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In this work, locally available tea wastes were used as precursors for the development of cost-effective bio-sorbent materials for heavy metal removal from wastewater. Chemical and thermal treatments to prepare magnetic/non-magnetic tea waste-based adsorbents were discussed and correlated their properties with corresponding Cr(VI) adsorption capacity. These bio-sorbents were thoroughly characterized by FT-IR, PXRD, N2 adsorption-desorption surface area techniques and Cr adsorption performance was investigated in batch reactor under different conditions such as adsorbent dosage, initial Cr concentration, solution pH and contact time. Careful bleaching steps, incorporation of magnetic iron nanoparticles and judicious temperature treatments of tea wastes resulted in high performing biosorbents with a complete removal of Cr at a dosage of 0.25 g/mL of the solution. Cr adsorption on these tea waste-based bio-sorbents were found to be fitting to a pseudo 2nd order kinetics.

Funding Information: G.D. thanks to the European Regional Development Fund within the Operational Programme Science and Education for Smart Growth 2014–2020 under the Project Center of Exellence: National center of mechatronics and clean technologies - BG05M2OP001-1.001-0008 for the financial support. Funding Information: This work was 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 ) as well as the PROTEOMASS Scientific Society (Portugal) for funding support (General Funding Grant 2022–2023). F.D. thanks to FCT / MEC (Portugal) for his doctoral grant 2021.05161.BD . E.O thanks FCT / MEC (Portugal) for the individual contract, CEECIND/00648/2017. J.F-.L. thanks the FCT / MEC (Portugal) for the individual research contract DL57. HMS acknowledges the Associate Laboratory for Green Chemistry-LAQV ( LA/P/0008/2020 ) funded by FCT / MCTES for his research contract. Funding Information: The financial support by the Bulgarian National Science Fund (BNSF) under grant – “Novel styryl and polymethine fluorophores as potential theranostic agents “contract N◦ КП-06-М59/1 from 15.11.2021 is gratefully acknowledged by A.K. This work is also developed and acknowledged by A.K. as part of contract №: BG-RRP-2.004-0002-C01, Laboratory of Organic Functional Materials (Project BiOrgaMCT), Procedure BG-RRP-2.004, Establishing of a network of research higher education institutions in Bulgaria”, funded by BULGARIAN NATIONAL RECOVERY AND RESILIENCE PLAN ”. Publisher Copyright: © 2023 The Authors Polarity-sensitive dansyl derivatives L1 and L2 were synthesized and their ability to sense pollutant metal ions was investigated. All compounds were found to be highly sensitive towards Cu2+ and Hg2+ metal ions, while L2 being able to detect and quantify Hg2+ concentrations as low as 2.5 μM. Both L1 and L2 exhibit positive solvatofluorochromic behaviour, modulated in the presence of water, which in turn results in fluorescence enhancement via aggregation-induced emission (AIE). Seeking stability and water solubility, luminescent L1-based polystyrene-block-polybutadiene-block-polystyrene (SBS) microparticles (size: 520 ± 76 nm) were successfully prepared while maintaining the fluorescence emission of fluorophore L1 (φ = 22%). This work exemplifies the multiple properties of dansyl-derivatives and their promising applications in biomedicine and environmental fields. publishersversion published

Funding Information: C. Costa, T. Casimiro and A. Aguiar-Ricardo are grateful for the financial support of the Associate Laboratory for Green Chemistry-LAQV, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa , Portugal, which is financed by national funds from FCT/MCTES ( UIDB/50006/2020 and UIDP/50006/2020 ). C. Costa thanks FCT (Fundação para a Ciência e Tecnologia) and ESF (European Social Fund) through POCH (Programa Operacional Capital Humano) for her PhD grant ref. PD/BD/142880/2018, COVID/BD/152744/2022 and Project PD/00184/2012-PDQS . C. Costa and A. Aguiar-Ricardo acknowledge also CA18224 GREENERING (“Green Chemical Engineering Network towards upscaling sustainable processes”). COST Actions are funded within the EU Horizon 2020 Programme . M.L. Corvo is grateful for the financial support of the Research Institute for Medicines (iMed.ULisboa), Faculty of Pharmacy, Universidade de Lisboa , Lisbon, Portugal, which is supported in part by UID/DTP/04138/2020 and UIDP/04138/2020 from FCT/MCTES , Portugal. The authors are grateful to Prof. M. Dionísio for the DSC facility. Publisher Copyright: © 2023 Enzyme-based inhalable therapeutics for lung inflammation are gaining interest as an alternative to long-term corticosteroids treatments. However, enzymes have poor pharmacokinetics. Encapsulating enzymes in liposomes can increase their half-live and modify their biodistribution. But both liposomes and enzymes are susceptible to destabilization during storage. This drawback can be surpassed, by converting liposomal suspension into solid dosage forms for different administration routes, including inhalation. In this study, Cu, Zn- superoxide dismutase (SOD) was encapsulated in liposomes, then dried using supercritical CO2-assisted spray-drying to make SOD-loaded liposomal dry powder formulations (SOD_Lip-DPFs). Upon resuspension in water, liposomes maintained structural integrity, with 99% SOD encapsulation efficiency and preserved enzymatic activity. Stability studies showed that SOD_Lip-DPFs maintained liposomal and enzyme stability for 50 days at 40% relative humidity. This offers a stable and efficient delivery system for enzyme-based inhalable therapeutics. publishersversion published

Membrane science and technology is growing rapidly worldwide and continues to play an increasingly important role in diverse fields by offering high separation efficiency with low energy consumption. Membranes have also shown great promise for “green” separation. A majority of the investigations in the field are devoted to the membrane fabrication and modification with the ultimate goals of enhancing the properties and separation performance of membranes. However, less attention has been paid to membrane life cycle management, particularly at the end of service. This is becoming very important, especially taking into account the trends toward sustainable development and carbon neutrality. On the contrary, this can be a great opportunity considering the large variety of membrane processes, especially in terms of the size and capacity of plants in operation. This work aims to highlight the prominent aspects that govern membrane life cycle management with special attention to life cycle assessment (LCA). While fabrication, application, and recycling are the three key aspects of LCA, we focus here on membrane (module) recycling at the end of life by elucidating the relevant aspects, potential criteria, and strategies that effectively contribute to the achievement of green development and sustainability goals.

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.

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.

