal treatment. The acid removal in the evaporation is another key factor to promote network condensation in this route. © 2013 American Chemical Society.

Institutional Self study for the Liaison Committee on Medical Education

Draft of the College of Medicine's Institutional Self-Study for the LCME. Includes an overview of the College of Medicine's history, development, and vision, as well as details regarding the organization of the college, educational programs and resources, and future goals.

Perceived Stress and Self‑rated Health of Haitian and African Americans with and without Type 2 Diabetes

Background: Blacks have a higher incidence of diabetes and its related complications. Self-rated health (SRH) and perceived stress indicators are associated with chronic diseases. The aim of this study was to examine the associations between SRH, perceived stress and diabetes status among two Black ethnicities. Materials and Methods: The cross-sectional study included 258 Haitian Americans and 249 African Americans with (n = 240) and without type 2 diabetes (n = 267) (N = 507). Recruitment was performed by community outreach. Results: Haitian-Americans were less likely to report ‘fair to poor’ health as compared to African Americans [OR=0.58 (95% CI: 0.35, 0.95), P = 0.032]; yet, Haitian Americans had greater perceived stress than African Americans (P = 0.002). Having diabetes was associated with ‘fair to poor’ SRH [OR=3.14 (95% CI: 2.09, 4.72),P < 0.001] but not perceived stress (P = 0.072). Haitian-Americans (P = 0.023), females (P = 0.003) and those participants having ‘poor or fair’ SRH (P < 0.001) were positively associated with perceived stress (Nagelkerke R2=0.151). Conclusion: Perceived stress associated with ‘poor or fair’ SRH suggests that screening for perceived stress should be considered part of routine medical care; albeit, further studies are required to confirm our results. The findings support the need for treatment plans that are patient-centered and culturally relevant and that address psychosocial issues.

Mechanochemistry for Active Materials and Devices

The coupling of mechanical stress fields in polymers to covalent chemistry (polymer mechanochemistry) has provided access to previously unattainable chemical reactions and polymer transformations. In the bulk, mechanochemical activation has been used as the basis for new classes of stress-responsive polymers that demonstrate stress/strain sensing, shear-induced intermolecular reactivity for molecular level remodeling and self-strengthening, and the release of acids and other small molecules that are potentially capable of triggering further chemical response. The potential utility of polymer mechanochemistry in functional materials is limited, however, by the fact that to date, all reported covalent activation in the bulk occurs in concert with plastic yield and deformation, so that the structure of the activated object is vastly different from its nascent form. Mechanochemically activated materials have thus been limited to “single use” demonstrations, rather than as multi-functional materials for structural and/or device applications. Here, we report that filled polydimethylsiloxane (PDMS) elastomers provide a robust elastic substrate into which mechanophores can be embedded and activated under conditions from which the sample regains its original shape and properties. Fabrication is straightforward and easily accessible, providing access for the first time to objects and devices that either release or reversibly activate chemical functionality over hundreds of loading cycles.

While the mechanically accelerated ring-opening reaction of spiropyran to merocyanine and associated color change provides a useful method by which to image the molecular scale stress/strain distribution within a polymer, the magnitude of the forces necessary for activation had yet to be quantified. Here, we report single molecule force spectroscopy studies of two spiropyran isomers. Ring opening on the timescale of tens of milliseconds is found to require forces of ~240 pN, well below that of previously characterized covalent mechanophores. The lower threshold force is a combination of a low force-free activation energy and the fact that the change in rate with force (activation length) of each isomer is greater than that inferred in other systems. Importantly, quantifying the magnitude of forces required to activate individual spiropyran-based force-probes enables the probe behave as a “scout” of molecular forces in materials; the observed behavior of which can be extrapolated to predict the reactivity of potential mechanophores within a given material and deformation.

We subsequently translated the design platform to existing dynamic soft technologies to fabricate the first mechanochemically responsive devices; first, by remotely inducing dielectric patterning of an elastic substrate to produce assorted fluorescent patterns in concert with topological changes; and second, by adopting a soft robotic platform to produce a color change from the strains inherent to pneumatically actuated robotic motion. Shown herein, covalent polymer mechanochemistry provides a viable mechanism to convert the same mechanical potential energy used for actuation into value-added, constructive covalent chemical responses. The color change associated with actuation suggests opportunities for not only new color changing or camouflaging strategies, but also the possibility for simultaneous activation of latent chemistry (e.g., release of small molecules, change in mechanical properties, activation of catalysts, etc.) in soft robots. In addition, mechanochromic stress mapping in a functional actuating device might provide a useful design and optimization tool, revealing spatial and temporal force evolution within the actuator in a way that might also be coupled to feedback loops that allow autonomous, self-regulation of activity.

