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Plant productivity varies due to environmental heterogeneity, and theory suggests that plant diversity can reduce this variation. While there is strong evidence of diversity effects on temporal variability of productivity, whether this mechanism extends to variability across space remains elusive. Here we determine the relationship between plant diversity and spatial variability of productivity in 83 grasslands, and quantify the effect of experimentally increased spatial heterogeneity in environmental conditions on this relationship. We found that communities with higher plant species richness (alpha and gamma diversity) have lower spatial variability of productivity as reduced abundance of some species can be compensated for by increased abundance of other species. In contrast, high species dissimilarity among local communities (beta diversity) is positively associated with spatial variability of productivity, suggesting that changes in species composition can scale up to affect productivity. Experimentally increased spatial environmental heterogeneity weakens the effect of plant alpha and gamma diversity, and reveals that beta diversity can simultaneously decrease and increase spatial variability of productivity. Our findings unveil the generality of the diversity-stability theory across space, and suggest that reduced local diversity and biotic homogenization can affect the spatial reliability of key ecosystem functions.

Funding Information: This work was supported by the European Research Council (ERC-2017-AdG, 788143-RECGLYCANMR to J.J.-B; ERC-2018-StG 804236-NEXTGEN-IO to A.P.) and the Marie-Skłodowska-Curie actions (ITN Glytunes grant agreement No 956758 to K.S.; ITN BactiVax under grant agreement no. 860325 to U.A. and ITN DIRNANO grant agreement No 956544 to F.C.). X-ray diffraction experiments described in this paper were performed using beamlines XALOC synchrotron at ALBA (Spain) and PXIII in Swiss Light Source (Switzerland). F.M., C.S. and H.C. acknowledge Fundação para a Ciência e a Tecnologia (FCT-Portugal) for funding projects: PTDC/BIA-MIB/31028/2017 and UCIBIO project (UIDP/04378/2020 and UIDB/04378/2020) and Associate Laboratory Institute for Health and Bioeconomy—i4HB project (LA/P/0140/2020), to the CEEC contracts 2020.00233.CEECIND and 2020.03261.CEECIND for F.M. and H.C., respectively, and to PhD grant 2022.11723.BD of C.S. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 22161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). F.M. and J.J.-B. acknowledge to the European funding for the GLYCOTwinning project (No. 101079417) and -COST Action GLYCONANOPROBES. A.P.’s research is funded by “La Caixa” Foundation (HR21-00925), AECC (LABAE211744PALA), Fundación FERO, Ikerbasque, and BIOEF EITB MARATOIA BIO19/CP/002. We thank Agencia Estatal de Investigación of Spain for grants PID2019-107956RA-I00 (A.P.), PID2019-107770RA-I00 (J.E.-O.), RTI2018-099592-B-C21 (F.C.), ID2020-114178GB (R.B. and J.D.S.), RYC2018-024183-I (A.P.), and the Severo Ochoa Center of Excellence Accreditation CEX2021-001136-S, all funded by MCIN/AEI/10.13039/501100011033 and by El FSE invierte en tu futuro, as well as CIBERES, and initiative of Instituto de Salud Carlos III (ISCIII, Spain) A.A.-V. receives funding from “La Caixa” Foundation (ID 100010434, LCF/BQ/DR20/11790022). A. B. (AECC Bizkaia Scientific Foundation, PRDVZ19003BOSC). F.C. acknowledges the Mizutani Foundation for Glycoscience (Grant 220115). Funding Information: This work was supported by the European Research Council (ERC-2017-AdG, 788143-RECGLYCANMR to J.J.-B; ERC-2018-StG 804236-NEXTGEN-IO to A.P.) and the Marie-Skłodowska-Curie actions (ITN Glytunes grant agreement No 956758 to K.S.; ITN BactiVax under grant agreement no. 860325 to U.A. and ITN DIRNANO grant agreement No 956544 to F.C.). X-ray diffraction experiments described in this paper were performed using beamlines XALOC synchrotron at ALBA (Spain) and PXIII in Swiss Light Source (Switzerland). F.M., C.S. and H.C. acknowledge Fundação para a Ciência e a Tecnologia (FCT-Portugal) for funding projects: PTDC/BIA-MIB/31028/2017 and UCIBIO project (UIDP/04378/2020 and UIDB/04378/2020) and Associate Laboratory Institute for Health and Bioeconomy—i4HB project (LA/P/0140/2020), to the CEEC contracts 2020.00233.CEECIND and 2020.03261.CEECIND for F.M. and H.C., respectively, and to PhD grant 2022.11723.BD of C.S. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 22161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). F.M. and J.J.-B. acknowledge to the European funding for the GLYCOTwinning project (No. 101079417) and -COST Action GLYCONANOPROBES. A.P.’s research is funded by “La Caixa” Foundation (HR21-00925), AECC (LABAE211744PALA), Fundación FERO, Ikerbasque, and BIOEF EITB MARATOIA BIO19/CP/002. We thank Agencia Estatal de Investigación of Spain for grants PID2019-107956RA-I00 (A.P.), PID2019-107770RA-I00 (J.E.-O.), RTI2018-099592-B-C21 (F.C.), ID2020-114178GB (R.B. and J.D.S.), RYC2018-024183-I (A.P.), and the Severo Ochoa Center of Excellence Accreditation CEX2021-001136-S, all funded by MCIN/AEI/10.13039/501100011033 and by El FSE invierte en tu futuro, as well as CIBERES, and initiative of Instituto de Salud Carlos III (ISCIII, Spain) A.A.-V. receives funding from “La Caixa” Foundation (ID 100010434, LCF/BQ/DR20/11790022). A. B. (AECC Bizkaia Scientific Foundation, PRDVZ19003BOSC). F.C. acknowledges the Mizutani Foundation for Glycoscience (Grant 220115). Publisher Copyright: © 2023, The Author(s). Sialic acid-binding Ig-like lectin 15 (Siglec-15) is an immune modulator and emerging cancer immunotherapy target. However, limited understanding of its structure and mechanism of action restrains the development of drug candidates that unleash its full therapeutic potential. In this study, we elucidate the crystal structure of Siglec-15 and its binding epitope via co-crystallization with an anti-Siglec-15 blocking antibody. Using saturation transfer-difference nuclear magnetic resonance (STD-NMR) spectroscopy and molecular dynamics simulations, we reveal Siglec-15 binding mode to α(2,3)- and α(2,6)-linked sialic acids and the cancer-associated sialyl-Tn (STn) glycoform. We demonstrate that binding of Siglec-15 to T cells, which lack STn expression, depends on the presence of α(2,3)- and α(2,6)-linked sialoglycans. Furthermore, we identify the leukocyte integrin CD11b as a Siglec-15 binding partner on human T cells. Collectively, our findings provide an integrated understanding of the structural features of Siglec-15 and emphasize glycosylation as a crucial factor in controlling T cell responses. publishersversion published

Alpha-1-antitrypsin (A1AT or SERPINA1) has been proposed as a putative biomarker distinguishing healthy from diseased donors throughout several proteomics studies. However, the SERPINA1 gene displays high variability of frequent occurring genotypes among the general population. These different genotypes may affect A1AT expression and serum protein concentrations, and this is often not known, ignored, and/or not reported in serum proteomics studies. Here, we address allele-specific protein serum levels of A1AT in donors carrying the normal M variants of A1AT by measuring the proteoform profiles of purified A1AT from 81 serum samples, originating from 52 donors. When focusing on heterozygous donors, our data clearly reveal a statistically relevant difference in allele-specific protein serum levels of A1AT. In donors with genotype PI*M1VM1A, the experimentally observed ratio was approximately 1:1 (M1V/M1A, 1.00:0.96 ± 0.07, n = 17). For individuals with genotype PI*M1VM2, this ratio was 1:1.28 (M1V/M2, 1.00:1.31, ±0.19, n = 7). For genotypes PI*M1VM3 and PI*M1AM3, a significant higher amount of M3 was observed compared to the M1-subtypes (M1V/M3, 1.00:1.84 ± 0.35, n = 8; M1A/M3, 1.00:1.61 ± 0.33, n = 5). We argue that these observations are important and should be considered when analyzing serum A1AT levels before proposing A1AT as a putative serum biomarker.