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 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

Funding Information: This research received funding from the Portuguese Foundation for Science and Technology (FCT/MCTES) under the project ToxApp4NanoCELFI (PTDC/SAUPUB/32587/2017) and projects UIDB/00009/2020 and UIDP/00009/2020 (ToxOmics). Publisher Copyright: © 2023 by the authors. DNA methylation is an epigenetic mechanism that involves the addition of a methyl group to a cytosine residue in CpG dinucleotides, which are particularly abundant in gene promoter regions. Several studies have highlighted the role that modifications of DNA methylation may have on the adverse health effects caused by exposure to environmental toxicants. One group of xenobiotics that is increasingly present in our daily lives are nanomaterials, whose unique physicochemical properties make them interesting for a large number of industrial and biomedical applications. Their widespread use has raised concerns about human exposure, and several toxicological studies have been performed, although the studies focusing on nanomaterials’ effect on DNA methylation are still limited. The aim of this review is to investigate the possible impact of nanomaterials on DNA methylation. From the 70 studies found eligible for data analysis, the majority were in vitro, with about half using cell models related to the lungs. Among the in vivo studies, several animal models were used, but most were mice models. Only two studies were performed on human exposed populations. Global DNA methylation analyses was the most frequently applied approach. Although no trend towards hypo- or hyper-methylation could be observed, the importance of this epigenetic mechanism in the molecular response to nanomaterials is evident. Furthermore, methylation analysis of target genes and, particularly, the application of comprehensive DNA methylation analysis techniques, such as genome-wide sequencing, allowed identifying differentially methylated genes after nanomaterial exposure and affected molecular pathways, contributing to the understanding of their possible adverse health effects. publishersversion published

Because of their extreme heterogeneity at multiple scales, carbonate rocks present a great challenge for studying and managing oil reservoirs. Depositional processes and diagenetic alterations of carbonates may have produced very complex pore structures and, consequently, variable fluid storage and flow properties of hydrocarbon reservoirs. To understand the impact of mineralogy on the pore system, we analyzed four carbonate rock samples (coquinas) from the Morro do Chaves Formation in Brazil. For this study, we used thin sections and XRD for their mineralogical characterization, together with routine core analysis, NMR, MICP and microCT for the petrophysical characterizations. The samples revealed very similar porosity values but considerably different permeabilities. Samples with a relatively high quartz content (terrigenous material) generally had lower permeabilities, mostly caused by more mineral fragmentation. Samples with little or no quartz in turn exhibited high permeabilities due to less fragmentation and more diagenetic actions (e.g., dissolution of shells). Results confirm that carbonate minerals are very susceptible to diagenesis, leading to modifications in their pore body and pore throat sizes, and creating pores classified as moldic and vug pores, or even clogging them. For one of the samples, we acquired detailed pore skeleton information based on microCT images to obtain a more complete understanding of its structural characteristics.

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.

A straightforward approach is presented to prepare highly hydrophilic ultrafiltration polyaniline poly(2-acrylamido-2-methyl-1-propanesulfonic acid (PANI PAMPSA) membranes. Their application in the fractionation of phytosterols and proteins from fruit juice is described. Poly(2-acrylamido-2-methyl-1-propanesulfonic (PAMPSA) is added to aniline during the polymer synthesis and the membrane is prepared via phase inversion forming a highly hydrophilic and mechanically stable ultrafiltration membrane of 200 µm thickness and pure water flux of 126 LMH at 1 bar. The membrane so produced is benchmarked against a hydrophilic commercial regenerated cellulose acetate membrane (RCA) for the separation of phytosterols and proteins from orange juice. Cross-flow filtration experiments show comparable protein separation efficiency of the membranes, but better rejection of phytosterols for the commercial RCA membrane. Both commercial and lab prepared membranes are subject to fouling, with the PANI PAMPSA membrane showing higher irreversible fouling. Nevertheless, the PANI PAMPSA membrane showed a good cleaning efficiency of 74% after three fouling-cleaning cycles. Overall, this work has demonstrated the possibility of use PANI PAMPSA for ultrafiltration application and provided a better understanding of its fouling ability when compared to a commercial membrane in a multicomponent system.

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

Funding Information: This research was funded by the Portuguese National Funding Agency (FCT-MCTES), the Radiation Biology and Biophysics Doctoral Training Programme (RaBBiT, PD/00193/2012), the Applied Molecular Biosciences Unit—UCIBIO (UIDB/04378/2020), the CEFITEC Unit (UIDB/00068/2020), UIDB/04559/2020 (LIBPhys), and UIDP/04559/2020 (LIBPhys)), and the scholarships grant numbers PD/BD/142765/2018 and COVID/BD/152660/2022 to C.J.F.C. from the RaBBiT Doctoral Training Programme. Publisher Copyright: © 2023 by the authors. The development of a lipid nano-delivery system was attempted for three specific poly (ADP-ribose) polymerase 1 (PARP1) inhibitors: Veliparib, Rucaparib, and Niraparib. Simple lipid and dual lipid formulations with 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1′-glycerol) sodium salt (DPPG) and 1,2-dipalmitoyl-sn-glycero-3-phosphocoline (DPPC) were developed and tested following the thin-film method. DPPG-encapsulating inhibitors presented the best fit in terms of encapsulation efficiency (>40%, translates into concentrations as high as 100 µM), zeta potential values (below −30 mV), and population distribution (single population profile). The particle size of the main population of interest was ~130 nm in diameter. Kinetic release studies showed that DPPG-encapsulating PARP1 inhibitors present slower drug release rates than liposome control samples, and complex drug release mechanisms were identified. DPPG + Veliparib/Niraparib presented a combination of diffusion-controlled and non-Fickian diffusion, while anomalous and super case II transport was verified for DPPG + Rucaparib. Spectroscopic analysis revealed that PARP1 inhibitors interact with the DPPG lipid membrane, promoting membrane water displacement from hydration centers. A preferential membrane interaction with lipid carbonyl groups was observed through hydrogen bonding, where the inhibitors’ protonated amine groups may be the major players in the PARP1 inhibitor encapsulation mode. publishersversion published

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 Information: This work was financed by national funds from FCT—Fundação para a Ciência e a Tecnologia, I.P., in the scope of the All-FiBRE project with the reference PTDC/CTM-CTM/1571/2020, and the projects LA/P/0037/2020, UIDP/50025/2020 and UIDB/50025/2020 of the Associate Laboratory Institute of Nanostructures, Nanomodelling and Nanofabrication—i3N. This work was also supported by ERC-CoG-2014, CapTherPV, 647596. Publisher Copyright: © 2023 by the authors. Controlled drug release via electrical stimulation from drug-impregnated fibres was studied using electrospun cellulose acetate (CA) membranes and encapsulated ibuprofen (IBU). This research outlines the influence of polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT)-functionalised CA membranes and their suitability for dermal electronic-controlled drug release. Micro Raman analysis confirmed polymer functionalisation of CA membranes and drug incorporation. Scanning electron microscopy (SEM) images evidenced the presence of PPy and PEDOT coatings. The kinetic of drug release was analysed, and the passive and active release was compared. In the proposed systems, the drug release is controlled by very low electrical potentials. A potential of −0.3 V applied to membranes showed the ibuprofen retention, and a positive potential of +0.3 V, +0.5 V, or +0.8 V, depending on the conductive polymer and membrane configuration, enhanced the drug release. A small adhesive patch was constructed to validate this system for cutaneous application and verified an “ON/OFF” ibuprofen release pattern from membranes. publishersversion published

