Modifying the product distribution of a reaction within the controlled microenvironment of a colloidosome

A water-soluble colloidosome composed of PGMA–PS latex was used as a microcapsule to host a catalyzed oxidation reaction within its dodecane core. When compared to a control reaction a significant colloidosome effect was observed. Specifically, a 233% increase in the relative yield of all products was observed for the colloidosome reaction. Furthermore, when the product distributions were calculated it was evident that a switch in selectivity had taken place. These studies showed there is a significant reduction in the relative yield of the epoxide product compared to the remaining oxidation products. Additional control experiments confirmed that rate enhancements were not simply a result of concentration and that reactions were not occurring in the outer latex phase. As a consequence of these control experiments, we suggest that the colloidosome enhancement and shift in product distribution, comes about from differences in electronic environment at or close to the interface between the internal oil phase and the outer colloidal particles. This environment is able to stabilize any specific intermediates and or transition states leading to enhanced reactions for these products and higher relative yields

Automation in the simulation of processes with Aspen HYSYS: An academic approach

Aspen HYSYS is a typical tool used in some Master in Chemical Engineering courses at the University of Castilla-La Mancha like “Analysis and Optimization of Chemical Processes” and “Dynamic of Process: Regulation of Chemical Plants.” Automation is the process of linking commercial software to third-parties applications built in EXCEL-Visual Basic for Applications. The capability of automation as a powerful tool for simulating unprecedented complex processes suggests that it could be a relevant background complement to the classical one offered by a university. In this sense, a seminar about automation based on the study of two cases: a refrigeration process and a production one taken from literature, has been proposed at the University of Castilla-La Mancha. The analysis of the survey performed for the subject evaluation resulted to be very positive. Students consider the methodology of the course and the potentiality of automation for developing their research and professional skills appropriately. However, more examples are required to better understand the automation concept and its potential application to other situations. Finally, they declare that the concept of automation requires a lot of expertise and deep knowledge of programming and the correct application of numerical methods for solving complex problem

Total oxidation of propene at low temperature over Co3O4-CeO2 mixed oxides: Role of surface oxygen vacancies and bulk oxygen mobility in the catalytic activity

Co3O4, CeO2 and Co3O4\u2013CeO2 mixed oxides with Co/Ce nominal atomic ratio 0.1:5, prepared by coprecipitation method with sodium carbonate, were tested in the oxidation of propene under lean condition and the catalyst stability was checked by performing three consecutive heating\u2013cooling cycles. Characterization of the textural properties were performed by surface area measurement BET, X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements. Among the Co3O4\u2013CeO2 mixed oxides, Co3O4 (30 wt%)\u2013CeO2 (70 wt%) gives the best activity attaining full propene conversion at 250 \ub0C. This sample is characterized by the presence of Co3O4 particles well dispersed and in good contact with ceria according to BET and XRD data and as evidenced by SEM micrographs. Oxygen temperature-programmed desorption (O2 -TPD) and C3H6 -temperature-programmed reduction (C3H6-TPR) experiments were carried out in order to study the surface and bulk oxygen mobility and to correlate it to the activity. At temperature around 200 \ub0C, O2-TPD experiments showed the desorption of mobile surface oxygen species for the most active samples, Co3O4 and Co3O4 (30 wt%)\u2013 CeO2 (70 wt%). C3H6-TPR experiments for both of the oxides also evidenced a high reactivity at low temperature, especially, for Co3O4 (30 wt%)\u2013 CeO2 (70 wt%) giving at 345 \ub0C an intense peak of CO2 formation. Conversely, the ceria sample showed by C3H6-TPR much less pronounced oxygen bulk mobility, starting to react with propene above 500 \ub0C and forming only CO. In this case, the catalytic activity of ceria was explained in terms of formation of surface oxygen vacancies which are relevant to the propene oxidation in presence of gaseous oxygen

Salen-Based Amphiphiles:Directing Self-Assembly in Water by Metal Complexation

Tuning morphologies of self‐assembled structures in water is a major challenge. Herein we present a salen‐based amphiphile which, using complexation with distinct transition metal ions, allows to control effectively the self‐assembly morphology in water, as observed by Cryo‐TEM and confirmed by DLS measurements. Applying this strategy with various metal ions gives a broad spectrum of self‐assembled structures starting from the same amphiphilic ligand (from cubic structures to vesicles and micelles). Thermogravimetric analysis and electric conductivity measurements reveal a key role for water coordination apparently being responsible for the distinct assembly behavior.Supramolecular & Biomaterials Chemistr