Funding Information: The authors acknowledge the support of FCT-Fundação para a Ciência e a Tecnologia, I.P., in the scope of the projects LA/P/0037/2020, UIDP/50025/2020 and UIDB/50025/2020 of the Associate Laboratory Institute of Nanostructures, Nanomodelling and Nanofabrication-i3N and the PTNMR Network. Publisher Copyright: © 2023 Informa UK Limited, trading as Taylor & Francis Group. NMR spectroscopy was used to characterise the velocity profile in nematic solutions of poly(γ-benzyl-L-glutamate) (PBLG) in m-cresol during the application of a simple shear-flow at constant shear-rate values. In this study, the rheo-NMR technique was used that allows an insight over the fluid dynamics during the application of a shear flow in the presence of an external magnetic field, in a perpendicular direction to the shear gradient. Using this Magnetic Resonance Imaging (MRI) based technique, the velocity profile developed inside the system is accessed. publishersversion inpress

Funding Information: The authors are grateful for the financial support from Fundação para a Ciência e a Tecnologia ( FCT ), Portugal, through projects UIDB/00100/2020 , UIDP/00100/2020 and LA/P/0056/2020 of Centro de Quίmica Estrutural ; projects UIDB/04565/2020 , UIDP/04565/2020 , and LA/P/0140/2020 of Institute for Bioengineering and Biosciences – iBB and the Associate Laboratory Institute for Health and Bioeconomy - i4HB and projects UIDB/50020/2020 and UIDP/50020/2020 (LSRE-LCM). The work was also funded by national funds through FCT, under the Scientific Employment Stimulus-Institutional Call (CEEC-INST/00102/2018). We also acknowledge the Associate Laboratory for Green Chemistry – LAQV financed by national funds from FCT/MCTES ( UIDB/50006/2020 and UIDP/5006/2020 ) and Base-UIDB/50020/ 2020 and Programmatic UIDP/50020/2020 funding of the Associate Laboratory LSRE-LCM. AGM is grateful to Associação do Instituto Superior Técnico para a Investigação e Desenvolvimento ( IST-ID ) for his post-doctoral fellowship through grant no. BL133/2021-IST-ID . ILL acknowledges the CATSUS PhD Program from FCT for her grant PD/BD/135555/2018 . AP and AMF are grateful to FCT and Instituto Superior Técnico (IST), Portugal through DL/57/2017 (Contract no. IST-ID/197/2019 and IST-ID/131/2018). This publication is also supported by the RUDN University Strategic Academic Leadership Program (recipient AJLP, preparation). The authors also acknowledge the Portuguese NMR Network (IST-UL Centre) for access to the NMR facility. CFGCG thanks the FCT for funding of CQC-IMS through the projects UIDB/ 00313/2020 and UIDP/00313/2020 . Publisher Copyright: © 2023 Elsevier B.V. New organotin compounds with general formula [(PTA-CH2-C6H4-p-COO)SnR3]Br (where R is Me for 3 and Ph for 4; PTA = 1,3,5-triaza-7-phosphaadamantane), bearing the methylene benzoate PTA derivative, were synthesized through a mild two-step process. The compounds were characterized by Fourier transform infrared spectroscopy, electrospray ionization mass spectrometry, elemental analysis and nuclear magnetic resonance spectroscopy (NMR). They were heterogenized on commercially available activated carbon (AC) and multi-walled carbon nanotubes (CNT), as well as on their chemically modified analogues. The obtained materials were characterized by scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. Complex 3 supported on activated carbon (3-AC) was found to be an active and recyclable catalyst for the cyanosilylation of several aromatic and aliphatic aldehydes. Using 3-AC with a low loading of 0.1 mol% several substrates were quantitatively converted, within just 5 min at 50 °C and under microwave irradiation in solvent-free conditions. Multinuclear NMR analysis suggested a mechanism that potentially involves a double activation process, where the nucleophilic phosphorus at the PTA derivative acts as a Lewis base and the Sn(IV) metal centre as a Lewis acid. publishersversion published

The impact of solution stoichiometry, upon formation of BaSO4 crystals in 0.02 M NaCl suspensions, on the development of particle size was investigated using dynamic light scattering (DLS). Measurements were performed on a set of suspensions prepared with predefined initial supersaturation, based on the quotient of the constituent ion activity product {Ba2+}{SO42-} over the solubility product Ksp (Ωbarite = {Ba2+}{SO42-}/Ksp = 100, 500, or 1000-11,000 in steps of 1000), and ion activity solution stoichiometries (raq = {Ba2+}:{SO42-} = 0.01, 0.1, 1, 10 and 100), at circumneutral pH of 5.5-6.0, and ambient temperature and pressure. DLS showed that for batch experiments, crystal formation with varying raq was best investigated at an initial Ωbarite of 1000 and using the forward detection angle. At this Ωbarite and set of raq, the average apparent hydrodynamic particle size of the largest population present in all suspensions increased from ∼200 to ∼700 nm within 10-15 min and was independently confirmed by transmission electron microscopy (TEM) imaging. Additional DLS measurements conducted at the same conditions in flow confirmed that the BaSO4 formation kinetics were very fast for our specifically chosen conditions. The DLS flow measurements, monitoring the first minute of BaSO4 formation, showed strong signs of aggregation of prenucleation clusters forming particles with a size in the range of 200-300 nm for every raq. The estimated initial bulk growth rates from batch DLS results show that BaSO4 crystals formed fastest at near-stoichiometric conditions and more slowly at nonstoichiometric conditions. Moreover, at extreme SO4-limiting conditions, barite formation was slower compared to Ba-limiting conditions. Our results show that DLS can be used to investigate nucleation and growth at carefully selected experimental and analytical conditions. The combined DLS and TEM results imply that BaSO4 formation is influenced by solution stoichiometry and may aid to optimize antiscalant efficiency and regulate BaSO4 (scale) formation processes.

Electrodeposition from an environmentally friendly iron sulfate electrolyte with citric acid as carbon source has gained attention recently, because of excellent mechanical properties of the resulting Fe–C coatings with intentionally codeposited high-carbon concentrations. While being very attractive as protective coatings and sustainable alternatives for hard chrome coatings, comprehensive understanding of the coatings' chemical constitution including the type and location of carbon-containing phases is still lacking. The amount of codeposited carbon of up to about 0.8 wt.% significantly exceeds the solubility of carbon in ferrite, although carbon-free ferrite is the only unambiguously reported phase in as-deposited Fe–C coatings so far. In the present work, time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy, and soft X-ray emission spectroscopy have been applied to identify the carbon-containing phases, which are present as minor secondary phases in the coatings but are known to have an important influence on the coatings' properties. Three carbon-containing phases could be distinguished, homogeneously distributed in the nanocrystalline ferrite base material. Iron acetates, amorphous carbon, and carbides were found in both as-deposited and annealed Fe–C coatings up to 300°C, but their fraction changes during postdeposition annealing.