The focus of this research is to identify the best set of factors that influence the heat-reflux recovery of total phenolic content and antioxidant activities under multiple quality characteristics. Parametric Taguchi L9 orthogonal design and grey relational analysis technique were used to investigate the effect of three variables—reflux duration, particle size, and feed-to-solvent ratio on the multiple responses of total phenolic contents, DPPH, and H2O2 activities. According to the grey relational grades response table, the ideal number of criteria for the heat reflux results were 120 min of reflux duration, 0.2 mm of particle size, and a feed-solvent ratio of 1:16. The total phenolic content, DPPH, and H2O2 scavenging activities were measured as 35.23 ± 0.004 mgGAE/g d.w, 107.57 ± 0.04 g/mL, and 87.78 ± 0.32 g/mL, respectively. Moreover, with the Levenberg–Marquardt (LM) neural network architecture, the trained network has a mean square error (MSE) of 3.7646E−07 and an R2 of 0.9500 as the training function outcome, indicating a significant predicted endpoint. The confirmatory experimental results show a 41.9 per cent improvement in relation to the predicted values. The results of this study indicated that, optimising the heat reflux process would be an innovative and beneficial approach for preparing bioactive compounds from functional plants, resulting in cost savings while increasing antioxidant capacity and overall phenolic recovery.

Mutemi, A., Bação, F. (2023). The Discriminants of Long and Short Duration Failures in Fulfillment Sortation Equipment: A Machine Learning Approach. Journal of Engineering, 2023. https://doi.org/10.1155/2023/8557487 Due to the difficulties inherent in diagnostics and prognostics, maintaining machine health remains a substantial issue in industrial production. Current approaches rely substantially on human engagement, making them costly and unsustainable, especially in high-volume industrial complexes like fulfillment centers. The length of time that fulfillment center equipment failures last is particularly important because it affects operational costs dramatically. A machine learning approach for identifying long and short equipment failures is presented using historical equipment failure and fault data. Under a variety of hyperparameter configurations, we test and compare the outcomes of eight different machine learning classification algorithms, seven individual classifiers, and a stacked ensemble. The gradient boosting classifier (GBC) produces state-of-the-art results in this setting, with precision of 0.76, recall of 0.82, and false positive rate (FPR) of 0.002. This model has since been applied successfully to automate the detection of long- and short-term defects, which has improved equipment maintenance schedules and personnel allocation towards fulfillment operations. Since its launch, this system has contributed to saving over $500 million in fulfillment expenses. It has also resulted in a better understanding of the flaws that cause long-term failures, which is now being used to build more sophisticated failure prediction and risk-mitigation systems for fulfillment equipment. publishersversion published

Funding Information: The authors are grateful for the FEDER funds through the COMPETE 2020 Program and National Funds through 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 DENTALBLAST project (ref. n° 17956). Publisher Copyright: © 2023 by the authors. The use of orthopaedic and dental implants is expanding as a consequence of an ageing population and also due to illness or trauma in younger age groups. The implant must be biocompatible, bioactive and interact favourably with the recipient’s bone, as rapid osseointegration is key to success. In this work, Ti-6Al-4V plates were coated using the CoBlastTM technique, with hydroxyapatite (HAp) and HAp/BaTiO3 (barium titanate, BT) non-piezoelectric cubic nanopowders (HAp/cBT) and piezoelectric tetragonal micropowders (HAp/tBT). The addition of BT, a piezoelectric ceramic, is a strategy to accelerate osseointegration by using surface electric charges as cues for cells. For comparison with commercial coatings, plates were coated with HAp using the plasma spray technique. Using XRD and FTIR, both plasma spray and CoBlastTM coatings showed crystalline HAp and no presence of by-products. However, the XRD of the plasma-sprayed coatings revealed the presence of amorphous HAp. The average surface roughness was close to the coatings’ thickness (≈5 μm for CoBlastTM and ≈13 μm for plasma spray). Cytotoxicity assays proved that the coatings are biocompatible. Therefore, it can be concluded that for HAp-based coatings, CoBlastTM is a viable alternative to plasma spray, with the advantage of facilitating room temperature addition of other ceramics, like piezoelectric BaTiO3. publishersversion published

Funding Information: This work was financed by national funds from FCT-Fundação para a Ciência e a Tecnologia, I.P., within the scope of projects UI/BD/151292/2021 (Ph.D. research scholarship), LA/P/0037/2020, UIDP/50025/2020 and UIDB/50025/2020 of the Associate Laboratory Institute of Nanostructures, Nanomodelling, and Nanofabrication-i3N, but also the 2021.03825.CEECIND. Acknowledgments are also given to the EC project SYNERGY H2020-WIDESPREAD-2020-5, CSA, proposal nº 952169, EMERGE-2020-INFRAIA-2020-1, proposal nº 101008701, and to the European Community’s H2020 program under grant agreement No. 787410 (ERC-2018-AdG DIGISMART). Publisher Copyright: © 2023 by the authors. The preparation of visible-light-driven photocatalysts has become highly appealing for environmental remediation through simple, fast and green chemical methods. The current study reports the synthesis and characterization of graphitic carbon nitride/titanium dioxide (g-C3N4/TiO2) heterostructures through a fast (1 h) and simple microwave-assisted approach. Different g-C3N4 amounts mixed with TiO2 (15, 30 and 45 wt. %) were investigated for the photocatalytic degradation of a recalcitrant azo dye (methyl orange (MO)) under solar simulating light. X-ray diffraction (XRD) revealed the anatase TiO2 phase for the pure material and all heterostructures produced. Scanning electron microscopy (SEM) showed that by increasing the amount of g-C3N4 in the synthesis, large TiO2 aggregates composed of irregularly shaped particles were disintegrated and resulted in smaller ones, composing a film that covered the g-C3N4 nanosheets. Scanning transmission electron microscopy (STEM) analyses confirmed the existence of an effective interface between a g-C3N4 nanosheet and a TiO2 nanocrystal. X-ray photoelectron spectroscopy (XPS) evidenced no chemical alterations to both g-C3N4 and TiO2 at the heterostructure. The visible-light absorption shift was indicated by the red shift in the absorption onset through the ultraviolet-visible (UV-VIS) absorption spectra. The 30 wt. % of g-C3N4/TiO2 heterostructure showed the best photocatalytic performance, with a MO dye degradation of 85% in 4 h, corresponding to an enhanced efficiency of almost 2 and 10 times greater than that of pure TiO2 and g-C3N4 nanosheets, respectively. Superoxide radical species were found to be the most active radical species in the MO photodegradation process. The creation of a type-II heterostructure is highly suggested due to the negligible participation of hydroxyl radical species in the photodegradation process. The superior photocatalytic activity was attributed to the synergy of g-C3N4 and TiO2 materials. publishersversion published

Digital light processing (DLP) 3D printing is rapidly advancing and has emerged as a powerful additive manufacturing approach to fabricate analytical microdevices. DLP 3D-printing utilizes a digital micromirror device to direct the projected light and photopolymerize a liquid resin, in a layer-by-layer approach. Advances in vat and lift design, projector technology, and resin composition, allow accurate fabrication of microchannel structures as small as 18 × 20 µm. This review describes the latest advances in DLP 3D-printing technology with respect to instrument set-up and resin formulation and highlights key efforts to fabricate microdevices targeting emerging (bio-)analytical chemistry applications, including colorimetric assays, extraction, and separation.