Universal Negative Poisson Ratio of Self Avoiding Fixed Connectivity Membranes

We determine the Poisson ratio of self-avoiding fixed-connectivity membranes, modeled as impenetrable plaquettes, to be sigma=-0.37(6), in statistical agreement with the Poisson ratio of phantom fixed-connectivity membranes sigma=-0.32(4). Together with the equality of critical exponents, this result implies a unique universality class for fixed-connectivity membranes. Our findings thus establish that physical fixed-connectivity membranes provide a wide class of auxetic (negative Poisson ratio) materials with significant potential applications in materials science.Comment: 4 pages, 3 figures, LaTeX (revtex) Published version - title changed, one figure improved and one reference change

Correlation functions near Modulated and Rough Surfaces

In a system with long-ranged correlations, the behavior of correlation functions is sensitive to the presence of a boundary. We show that surface deformations strongly modify this behavior as compared to a flat surface. The modified near surface correlations can be measured by scattering probes. To determine these correlations, we develop a perturbative calculation in the deformations in height from a flat surface. Detailed results are given for a regularly patterned surface, as well as for a self-affinely rough surface with roughness exponent $\zeta$. By combining this perturbative calculation in height deformations with the field-theoretic renormalization group approach, we also estimate the values of critical exponents governing the behavior of the decay of correlation functions near a self-affinely rough surface. We find that for the interacting theory, a large enough $\zeta$ can lead to novel surface critical behavior. We also provide scaling relations between roughness induced critical exponents for thermodynamic surface quantities.Comment: 31 pages, 2 figure

On twisted Fourier analysis and convergence of Fourier series on discrete groups

We study norm convergence and summability of Fourier series in the setting of reduced twisted group $C^*$-algebras of discrete groups. For amenable groups, F{\o}lner nets give the key to Fej\'er summation. We show that Abel-Poisson summation holds for a large class of groups, including e.g. all Coxeter groups and all Gromov hyperbolic groups. As a tool in our presentation, we introduce notions of polynomial and subexponential H-growth for countable groups w.r.t. proper scale functions, usually chosen as length functions. These coincide with the classical notions of growth in the case of amenable groups.Comment: 35 pages; abridged, revised and update

Kinetic study of the reaction of leuco methylene blue with 2,6-dimethyl-p-benzoquinone in a reverse micellar system

The kinetics of the reaction of leuco methylene blue (MBH) with 2,6-dimethyl-p-benzoquinone (DMBQ) were studied in a heptane/bis(2-ethylhexyl)-sulfosuccinate (AOT)/water reverse micellar system. The pseudo-first-order rate constant (k (obsd)) obtained in the presence of excess of DMBQ was found to be proportional to the initial concentration of DMBQ for W (0)=3, 5, 10, 15 and 20 (W (0)=[H2O]/[AOT]). The second-order rate constant (k (2)=k (obsd)/[DMBQ](0)) increased with an increase in the W (0) value, but was almost independent of the concentration of the water pool. A mechanism involving the distribution of DMBQ between the reverse micellar interface and bulk organic solvent was proposed to explain these findings.</p

Engaging with childhood: student placements and the employability agenda.

Employability is a particular organising narrative within the global, neoliberal economic discourse, with increasing relevance across different educational contexts. For universities in the UK, student employability, that is the readiness of students to gain and maintain employment and contribute to the economy, is a significant feature of accountability with employability outcomes increasingly used by students in making their decision of which university to attend. Yet little attention is paid to the organizing power of the employability agenda and to university students’ participation in that agenda apart from focussing on knowledge and skills relevant to gain employment. This is particularly concerning in university programmes that develop professionals who work with children. Placement, gaining knowledge, skills and experience in the places where children and young people are found, is a common aspect of employability being embedded within programme curricula. This article explores the organising power of the employability agenda for children and young people in a context of university placements. Focused on student experiences on placement in primary school settings in the north of England analysis considers students’ engagement with their own learning and the children who are essential to that learning

Rare region effects at classical, quantum, and non-equilibrium phase transitions

Rare regions, i.e., rare large spatial disorder fluctuations, can dramatically change the properties of a phase transition in a quenched disordered system. In generic classical equilibrium systems, they lead to an essential singularity, the so-called Griffiths singularity, of the free energy in the vicinity of the phase transition. Stronger effects can be observed at zero-temperature quantum phase transitions, at nonequilibrium phase transitions, and in systems with correlated disorder. In some cases, rare regions can actually completely destroy the sharp phase transition by smearing. This topical review presents a unifying framework for rare region effects at weakly disordered classical, quantum, and nonequilibrium phase transitions based on the effective dimensionality of the rare regions. Explicit examples include disordered classical Ising and Heisenberg models, insulating and metallic random quantum magnets, and the disordered contact process.Comment: Topical review, 68 pages, 14 figures, final version as publishe