Funding Information: This work was supported by the Associated Laboratory for Sustainable Chemistry-Clean Processes and Technologies-LAQV, which is financed by national funds from FCT/MEC (UID/QUI/50006/2019) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER–007265). The NMR spectrometers are part of The National NMR Facility, supported by Fundação para a Ciência e a Tecnologia (RECI/BBB-BQB/0230/2012). This work was also supported by Fundação para a Ciência e a Tecnologia (FCT) through the projects UIDB/00100/2020, and by Fundação para a Ciência e a Tecnologia through the contract no IST-ID/077/2018 (Bernardo Monteiro). Cláudia C. L. Pereira thanks Fundação para a Ciência e a Tecnologia, MCTES, for the Norma transitória DL 57/2016 Program Contract. Fundação para a Ciência e a Tecnologia I.P. for the national funds in the scope of the project UIDB/00100/2020. Publisher Copyright: © 2023 The Royal Society of Chemistry. A wearable, small size, flexible and energy consumable free colorimetric detector of UVA radiation and UVB/UVA differentiation was created based on the peculiar stimuli-responsive behaviour of an imidazolium based ionic liquid. Semi-transparent polysulfone films are transformed into opaque and homogenous red films under UVA radiation (315-360 nm), while lower wavelength exposure (280-315 nm) induces increased emission detectable under dark light, with no colour modification of the film under visible light. Thermal analysis (TGA and DSC), spectroscopic analysis (FT-IR, 1H-NMR and UV-Vis), scanning electronic microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were conducted to elucidate confinement mechanism and irradiation effects. publishersversion published

Self-organisation is the spontaneous emergence of spatio-temporal structures and patterns from the interaction of smaller individual units. Examples are found across many scales in very different systems and scientific disciplines, from physics, materials science and robotics to biology, geophysics andastronomy. Recent research has highlighted how self-organisation can be both mediated and controlled by confinement. Confinement is an action over a system that limits its units’ translational and rotational degrees of freedom, thus also influencing the system’s phase space probability density; it can functionas either a catalyst or inhibitor of self-organisation. Confinement can then become a means to actively steer the emergence or suppression of collective phenomena in space and time. Here, to provide a common framework and perspective for future research, we examine the role of confinement in the self-organisation of soft-matter systems and identify overarching scientific challenges that need to be addressed to harness its full scientific and technological potential in soft matter and related fields.By drawing analogies with other disciplines, this framework will accelerate a common deeper understanding of self-organisation and trigger the development of innovative strategies to steer it using confinement, with impact on, e.g., the design of smarter materials, tissue engineering for biomedicineand in guiding active matter.

Finding simple, easily controlled, and flexible synthetic routes for the preparation of ternary and hybrid nanostructured semiconductors is always highly desirable, especially to fulfill the requirements for mass production to enable application to many fields such as optoelectronics, thermoelectricity, and catalysis. Moreover, understanding the underlying reaction mechanisms is equally important, offering a starting point for its extrapolation from one system to another. In this work, we developed a new and more straightforward colloidal synthetic way to form hybrid Au-Ag2X (X = S, Se) nanoparticles under mild conditions through the reaction of Au and Ag2X nanostructured precursors in solution. At the solid-solid interface between metallic domains and the binary chalcogenide domains, a small fraction of a ternary AuAg3X2phase was observed to have grown as a consequence of a solid-state electrochemical reaction, as confirmed by computational studies. Thus, the formation of stable ternary phases drives the selective hetero-attachment of Au and Ag2X nanoparticles in solution, consolidates the interface between their domains, and stabilizes the whole hybrid Au-Ag2X systems.

The role of Cu:Co composition in bi-metallic Cu-Co/ZnAl₂O₄ catalysts on higher alcohol synthesis (HAS) was investigated at H₂:CO = 4. The addition of Cu strongly facilitated Co reduction upon catalyst activation and suppressed coke deposition during HAS. Formation of predominantly hydrocarbons and higher alcohols was observed on the bi-metallic catalysts. Co/ZnAl₂O₄ produced mainly CH₄ and Cu/ZnAl₂O₄ mainly CH₃OH, while at Cu:Co = 0.6 the best ethanol selectivity of 4.5 % was reached. The microstructure of the spent catalysts confirmed a close interaction of Cu and Co. in press

Inexpensive protic ionic liquids, synthesized from di- or triamines and excess sulfuric acid, were used as solvents and catalysts for the Beckmann rearrangement. The use of ionic liquids in place of oleum or sulfuric acid allowed the base neutralization step, which is required in the conventional Beckmann rearrangement, to be entirely avoided, thereby dramatically improving the atom economy. Using a biphasic water/organic solvent extraction system, it was possible to recover and reuse the ionic liquid. The proposed method was found applicable for the synthesis of a range of primary and secondary amides.

This work was developed within the scope of project i3N (LA/P/0037/2020. I.P. N. F. Santos thanks i3N for the BPD Grant BPD/UI96/5177/2020. S. O. Pereira thanks i3N for the BPD Grant BPD/UI96/5808/2017. The authors also thank Jonas Deuermeier for the XPS measurements. Publisher Copyright: © 2022 Elsevier Ltd Laser-induced graphene from paper (paper-LIG) was applied in non-enzymatic electrochemical sensing of uric acid (UA) in human urine. Paper-LIG was formed by CO2 laser modification of paper into a 3D graphene arrangement. Kinetic analysis of paper-LIG electrodes returned effective heterogeneous electron transfer standard rate constants of 1.4 × 10−3 cm s−1 and 7.8 × 10−4 cm s−1 for [Ru(NH3)6]2+/3+ and [Fe(CN)6]4−/3− redox probes, respectively. These electrodes were able to detect and quantify uric acid in PBS within the 10–300 μM range at pH between 5.6 and 7.4. At pH 7.4, a linear response (R2 = 0.999) from 10 to 250 μM was achieved, with a limit of detection of 3.97 μM and a sensitivity of 0.363 μA cm−2 μM−1. Paper-LIG electrodes denoted adequate selectivity in synthetic urine as well as in ascorbic acid (AA) and dopamine (DA)-containing electrolytes. Determination of urinary UA content in human samples returned a concentration of c.a. 1.8–1.9 mM, within the range for healthy individuals. Recoveries of samples spiked with 50 and 100 μM UA were 100.6% and 95.4%, respectively, with satisfactory reproducibility and stability. These cheap, lightweight, flexible, and eco-friendly paper-LIG biosensors for non-enzymatic quantification of UA in human urine pave the way to widespread application in the detection of other important biomarkers. publishersversion published

Since its first use several decades ago, scanning electron microscopy has been used in numerous investigations dedicated to biological systems. This contribution focuses on observations on pathological calcifications in order to review several major applications of primary importance to the clinician. Among these, we highlight such observations as medical diagnostic tools in pathologies arising from primary hyperoxaluria and urinary infections.