Funding Information: This research was funded by FEDER funds through the COMPETE 2020 Program and National Funds through FCT—Portuguese Foundation for Science and Technology under the project LIS-BOA-01-0247-FEDER-039985/POCI-01-0247-FEDER-039985, LA/P/0037/2022, UIDP/50025/2020 and UIDB/50025/2020 of the Associate Laboratory Institute of Nanostructures, Nanomodelling and Nanofabrication—i3N, and CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020, financed by national funds through the FCT/MEC (PIDDAC). Publisher Copyright: © 2023 by the authors. Atmospheric plasma spray (APS) remains the only certified industrial process to produce hydroxyapatite (Hap) coatings on orthopaedic and dental implants intended for commercialization. Despite the established clinical success of Hap-coated implants, such as hip and knee arthroplasties, a concern is being raised regarding the failure and revision rates in younger patients, which are increasing rapidly worldwide. The lifetime risk of replacement for patients in the 50–60 age interval is about 35%, which is significantly higher than 5% for patients aged 70 or older. Improved implants targeted at younger patients are a necessity that experts have been alerted to. One approach is to enhance their bioactivity. For this purpose, the method with the most outstanding biological results is the electrical polarization of Hap, which remarkably accelerates implant osteointegration. There is, however, the technical challenge of charging the coatings. Although this is straightforward on bulk samples with planar faces, it is not easy on coatings, and there are several problems regarding the application of electrodes. To the best of our knowledge, this study demonstrates, for the first time, the electrical charging of APS Hap coatings using a non-contact, electrode-free method: corona charging. Bioactivity enhancement is observed, establishing the promising potential of corona charging in orthopedics and dental implantology. It is found that the coatings can store charge at the surface and bulk levels up to high surface potentials (>1000 V). The biological in vitro results show higher Ca2+ and P5+ intakes in charged coatings compared to non-charged coatings. Moreover, a higher osteoblastic cellular proliferation is promoted in the charged coatings, indicating the promising potential of corona-charged coatings when applied in orthopedics and dental implantology. publishersversion published

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.

Funding Information: The authors gratefully acknowledge the financial support given by Ministerio de Universidades de España (European Union – Next Generation EU) and CNPq (grant numbers 408282/2018-5 and 117290/2021-1). This study was also financed by Grant RTI2018-101341-B-C21 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”. Publisher Copyright: © 2023 The Author(s) In recent years, electrodialysis has been often considered as an appropriate method to treat industrial and/or municipal wastewater containing pharmaceutically active compounds. However, the scarcity of information on the ion transport mechanisms through the membranes, especially concerning occurrence of possible sorption phenomena, has limited the process implementation in practice. The present work aims to evaluate, by chronopotentiometry, the transport of sulfamethoxazole (SMX) through a cation- (CEM) and anion-exchange membrane (AEM) using synthetic solutions at different concentrations (0.001–0.1 g/L) and pH conditions (1.6 for CEM and 9 for AEM). The dominant mechanism of mass transfer under overlimiting current conditions at each membrane/solution system was determined. The potential drop profile measured during and after application of current pulses, as well as the transition times obtained from the curves, showed that sorption occurs at/in both membranes, especially for the AEM. Besides, this phenomenon was reversible for the CEM and irreversible for the AEM under the conditions evaluated herein. The chronopotentiograms of the AEM showed that the intense occurrence of water dissociation with the most diluted solution caused chemical equilibrium shifts in the membrane/electrolyte system, leading to formation of neutral SMX species that can impair the electrodialysis performance. The results obtained are useful for optimizing the electrodialytic treatment of SMX-containing solutions as well as of other compounds with similar physicochemical properties. publishersversion published

International audience; The Safe-by-Design (SbD) concept aims to facilitate the development of safer materials/products, safer production, and safer use and end-of-life by performing timely SbD interventions to reduce hazard, exposure, or both. Early hazard screening is a crucial first step in this process. In this review, for the first time, commonly used in vitro assays are evaluated for their suitability for SbD hazard testing of nanomaterials (NMs). The goal of SbD hazard testing is identifying hazard warnings in the early stages of innovation. For this purpose, assays should be simple, cost-effective, predictive, robust, and compatible. For several toxicological endpoints, there are indications that commonly used in vitro assays are able to predict hazard warnings. In addition to the evaluation of assays, this review provides insights into the effects of the choice of cell type, exposure and dispersion protocol, and the (in)accurate determination of dose delivered to cells on predictivity. Furthermore, compatibility of assays with challenging advanced materials and NMs released from nano-enabled products (NEPs) during the lifecycle is assessed, as these aspects are crucial for SbD hazard testing. To conclude, hazard screening of NMs is complex and joint efforts between innovators, scientists, and regulators are needed to further improve SbD hazard testing.

Currently, excessive CO2 emissions have become a global challenge due to their influence on the climate. According to the Paris Agreement, global warming should be limited to 1.5 °C by 2100. Carbon capture and utilisation (CCU) are attractive as they can both reduce CO2 content and utilise CO2 as a carbon resource. However, in conventional CCU processes, CO2 needs first to be extracted and purified for the following utilisation. In contrast, the recently reported Integrated Carbon Capture and Utilisation (ICCU) was designed to realise the overall process in one reactor, where CO2 is captured by adsorbents (e.g., CaO) and utilised in-situ with the introduction of a reducing agent (e.g., H2). This ICCU technology can promote CO2 conversion with fewer intermediate steps, leading to a reduction in overall cost. Energy and economic analysis of ICCU are thus urgently required. According to several recent research, the operational cost of ICCU has been reported to be cheaper than that of CCU. However, a comprehensive view of ICCU is still expected due to further application. This paper focuses on comparing ICCU and conventional CCU processes based on Aspen simulations covering mass balance (i.e., CaCO3 consumption, purge production, annual CO production), energy balance, the total annual cost and the CO cost, etc. Analysis shows that the ICCU process can produce more CO (1.20 Mt year−1), less purge (0.21 Mt year−1), and less consumption of CaCO3 (0.62 Mt year−1) with higher energy efficiency (37.1 %) than the CCU process. The results also show that the total annual cost of ICCU is $867.07 million, corresponding to a total cost of CO of $720.25 per tonne. In contrast, CCU has higher costs, with a total annual cost of $1027.61 million and a total cost of CO of $1004.53 per tonne. The Cost of CO2 Avoided of ICCU (317.11$/ton) is much lower than that CCU (1230.27 $/ton). Therefore, ICCU was confirmed as a better choice for further industrial applications. In addition, H2 is shown to have a significant influence on economic performance, which remains a challenge for further application.

