Chemistry on the inside: green chemistry in mesoporous materials

An overview of the rapidly expanding area of tailored mesoporous solids is presented. The synthesis of a wide range of the materials is covered, both inorganically and organically modified. Their applications, in particular those relating to green chemistry, are also highlighted. Finally, potential future directions for these materials are discussed

Post-polymerisation modification of bio-derived unsaturated polyester resins via Michael additions of 1,3-dicarbonyls

Post-polymerisation modification of α,β-unsaturated polyesters (UPEs) is useful to deliver polymers with tuneable properties and applications different from their parent backbone. Bio-derivable itaconate unsaturated polyesters, with a range of co-monomers, were modified via a heterogeneously catalysed microwave-assisted Michael addition of pendants, acetylacetone (Hacac) and dimethyl malonate (DMM), to the polymer backbones with very short reaction times. Differential scanning calorimetry analysis showed an increase in the glass-transition temperatures of most of the saturated polyesters considered. Solubility and complexation studies demonstrated metal chelating abilities of the acetylacetone pendant can be retained, even following tethering to a polyester backbone. Additionally, it is demonstrated for the first time that Michael addition with Hacac and DMM can be used to reverse Ordelt saturation, an unwanted side-reaction in the synthesis of UPEs

Subtle Microwave-Induced Overheating Effects in an Industrial Demethylation Reaction and Their Direct Use in the Development of an Innovative Microwave Reactor

A systematic study of the conventional and microwave (MW) kinetics of an industrially relevant demethylation reaction is presented. In using industrially relevant reaction conditions the dominant influence of the solvent on the MW energy dissipation is avoided. Below the boiling point, the effect of MWs on the activation energy Ea and k0 is found nonexistent. Interestingly, under reflux conditions, the microwave-heated (MWH) reaction displays very pronounced zero-order kinetics, displaying a much higher reaction rate than observed for the conventionally thermal-heated (CTH) reaction. This is related to a different gas product (methyl bromide, MeBr) removal mechanism, changing from classic nucleation into gaseous bubbles to a facilitated removal through escaping gases/vapors. Additionally, the use of MWs compensates better for the strong heat losses in this reaction, associated with the boiling of HBr/water and the loss of MeBr, than under CTH. Through modeling, MWH was shown to occur inhomogeneously around gas/liquid interfaces, resulting in localized overheating in the very near vicinity of the bubbles, overall increasing the average heating rate in the bubble vicinity vis-à-vis the bulk of the liquid. Based on these observations and findings, a novel continuous reactor concept is proposed in which the escaping MeBr and the generated HBr/water vapors are the main driving forces for circulation. This reactor concept is generic in that it offers a viable and low cost option for the use of very strong acids and the managed removal/quenching of gaseous byproducts

The expressive stance: intentionality, expression, and machine art

This paper proposes a new interpretive stance for interpreting artistic works and performances that is relevant to artificial intelligence research but also has broader implications. Termed the expressive stance, this stance makes intelligible a critical distinction between present-day machine art and human art, but allows for the possibility that future machine art could find a place alongside our own. The expressive stance is elaborated as a response to Daniel Dennett's notion of the intentional stance, which is critically examined with respect to his specialized concept of rationality. The paper also shows that temporal scale implicitly serves to select between different modes of explanation in prominent theories of intentionality. It also considers the implications of the phenomenological background for systems that produce art

A new perspective in bio-refining : Levoglucosenone and cleaner lignin from waste biorefinery hydrolysis lignin by selective conversion of residual saccharides

An unexpected opportunity is reported to improve the sustainability of biorefineries whereby 8 wt% levoglucosenone (LGE) can be derived from unconverted saccharides in a lignin-rich biorefinery waste stream in a highly selective fashion (>90%). Additionally, in the process a purer lignin is obtained which can be used for further processing or materials applications. LGE is a valuable and versatile product with a plethora of applications

Strong mechanical driving of a single electron spin

Quantum devices for sensing and computing applications require coherent quantum systems which can be manipulated in a fast and robust way. Such quantum control is typically achieved using external electric or magnetic fields which drive the system's orbital or spin degrees of freedom. However, most of these approaches require complex and unwieldy antenna or gate structures, and with few exceptions are limited to the regime of weak driving. Here, we present a novel approach to strongly and coherently drive a single electron spin in the solid state using internal strain fields in an integrated quantum device. Specifically, we study individual Nitrogen-Vacancy (NV) spins embedded in diamond mechanical oscillators and exploit the intrinsic strain coupling between spin and oscillator to strongly drive the spins. As hallmarks of the strong driving regime, we directly observe the energy spectrum of the emerging phonon-dressed states and employ our strong, continuous driving for enhancement of the NV spin coherence time. Our results constitute a first step towards strain-driven, integrated quantum devices and open new perspectives to investigate unexplored regimes of strongly driven multi-level systems and to study exotic spin dynamics in hybrid spin-oscillator devices.We gratefully acknowledge financial support from SNI; NCCR QSIT; SNF grants 200021_143697; and EU FP7 grant 611143 (DIADEMS). AN holds a University Research Fellowship from the Royal Society and acknowledges support from the Winton Programme for the Physics of Sustainability.This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/nphys341

A Neutral Polyampholyte in an ionic solution

The behavior of a neutral polyampholyte ($PA$) chain with $N$ monomers, in an ionic solution, is analyzed in the framework of the full Debye-H$\ddot u$ckel-Bjerrum-Flory $(DHBjF)$ theory. A $PA$ chain, that in addition to the neutral monomers, also contains an equal number of positively and negatively charged monomers, is dissolved in an ionic solution. For \underline{high} concentrations of salt and at high temperatures, the $PA$ exists in an extended state. As the temperature is decreased, the electrostatic energy becomes more relevant and at a $T=T_{\theta}$ the system collapses into a dilute globular state, or microelectrolyte. This state contains a concentration of salt higher than the surrounding medium. As the temperature is decreased even further, association between the monomers of the polymer and the ions of the salt becomes relevant and there is a crossover from this globular state to a low temperature extended state. For \underline{low} densities of salt, the system is collapsed for almost all temperatures and exhibits a first-order phase transition to an extended state at an unphysical low temperature.Comment: 10 pages, Revtex with epsf, 9 Postscript figures. Submitted to PR

The school environment and adolescent physical activity and sedentary behaviour : A mixed-studies systematic review

There is increasing academic and policy interest in interventions aiming to promote young people's health by ensuring that the school environment supports healthy behaviours. The purpose of this review was to summarize the current evidence on school-based policy, physical and social-environmental influences on adolescent physical activity and sedentary behaviour. Electronic databases were searched to identify studies that (1) involved healthy adolescents (11-18years old), (2) investigated school-environmental influences and (3) reported a physical activity and/or sedentary behaviour outcome or theme. Findings were synthesized using a non-quantitative synthesis and thematic analysis. Ninety-three papers of mixed methodological quality were included. A range of school-based policy (e.g. break time length), physical (e.g. facilities) and social-environmental (e.g. teacher behaviours) factors were associated with adolescent physical activity, with limited research on sedentary behaviour. The mixed-studies synthesis revealed the importance of specific activity settings (type and location) and intramural sport opportunities for all students. Important physical education-related factors were a mastery-oriented motivational climate and autonomy supportive teaching behaviours. Qualitative evidence highlighted the influence of the wider school climate and shed light on complexities of the associations observed in the quantitative literature. This review identifies future research needs and discusses potential intervention approaches to be considered