Often lab-scale adsorptive breakthrough experiments are conducted in an isothermal manner, whereas industrial-scale adsorption processes are near-adiabatic. In this work, a polyurethane (PUR) insulating column was manufactured to mimic large-scale non-isothermal behavior via laboratory-scale breakthrough tests. Breakthrough tests with a CO2/N2 gas mixture on zeolite 13X (∼5 g) were performed. A bed temperature increase of 62 °C and long cooling times were observed. When compared to a regular steel column, showing a temperature rise of only 12 °C, the column efficiency was approximately 20% lower due to adiabatic effects. The heat evacuated from the adsorbent bed via the column exhaust was used as a measure for the degree of adiabaticity. Up to 46% of the theoretical heat of adsorption could be detected at the PUR column exhaust compared to 4% at the steel column exhaust. The important difference between isothermal, non-isothermal and adiabatic limit behavior was demonstrated through breakthrough experiments and simulations.

Funding Information: This work is funded by national funds through the FCT - Fundação para a Ciência e a Tecnologia , I.P., under the scope of the project DSAIPA/DS/0088/2019 and research and development units UNIDEMI (project UIDB/00667/2020 ) and NOVAMath (projects UIDB/00297/2020 and UIDP/00297/2020 ). Publisher Copyright: © 2023 The Author(s) Fires in urban areas typically carry severe consequences. High population density together with the complexity of urban network potentially imply significant impacts in property loss, physical damage and life losses. However, despite the impact that fires may have in urban areas, research in urban fire prediction remains limited. In this study, we modelled urban fire occurrences while making a comparative analysis of different strategies to account for spatial autocorrelation. Considering space dependence in addition to a range of social-economic explanatory variables has proven to strengthen the validity of the fitted models. The spatial Durbin error model, including population density, degraded buildings density and buying power, was selected as having the best fit. This model allowed to map the estimated probability of fire occurrence across Portugal, revealing a spatial pattern with clusters centred on the two main Portuguese city districts (Lisboa and Porto). Ultimately, the analysis of the relation between the observed urban fire incidence and the actual number of fire stations in each municipality allowed to underline the need for planning the spatial configuration of fire stations, both in number and location, at a regional scale. publishersversion published

Funding Information: We would like to thank Telmo Pereira from the Microscopy Facility for technical support, the Fly Facility at Nova Medical Research; CONGENTO: consortium for genetically tractable organisms. We thank the Developmental Studies Hybridoma Bank, Bloomington Drosophila Stock Center and VDRC for antibodies and fly stocks. This work was supported by PTDC-01778/2022- NeuroDev3D to R.O.T. GEMiNI and PTDC/BIA-COM/0151/2020 to C.S.M and European Research Council H2020-GA 810207-ARPCOMPLEXITY to E.R.G. A.R.F. is supported with a PhD scholarship from Fundação para a Ciência e Tecnologia, Portugal, reference SFRH/BD/144488/2019, and J.P.M. with a reference SFRH/BD/130920/2017. This work also supported by iNOVA4Health (UIDB/04462/2020 and UIDP/04462/2020), and LS4FUTURE (LA/P/0087/2020). Funding Information: We would like to thank Telmo Pereira from the Microscopy Facility for technical support, the Fly Facility at Nova Medical Research; CONGENTO: consortium for genetically tractable organisms. We thank the Developmental Studies Hybridoma Bank, Bloomington Drosophila Stock Center and VDRC for antibodies and fly stocks. This work was supported by PTDC-01778/2022- NeuroDev3D to R.O.T. GEMiNI and PTDC/BIA-COM/0151/2020 to C.S.M and European Research Council H2020-GA 810207-ARPCOMPLEXITY to E.R.G.. A.R.F. is supported with a PhD scholarship from Fundação para a Ciência e Tecnologia, Portugal, reference SFRH/BD/144488/2019, and J.P.M. with a reference SFRH/BD/130920/2017. This work also supported by iNOVA4Health (UIDB/04462/2020 and UIDP/04462/2020), and LS4FUTURE (LA/P/0087/2020). Publisher Copyright: © 2023, The Author(s). Wired neurons form new presynaptic boutons in response to increased synaptic activity, however the mechanism(s) by which this occurs remains uncertain. Drosophila motor neurons (MNs) have clearly discernible boutons that display robust structural plasticity, being therefore an ideal system in which to study activity-dependent bouton genesis. Here, we show that in response to depolarization and in resting conditions, MNs form new boutons by membrane blebbing, a pressure-driven mechanism that occurs in 3-D cell migration, but to our knowledge not previously described to occur in neurons. Accordingly, F-actin is decreased in boutons during outgrowth, and non-muscle myosin-II is dynamically recruited to newly formed boutons. Furthermore, muscle contraction plays a mechanical role, which we hypothesize promotes bouton addition by increasing MN confinement. Overall, we identified a mechanism by which established circuits form new boutons allowing their structural expansion and plasticity, using trans-synaptic physical forces as the main driving force. publishersversion published

Presentatie voor bezoek BASF

Funding Information: This work was supported by the NERC discipline hopping activities to tackle environmental challenges project (SEED-2022-317475). A. Jain would like to acknowledge National Centre for Research and Development (NCBR, Poland); Project number: V4-Japan/2/17/AtomDeC/2022 under the Visegrad Group-Japan 2021 Joint Call on Advanced Materials in cooperation with the International Visegrad Fund. S. Goswami and L. Pereira would like to thank to Lisboa2020 Programme, Centro 2020 program, Portugal 2020, European Union, through the European Social Fund who supported LISBOA-05-3559-FSE-000007 and CENTRO-04-3559-FSE-000094 operations as well as to Fundação para a Ciência e Tecnologia (FCT) and Agência Nacional de Inovação (ANI). This work was also supported by Science Foundation Ireland (SFI-20/EPSRC/3710). Publisher Copyright: © 2023 Naturally abundant materials play a crucial role in the development of sustainable electrochemical energy storage (EES) devices including batteries and supercapacitors (SCs). This is due to limited available resources with regards to energy storage materials, and the environmental pollution produced by the toxic materials utilized in conventional EESs. In the current review, development in the field of natural bast fibres (jute, flax, hemp and kenaf) based EES devices performances is highlighted. This review emphasizes methods such as the direct use of modified fibres and activated carbon from biomass for the design of EES devices. Activated fibres were developed using both physical and chemical activation methods. Key challenges including active electrode materials preparation, capacitive retention, and the implementation of the fibre based EES devices are critically discussed. Furthermore, the recent surge in the use of wearables and portable technologies that demand further development of flexible/non-flexible EES devices are also explored. Future trends and perspectives on materials development, power management interface, recycling, biodegradability and circular economy are also addressed. It is concluded that the development of new renewable energy systems using bast fibres has many remarkable advances in device performance. For this, an innovative approach is required to develop high energy density bast fibre based sustainable EES devices which will be potentially implemented for clean energy solutions. publishersversion published

Bipolar membrane electrodialysis (BPMED) could allow for the complete electrification of direct air capture (DAC) technologies. In this work, we have modeled and optimized two DAC processes based on different electrodialysis cell designs. The technical assessment has been complemented by a detailed economic analysis, showing the advantages but also the current shortcomings of this technology and pathways for advancement. A minimum energy demand of 24 MJ kgCO2-1has been estimated for the base-case scenario, a result comparable to what has been reported for other liquid-scrubbing DAC technologies. Several solutions to further abate power consumption have been reviewed, with the most promising case providing a 29% reduction. Membrane cost and performance are currently the main limiting factors. In a scenario where cheaper membranes with better performance are assumed to be available, total costs below $250 tonCO2-1may be feasible, making BPMED a viable fully electrified alternative to other technologies requiring natural gas.

Fast and accurate computational approaches to predicting reactivity in sulfa-Michael additions are required for high-throughput screening in toxicology (e.g., predicting excess aquatic toxicity and skin sensitization), chemical synthesis, covalent drug design (e.g., targeting cysteine), and data set generation for machine learning. The kinetic glutathione chemoassay is a time-consuming in chemico method used to extract kinetic data in the form of log(kGSH) for organic electrophiles. In this work, we use density functional theory to compare the use of transition states (TSs) and enolate intermediate structures following C–S bond formation in the prediction of log(kGSH) for a diverse group of 1,4 Michael acceptors. Despite the widespread use of transition state calculations in the literature to predict sulfa-Michael reactivity, we observe that intermediate structures show much better performance for the prediction of log(kGSH), are faster to calculate, and easier to obtain than TSs. Furthermore, we show how linear combinations of atomic charges from the isolated Michael acceptors can further improve predictions, even when using inexpensive semiempirical quantum chemistry methods. Our models can be used widely in the chemical sciences (e.g., in the prediction of toxicity relevant to the environment and human health, synthesis planning, and the design of cysteine-targeting covalent inhibitors), and represent a low-cost, sustainable approach to reactivity assessment.

This article reports about a lesson series that focuses on engaging students in sustainability, plastics, and life cycle assessment (LCA). The purpose of the lesson series is to give students insights into sustainability in the context of plastics and to foster awareness of and insights into the benefits of the LCA method. The lesson series introduces students to sustainability by enabling them to watch a video, answer questions, read articles, conduct laboratory experiments, and experience the four stages of LCA. In general, the findings reveal that the lesson series evoked in students a more critical view of the life cycle of plastics. The students showed increasing awareness of the complexity of the sustainability issue at hand. In addition, students used their acquired knowledge about LCA and mentioned impact categories in their argumentation. The lesson series evoked predominantly life cycle thinking, and the qualitative part of an LCA, and might thus serve as a stepping stone toward the quantitative assessment. The preliminary results show that the lesson series is effective for evoking life cycle thinking among students and serves as a stepping stone towards life cycle assessment. Future research could focus on setting the goal and scope of the process to be assessed, with emphasis on the functional unit in the context of plastics, and providing students a complete and coherent understanding of the entire cycle of production, use and recycling of plastics.

Bezoek aan Braganza over biobased en circulaire chemie bij de Hanze.

Funding Information: Thanks are also due to FCT for the project PTDC/BII-BIO/30884/2017. A.F.P. and M.M.M. thank FCT for funding through the Individual Call to Scientific Employment Stimulus (ref. 2020.01614.CEECIND/CP1596/CT0007 and CEEC-IND/02702/2017, respectively). O.D. is thankful for the Ph.D. grant supported by FCT (2021.05322.BD). Funding Information: This work was funded by Portuguese funds through Fundação para a Ciência e a Tecnologia (FCT/MCTES) in the framework of the projects UIDB/50006/2020, UIDP/50006/2020, and EXPL/BII-BIO/0436/2021 and also by BIP Proof 2022/2023 through UI-Transfer, a cofunding project by European Union through COMPETE 2020-Portugal 2020, CIQUP, Centro de Investigação em Química da Universidade do Porto (UIDB/00081/2020), and IMS, Institute of Molecular Sciences (LA/P/0056/2020). Publisher Copyright: © 2023 The Authors. Published by American Chemical Society. The control of the oxidative stability of biodiesel and blends of biodiesel with diesel is one of the major concerns of the biofuel industry. The oxidative degradation of biodiesel can be accelerated by several factors, and this is most critical in the so-called second generation biodiesel, which is produced from low-cost raw materials with lower environmental impacts. The addition of antioxidants is imperative to ensure the oxidative stability of biodiesel, and these are considered products of high commercial value. The antioxidants currently available on the market are from synthetic origin, so the existence/availability of alternative antioxidants of natural origin (less dependent on fossil sources) at a competitive price presents itself as a strong business opportunity. This work describes and characterizes a sustainable alternative to synthetic antioxidants used in the biodiesel market developed from extracts of vineyard pruning waste (VPW), which are naturally rich in phenolic compounds with antioxidant properties. A hydrothermal extraction process was applied as a more efficient and sustainable technology than the conventional one with the potential of the extracts as antioxidant additives in biodiesel evaluated in Rancitech equipment. The VPW extract showed comparable antioxidant activity as the commercial antioxidant butylated hydroxytoluene (BHT) typically used in biodiesel. The stability of the biodiesel is dependent from the amount of the extract added. Further, for the first time, the assessment of the environmental impacts of using natural extracts to control the oxidative stability of biodiesel in the production process is also discussed as a key factor of the process environmental sustainability. publishersversion published

Actively targeted drug loaded nanoparticles represent an exciting new form of therapeutics for cancer and other diseases. These formulations are complex and in order to realize their ultimate potential, optimization of their preparation is required. In this current study, we have examined the conjugation of a model targeting ligand, conjugated in a site-specific manner using a vinyl sulfone coupling approach. A disulfide-functionalized poly(L-lactide)-b-poly(oligo(ethylene glycol) methacrylate)-stat-(bis(2-methacryloyl)oxyethyl disulfide) (PLA-b-P(OEGMA-stat-DSDMA)) diblock copolymer was synthesized by simultaneous ring opening polymerization (ROP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. Subsequently, the disulfide bonds of the polymer were reduced to thiols and divinyl sulfone was attached to the polymer using thiol–ene chemistry to produce the vinyl sulfone (VS)-functionalized PLA-b-P(OEGMA-stat-VSTEMA) amphiphilic block copolymer. Single emulsion – solvent evaporation was employed using a blend of this polymer with poly(D,L-lactide-co-glycolide) (PLGA) to produce VS-functionalized polymeric nanoparticles. The ability of these novel nanoparticles to attach ligands was then exemplified using a single domain variable new antigen receptor (VNAR) with a free carboxyl terminal cysteine residue. The resulting VNAR-functionalized nanoparticles were found to maintain specific affinity to their cognate antigen (DLL4) for at least 72 h at 4 °C. The simplicity of the degradable amphiphilic block copolymer synthesis and the efficiency of VNAR conjugation to the VS-functionalized nanoparticles show the potential of this platform for therapeutic development.

Antarctica’s continental margins pose an unknown submarine landslide-generated tsunami risk to Southern Hemisphere populations and infrastructure. Understanding the factors driving slope failure is essential to assessing future geohazards. Here, we present a multidisciplinary study of a major submarine landslide complex along the eastern Ross Sea continental slope (Antarctica) that identifies preconditioning factors and failure mechanisms. Weak layers, identified beneath three submarine landslides, consist of distinct packages of interbedded Miocene- to Pliocene-age diatom oozes and glaciomarine diamicts. The observed lithological differences, which arise from glacial to interglacial variations in biological productivity, ice proximity, and ocean circulation, caused changes in sediment deposition that inherently preconditioned slope failure. These recurrent Antarctic submarine landslides were likely triggered by seismicity associated with glacioisostatic readjustment, leading to failure within the preconditioned weak layers. Ongoing climate warming and ice retreat may increase regional glacioisostatic seismicity, triggering Antarctic submarine landslides.

Funding Information: This work was supported by the MEtRICs unit, which is financed by national funds from FCT/MCTES (UIDB/04077/2020 and UIDP/04077/2020). This work was also supported by the Associate Laboratory for Green Chemistry—LAQV, which is financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020). The authors also acknowledge FCT/MCTES for funding João Pires’ Ph.D. fellowship (SFRH/BD/144346/2019) and Carolina Rodrigues’ Ph.D. fellowship (2020.04441.BD). Publisher Copyright: © 2023 by the authors. Nanotechnology advances are rapidly spreading through the food science field; however, their major application has been focused on the development of novel packaging materials reinforced with nanoparticles. Bionanocomposites are formed with a bio-based polymeric material incorporated with components at a nanoscale size. These bionanocomposites can also be applied to preparing an encapsulation system aimed at the controlled release of active compounds, which is more related to the development of novel ingredients in the food science and technology field. The fast development of this knowledge is driven by consumer demand for more natural and environmentally friendly products, which explains the preference for biodegradable materials and additives obtained from natural sources. In this review, the latest developments of bionanocomposites for food processing (encapsulation technology) and food packaging applications are gathered. publishersversion published

Eutectogels are an emerging family of soft ionic materials alternative to ionic liquid gels and organogels, offering fresh perspectives for designing functional dynamic platforms in water-free environments. Herein, the first example of mixed ionic and electronic conducting supramolecular eutectogel composites is reported. A fluorescent glutamic acid-derived low-molecular-weight gelator (LMWG) was found to self-assemble into nanofibrillar networks in deep eutectic solvents (DES)/poly(3,4-ethylenedioxythiophene) (PEDOT): chondroitin sulfate dispersions. These dynamic materials displayed excellent injectability and self-healing properties, high ionic conductivity (up to 10−2 S cm−1), good biocompatibility, and fluorescence imaging ability. This set of features turns the mixed conducting supramolecular eutectogels into promising adaptive materials for bioimaging and electrostimulation applications. This work was supported by Marie Sklodowska-Curie Research and Innovation Staff Exchanges (RISE) under the grant agreement No 823989 “IONBIKE”. The financial support received from CONICET and ANPCyT (Argentina) is also gratefully acknowledged. M. C.-G. thanks Emakiker Grant Program of POLYMAT. L. C. T. is grateful to Fundação para a Ciência e a Tecnologia (FCT/MCTES) in Portugal for her research contract under Scientific Employment Stimulus (2020.01555.CEECIND), and Associate Laboratory for Green Chemistry—LAQV, which is also financed by FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020). D. M. thanks “Ayuda RYC2021-031668-I financiada por MCIN/AEI/10.13039/501100011033 y por la Unión Europea NextGenerationEU/PRTR”. The authors thank the technical and human support provided by SGIker (UPV/EHU/ERDF, EU).

Funding Information: This work was financed by national funds from FCT—Fundação para a Ciência e a Tecnologia, I.P., in the scope of the projects LA/P/0037/2020, UIDP/50025/2020 and UIDB/50025/2020 of the Associate Laboratory Institute of Nanostructures, Nanomodelling and Nanofabrication—i3N. Furthermore, the work received funding from FCT in the scope of projects UIDP/04378/2020 and UIDB/04378/2020 of the Research Unit on Applied Molecular Biosciences—UCIBIO and the project LA/P/0140/2020 of the Associate Laboratory Institute for Health and Bioeconomy—i4HB. This work also received funding from the European Community’s H2020 program under grant agreements 716510 (ERC-2016-StG TREND), 787410 (ERC-2019-AdG DIGISMART) and 952169 (SYNERGY, H2020-WIDESPREAD-2020-5, CSA), 101008701 (EMERGE, H2020-INFRAIA-2018-2020). B. J. Coelho acknowledges FCT for the attribution of grant SFRH/BD/132904/2017 and grant COVID/BD/152453/2022. Publisher Copyright: © 2023 by the authors. Poly(p-xylylene) derivatives, widely known as Parylenes, have been considerably adopted by the scientific community for several applications, ranging from simple passive coatings to active device components. Here, we explore the thermal, structural, and electrical properties of Parylene C, and further present a variety of electronic devices featuring this polymer: transistors, capacitors, and digital microfluidic (DMF) devices. We evaluate transistors produced with Parylene C as a dielectric, substrate, and encapsulation layer, either semitransparent or fully transparent. Such transistors exhibit steep transfer curves and subthreshold slopes of 0.26 V/dec, negligible gate leak currents, and fair mobilities. Furthermore, we characterize MIM (metal–insulator–metal) structures with Parylene C as a dielectric and demonstrate the functionality of the polymer deposited in single and double layers under temperature and AC signal stimuli, mimicking the DMF stimuli. Applying temperature generally leads to a decrease in the capacitance of the dielectric layer, whereas applying an AC signal leads to an increase in said capacitance for double-layered Parylene C only. By applying the two stimuli, the capacitance seems to suffer from a balanced influence of both the separated stimuli. Lastly, we demonstrate that DMF devices with double-layered Parylene C allow for faster droplet motion and enable long nucleic acid amplification reactions. publishersversion published

There is an urgent need for new treatment options for carbapenem-resistant Klebsiella pneumoniae (K. pneumoniae), which is a common cause of life-threatening hospital- and community-acquired infections. Prophylactic or therapeutic vaccination may offer an approach to control these infections, however, none has yet been approved for human use. Here, we report the chemical synthesis of an outer core tetra- and pentasaccharide derived from the lipopolysaccharide of K. pneumoniae. The oligosaccharides were equipped with an aminopentyl linker, which facilitated conjugation to the carrier proteins CRM197 and BSA. Mice immunized with the glycoconjugate vaccine candidates elicited antibodies that recognized isolated LPS as well as various strains of K. pneumoniae. The successful preparation of the oligosaccharides relied on the selection of monosaccharide building blocks equipped with orthogonal hydroxyl and amino protecting groups. It allowed the differentiation of three types of amines of the target compounds and the installation of a crowded 4,5-branched Kdo moiety.

