Biomass gasification, catalytic technologies and energy integration for production of circular methanol: New horizons for industry decarbonisation.

The Intergovernmental Panel on Climate Change (IPCC) recognises the pivotal role of renewable energies in the future energy system and the achievement of the zero-emission target. The implementation of renewables should provide major opportunities and enable a more secure and decentralised energy supply system. Renewable fuels provide long-term solutions for the transport sector, particularly for applications where fuels with high energy density are required. In addition, it helps reducing the carbon footprint of these sectors in the long-term. Information on biomass characteristics feedstock is essential for scaling-up gasification from the laboratory to industrial-scale. This review deals with the transformation biogenic residues into a valuable bioenergy carrier like biomethanol as the liquid sunshine based on the combination of modified mature technologies such as gasification with other innovative solutions such as membranes and microchannel reactors. Tar abatement is a critical process in product gas upgrading since tars compromise downstream processes and equipment, for this, membrane technology for upgrading syngas quality is discussed in this paper. Microchannel reactor technology with the design of state-of-the-art multifunctional catalysts provides a path to develop decentralised biomethanol synthesis from biogenic residues. Finally, the development of a process chain for the production of (i) methanol as an intermediate energy carrier, (ii) electricity and (iii) heat for decentralised applications based on biomass feedstock flexible gasification, gas upgrading and methanol synthesis is analysed.

Manipulation of Magnetic Dipole Emission from Eu3+ with Mie-Resonant Dielectric Metasurfaces.

Mie-resonant high-index dielectric nanoparticles and metasurfaces have been suggested as a viable platform for enhancing both electric and magnetic dipole transitions of fluorescent emitters. While the enhancement of the electric dipole transitions by such dielectric nanoparticles has been demonstrated experimentally, the case of magnetic-dipole transitions remains largely unexplored. Here, we study the enhancement of spontaneous emission of Eu3+ ions, featuring both electric and magnetic-dominated dipole transitions, by dielectric metasurfaces composed of Mie-resonant silicon nanocylinders. By coating the metasurfaces with a layer of an Eu3+ doped polymer, we observe an enhancement of the Eu3+ emission associated with the electric (at 610 nm) and magnetic-dominated (at 590 nm) dipole transitions. The enhancement factor depends systematically on the spectral proximity of the atomic transitions to the Mie resonances as well as their multipolar order, both controlled by the nanocylinder size. Importantly, the branching ratio of emission via the electric or magnetic transition channel can be modified by carefully designing the metasurface, where the magnetic dipole transition is enhanced more than the electric transition for cylinders with radii of about 130 nm. We confirm our observations by numerical simulations based on the reciprocity principle. Our results open new opportunities for bright nanoscale light sources based on magnetic transitions.

Active Tuning of Spontaneous Emission by Mie-Resonant Dielectric Metasurfaces.

Mie-resonant dielectric metasurfaces offer comprehensive opportunities for the manipulation of light fields with high efficiency. Additionally, various strategies for the dynamic tuning of the optical response of such metasurfaces were demonstrated, making them important candidates for reconfigurable optical devices. However, dynamic control of the light-emission properties of active Mie-resonant dielectric metasurfaces by an external control parameter has not been demonstrated so far. Here, we experimentally demonstrate the dynamic tuning of spontaneous emission from a Mie-resonant dielectric metasurface that is situated on a fluorescent substrate and embedded into a liquid crystal cell. By switching the liquid crystal from the nematic state to the isotropic state via control of the cell temperature, we induce a shift of the spectral position of the metasurface resonances. This results in a change of the local photonic density of states, which, in turn, governs the enhancement of spontaneous emission from the substrate. Specifically, we observe spectral tuning of both the electric and magnetic dipole resonances, resulting in a 2-fold increase of the emission intensity at λ ≈ 900 nm. Our results demonstrate a viable strategy to realize flat tunable light sources based on dielectric metasurfaces.

Multifold Enhancement of Third-Harmonic Generation in Dielectric Nanoparticles Driven by Magnetic Fano Resonances.

Strong Mie-type magnetic dipole resonances in all-dielectric nanostructures provide novel opportunities for enhancing nonlinear effects at the nanoscale due to the intense electric and magnetic fields trapped within the individual nanoparticles. Here we study third-harmonic generation from quadrumers of silicon nanodisks supporting high-quality collective modes associated with the magnetic Fano resonance. We observe nontrivial wavelength and angular dependencies of the generated harmonic signal featuring a multifold enhancement of the nonlinear response in oligomeric systems.

Ultrafast All-Optical Switching with Magnetic Resonances in Nonlinear Dielectric Nanostructures.

We demonstrate experimentally ultrafast all-optical switching in subwavelength nonlinear dielectric nanostructures exhibiting localized magnetic Mie resonances. We employ amorphous silicon nanodisks to achieve strong self-modulation of femtosecond pulses with a depth of 60% at picojoule-per-disk pump energies. In the pump-probe measurements, we reveal that switching in the nanodisks can be governed by pulse-limited 65 fs-long two-photon absorption being enhanced by a factor of 80 with respect to the unstructured silicon film. We also show that undesirable free-carrier effects can be suppressed by a proper spectral positioning of the magnetic resonance, making such a structure the fastest all-optical switch operating at the nanoscale.

Polarization-Independent Silicon Metadevices for Efficient Optical Wavefront Control.

We experimentally demonstrate a functional silicon metadevice at telecom wavelengths that can efficiently control the wavefront of optical beams by imprinting a spatially varying transmittance phase independent of the polarization of the incident beam. Near-unity transmittance efficiency and close to 0-2π phase coverage are enabled by utilizing the localized electric and magnetic Mie-type resonances of low-loss silicon nanoparticles tailored to behave as electromagnetically dual-symmetric scatterers. We apply this concept to realize a metadevice that converts a Gaussian beam into a vortex beam. The required spatial distribution of transmittance phases is achieved by a variation of the lattice spacing as a single geometric control parameter.

Observation of Fano resonances in all-dielectric nanoparticle oligomers.

It is well-known that oligomers made of metallic nanoparticles are able to support sharp Fano resonances originating from the interference of two plasmonic resonant modes with different spectral width. While such plasmonic oligomers suffer from high dissipative losses, a new route for achieving Fano resonances in nanoparticle oligomers has opened up after the recent experimental observations of electric and magnetic resonances in low-loss dielectric nanoparticles. Here, light scattering by all-dielectric oligomers composed of silicon nanoparticles is studied experimentally for the first time. Pronounced Fano resonances are observed for a variety of lithographically-fabricated heptamer nanostructures consisting of a central particle of varying size, encircled by six nanoparticles of constant size. Based on a full collective mode analysis, the origin of the observed Fano resonances is revealed as a result of interference of the optically-induced magnetic dipole mode of the central particle with the collective mode of the nanoparticle structure. This allows for effective tuning of the Fano resonance to a desired spectral position by a controlled size variation of the central particle. Such optically-induced magnetic Fano resonances in all-dielectric oligomers offer new opportunities for sensing and nonlinear applications.

Improving the analysis of phase-separated bio-fuel samples with slice-selective total correlation NMR spectroscopy.

Separated samples are a particular challenge for NMR experiments. The boundary is severely detrimental to high-resolution spectra and normal NMR experiments simply add the two spectra of the two layers together. Pyrolysis bio-oils represent an increasingly important alternative fuel resource yet readily separate, whether due to naturally high water content or due to blending, a common practice for producing a more viable fuel. Slice-selective NMR, where the NMR spectrum of only a thin slice of the total sample is acquired, is extended here and improved, with slice-selective two-dimensional correlation experiments used to resolve the distinct chemical spectra of the various components of the phase-separated blended fuel mixtures. Analysis of how the components of any blended biofuel samples partition between the two layers is an important step towards understanding the separation process and may provide insight into mitigating the problem.

Quantitative Low-Field 19 F Nuclear Magnetic Resonance Analysis of Carbonyl Groups in Pyrolysis Oils.

Invited for this month's cover is the collaboration between Dr Rob Evans at Aston University, Birmingham, UK and Prof. Art Ragauskas at University of Tennessee, Knoxville and Oak Ridge National Laboratory, Oak Ridge, USA. The image illustrates that low-field, or benchtop, NMR spectrometers can be as effective as their higher-field counterparts in the accurate, quantitative analysis of bio-oils. The Research Article itself is available at 10.1002/cssc.202300625.

Quantitative Low-Field 19 F Nuclear Magnetic Resonance Analysis of Carbonyl Groups in Pyrolysis Oils.

Pyrolysis bio-oils, one of the products of lignocellulosic biomass pyrolysis, have the potential to be widely used as fuels. The chemical composition of bio-oils is very complicated as they contain hundreds, if not thousands, of different, mostly oxygen-containing, compounds with a wide distribution of physical properties, chemical structures, and concentrations. Detailed knowledge of bio-oil composition is crucial for optimizing both the pyrolysis processes and for any subsequent upgrading into a more viable fuel resource. Here we report the successful use of low-field, or benchtop, nuclear magnetic resonance (NMR) spectrometers in the analysis of pyrolysis oils. Pyrolysis oils from four different feedstocks were derivatized and analyzed using 19 F NMR techniques. The NMR results compare favorably with titrations for total carbonyl content. In addition, the benchtop NMR spectrometer proves able to reveal key spectral features, thus allowing the quantification of different carbonyl groups, such as aldehydes, ketones and quinones. Benchtop NMR spectrometers are typically compact, cheaper than their superconducting counterparts and do not require cryogens. Their use will make NMR analysis of pyrolysis oils easier and more accessible to a wide range of different potential users.

Quantitative Interpretation of Protein Diffusion Coefficients in Mixed Protiated-Deuteriated Aqueous Solvents.

Diffusion-ordered nuclear magnetic resonance (NMR) spectroscopy is widely used for the analysis of mixtures, dispersing the signals of different species in a two-dimensional spectrum according to their diffusion coefficients. However, interpretation of these diffusion coefficients is typically purely qualitative, for example, to deduce which species are bigger or smaller. In studies of proteins in solution, important questions concern the molecular weight of the proteins, the presence or absence of aggregation, and the degree of folding. The Stokes-Einstein Gierer-Wirtz estimation (SEGWE) method has been previously developed to simplify the complex relationship between diffusion coefficient and molecular mass, allowing the prediction of a species' diffusion coefficient in a pure solvent based on its molecular weight. Here, we show that SEGWE can be extended to successfully predict both peptide and protein diffusion coefficients in mixed protiated-deuteriated water samples and, hence, distinguish effectively between globular and disordered proteins.

Purification and immobilization of engineered glucose dehydrogenase: a new approach to producing gluconic acid from breadwaste.

BACKGROUND: Platform chemicals are essential to industrial processes. Used as starting materials for the manufacture of diverse products, their cheap availability and efficient sourcing are an industrial requirement. Increasing concerns about the depletion of natural resources and growing environmental consciousness have led to a focus on the economics and ecological viability of bio-based platform chemical production. Contemporary approaches include the use of immobilized enzymes that can be harnessed to produce high-value chemicals from waste. RESULTS: In this study, an engineered glucose dehydrogenase (GDH) was optimized for gluconic acid (GA) production. Sulfolobus solfataricus GDH was expressed in Escherichia coli. The K m and V max values for recombinant GDH were calculated as 0.87 mM and 5.91 U/mg, respectively. Recombinant GDH was immobilized on a hierarchically porous silica support (MM-SBA-15) and its activity was compared with GDH immobilized on three commercially available supports. MM-SBA-15 showed significantly higher immobilization efficiency (> 98%) than the commercial supports. After 5 cycles, GDH activity was at least 14% greater than the remaining activity on commercial supports. Glucose in bread waste hydrolysate was converted to GA by free-state and immobilized GDH. After the 10th reuse cycle on MM-SBA-15, a 22% conversion yield was observed, generating 25 gGA/gGDH. The highest GA production efficiency was 47 gGA/gGDH using free-state GDH. CONCLUSIONS: This study demonstrates the feasibility of enzymatically converting BWH to GA: immobilizing GDH on MM-SBA-15 renders the enzyme more stable and permits its multiple reuse.

Unusual presentation of haemoptysis following accidental inhalation of the 'superwarfarin' rodenticide brodifacoum.

Haemoptysis is a worrying symptom for patients and can represent a diagnostic challenge for clinicians. We present the case of a 56-year-old woman who presented to the emergency department with acute haemoptysis and associated sudden-onset dyspnoea. The patient remained haemodynamically stable and there was no demonstrable drop in haemoglobin concentration. Following rigorous investigations, on further questioning, the patient recalled inadvertent inhalation of the rodenticide brodifacoum. This exposure was deemed to represent the cause of their acute haemoptysis, which subsequently fully resolved without intervention.

Highly sensitive biosensors based on all-dielectric nanoresonators.

Biosensing based on nanophotonic structures has shown a great potential for cost-efficient, high-speed and compact personal medical diagnostics. While plasmonic nanosensors offer high sensitivity, their intrinsically restricted resonance quality factors and strong heating due to metal absorption impose severe limitations on real life applications. Here, we demonstrate an all-dielectric sensing platform based on silicon nanodisks with strong optically-induced magnetic resonances, which are able to detect a concentration of streptavidin of as low as 10-10 M (mol L-1) or 5 ng mL-1, thus pushing the current detection limit by at least two orders of magnitudes. Our study suggests a new direction in biosensing based on bio-compatible, non-toxic, robust and low-loss dielectric nanoresonators with potential applications in medicine, including disease diagnosis and drug detection.

Refractive index sensing with Fano resonances in silicon oligomers.

We demonstrate experimentally refractive index sensing with localized Fano resonances in silicon oligomers, consisting of six disks surrounding a central one of slightly different diameter. Owing to the low absorption and narrow Fano-resonant spectral features appearing as a result of the interference of the modes of the outer and the central disks, we demonstrate refractive index sensitivity of more than 150 nm RIU-1 with a figure of merit of 3.8.This article is part of the themed issue 'New horizons for nanophotonics'.

Spontaneous haemopneumothorax.

An 18-year-old man presented with a 2 day history of breathlessness and left-sided chest pain, with no preceding trauma. He had no medical history of note, and had never smoked. He was in hypovolaemic shock, with Hb of 8.1 g/dl, and received fluid resuscitation. Chest x-ray (CXR) revealed left-sided hydropneumothorax, with the effusion of blood-consistency on CT thorax. Tube thoracostomy drained 1.7 litres of blood immediately. He remained haemodynamically stable after 4 units of blood transfusion on the first day with post-transfusion Hb 11 g/dl. Following cardiothoracic surgeon advice, tube was removed on day 5 draining total of 3.5 litres, with good response clinically and radiologically. Patient was well when followed up at 1 week after hospital discharge, with no recurrence and complete re-expansion of left lung on CXR.