Functionalized Pyrolysis Products for High Value Chemical Production

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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

A single-molecule approach to ZnO defect studies: single photons and single defects

Investigations that probe defects one at a time offer a unique opportunity to observe properties and dynamics that are washed out of ensemble measurements. Here we present confocal fluorescence measurements of individual defects in Al-doped ZnO nanoparticles and undoped ZnO sputtered films that are excited with sub-bandgap energy light. Photon correlation measurements yield both antibunching and bunching, indicative of single-photon emission from isolated defects that possess a metastable shelving state. The single-photon emission is in the range 560 - 720 nm and typically exhibits two broad spectral peaks separated by approximately 150 meV. The excited state lifetimes range from 1 - 13 ns, consistent with the finite-size and surface effects of nanoparticles and small grains. We also observe discrete jumps in the fluorescence intensity between a bright state and a dark state. The dwell times in each state are exponentially distributed and the average dwell time in the bright (dark) state does (may) depend on the power of the exciting laser. Taken together, our measurements demonstrate the utility of a single-molecule approach to semiconductor defect studies and highlight ZnO as a potential host material for single-defect based applications.Comment: 33 pages, 7 figure

Comparison of numerical methods for simulating strongly non-linear and heterogeneous reactive transport problems – the MoMaS benchmark case

International audienceAlthough multicomponent reactive transport modeling is gaining wider application in various geoscience fields, it continues to present significant mathematical and computational challenges. There is a need to solve and compare the solutions to complex benchmark problems, using a variety of codes, because such intercomparisons can reveal promising numerical solution approaches and increase confidence in the application of reactive transport codes. In this contribution, the results and performance of five current reactive transport codes are compared for the 1D and 2D sub-problems of the so-called "Easy Test Case" of the MoMaS benchmark (Carrayrou et al., this issue). As a group, the codes include iterative and non-iterative operator splitting, and global implicit solution approaches. The 1D Easy Advective and 1D Easy Diffusive scenarios were solved using all codes and, in general, there was good agreement, with solution discrepancies limited to regions with rapid concentration changes. Computational demands were typically consistent with what was expected for the various solution approaches. The most important outcome of the benchmark exercise is that all codes are able to generate comparable results for problems of significant complexity and computational difficulty

Moving forward: Tackling stigma in a Tanzanian community

The International Center for Research on Women, the Muhimbili University College of the Health Sciences, the Population Council, and Family Health International conducted an evaluation of a community-based effort to reduce stigma surrounding HIV infections in a peri-urban community in Tanzania. Results presented a mixed, but hopeful, picture for a way forward in tackling stigma at the community level. Tackling stigma requires that the individuals tasked with doing this undergo personal change. Programs can start by focusing stigma-reduction efforts on a smaller, more manageable geographical area and adding specific anti-stigma components to their portfolio of activities. Engaging community opinion leaders (e.g., political, religious, and youth leaders, and healthcare workers) is a promising way forward for scaling up stigma-reduction at the community level

Synthesis of Biobased Diethyl Terephthalate via Diels-Alder Addition of Ethylene to 2,5-Furandicarboxylic Acid Diethyl Ester: An Alternative Route to 100% Biobased Poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) is a ubiquitous thermoplastic currently produced from nonrenewable fossil resources; as such, sustainable biobased routes to the key terephthalate monomer are being widely pursued. Herein is demonstrated a greener solventless route to biobased diethyl terephthalate via a one-pot heterogeneous Lewis acid catalyzed Diels-Alder addition and dehydration of 2,5-furandicarboxylic acid diethyl ester with ethylene, giving yields of terephthalate up to 59% for the key Diels-Alder addition step. A metrics-based comparison against alternative published biobased routes (available from sugars, cellulose and hemicellulose) shows that the clean synthetic pathway developed herein gives a practical atom economy, overall yield and selectivity, making it a viable alternative to routes currently under development

Waveguide-integrated silicon T centres

The performance of modular, networked quantum technologies will be strongly dependent upon the quality of their quantum light-matter interconnects. Solid-state colour centres, and in particular T centres in silicon, offer competitive technological and commercial advantages as the basis for quantum networking technologies and distributed quantum computing. These newly rediscovered silicon defects offer direct telecommunications-band photonic emission, long-lived electron and nuclear spin qubits, and proven native integration into industry-standard, CMOS-compatible, silicon-on-insulator (SOI) photonic chips at scale. Here we demonstrate further levels of integration by characterizing T centre spin ensembles in single-mode waveguides in SOI. In addition to measuring long spin T_1 times, we report on the integrated centres' optical properties. We find that the narrow homogeneous linewidth of these waveguide-integrated emitters is already sufficiently low to predict the future success of remote spin-entangling protocols with only modest cavity Purcell enhancements. We show that further improvements may still be possible by measuring nearly lifetime-limited homogeneous linewidths in isotopically pure bulk crystals. In each case the measured linewidths are more than an order of magnitude lower than previously reported and further support the view that high-performance, large-scale distributed quantum technologies based upon T centres in silicon may be attainable in the near term

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