Microfibrillated cellulose (MFC) has potential to be used as clean label texture modifier in foods due to its structural and mechanical properties. These properties deteriorate upon drying of MFC dispersions due to aggregation of the microfibrils. In this study dried MFC particles were prepared by spray-drying MFC dispersions in a surplus of maltodextrin to prevent hornification. The aim of this study was to evaluate the effect of MFC particle concentration and MFC:maltodextrin ratio of dried MFC powders on rheological, tribological and sensory texture properties of liquid foods. Scanning Electron Microscopy demonstrated that after spray-drying, MFC powders with polydisperse particle size distribution were obtained (1–30 μm). Upon suspension of spray-dried MFC powder in water, maltodextrin dissolved in the aqueous continuous phase whereas spherical MFC networks retained their shape and co-existed in a mixture with individual fibrils. Spray-dried MFC powders were added to skimmed milk and tomato soup at different concentrations. With increasing concentration of dried MFC particles, shear viscosity, consistency index K, storage and loss modulus of skimmed milks and tomato soups increased whereas flow index n decreased. Addition of spray-dried MFC particles to milks and soups significantly (p < 0.05) increased sensory thickness and creaminess. Milks displayed similar tribological properties irrespective of MFC particle concentration, which was presumably caused by exclusion of the MFC network from the tribological gap. Rheological properties, thickness and creaminess increased more effectively upon addition of low MFC:maltodextrin particles compared to particles with high MFC:maltodextrin ratio. We conclude that spray-dried microfibrillated cellulose particles can be used as thickener or fat replacer in liquid foods. Microfibrillated cellulose (MFC) has potential to be used as clean label texture modifier in foods due to its structural and mechanical properties. These properties deteriorate upon drying of MFC dispersions due to aggregation of the microfibrils. In this study dried MFC particles were prepared by spray-drying MFC dispersions in a surplus of maltodextrin to prevent hornification. The aim of this study was to evaluate the effect of MFC particle concentration and MFC:maltodextrin ratio of dried MFC powders on rheological, tribological and sensory texture properties of liquid foods. Scanning Electron Microscopy demonstrated that after spray-drying, MFC powders with polydisperse particle size distribution were obtained (1–30 μm). Upon suspension of spray-dried MFC powder in water, maltodextrin dissolved in the aqueous continuous phase whereas spherical MFC networks retained their shape and co-existed in a mixture with individual fibrils. Spray-dried MFC powders were added to skimmed milk and tomato soup at different concentrations. With increasing concentration of dried MFC particles, shear viscosity, consistency index K, storage and loss modulus of skimmed milks and tomato soups increased whereas flow index n decreased. Addition of spray-dried MFC particles to milks and soups significantly (p < 0.05) increased sensory thickness and creaminess. Milks displayed similar tribological properties irrespective of MFC particle concentration, which was presumably caused by exclusion of the MFC network from the tribological gap. Rheological properties, thickness and creaminess increased more effectively upon addition of low MFC:maltodextrin particles compared to particles with high MFC:maltodextrin ratio. We conclude that spray-dried microfibrillated cellulose particles can be used as thickener or fat replacer in liquid foods.

Effect of bisulfite (HSO3-) on the stress corrosion cracking (SCC) behavior of 7050-T7451 aluminum alloy in the thin electrolyte layer environment in the presence of Cl- is investigated. Addition of HSO3- inhibits the corrosion initiation but promotes the corrosion propagation and hydrogen uptake. With a quantitative calculation, the HSO3- is demonstrated to significantly facilitate the synergistic effect between stress, corrosion, and hydrogen during the in-situ tensile test, resulting in the change of the SCC controlling step from corrosion-induced hydrogen to mechanical-electrochemical-hydrogen interactions. The buffer effect of HSO3- plays a dominant role in the HSO3--induced acceleration of the SCC degradation.

Funding: Financial support from the University of St. Andrews under a St Leonard's College Scholarship (CDT) is gratefully acknowledged. Modelling crystal growth is important for example in crystal engineering, materials science, and the life sciences. Molecular modelling techniques can provide fundamental insights into the atomic processes underlying crystal growth but do not always give direct information about growth rates and growth modes on spatial and temporal scales relevant in nature and for applications. The phase-field (PF) approach is a relatively simple model that can provide results on length and time scales directly comparable to experiments, but it has not extensively been employed to investigate crystallization of ionic solids, and not many quantitative results have been reported. In the present study we model the growth of cubic NaCl crystals in two dimensions. We have used small crystal seeds with an appropriate anisotropy term to investigate both the growth speed and the growth mode. Results are compared to experimental data from the literature. The PF model displays the concentration dependent transition from compact to non-compact growth of NaCl reasonably well on spatial and temporal scales that are not easily accessible with other theoretical models. Publisher PDF

Presentatie over de recycling van PHA voor Interreg.

Presentatie over de vraagstukken rond de energietransitie en de biobased transitie.

Parkinson’s Disease (PD) is a common neurodegenerative disorder affecting millions of people worldwide for which there are only symptomatic therapies. Small molecules able to target key pathological processes in PD have emerged as interesting options for modifying disease progression. We have previously shown that a (poly)phenol-enriched fraction (PEF) of Corema album L. leaf extract modulates central events in PD pathogenesis, namely α-synuclein (αSyn) toxicity, aggregation and clearance. PEF was now subjected to a bio-guided fractionation with the aim of identifying the critical bioactive compound. We identified genipin, an iridoid, which relieves αSyn toxicity and aggregation. Furthermore, genipin promotes metabolic alterations and modulates lipid storage and endocytosis. Importantly, genipin was able to prevent the motor deficits caused by the overexpression of αSyn in a Drosophila melanogaster model of PD. These findings widens the possibility for the exploitation of genipin for PD therapeutics.

De lectorale rede gehouden door Janneke Krooneman tijdens haar lectorinstallatie op 5 april.

Keynote lecture during Go!PHA WG Science & Technology

Pickering emulsions represent an important class of functional materials with potential applications in sustainability and healthcare. Currently, the synthesis of Pickering emulsions relies heavily on the use of strongly adsorbing molecular modifiers to tune the surface chemistry of the nanoparticle constituents. This approach is inconvenient and potentially a dead-end for many applications since the adsorbed modifiers prevent interactions between the functional nanosurface and its surroundings. Here, we demonstrate a general modifier-free approach to construct Pickering emulsions by using a combination of stabilizer particles, which stabilize the emulsion droplet, and a second population of unmodified functional particles that sit alongside the stabilizers at the interface. Freeing Pickering emulsions from chemical modifiers unlocks their potential across a range of applications including plasmonic sensing and interfacial catalysis that have previously been challenging to achieve. More broadly, this strategy provides an approach to the development of surface-accessible nanomaterials with enhanced and/or additional properties from a wide range of nano-building blocks including organic nanocrystals, carbonaceous materials, metals and oxides.

Presentatie over de klimaatexpeditie naar Spitsbergen, met een focus op Janneke Krooneman's ervaringen en bijdragen.

This study introduces for the first time an electroanalytical investigation and novel voltammetric method for the determination of emamectin benzoate (EB) using a cathodically pretreated boron-doped diamond electrode (CTP-BDDE). The CPT-BDDE electrode exhibited a well-defined irreversible signal at ∼1.35 V (vs. Ag/AgCl) using cyclic voltammetry. Different scan rates (from 10 to 750 mV s−1) suggested that the oxidation of EB on the BDDE surface is a diffusion-controlled process. Using square wave voltammetry, the anodic peak current was linear with EB concentrations from 0.25 mg L-1 to 12.5 mg L-1, with LOD and LOQ found to be 0.079 and 0.263 mg L-1, respectively. The effect of other insecticides used to treat sea lice and inorganic ions found in seawater on the voltammetric detection of EB was negligible. The proposed method was successfully applied to the determination of EB at different concentrations in real sea water samples. To the best of our knowledge, the voltammetric behaviour of EB and the electrochemical method for EB determination is reported for the first time.

Synthesis of azetidine-derived natural products by the opportunistic pathogen Pseudomonas aeruginosa is controlled by quorum sensing, a process involving the production and sensing of diffusible signal molecules that is decisive for virulence regulation. In this study, we engineered P. aeruginosa for the titratable expression of the biosynthetic aze gene cluster, which allowed the purification and identification of two new products, azetidomonamide C and diazetidomonapyridone. Diazetidomonapyridone was shown to have a highly unusual structure with two azetidine rings and an open-chain diimide moiety. Expression of aze genes strongly increased biofilm formation and production of phenazine and alkyl quinolone virulence factors. Further physiological studies revealed that all effects were mainly mediated by azetidomonamide A and diazetidomonapyridone, whereas azetidomonamides B and C had little or no phenotypic impact. The P450 monooxygenase AzeF which catalyzes a challenging, stereoselective hydroxylation of the azetidine ring converting azetidomonamide C into azetidomonamide A is therefore crucial for biological activity. Based on our findings, we propose this group of metabolites to constitute a new class of diffusible regulatory molecules with community-related effects in P. aeruginosa.

Funding: This research was carried out in part due to funding from the Max Planck-UBC-UTokyo Centre for Quantum Materials. Part of the research described in this paper was performed at the Canadian Light Source, a national research facility of the University of Saskatchewan, which is supported by the Canada Foundation for Innovation, the Natural Sciences and Engineering Research Council, the National Research Council, the Canadian Institutes of Health Research, the Government of Saskatchewan and the University of Saskatchewan. We thank the Science and Technology Facilities Council ISIS facility for the provision of beamtime. (Ba,K)BiO3 constitute an interesting class of superconductors, where the remarkably high superconducting transition temperature Tc of 30 K arises in proximity to charge density wave order. However, the precise mechanism behind these phases remains unclear. Here, enabled by high-pressure synthesis, we report superconductivity in (Ba,K)SbO3 with a positive oxygen–metal charge transfer energy in contrast to (Ba,K)BiO3. The parent compound BaSbO3−δ shows a larger charge density wave gap compared to BaBiO3. As the charge density wave order is suppressed via potassium substitution up to 65%, superconductivity emerges, rising up to Tc = 15 K. This value is lower than the maximum Tc of (Ba,K)BiO3, but higher by more than a factor of two at comparable potassium concentrations. The discovery of an enhanced charge density wave gap and superconductivity in (Ba,K)SbO3 indicates that strong oxygen–metal covalency may be more essential than the sign of the charge transfer energy in the main-group perovskite superconductors. Publisher PDF

The effect of hot stamping on the corrosion properties of boron-manganese 22MnB5 steel coated with hot-dip aluminum-silicon was evaluated under severe conditions by a continuous salt spray test (SST). The corrosion mechanism changed from localized to generalized, as cathodic precipitates were not present after hot stamping. Intrinsic defects in press-hardened steel samples were the reason for severe damage in both metallic coating and steel substrate under SST conditions. The red rust formed at the top surface, characterized as different iron-based compounds, is due to both the iron diffusion from the steel substrate toward the surface and the corrosion of the steel substrate.

Hydrothermal degreening and ageing procedures were applied to a tri-metal (Pt-Pd-Rh) fully formulated lean NOx Trap catalyst to evaluate the effects of thermal stress on the performances and structural properties. X-ray absorption fine structure (XAFS) analysis revealed that the average size of the platinum particles was the same after degreening and ageing treatments. The formation of a new phase of alloyed Pt-Pd was observed to increase with the thermal load. The size of the ceria particles also increased after the ageing treatment. NOx storage capacity experiments revealed a substantial decrease of the concentration of active NOx storage sites which correlated with both ageing and degreening protocols. The performances of the treated catalyst were evaluated through spatially resolved (SpaciMS) lean-rich cycles. During the lean phase, the impact of the decrease in storage sites was significant on the aged sample, where an enlargement of the area required to achieve full storage was observed. On the other hand, the regeneration functionalities did not appear to be particularly affected by ageing. Rather, the aged sample showed a decrease of oxygen storage capacity (OSC), which promoted a lower reductant consumption and therefore a quicker and more efficient reduction process. On the other hand, the different distributions of adsorbed species by the end of the lean phase produced greater spread presence of NH3 and NOx slip along the channels of the aged sample during the reduction.

Publisher Copyright: © 2022 American Chemical Society The kinetics and thermodynamics of the pH-dependent reversible and irreversible processes leading to color fading of pelargonidin-3-O-glucoside, peonidin-3-O-glucoside, malvidin-3-O-glucoside, and cyanidin-3-O-glucoside dyes in aqueous solutions are reported. Following the addition of base to the flavylium cation, the quinoidal bases disappear by three distinct steps: (i) in an acidic medium by a biexponential process, in which the faster step is controlled by the hydration reaction and the slower one by cis–trans isomerization; the degradation process occurs essentially from the anionic quinoidal base; (ii) in a basic medium (pH > 9.5), in which the disappearance of the anionic bases is monoexponential, with the rate proportional to the hydroxyl concentration (hydroxyl attack), leading to anionic chalcones (cis and trans) at equilibrium─the slower degradation step occurs from the di- and trianionic chalcones; and (iii) in the pH region circa 7.7 < pH < 9.5, in which hydration and hydroxyl attacks are much slower than anionic quinoidal base degradation (which is the rate-controlling step) and the equilibrium cannot be attained. authorsversion published

The paper reports new results that compare the group of performance figures of merit of piezo-active 2-2-type composites based on [011]-poled domain-engineered (1 - x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 single crystals, where the main crystallographic axes in the crystal layers are rotated to tailor effective electromechanical properties and related parameters. Examples of the orientation and volume-fraction dependences of the figures of merit are analysed for the first time for the system of 2-2 single crystal/polymer composites and 2-0-2 single crystal/corundum ceramic/polymer composites at x = 0.0475-0.09. The connections between the piezoelectric coefficients, energy-harvesting figures of merit and modified figures of merit (j = 1, 2 and 3) are highlighted during rotation of the main X and Y crystallographic axes around the Z axis of the crystal layers. A similar orientation behaviour of, and and their large anisotropy are studied at specific volume fractions of the single-crystal component and for a variety of microgeometric architectures of a corundum ceramic/polymer layer with 0-3 connectivity. Maxima of the longitudinal parameters, and at x = 0.0475-0.09 and constant volume fraction of the single-crystal component of the 2-2-type composites are observed in a relatively narrow orientation range. A new performance diagram is built to show regions of a large anisotropy of and in a 2-0-2 composite and, as a result of the large piezoelectric coefficients and figures of merit, the composites show significant potential in the field of piezoelectric energy-harvesting and sensor applications. This journal is

Metamaterials can display unusual and superior properties that come from their carefully designed structure rather than their composition. Metamaterials have permeated large swatches of science, including electromagnetics and mechanics. Although metamaterials hold the promise for realizing technological advances, their potential to enhance interactions between humans and materials has largely remained unexplored. Here, we devise a class edible mechanical metamaterials with tailored fracture properties to control mouthfeel sensory experience. Using chocolate as a model material, we first demonstrate how to create and control the fracture anisotropy, and the number of cracks, and demonstrate that these properties are captured in mouthfeel experience. We further use topology optimization to rationally design edible metamaterials with maximally anisotropic fracture strength. Our work opens avenues for the use of metamaterials to control fracture and to enhance human-matter interactions.

Quaternary benzylic centers are accessed with high atom and step economy by Ir-catalyzed alkene hydroarylation. These studies provide unique examples of the use of non-polarized 1,1-disubstituted alkenes in branch selective Murai-type hydro(hetero)arylations. Detailed mechanistic studies have been undertaken, and these indicate that the first irreversible step is the demanding alkene carbometallation process. Structure-reactivity studies show that the efficiency of this is critically dependent on key structural features of the ligand. Computational studies have been undertaken to rationalize this experimental data, showing how more sterically demanding ligands reduce the reaction barrier via predistortion of the reacting intermediate. The key insight disclosed here will underpin the ongoing development of increasingly sophisticated branch selective Murai hydroarylations.