In the future, both the specific material and the general approach should be useful in enriching the responsive functionality of soft elastomeric materials and devices. We anticipate the development of new mechanophores that, like the materials, are reversibly and repeatedly activated, expanding the capabilities of soft, active devices and further permitting dynamic control over chemical reactivity that is otherwise inaccessible, each in response to a single remote signal.

D6.6 – Summary, Analysis, Road-mapping and Production of Training materials

This deliverable summarizes, validates and explains the purpose and concept behind the RAGE knowledge and innovation management platform as a self-sustainable Ecosystem, supporting innovation processes in the Applied Gaming (AG) industry. The Ecosystem portal will be developed with particular consideration of the demand and requirements of small and medium sized game developing companies, education providers and related stakeholders like AG researchers and AG end-users. The innovation potential of the new platform underlies the following factors: a huge, mostly entire collection of community specific knowledge (e.g., content like media objects, software components and best practices), a structured approach of knowledge access, search and browse, collaboration tools as well as social network analysis tools to foster efficient knowledge creation and transformation processes into marketable technology assets. The deliverable provides an overview of the current status and the remaining work to come, preceding the final version in month 48 of the RAGE project.

Education and self-regulation of learning for gifted pupils: Systemic design and development.

Gifted pupils differ from their age-mates with respect to development potential, actual competencies, self-regulatory capabilities, and learning styles in one or more domains of competence. The question is how to design and develop education that fits and further supports such characteristics and competencies of gifted pupils. Analysis of various types of educational interventions for gifted pupils reflects positive cognitive or intellectual effects and differentiated social comparison or group-related effects on these pupils. Systemic preventive combination of such interventions could make these more effective and sustainable. The systemic design is characterised by three conditional dimensions: differentiation of learning materials and procedures, integration by and use of ICT support, and strategies to improve development and learning. The relationships to diagnostic, instructional, managerial, and systemic learning aspects are expressed in guidelines to develop or transform education. The guidelines imply the facilitation of learning arrangements that provide flexible self-regulation for gifted pupils. A three-year pilot in Dutch nursery and primary school is conducted to develop and implement the design in collaboration with teachers. The results constitute prototypes of structured competence domains and supportive software. These support the screening of entry characteristics of all four-year old pupils and assignment of adequate play and learning processes and activities throughout the school career. Gifted and other pupils are supported to work at their actual achievement or competency levels since their start in nursery school, in self-regulated learning arrangements either in or out of class. Each pupil can choose other pupils to collaborate with in small groups, at self-chosen tasks or activities, while being coached by the teacher. Formative evaluation of the school development process shows that the systemic prevention guidelines seem to improve learning and social progress of gifted pupils, including their self-regulation. Further development and implementation steps are discussed.

Learning for self-regulation: Improving instructional benefits for pupils, teachers, parents, schools, and society at large

Compulsory education laws oblige primary and secondary schools to give each pupil positive encouragement in, for example, social, emotional, cognitive, creative, and ethical respects. This is a fairly smooth process for most pupils, but it is not as easy to achieve with others. A pattern of pupil, home or family, and school variables turns out to be responsible for a long-term process that may lead to a pupil’s dropping out of education. A systemic approach will do much to introduce more clarity into the diagnosis, potential reduction and possible prevention of some persistent educational problems that express themselves in related phenomena, for example low school motivation and achievement; forced underachievement of high ability pupils; concentration of bullying and violent behaviour in and around some types of classes and schools; and drop-out percentages that are relatively constant across time. Such problems have a negative effect on pupils, teachers, parents, schools, and society alike. In this address, I would therefore like to clarify some of the systemic causes and processes that we have identified between specific educational and pupil characteristics. Both theory and practice can assist in developing, implementing, and checking better learning methods and coaching procedures, particularly for pupils at risk. This development approach will take time and require co-ordination, but it will result in much better processes and outcomes than we are used to. First, I will diagnose some systemic aspects of education that do not seem to optimise the learning processes and school careers of some types of pupils in particular. Second, I will specify cognitive, social, motivational, and self-regulative aspects of learning tasks and relate corresponding learning processes to relevant instructional and wider educational contexts. I will elaborate these theoretical notions into an educational design with systemic instructional guidelines and multilevel procedures that may improve learning processes for different types of pupils. Internet-based Information and Communication Technology, or ICT, also plays a major role here. Third, I will report on concrete developments made in prototype research and trials. The development process concerns ICT-based differentiation of learning materials and procedures, and ICT-based strategies to improve pupil development and learning. Fourth, I will focus on the experience gained in primary and secondary educational practice with respect to implementation. We can learn much from such practical experience, in particular about the conditions for developing and implementing the necessary changes in and around schools. Finally, I will propose future research. As I hope to make clear, theory-based development and implementation research can join forces with systemic innovation and differentiated assessment in educational practice, to pave the way for optimal “learning for self-regulation” for pupils, teachers, parents, schools, and society at large.

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials.