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The majority of photovoltaic (PV) systems in the Netherlands are small scale, installed on rooftops, where the lack of onsite global tilted irradiance (GTI) measurements and the frequent presence of shadow due to objects in the close vicinity oppose challenge in their monitoring process. In this study, a new algorithmic tool is introduced that creates a reference data-set through the combination of data-sets of the unshaded PV systems in the surrounding area. It subsequently compares the created reference data-set with the one of the PV system of interest, detects any energy loss and clusters the distinctive loss due to shadow, created by the surrounding objects. The new algorithm is applied successfully to a number of different cases of shaded PV systems. Finally, suggestions on the unsupervised use of the algorithm by any monitoring platform are discussed, along with its limitations algorithm and suggestions for further research.

Dilute Pd-in-Au alloys are valuable materials for selectively hydrogenating alkynes and isomerizing alkenes. By diluting Pd in a Au host, the selectivity toward semihydrogenated alkene isomers can be significantly enhanced and the unfavorable overhydrogenation to alkanes is suppressed. However, a detailed mechanistic study on the origin of the enhanced alkene selectivity over dilute alloy catalysts is still missing. Here, we combine experiment and theory to unravel the reaction mechanism, identifying rate-limiting and selectivity-controlling steps in 1-hexene hydrogenation over dilute Pd-in-Au catalysts. Using isotope-exchange hydrogenation experiments, we show that 1-hexene and hydrogen over a bimetallic Pd4Au96 in silica catalyst preferentially form 1-hexene isomers, (trans and cis) 2- and 3-hexene and only a small amounts of hexane. The reaction is consistent with a Horiuti-Polanyi mechanism, similar to a monometallic Pd nanoparticle catalyst. Computation of the free-energy profiles for 1-hexene hydrogenation and isomerization over a single Pd atom in a Au surface using first principles calculations indicated that the isomerization of 1-hexene to 2-hexene is energetically favorable due to the relatively large barrier for H2 dissociation preventing hydrogenation to n-hexane. Microkinetic modeling established that H2 dissociation on the single-atom Pd sites and H spillover from these sites onto the Au host are rate-limiting and key in steering the selectivity of dilute Pd-in-Au alloys toward the hexene isomers. The mechanistic insights from this study contribute to the rational design of optimized dilute alloy catalysts for selective alkene isomerization.

Three quantum dot luminescent solar concentrators (QDLSCs) are constructed to assess their performance in an outdoor environment over an entire year. The QDLSCs have a (Formula presented.) PMMA-Kraton-PMMA sandwich structure with either InP/ZnSe/ZnS, (Formula presented.), or CdSe/CdS/ZnS core/shell quantum dots incorporated in the Kraton interlayer. Furthermore, two reference LSCs are included: one using Lumogen F Red 305 as the luminophore and one without a luminophore in the Kraton layer. The power conversion efficiency is assessed for a cloudy and a sunny day, showing the influence of diffuse and direct irradiance. Moreover, the influence of mounting orientation and direct irradiance is analyzed for individual solar strips attached to the sides. Long-term results show an efficiency increase of (Formula presented.) and InP/ZnSe/ZnS QDLSC while the CdSe/CdS/ZnS QDLSCs and the Lumogen LSC show a pronounced drop in efficiency in the first 3 months. Photodegradation studies under continuous white light exposure for 420 h are performed on smaller pieces cut from the QDLSCs before their assembly outdoors and show similar trends to those observed in the 1 year outdoor study. Future research will focus on the postmortem analysis of the QDLSCs and increasing the efficiencies.

Designing compatible electrode–electrolyte interfaces is critical to achieve high and consistent performance and life span in next-generation rechargeable lithium batteries. In the study of nanoscopic interfaces, ab initio molecular dynamics (AIMD) simulations allow for a highly accurate description of interface dynamics and reactions. However, due to the high computational cost, simulations are limited in the size and time domains and therefore merit the need for a new interpretational approach that can deduce the long-term reactivity from such short yet highly accurate simulations. In this study, this is established by means of bond length distribution analysis through which the reactivity of key solid polymer electrolyte (SPE) polymer functional groups in contact with key electrode materials (graphite, silicon, lithium) and the influence of the electric field and temperature was successfully determined. Bond length distributions were found to respond to environmental changes and relate to the long-term reactivity in which the strength of electrode surface interactions and the accessibility of functional groups were found to be critical factors. Furthermore, the balancing of the SPE polymer mobility and functional group–electrode surface attraction, respectively, kinetic and thermodynamic properties, further suggests a selective spatial orientation of functional groups when exposed to an electric field, which could have great implications for low-temperature and high-current-density environments. The obtained knowledge on how reactive key SPE polymer functional groups are and also how their reactivity changes in terms of the electric field orientation effect could provide new insights for designing new stable SPE polymers.

Materials with temperature-dependent luminescence can be used as local thermometers when incorporated in, for example, a biological environment or chemical reactor. Researchers have continuously developed new materials aiming for the highest sensitivity of luminescence to temperature. Although the comparison of luminescent materials based on their temperature sensitivity is convenient, this parameter gives an incomplete description of the potential performance of the materials in applications. Here, we demonstrate how the precision of a temperature measurement with luminescent nanocrystals depends not only on the temperature sensitivity of the nanocrystals but also on their luminescence strength compared to measurement noise and background signal. After first determining the noise characteristics of our instrumentation, we show how the uncertainty of a temperature measurement can be predicted quantitatively. Our predictions match the temperature uncertainties that we extract from repeated measurements, over a wide temperature range (303-473 K), for different CCD readout settings, and for different background levels. The work presented here is the first study that incorporates all of these practical issues to accurately calculate the uncertainty of luminescent nanothermometers. This method will be important for the optimization and development of luminescent nanothermometers.

Hypothesis Imbibition of a fluid into a porous material involves the invasion of a wetting fluid in the pore space through piston-like displacement, film and corner flow, snap-off and pore bypassing. These processes have been studied extensively in two-dimensional (2D) porous systems; however, their relevance to three-dimensional (3D) natural porous media is poorly understood. Here, we investigate these pore-scale processes in a natural rock sample using time-resolved 3D (i.e., four-dimensional or 4D) X-ray imaging. Experiments We performed a capillary-controlled drainage-imbibition experiment on an initially brine-saturated carbonate rock sample. The sample was imaged continuously during imbibition using 4D X-ray imaging to visualize and analyze fluid displacement and snap-off processes at the pore-scale. Findings We discover a new type of snap-off that occurs in pores, resulting in the entrapment of a small portion of the non-wetting phase in pore corners. This contrasts with previously-observed snap-off in throats which traps the non-wetting phase in pore centers. We relate the new type of pore-snap-off to the pinning of fluid-fluid interfaces at rough surfaces, creating contact angles close to 90°. Subsequently, we provide correlations for displacement events as a function of pore-throat geometry. Our findings indicate that having a small throat does not necessarily favor snap-off: the key criterion is the throat radius in relation to the pore radius involved in a displacement event, captured by the aspect ratio.

The interaction of water with oriented NiO films is studied by using a combination of photoelectron spectroscopy with in situ sample preparation and electrochemical measurements in the stability window of water. In contrast to NiO(100), room temperature water exposure induces a downward band bending on the (110)- and (111)-oriented films, indicating a more positive surface charge. The surface charge is assigned to a dissociative adsorption of water accompanied by a removal of oxygen, which corresponds to a preferential adsorption of protons. Photoelectron spectroscopy suggests that the nonstoichiometric adsorption is related to the presence of adsorbed oxygen species prior to water exposure. For the NiO(110) surface, the stability of adsorbed bridging oxygen dimers is confirmed by density functional theory calculations. The preferential adsorption of protons, which requires interaction of two water molecules with the oxygen dimers, explains that water acts as an electron donor on many oxide surfaces. The different adsorption behavior is consistent with a lower electrochemical activity of the (110)- and (111)-oriented surfaces toward hydrogen adsorption due to an effective reduction of Lewis base sites.

Bimetallic nanoparticles (BMNPs) are frontrunners in various fields including heterogeneous catalysis, medicinal applications, and medical imaging. Tailoring their properties requires adequate control over their structure and composition, which still presents a non-trivial endeavor. We present a flexible strategy to deposit phase-controlled BMNPs by vapor-phase “titration” of a secondary metal to a pre-deposited monometallic nanoparticle (NP) host. The strategy is exemplified for archetypal Pt–Sn BMNPs but transferrable to other BMNPs which alloy noble and non-noble metals. When exposing Pt NPs on a SiO2 support to discrete TDMASn (tetrakis(dimethylamino)tin) vapor pulses from 150 to 300 °C, TDMASn selectively decomposes on Pt NPs. This leads to saturated infiltration of Sn into Pt NPs through reactive solid-state diffusion, resulting in the formation of Pt–Sn BMNPs with phase/composition control via the substrate temperature. An additional H2 pulse after each TDMASn pulse removes the surface ligands and excess Sn on the surface as SnH4, preserving the small sizes of the pre-deposited Pt NPs. This approach provides a single-step, selective “vapor-phase conversion” of Pt NPs into PtxSny BMNPs with great potential for catalysis. Hereto, a proof of concept is provided by converting wet impregnated Pt NPs into Pt–Sn BMNPs on high surface area supports.

Semiconductor superstructures made from assembled and epitaxially connected colloidal nanocrystals (NCs) hold promise for crystalline solids with atomic and nanoscale periodicity, whereby the band structure can be tuned by the geometry. The formation of especially the honeycomb superstructure on a liquid substrate is far from understood and suffers from weak replicability. Here, we introduce 1,4-butanediol as an unreactive substrate component, which is mixed with reactive ethylene glycol to tune for optimal reactivity. It shows us that the honeycomb superlattice has a NC precursor state before oriented attachment occurs, in the form of a self-assembled hexagonal bilayer. We propose that the difference between the formation of the square or honeycomb superstructure occurs during the self-assembly phase. To form a honeycomb superstructure, it is crucial to stabilize the hexagonal bilayer in the presence of solvent-mediated repulsion. In contrast, a square superstructure benefits from the contraction of a hexagonal monolayer due to the absence of a solvent. A second experiment shows the very last stage of the process, where the increasing alignment of NCs is quantified using selected-area electron diffraction (SAED). The combination of transmission electron microscopy (TEM), SAED, and tomography used in these experiments shows that the (100)/(100) facet-to-facet attraction is the main driving force for NC alignment and attachment. These findings are validated by coarse-grained molecular dynamic simulations, where we show that an optimal NC repulsion is crucial to create the honeycomb superstructure.

In high-temperature cuprate superconductors, stripe order refers broadly to a coupled spin and charge modulation with a commensuration of eight and four lattice units, respectively. How this stripe order evolves across optimal doping remains a controversial question. Here we present a systematic resonant inelastic x-ray scattering study of weak charge correlations in La2−xSrxCuO4 and La1.8−xEu0.2SrxCuO4. Ultra high energy resolution experiments demonstrate the importance of the separation of inelastic and elastic scattering processes. Long-range temperature-dependent stripe order is only found below optimal doping. At higher doping, short-range temperature-independent correlations are present up to the highest doping measured. This transformation is distinct from and preempts the pseudogap critical doping. We argue that the doping and temperature-independent short-range correlations originate from unresolved electron–phonon coupling that broadly peaks at the stripe ordering vector. In La2−xSrxCuO4, long-range static stripe order vanishes around optimal doping and we discuss both quantum critical and crossover scenarios.

The crystalline texture of arrays of low diameter Co nanowires (NWs) synthesized by electrodeposition using electrolytes with different acidities (pH in the range 2.0–6.6) was studied by the switching field distribution (SFD) and first order reversal curve (FORC) diagrams. Particularly, the SFD determined as the derivative d M / d H of the descending part of the major hysteresis loop has proven to be a reliable and powerful method for the identification of different crystalline textures in the NWs and the quantification of their corresponding texture percentages. The presence of the face centered cubic-like texture at low pH values and hexagonal close packed textures with the c-axis perpendicular and parallel to the NWs axis at higher pH values have been identified by performing multiple Gaussian fits to the SFD by virtue of their different magnetic behavior observed during reversal of the magnetization. The field position and size of each curve in the multiple Gaussian fit provide information about the corresponding magnetic contribution and volumetric texture percentage of each crystalline texture in the NWs, respectively. The analysis of the SFD has been complemented and validated with FORC diagram measurements, showing that the width of the coercive field distribution is in good agreement with the width of the SFD. Also, it has been found that the different branches observed in the FORC diagrams along the interaction axis provide further insight on the interaction between magnetocrystalline fields. This work provides a novel methodology for the use of magnetometry as a reliable technique for the study of the interplay between the microstructure and magnetic behavior of arrays of NWs.

Lanthanide-doped (nano)crystals are an important class of materials in luminescence thermometry. The working mechanism of these thermometers is diverse but most often relies on variation of the ratio of emission intensities from two thermally coupled excited states with temperature. At low temperatures, nonradiative coupling between the states can be slow compared to radiative decay, but, at higher temperatures, the two states reach thermal equilibrium due to faster nonradiative coupling. In thermal equilibrium, the intensity ratio follows Boltzmann statistics, which gives a convenient model to calibrate the thermometer. Here, we investigate multiple strategies to shift the onset of thermal equilibrium to lower temperatures, which enables Boltzmann thermometry in a wider dynamic range. We use Eu3+-doped microcrystals as a model system and find that the nonradiative coupling rates increase for host lattices with higher vibrational energies and shorter lanthanide–ligand distances, which reduces the onset temperature of thermal equilibrium by more than 400 K. We additionally reveal that thermometers with excited states coupled by electric-dipole transitions have lower onset temperatures than those with magnetic-dipole-coupled states due to selection rules. These insights provide essential guidelines for the optimization of Boltzmann thermometers to operate in an extended temperature range.

The unique properties of yolk-shell or rattle-type particles make them promising candidates for applications ranging from switchable photonic crystals, to catalysts, to sensors. To realize many of these applications it is important to gain control over the dynamics of the core particle independently of the shell. Hypothesis: The core particle may be manipulated by an AC electric field with rich frequency-dependent behavior. Experiments: Here, we explore the frequency-dependent dynamic electrophoretic mobility of a charged core particle within a charged, porous shell in AC electric fields both experimentally using liquid-phase electron microscopy and numerically via the finite-element method. These calculations solve the Poisson-Nernst-Planck-Stokes equations, where the core particle moves according to the hydrodynamic and electric forces acting on it. Findings: In experiments the core exhibited three frequency-dependent regimes of field-driven motion: (i) parallel to the field, (ii) diffusive in a plane orthogonal to the field, and (iii) unbiased random motion. The transitions between the three observed regimes can be explained by the level of matching between the time required to establish ionic gradients in the shell and the period of the AC field. We further investigated the effect of shell porosity, ionic strength, and inner-shell radius. The former strongly impacted the core's behavior by attenuating the field inside the shell. Our results provide physical understanding on how the behavior of yolk-shell particles may be tuned, thereby enhancing their potential for use as building blocks for switchable photonic crystals.

first_pagesettingsOrder Article Reprints Open AccessArticle The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 by Rafaela T. Marques 1,Frederico F. Martins 2,†ORCID,Deniz F. Bekiş 2,‡ORCID,Ana I. Vicente 1,Liliana P. Ferreira 2,3,Clara S. B. Gomes 4,5,6ORCID,Sónia Barroso 5,6,§ORCID,Varun Kumar 7,Yann Garcia 7ORCID,Nuno A. G. Bandeira 2ORCID,Maria José Calhorda 2 andPaulo N. Martinho 1,*ORCID 1 Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal 2 BioISI—Biosystems & Integrative Sciences Institute, Departamento de Química e Bioquímia, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal 3 Department of Physics, University of Coimbra, 3004-516 Coimbra, Portugal 4 LAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal 5 UCIBIO, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal 6 i4HB, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal 7 Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN/MOST), Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium * Author to whom correspondence should be addressed. † Current address: IQCC & Department Química, Universitat de Girona, Campus Montilivi (Ciències), 17003 Girona, Spain. ‡ Current address: Anorganische Chemie, Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032 Marburg, Germany. § Current address: MARE—Marine and Environmental Sciences Centre/ARNET—Aquatic Research Network, Polytechnic of Leiria, Cetemares, 2520-620 Peniche, Portugal. Magnetochemistry 2022, 8(12), 162; https://doi.org/10.3390/magnetochemistry8120162 Received: 31 October 2022 / Revised: 15 November 2022 / Accepted: 16 November 2022 / Published: 22 November 2022 (This article belongs to the Special Issue Molecular Spin Crossover Materials: Recent Trends, Emerging Properties and Applications) Download Browse Figures Review Reports Versions Notes Abstract Complexes [Fe(X-salEen)2]BPh4·DMF, with X = Br (1), Cl (2), and F (3), were crystallised from N,N′-dimethylformamide with the aim of understanding the role of a high boiling point N,N′-dimethylformamide solvate in the spin crossover phenomenon. The counter ion was chosen for only being able to participate in weak intermolecular interactions. The compounds were structurally characterised by single crystal X-ray diffraction. Complex 1 crystallised in the orthorhombic space group P212121, and complexes 2 and 3 in the monoclinic space group P21/n. Even at room temperature, low spin was the predominant form, although complex 2 exhibited the largest proportion of the high-spin species according to both the magnetisation measurements and the Mössbauer spectra. Density Functional Theory calculations were performed both on the periodic solids and on molecular models for complexes 1–3 and the iodide analogue 4. While all approaches reproduced the experimental structures very well, the energy balance between the high-spin and low-spin forms was harder to reproduce, though some calculations pointed to the easier spin crossover of complex 2, as observed. Periodic calculations with the functional PBE led to very similar ΔEHS-LS values for all complexes but showed a preference for the low-spin form. However, the single-point calculations with B3LYP* showed, for the model without solvate, that the Cl complex should undergo spin crossover more easily. The molecular calculations also reflected this fact, which was more clearly defined when the cation–anion–solvate model was used. In the other models there was not much difference between the Cl, Br, and I complexes.

Altres ajuts: J.Y., P.K., M.G.M., and Z.Z. acknowledge the computer resources at MareNostrum and the technical support provided by the Barcelona Supercomputing Center through Red Española de Supercomputación (Grants No. RES-FI-2020-1-0018, No. RES-FI-2020-1-0014, and No. RES-FI-2020-2-0039). ICN2 is funded by the Generalitat de Catalunya (CERCA Programme). We acknowledge a PRACE award granting access to MareNostrum4 at Barcelona Supercomputing Center (BSC), Spain (OptoSpin project id. 2020225411). We evidence the possibility for coherent electrical manipulation of the spin orientation of topologically protected edge states in a low-symmetry quantum spin Hall insulator. By using a combination of ab initio simulations, symmetry-based modeling, and large-scale calculations of the spin Hall conductivity, it is shown that small electric fields can efficiently vary the spin textures of edge currents in monolayer 1T'-WTe2 by up to a 90-degree spin rotation, without jeopardizing their topological character. These findings suggest a new kind of gate-controllable spin-based device, topologically protected against disorder and of relevance for the development of topological spintronics.

Fetal therapies regularly result in iatrogenic preterm premature rupture of the fetal membranes (iPPROM), which is associated with preterm birth. Biomaterials that promote the healing of traumatized fetal membranes (FMs) may prevent iPPROM-associated preterm births, addressing this unmet clinical need. Here, a fully defined synthetic poly(ethylene glycol) (PEG) hydrogel is developed to study the healing functions of human amnion-derived mesenchymal stromal cells (hAMCs) in 3D cultures. A pipeline to analyze extracellular matrix (ECM) proteins deposited by hAMCs in PEG hydrogels is established involving label-free quantification of mass-spectrometry data. Owing to the contaminant-free PEG hydrogels and a short fetal bovine serum (FBS)-free culture period, 128 ECM proteins, of which 97 are present in the native amnion, are identified. Upon stimulation with platelet-derived growth factor BB (PDGF-BB), a cell proliferation and migration inducing factor, hAMCs remodel their surroundings and deposit ECM proteins pericellularly. Among the most abundantly deposited amnion proteins, transforming growth factor beta-induced protein ig-h3 (TGF beta i), a very distinctive amnion protein that is involved in the wound healing cascade, is identified. These data support the potential of PDGF-BB to promote the repair of traumatized FMs and encourage its use for the engineering of biomaterials for FM healing, to ultimately prevent iPPROM., Advanced Functional Materials, 32 (40), ISSN:1616-3028, ISSN:1616-301X

The last decade has seen the development of a wide set of tools, such as wavefront shaping, computational or fundamental methods, that allow to understand and control light propagation in a complex medium, such as biological tissues or multimode fibers. A vibrant and diverse community is now working on this field, that has revolutionized the prospect of diffraction-limited imaging at depth in tissues. This roadmap highlights several key aspects of this fast developing field, and some of the challenges and opportunities ahead., submitted to J.Phys Photonics (IOP), 116 pages, 23 sections

Supported nanoparticulate Au/Ti-SiO2 catalysts are a promising candidate for selective epoxidation of propene with H2/O2 mixtures. Here, we demonstrate that by altering the acidity of the surface titanol groups in Au/Ti-SiO2, the selectivity of these catalysts in propene oxidation can be controlled. That is, Au/Ti-SiO2 prepared using an alkali base during gold deposition shows basic properties due to the formation of Ti-ONa groups. The catalysts that contained Na+ and neutralized acid sites demonstrate high selectivity toward propene oxide. On the contrary, when the acidity of the Ti-OH groups is preserved by using NH4OH as a base during gold deposition, the catalyst is highly selective toward propanal at a similar propene conversion. This difference in selectivity is explained by the isomerization of initially formed propene oxide into propanal over acidic Ti-OH groups as we demonstrated using stacked bed experiments, where the Ti-support was exposed to propene oxide. When Na+ was present, no isomerization was observed, while without Na+ present, propene oxide was isomerized to propanal. In short, we demonstrate the crucial role of Na+ and acidic Ti-sites in steering the selectivity in gold-catalyzed propene epoxidation.

International audience; Metal additive manufacturing processes, such as laser beam melting (LBM), can play a key role in developing antenna-feed chains because monolithic and multifunctional parts can be manufactured with high geometric freedom in the design phase. Using LBM technology, lighter and more compact antennas can be produced and manufac-turing costs can be reduced. However, the surface roughness of internal surfaces in waveguides produced by LBM is much higher (about 10 μm Ra) than that produced by conventional manufacturing tech-nologies. Consequently, such high surface roughness of the internal surface can affect electrical current propagation through the waveguide and corresponding transmitted power. In this paper, abrasive flow machining (AFM) was used to reduce the surface roughness of the internal surfaces of four different waveguides used at both K and Q bands. A significant reduction in the transmission loss at both K and Q bands was observed as their internal surface rough-ness decreased from about 10 μmto1μm Ra. This was assumed to be due to an increase of the internal surface electrical conductivity with the decrease of roughness in waveguides channels.

Colloidal quantum dots (QDs) are excellent optical gain materials that combine high material gain, a strong absorption of pump light, stability under strong light exposure and a suitability for solution-based processing. The integration of QDs in laser cavities that fully exploit the potential of these emerging optical materials remains, however, a challenge. In this work, we report on a vertical cavity surface emitting laser, which consists of a thin film of QDs embedded between two layers of polymerized chiral liquid crystal. Forward directed, circularly polarized defect mode lasing under nanosecond-pulsed excitation is demonstrated within the photonic band gap of the chiral liquid crystal. Stable and long-term narrow-linewidth lasing of an exfoliated free-standing, flexible film under water is obtained at room temperature. Moreover, we show that the lasing wavelength of this flexible cavity shifts under influence of pressure, strain or temperature. As such, the combination of solution processable and stable inorganic QDs with high chiral liquid crystal reflectivity and effective polymer encapsulation leads to a flexible device with long operational lifetime, that can be immersed in different protic solvents to act as a sensor.

For a wide range of nonclassical magnonic states that have been proposed and demonstrated recently, a new time scale besides the magnon lifetime - the magnon dephasing time - becomes important, but this time scale is rarely studied. Considering exchange interaction and spin-phonon coupling, we evaluate the pure magnon dephasing time and find it to be smaller than the magnon lifetime at temperatures of a few Kelvins. By examining a magnonic cat state as an example, we show how pure dephasing of magnons destroys and limits the survival of quantum superpositions. Thus it will be critical to perform quantum operations within the pure dephasing time. We further derive the master equation for the density matrix describing such magnonic quantum states taking into account the role of pure dephasing, whose methodology can be generalized to include additional dephasing channels that experiments are likely to encounter in the future. Our findings enable one to design and manipulate robust quantum states of magnons for information processing., Comment: 6 pages, 3 figures

Several rare-earth transition-metal ferrimagnetic systems exhibit all-optical magnetization switching upon excitation with a femtosecond laser pulse. Although this phenomenon is very promising for future opto-magnetic data storage applications, the role of non-local spin transport in these systems is scarcely understood. Using Co/Gd and Co/Tb bilayers we isolate the contribution of the rare-earth materials to the generated spin currents by using the precessional dynamics they excite in an adjacent ferromagnetic layer as a probe. By measuring THz standing spin-waves as well as GHz homogeneous precessional modes, we probe both the high- and low-frequency components of these spin currents. The low-frequency homogeneous mode indicates a significant contribution of Gd to the spin current, but not from Tb, consistent with the difficulty in achieving all-optical switching in Tb-containing systems. Measurements on the THz frequency spin waves reveal the inability of the rare-earth generated spin currents to excite dynamics at the sub-ps timescale. We present modelling efforts using the $s$-$d$ model, which effectively reproduce our results and allow us to explain the behavior in terms of the temporal profile of the spin current., Supplementary information appended

We present a refinement of the widely accepted spin-wave spectrum that Kalinikos and Slavin (Kalinikos, 1981; Kalinikos and Slavin, 1986) computed for magnetic films with an in-plane magnetization. The spin wave spectrum that follows from the diagonal approximation in this theory becomes inaccurate for relatively thick films, as has already been noted by Kreisel et al. (2009). Rather than solving an integrodifferential equation which follows from the magnetostatic Green's function, as done by Kalinikos and Slavin (Kalinikos, 1981; Kalinikos and Slavin, 1986), we impose the exchange and magnetostatic boundary conditions on bulk spin-wave solutions. This boundary problem has an accurate analytical solution which is quantitatively different from the commonly used diagonal theory (Kalinikos, 1981; Kalinikos and Slavin, 1986) for magnetic films.

Here we report on carbon monoxide-photoreleasable compounds (photoCORMs) that combine heptamethine cyanine and flavonol chromophores and are activated upon irradiation with near-infrared light. Excellent CO-release yields and uncaging cross sections in aqueous solutions, enhanced water solubilities thanks to polar substituents or a host-guest approach using cucurbit[7]uril are demonstrated. The hybrids display outstanding biocompatibility and diverse, structure-dependent cell penetrability and internalization.

Hypothesis: Colloidal molecules with anisotropic shapes and interactions are powerful model systems for deciphering the behavior of real molecules and building units for creating materials with designed properties. While many strategies for their assembly have been developed, they typically yield a broad distribution or are limited to a specific type. We hypothesize that the shape and relative sizes of colloidal particles can be exploited to efficiently direct their assembly into colloidal molecules of desired valence. Experiments: We exploit electrostatic self-assembly of negatively charged spheres made from either polystyrene or silica onto positively charged hematite cubes. We thoroughly analyze the role of the shape and size ratio of particles on the cluster size and yield of colloidal molecules. Findings: Using a combination of experiments and simulations, we demonstrate that cubic particle shape is crucial to generate high yields of distinct colloidal molecules over a wide variety of size ratios. We find that electrostatic repulsion between the satellite spheres is important to leverage the templating effect of the cubes, leading the spheres to preferentially assemble on the facets rather than the edges and corners of the cube. The sixfold symmetry of cubes favors the assembly of molecules with six, four, and two satellite spheres at appropriate size ratios and interaction strength. Furthermore, we reveal that our protocol is not affected by the specific choice of the material of the colloidal particles. Finally, we show that the permanent magnetic dipole moment of the hematite cubes can be utilized to separate colloidal molecules from non-assembled satellite particles. Our simple and effective strategy might be extended to other templating particle shapes, thereby greatly expanding the library of colloidal molecules that can be achieved with high yield and purity.

Partial shading is widely considered to be a limiting factor in the performance of photovoltaic (PV) systems applied in urban environments. Modern system architectures combined with per module deployment of power electronics have been used to improve performance especially at heterogeneous irradiance conditions. In this work another approach is used to combine modern system architecture with alternate module designs. The granularity of cell groups in PV modules is investigated together with the so-called Tessera concept, in which single cells are cut in 16 parts. Typical meteorological year yield calculations show that these alternate module designs in combination with modern system architectures can retrieve up to half the shading losses compared to standard modules and string inverters under identical shading conditions.

Commercial lighting for ambient and display applications is mostly based on blue light-emitting diodes (LEDs) combined with phosphor materials that convert some of the blue light into green, yellow, orange, and red. Not many phosphor materials can offer stable output under high incident light intensities for thousands of operating hours. Even the most promising LED phosphors saturate in high-power applications, that is, they show decreased light output. The saturation behavior is often poorly understood. Here, we review three popular commercial LED phosphor materials, Y3Al5O12 doped with Ce3+, CaAlSiN3 doped with Eu2+, and K2SiF6 doped with Mn4+, and unravel their saturation mechanisms. Experiments with square-wave-modulated laser excitation reveal the dynamics of absorption and decay of the luminescent centers. By modeling these dynamics and linking them to the saturation of the phosphor output intensity, we distinguish saturation by ground-state depletion, thermal quenching, and ionization of the centers. We discuss the implications of each of these processes for LED applications. Understanding the saturation mechanisms of popular LED phosphors could lead to strategies to improve their performance and efficiency or guide the development of new materials.

This paper proposes an original approach to separately characterize self-heating and substrate effects in Fully-Depleted Silicon-on-Insulator (FD-SOI) devices. As both dynamic self-heating and drain to source coupling through the back-gate and substrate of an FD-SOI MOSFET induce a frequency transition in the Y-parameters in a common frequency range, it is crucial to properly separate them for further modeling. The proposed novel method is based on the extraction of the back-gate and substrate networks from the S-parameters measured at the zero-temperature coefficient bias. It enables the accurate and unambiguous extraction of thermal impedance for different biases, thus providing the extraction of the device thermal resistance and capacitance for different power levels from S-parameters measurements.

The enhancing effect of extraframework Al (EFAl) species on the acidity of bridging hydroxyl groups in a steam-calcined faujasite zeolite (ultrastabilized Y, USY) was investigated by in situ monitoring the H/D exchange reaction between benzene and deuterated zeolites by 1H MAS NMR spectroscopy. This exchange reaction involves Brønsted acid sites (BAS) located in sodalite cages and supercages. In a reference faujasite zeolite free from EFAl, both populations of BAS are equally and relatively slowly reactive toward C6H6. In USY, in stark contrast, the H/D exchange of sodalite hydroxyl groups is significantly faster than that of hydroxyl groups located in the faujasite supercages, even though benzene has only access to the supercages. This evidences selective enhancement of BAS near Lewis acidic EFAl species, which according to the NMR findings are located in the faujasite sodalite cages.

The United Nations’ Sustainable Development Goals have sparked growing interest in biosurfactants from many surfactant-loaded industries including those utilizing froth flotation for mineral separation. However, the interaction of biosurfactants with mineral surfaces is currently poorly understood. We bridge this gap by studying adsorption of a yeast-derived bola acidic sophorolipid (ASL) biosurfactant on djurleite (Cu1.94S). The methods used include Hallimond flotation, contact angle, adsorption isotherm, zeta potential, leaching measurements, and X-ray photoelectron spectroscopy (XPS). To facilitate the interpretation of the adsorption results, we characterize the activity of ASL at the air-water interface and measure its critical micelle concentration (CMC) at different pH using static surface tension. We find ASL to be a multifunctional surfactant with an unusual, pH-sensitive interfacial behavior. At the air-water interface, ASL is most active at pH 8, while its CMC goes through minimum as low as 40 μM at pH 7. The surfactant adsorption at the djurleite-water interface makes the sulfide surface hydrophilic at acidic pH and hydrophobic at neutral and basic pH. In addition, ASL has strong affinity to copper sulfide and demonstrates metal leaching properties. Finally, ASL demonstrates detergency properties. We offer a mechanistic interpretation of these findings. Our results provide a basis for the application of acidic glycolipids in froth flotation and have implications for their application in ion separation using hydrometallurgical routes, as well as for the chemical stability of metal sulfides in environmental systems. © 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

We report a method of glycosylated enzymes' surface immobilisation and stabilisation. The enzyme is immobilised at the surface of silica nanoparticles through the reversible covalent binding of vicinal diols of the enzyme glycans with a surface-attached boronate derivative. A soft organosilica layer of controlled thickness is grown at the silica surface, entrapping the enzyme and thus avoiding enzyme leaching. We demonstrate that this approach results not only in high and durable activity retention but also enzyme stabilisation.