Funding Information: This work was also financed by national funds from FCT/MCETS (Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) in the scope of the projects LA/P/0037/2020, Nanomodelling and Nanofabrication, i3N, LA/P/0006/2020, CICECO-Aveiro Institute of Materials. Publisher Copyright: © 2023 by the authors. The present contribution aims to enhance solar cells’ performance via the development of advanced luminescent down-shifting based on encapsulated nanostructured perovskite materials. Here, thin films of inorganic lead halide (CsPbBr3) perovskite nanocrystal luminophores were synthetized, by hot-injection, deposited on glass substrates by spin-coating, and encapsulated with parylene type C, via chemical vapor deposition, to protect and stabilize the films. The optical properties of these thin films were characterized by absorption, emission and 2D contour spectra, their structure by X-ray diffraction and X-ray photoelectron spectroscopy, and the morphology by Scanning Transmission Electron microscopy. I–V curve and spectral response nanocrystalline silicon photovoltaic (nc-Si:H PV) cells were studied in the absence and presence of the perovskite and parylene luminescent down-shifting layers. The incorporation of the CsPbBr3 nanocrystals and their encapsulation with the parylene type C polymeric coating led to an increase in the current generated and the spectral response of the PV cells in the regime of the nanocrystals’ fluorescence emission. A 3.1% increase in the short circuit current density and a 5.6% increase in the power conversion efficiency were observed. publishersversion published

Funding Information: S.T., B.M., and J.C. contributed equally to this work. The authors are grateful for funding received from the Australian Research Council Centre of Excellence program (Project Number CE 140100012). J.C. acknowledges the European Research Council Starting Grant (ERC‐StG‐2019‐848325). S.N. and F.D. acknowledge the financial support of Australian Research Council through DP200102164. Publisher Copyright: © 2023 The Authors. Advanced Science published by Wiley-VCH GmbH. The deployment of structures that enable localized release of bioactive molecules can result in more efficacious treatment of disease and better integration of implantable bionic devices. The strategic design of a biopolymeric coating can be used to engineer the optimal release profile depending on the task at hand. As illustrative examples, here advances in delivery of drugs from bone, brain, ocular, and cardiovascular implants are reviewed. These areas are focused to highlight that both hard and soft tissue implants can benefit from controlled localized delivery. The composition of biopolymers used to achieve appropriate delivery to the selected tissue types, and their corresponding outcomes are brought to the fore. To conclude, key factors in designing drug-loaded biopolymeric coatings for biomedical implants are highlighted. publishersversion epub_ahead_of_print

Microfibrillated cellulose (MFC) is obtained by high-shear treatment of cellulose. MFC is suitable for use as clean-label, low-calorie thickener in semi-solid foods such as mayonnaises due to its high water holding capacity. The aim of this study was to determine the effect of type and concentration of thickener on rheological, tribological and sensory properties of low-fat mayonnaises. Low-fat mayonnaises were prepared with four types of thickeners (MFC, chemically modified starch, native waxy corn starch, xanthan gum) at three concentrations. Higher biopolymer concentrations resulted in increased shear viscosities, G′ and G″, yield stress and enhanced lubrication (i.e. lower friction coefficients). Mayonnaises with modified starch and xanthan gum generally had higher shear viscosity and yield stress compared to mayonnaises with comparable concentrations of MFC and waxy corn starch. MFC-thickened mayonnaises had highest G’, G” and boundary friction coefficients. Sensory properties of mayonnaises were determined using the Rate-All-That-Apply (RATA) method (n = 80). Addition of xanthan gum induced high sliminess and pulpiness, and low melting, creaminess and smoothness. Sensory properties of mayonnaises with MFC were generally similar to those with modified and waxy corn starch, despite differences in appearance (increased yellowness and slightly lower glossiness). Multiple Factor Analysis revealed that more shear-thinning mayonnaises were perceived as slimy. Boundary friction was negatively correlated with stickiness, while friction at the start of the hydrodynamic regime was positively correlated with melting sensations. We conclude that microfibrillated cellulose can be used as a thickener in low-fat mayonnaise as an alternative to commercially used chemically modified starch without considerably affecting its sensory texture properties.

Funding Information: The study was performed in the scope of the H2020/MSCA/RISE/SSHARE number 871284 project, RO-JINR project No. 366/2021 item tion81, RO-JINR grant No. 367/2021 item 27, Poland-JINR cooperation Projects PPPB/168-26/1128/2021, PPPB/120-25/1128/2022, PPPB/120-26/1128/2022, Serbia—JINR cooperation Projects No. 178 2021 items 7 and 8, Vietnam—the International Center of Physics at the Institute of Physics Grant ICP.2022.04. Publisher Copyright: © 2022 by the authors. The paper considers the new effects of the nanoscale state of matter, which open up prospects for the development of electronic devices using new physical principles. The contacts of chemically homogeneous nanoparticles of yttrium-stabilized zirconium oxide (ZrO2—x mol% Y2O3, x = 0, 3, 4, 8; YSZ) with different sizes of 7.5 nm and 9 nm; 7.5 nm and 11 nm; and 7.5 nm and 14 nm, respectively, was studied on direct current using nanostructured objects in the form of compacts obtained by high-hydrostatic pressure (HP-compacts of 300MPa). A unique size effect of the nonlinear (rectifying-type contact) dependence of the electrical properties (in the region U < 2.5 V, I ≤ 2.7 mA) of the contact of different-sized YSZ nanoparticles of the same chemical composition is revealed, which indicates the possibility of creating semiconductor structures of a new type (homogeneous electronics). The electronic structure of the near-surface regions of nanoparticles of studied oxide materials and the possibility of obtaining specifically rectifying properties of the contacts were studied theoretically. Models of surface states of the Tamm-type are constructed considering the Coulomb long-range action. The discovered energy variance and its dependence on the curvature of the surface of nanoparticles made it possible to study the conditions for the formation of a contact potential difference in cases of nanoparticles of the same radius (synergistic effect), different radii (doped and undoped variants), as well as to discover the possibility of describing a group of powder particles within the Anderson model. The determined effect makes it possible to solve the problem of diffusion instability of semiconductor heterojunctions and opens up prospects for creating electronic devices with a fundamentally new level of properties for use in various fields of the economy and breakthrough critical technologies. publishersversion published

The authors extend their appreciation to the FEDER funds through the COMPETE 2020 Program and National Funds through FCT—Portuguese Foundation for Science and Technology under the project LISBOA-01-0247-FEDER-039985/POCI-01-0247-FEDER-039985, and Associate Laboratory i4HB (LA/P/0140/2020). Publisher Copyright: © 2022 by the authors. The main reason for the increased use of dental implants in clinical practice is associated with aesthetic parameters. Implants are also presented as the only technique that conserves and stimulates natural bone. However, there are several problems associated with infections, such as peri-implantitis. This disease reveals a progressive inflammatory action that affects the hard and soft tissues surrounding the implant, leading to implant loss. To prevent the onset of this disease, coating the implant with bioactive glasses has been suggested. In addition to its intrinsic function of promoting bone regeneration, it is also possible to insert therapeutic ions, such as cerium. Cerium has several advantages when the aim is to improve osseointegration and prevent infectious problems with dental implant placement. It promotes increased growth and the differentiation of osteoblasts, improves the mechanical properties of bone, and prevents bacterial adhesion and proliferation that may occur on the implant surface. This antibacterial effect is due to its ability to disrupt the cell wall and membrane of bacteria, thus interfering with vital metabolic functions such as respiration. In addition, its antioxidant effect reverses oxidative stress after implantation in bone. In this work, Bioglass 45S5 with CeO2 with different percentages (0.25, 0.5, 1, and 2 mol%) was developed by the melt-quenching method. The materials were analyzed in terms of morphological, structural, and biological (cytotoxicity, bioactivity, and antibacterial activity) properties. The addition of cerium did not promote structural changes to the bioactive glass, which shows no cytotoxicity for the Saos-2 cell line up to 25 mg/mL of extract concentration for all cerium contents. For the maximum cerium concentration (2 mol%) the bioactive glass shows an evident inhibitory effect for Escherichia coli and Streptococcus mutans bacteria. Furthermore, all samples showed the beginning of the deposition of a CaP-rich layer on the surface of the material after 24 h. publishersversion published

Associate Laboratory for Green Chemistry- LAQV co-financed by the ERDF under the PT2020 Partnership Agreement ( POCI-01-0145-FEDER-007265 ). Publisher Copyright: © 2022 The Author(s) Heritage materials are highly complex systems of unknown and intrinsically heterogeneous compositions and unmonitored long-term modifications. In this microreview, we describe our interdisciplinary approach, its importance to new treatments tailored to prevent changes to historical colours, and innovative strategies for their identification in artworks. We illustrate our methodology through the study of medieval Islamic manuscripts from the Fondo Ka'ti. These advanced studies have shown the remarkable properties of ancient dyes, their resilience and durability, properties designed by our ancestors through sustainable materials processing. This lost knowledge can be shared with the community empowering them to create new sustainable applications, from unique art pieces to regional value-added products. publishersversion published

Spruce is the most resistant type of lignocellulosic material to anaerobic digestion. Different parts of spruce tree, i.e., leaves, wood, branches, bark, fruit, and mixtures of these parts, were pretreated using the leading pretreatments, i.e., concentrated phosphoric acid, dilute sulfuric acid, and ethanolic organosolv pretreatment, to improve biogas production. The pretreatment effects on methane yield from both solid and liquid fractions of the pretreatments were evaluated. Different parts of the tree showed different behaviors. The maximum methane yields from the pretreated solids were obtained after phosphoric acid pretreatment, which yielded methane yields of 211.7 and 225.5 mL per g volatile solids (VS) of pretreated spruce leaves and mixture, respectively. The improvements were related to opened-up structure, crystallinity reduction, and delignification. Sulfuric acid pretreatment improved biomethane yield from liquids, but not solids. Moreover, organosolv pretreatment improved the yield from solids, but not wood, bark, and the mixture. The maximum methane production yield was 245.3 NmL CH4/gVS which was obtained from the organosolv liquor of spruce leaves. The highest overall methane production (252.9 L per Kg) was gained from the whole solid and liquid fractions from organosolv pretreatment of leaves. This methane yield corresponded to 2.4-fold improvement compared to that of the untreated leaves (107 NmL CH4/gVS). Thus, leaves and branches are less recalcitrant parts and do not need severe pretreatment, while bark and wood are the most recalcitrant parts and required severe pretreatment like concentrated phosphoric acid. Moreover, the mixture of all parts also required severe pretreatment for efficient biogas production.

Chondroitin sulfate (CS) and hyaluronic acid (HA) methacrylate (MA) hydrogels are under investigation for biomedical applications. Here, the hydrolytic (in)stability of the MA esters in these polysaccharides and hydrogels is investigated. Hydrogels made with glycidyl methacrylate-derivatized CS (CSGMA) or methacrylic anhydride (CSMA) degraded after 2-25 days in a cross-linking density-dependent manner (pH 7.4, 37 °C). HA methacrylate (HAMA) hydrogels were stable over 50 days under the same conditions. CS(G)MA hydrogel degradation rates increased with pH, due to hydroxide-driven ester hydrolysis. Desulfated chondroitin MA hydrogels also degrade, indicating that sulfate groups are not responsible for CS(G)MA's hydrolytic sensitivity (pH 7.0-8.0, 37 °C). This sensitivity is likely because CS(G)MA's N-acetyl-galactosamines do not form hydrogen bonds with adjacent glucuronic acid oxygens, whereas HAMA's N-acetyl-glucosamines do. This bond absence allows CS(G)MA higher chain flexibility and hydration and could increase ester hydrolysis sensitivity in CS(G)MA networks. This report helps in biodegradable hydrogel development based on endogenous polysaccharides for clinical applications.

Green pathways for nonisocyanate polyurethane (NIPU) production have attracted increasing levels of interest. The reaction between 5-membered cyclic carbonate and polyamines is one of the most promising pathways to produce NIPU polymers. Though promising, major technical hurdles such as slow polymerization rate and poor performance hinder the commercialization of NIPU. In this paper, we screened several commercially available triglyceride oil feedstocks for NIPU products, focusing on polymerization kinetics and product performance for industrial application. The impact of carbonated group density on polymerization rate and mechanical strength was determined. We have demonstrated a remarkably higher reactivity of carbonated oil derived from feedstocks with polyunsaturated fatty acid (PUFA). The NIPU derived from such feedstocks also showed improved performance for industrial application. Unlike traditional polyurethane foam production that uses isocyanate and water to generate CO2 as a blowing reagent, there is no gas formation in NIPU polymerization. We have demonstrated a practical and cost-effective approach to produce NIPU foam material using bicarbonate as a blowing reagent. Furthermore, we conducted the first-ever technoeconomic analysis (TEA), revealing that profitable commercial NIPU production can be achieved when operating at sufficient production capacities.

On the cusp of a miniaturized device era, a number of promising methods have been developed to attain large-scale assemblies of micro- and nanoparticles. In this study, a novel method is proposed to firmly capture dispersed microparticles of nominal sizes of 10 μm on a two-dimensional array (1.0 × 1.0 mm2) of through-pores on a surface. This is obtained by dispensing a droplet of the particle dispersion on the pores, which drains by applying a vacuum-driven force at the backside of the pores. The assembled particles are captured on the surface in a reversible way, making them available for direct manipulation and inspection, or subsequent transfer of the particles to a second surface. The relevant process parameters dispersant concentration, dispersant type, particle properties, and pitch distance d, are optimized to obtain (near-)perfect ordered particle arrays. Furthermore, to significantly improve the quality of the particle assembly, washing steps are added to remove excess particles from the surface. Silica or polystyrene (PS) particle assemblies with an error ratio (ER) as low as 0.2% are obtained, demonstrating the universality of the proposed method. For the smallest pitch, d = 1.25 μm, even with optimal process parameters, higher ER-values (=1.1%) are obtained.

The evaluation of various types of data and the understanding of their properties is the backbone of scientific work. Time series data are abundant in the investigation of manufacturing processes. Since they result from measurements of parameters over time, time series have distinctive statistical characteristics. Focused on bulk solid dosing, the authors illustrate the potential for misinterpretations if these characteristics are ignored in data evaluation. The sums of amplitudes analysis (SAA) is developed, based on discrete Fourier transformations as a novel non-parametric statistical method for description of time series. Subsequently, the authors use the SAA to investigate bulk solid dosing data. In this process, artifications of data of external catch scales, commonly used for the evaluation of bulk solid dosing, are found, and discussed.

The use of microwave heating for the thermal regeneration of a porous carbon adsorbent in adsorptive carbon capture was evaluated. In this Microwave Swing Adsorption (MSA) process, a multimode microwave oven has been used to accelerate the desorption of CO2 after the adsorption of a CO2 / N2 (15/85 v/v) mixture. Starting from a commercial activated carbon (AC) material (MSP-20X), sorbent extrudates were prepared and loaded in a Teflon column. The heating of the sorbent bed inside the microwave (MW) cavity was characterised at different locations. Although the adsorption bed is not heated uniformly due to hot spots in the multimode MW cavity, flowing a purge gas reduces the non-uniform heating during the regeneration step. This study also reports that MSA regeneration achieves extremely fast total desorption (in 56 to 79 s), the quickest regeneration reported up to date in MSA, and very rapid desorption rates allowing swift adsorption–desorption cycles. This fast desorption is associated with the extremely high heating rates achieved (100 to 400 °C/min). We show that the desorption rate is faster when using higher powers at practically identical MW energy inputs. Complete CO2 desorption can be achieved at slightly longer durations when using 2-step MW heating. When comparing the MSA results with a reference TSA process, MSA outperforms TSA, due to the higher heating rates achieved by MSA. During eleven adsorption–desorption cycles, it is evidenced that the MSA process can regenerate the adsorption bed at a high reproducibility. The microporosity of the material remained intact during the MSA, revealing that localised heating and the high heating rates are not damaging the sorbent material.

Funding Information: The authors acknowledge the financial support of EU-Horizon 2020 (Symbiotic, FET-Open, GA665046), and from 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, UIDB/50025/2020 and UID/EMS/00532/2019. Nádia Ferreira (SFRH/BD/122955/2016), Liliana Carneiro (SFRH/BD/122954/2016), and Ana Carolina Marques (SFRH/BD/115173/2016) acknowledge Fundação para a Ciência e Tecnologia (FCT) for financial support. Publisher Copyright: © 2022 The Author(s) This work describes an innovative electrochemical biosensor that advances its autonomy toward an equipment-free design. The biosensor is powered by a passive direct methanol fuel cell (DMFC) and signals the response via an electrochromic display. Briefly, the anode side of the DMFC power source was modified with a biosensor layer developed using molecularly imprinted polymer (MIP) technology to detect sarcosine (an amino acid derivative that is a potential cancer biomarker). The biosensor layer was anchored on the surface of the anode carbon electrode (carbon black with Pt/Ru, 40:20). This was done by bulk radical polymerization with acrylamide, bis-acrylamide, and vinyl phosphonic acid. This layer selectively interacted with sarcosine when integrated into the passive DMFC (single or multiple, in a stack of 4), which acted as a transducer element in a concentration-dependent process. Serial assembly of a stack of hybrid DMFC/biosensor devices triggered an external electrochromic cell (EC) that produced a colour change. Calibrations showed a concentration-dependent sarcosine response from 3.2 to 2000 µM, which is compatible with the concentration of sarcosine in the blood of prostate cancer patients. The final DMFC/biosensor-EC platform showed a colour change perceptible to the naked eye in the presence of increasing sarcosine concentrations. This colour change was controlled by the DMFC operation, making this approach a self-controlled and self-signalling device. Overall, this approach is a proof-of-concept for a fully autonomous biosensor powered by a chemical fuel. This simple and low-cost approach offers the potential to be deployed anywhere and is particularly suitable for point-of-care (POC) analysis. publishersversion published

Advanced science 9(27), 2201169 (2023). doi:10.1002/advs.202201169, Published by Wiley-VCH, Weinheim

Funding Information: This work was supported by Conselho Nacional de Desenvolvimento Científico e Tecnológico (BR) - CNPq [PQ-2/2018: 313831/2018-1], Fundação Carlos Chagas de Amparo à Pesquisa do Estado do Rio de Janeiro - FAPERJ [JCNE 2018: E-26/203.023/2018; Apoio às Universidades Estaduais: E-26/010.101141/2018; Projetos Temáticos: SEI-260003/001198/2020; PD10 2020: E-26/290.125/2020 post-doctoral Scholarship], and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) [Finance Code 001]. The authors would like to acknowledge NANOFAB/UERJ for the SEM measurements, LCM/CAIPE-UFF for the Raman analyses, G2E-UFF for the RDE electrode, LACES-UFRJ for the thermogravimetric analysis, Multiuser Laboratory of Pontal at the Federal University of Uberlândia for the ASAP analyses (FINEP/2013 INFR13 01.13.0371.00), and LCS/LNNano-CNPEM for the use of AFM in its open facilities. Funding Information: This work was supported by Conselho Nacional de Desenvolvimento Científico e Tecnológico (BR) – CNPq [PQ-2/2018: 313831/2018-1], Fundação Carlos Chagas de Amparo à Pesquisa do Estado do Rio de Janeiro – FAPERJ [JCNE 2018: E-26/203.023/2018; Apoio às Universidades Estaduais: E-26/010.101141/2018; Projetos Temáticos: SEI-260003/001198/2020; PD10 2020: E-26/290.125/2020 post-doctoral Scholarship], and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) [Finance Code 001]. The authors would like to acknowledge NANOFAB/UERJ for the SEM measurements, LCM/CAIPE-UFF for the Raman analyses, G2E-UFF for the RDE electrode, LACES-UFRJ for the thermogravimetric analysis, Multiuser Laboratory of Pontal at the Federal University of Uberlândia for the ASAP analyses (FINEP/2013 INFR13 01.13.0371.00), and LCS/LNNano-CNPEM for the use of AFM in its open facilities. Publisher Copyright: © 2022 The Royal Society of Chemistry. This work reports the application of Mn-doped Co3O4 oxides in the electrocatalytic oxygen evolution reaction (OER). The materials were characterized by structural, morphological, and electrochemical techniques. The oxides with higher Co : Mn molar ratio presented a lower electron transfer resistance, and consequently the most promising OER activities. Pure Co3O4 shows an overpotential at j = 10 mA cm−2 of 761, 490, and 240 mV, at pH 1, 7, and 14, respectively, and a high TOF of 1.01 × 10−1 s−1 at pH 14. Tafel slopes around 120 mV dec−1 at acidic pH and around 60 mV dec−1 at alkaline pH indicate different OER mechanisms. High stability for Co3O4 was achieved for up to 15 h in all pHs, and no change in the structure and morphology after the electrocatalysis was observed. The reported excellent OER activity of the Mn-Co oxides in a wide pH range is important to broaden the practical applicability in different electrolyte solutions. publishersversion published

As part of the global transformation to a circular economy, modern society faces the challenge of developing sustainable building materials that do not deplete nonrenewable resources or generate environmentally destructive waste. Bio-composites based on fungal mycelium grown on agricultural waste streams have the potential to serve this purpose, reducing the ecological impact of the construction industry and the conventional materials on which it currently relies. In addition to the possible advantages in the production and postuse phases of their life cycle, mycelium bio-composites are lightweight and highly insulating, thus providing valuable thermal properties for reducing energy consumption and emissions over the operational lifespan of the building. In this study, a comprehensive life cycle assessment of mycelium bio-composites was conducted, focusing on the embodied energy (EE) and embodied carbon (EC). Part of the CO2that is emitted is the result of the fungal growth. Therefore, a novel calculation method was developed to assess the metabolic carbon emissions as a function of weight loss during the growth period. Using a cradle-to-gate model of the production process, the EE of the mycelium bio-composite was estimated to be 860 MJ m-3, which represents a 1.5- to 6-fold reduction compared with that of the common construction materials. The EC was calculated to be -39.5 kg CO2eq m-3, its negative value indicating that the fungal bio-composite effectively functions as a CO2sink, in contrast to currently used construction materials that have a positive EC. The incubation stage of mycelium bio-composite production made up the largest portion (73%) of the overall energy, while metabolic CO2comprised a significant proportion (21%) of the overall emissions as well. Altogether, our results demonstrate that using bio-composite building materials based on fungal mycelium and local plant residues can provide a sustainable alternative to current practice.

Numerous mechanisms have been proposed to untangle the effect of a low concentration of dissolved salts in the water flooding medium. One potential mechanism for enhanced oil movement is proposed with osmosis effect, however, the process of water transport through the oil phase, due to a salinity contrast, is not fully understood. In our study, we used three aqueous solutions and two alkanes in a series of microfluidic experiments with hydrophobically coated glass micro-chips for mimicking the low-salinity waterflooding process in an oil-wet rock formation. We created multiple systems of low-salinity water-alkane/high-salinity water in the porous micromodel, and afterward, continuously monitored the domain for 70 hours. We noted that ionic strength and the hydrocarbon chain length both played important roles in water diffusion. A salinity contrast of 1.7 g/L-170 g/L caused a higher water volumetric flux than 50 g/L-170 g/L for both alkanes. The difference in water volumetric fluxes for those two contrasts were not proportional to the salinity contrast during the experimental period. There was no simple relationship between the chain length of hydrocarbon and water volumetric flux. Moreover, to investigate the effect of salinity on water behavior in heptane, we conducted molecular dynamic (MD) simulations by considering three different concentrations in the high-salinity water region featuring our experiments. The results indicated that high salinity limited the water diffusion from high-salinity phase into the oil phase and reduced the possibility of water entering the heptane phase. Therefore, the net flux of water from the pure water side to the salty waterside was enhanced. A quantitative study of salinity effect on water diffusion in n-alkane phases: from pore-scale experiments to molecular dynamic simulation

New facile and controllable approaches to fabricating metal chalcogenide thin films with adjustable properties can significantly expand the scope of these materials in numerous optoelectronic and photovoltaic devices. Most traditional and especially wet-chemical synthetic pathways suffer from a sluggish ability to regulate the composition and have difficulty achieving the high-quality structural properties of the sought-after metal chalcogenides, especially at large 2D length scales. In this effort, and for the first time, we illustrated the fast and complete inversion of continuous SnSe thin-films to Sb2Se3 using a scalable top-down ion-exchange approach. Processing in dense solution systems yielded the formation of Sb2Se3 films with favorable structural characteristics, while oxide phases, which are typically present in most Sb2Se3 films regardless of the synthetic protocols used, were eliminated. Density functional theory (DFT) calculations performed on intermediate phases show strong relaxations of the atomic lattice due to the presence of substitutional and vacancy defects, which likely enhances the mobility of cationic species during cation exchange. Our concept can be applied to customize the properties of other metal chalcogenides or manufacture layered structures.

Understanding electrochemical sub-processes occurring at solid oxide cells (SOCs) components, mainly air electrodes, is of high importance since they play a key role in improving the performance of SOC devices and their durability. Among various performance analysis methods, electrochemical impedance spectroscopy (EIS) is the most used one in studies. However, analyzing and interpreting EIS data have always been considered as a challenge given the fact that the information provided by the common approach of complex non-linear least square (CNLS) method is limited. Viewed in this sight, the distribution of relaxation time (DRT) approach has gained considerable attention in recent years as a potential approach to analyze EIS measurement results. This study aims at reviewing recent publications that used the DRT method to deconvolute the EIS data and at pathing the way to use DRT methodology and incorporate its results. Studies are focused on six categories of commonly used air electrodes, namely LSCF-based, LSM-based, lanthanide nickelates-based, BSCF-based, and double perovskite-based electrodes, and less-common-used ones.