Abstract: The transition of the chemical industry towards the utilization of feedstocks based on renewable energies results in a more dynamic process behavior. Advanced mathematical methods are a key factor to handle this complexity. In this contribution, methanol synthesis from hydrogen, carbon dioxide and carbon monoxide is investigated as promising power-2-X technology. Optimal experimental design is used to recalibrate an existing mechanistic kinetic model. Subsequently, the most uncertain sub-model, namely the reversible catalyst dynamics, is partially replaced by neural networks. Several architectures were evaluated, and optimal experimental design was applied to enhance the performance of a chosen architecture. All experiments were realized in an experimental setup able to acquire time-resolved data. A commercial CuO/ZnO/Al₂O₃ catalyst was used in a well-mixed Berty type reactor. The combination of optimal experimental design with hybrid modeling led to an improved quality of the kinetic model needed for process control and optimization.

Abstract: Supercapacitors (SCs) have attracted much attention due to their high-power density and long cycle life, where carbon materials have become the focus of electrode material research due to their excellent conductivity, stability, and reproducibility. However, the low specific capacitance and specific surface area of carbon materials lead to poor electrochemical properties, which seriously hinder their practical applications. The work here presents a simple but effective strategy to construct hollow nanocage structures by tannic acid etching ZIF-8. In this process, tannic acid releases protons to etch the MOF structure, and the remaining relatively large molecules are attached to the surface of ZIF-8 to prevent its structure from collapsing, and after high-temperature heat treatment, novel hollow nitrogen-doped carbon nanocage structures (HNCs) are obtained. Electrochemical tests show that the material has a capacity of 349.3 F g-1 at a current density of 0.5 A g-1, and still has a coulombic efficiency of 97.61% as well as a capacity retention of 97.86% after cycling for 10, 000 cycles at a current density of 3 A g-1. Therefore, this study provides a novel idea to explore the application of carbon materials with excellent electrochemical performance for energy storage.

Abstract: Uniformity in material coating is not only essential for ensuring durability and long-term reliability but also for reducing costs, optimizing resources, and maintaining high-quality standards in industrial applications. Zinc phosphate is notable for coating steel surfaces due to its excellent corrosion resistance and adhesion properties in various industries. This study investigates the optimal flow rate of a diaphragm pump for achieving effective and uniform coating of a steel cylinder. The coating uniformity was assessed using Scanning Electron Microscopy (SEM), focusing on layer thickness and elemental composition. A range of flow rates was analyzed to determine their influence on coating quality and regularity, with Energy Dispersive Spectroscopy (EDS) revealing the distribution and homogeneity of the applied layer. The results identified a flow rate of 30 L/min as optimal, as it minimized surface defects and ensured consistent thickness across the cylinder. This study provides valuable insights for optimizing industrial coating processes, contributing to improved efficiency and reduced resource waste.

Abstract: This paper presents the results of a study of the effect of a biochar additive produced by pyrolysis at 400^oC and 500^oC from waste biomass, i.e. walnut shells, on the tribological and rheological properties of vegetable lubricating compositions. Sunflower oil, and amorphous silica as a thickener were used to prepare the lubricants. To the base lubricant prepared in this way, 1 and 5 % of biochar additive was introduced and, for comparison, take the same amounts of graphite. Tests were carried out on the anti-wear properties, coefficient of friction and changes in dynamic viscosity during the tribological test, as well as on the anti-scuffing properties for the tested lubricant compositions. The effect of the applied modifying additive on the lubricating and rheological properties of the prepared lubricating greases was evaluated. On the basis of the study of vegetable greases, it was found that the addition of 5% biochar from walnuts shell produced during pyrolysis in 500^oC had the most favourable effect on the anti-wear properties of the tested greases, while the 5% of biochar from walnuts shell prepared in pyrolysis in 400^oC had the best antiscuffing protection. The use of the biochar additive in vegetable greases resulted in a reduction in the dynamic viscosity of the tested greases, particularly for greases modified with 5% of walnut shell biochar produced at 500^oC, which is particularly important during the work of steel friction nodes and in central lubrication systems.

Abstract: The pine cone is an important forest product for the Portuguese economy. However, it is associated with environmental impacts, such as the generation of waste and the increased risk of forest fires. The objective of this research is to valorise waste from the production of Pinus pinaster Aiton in the form of natural dyes. The pine cone extracts were characterised in different alkaline solutions (1%, 5% and 10% NaOH) in order to evaluate the dyeing process on cotton knitwear, using the CIELab coordinates. The dyed samples were also subjected to light and water fastness tests. The extracts showed an increase in solids content with increasing alkalinity and a reduction in antioxidant content. The phenol content increased in the extract with 5% but decreased with the 10% concentration. All the dyes expressed a pink colour, but with different shades. About the L* coordinate (luminosity), the colours became lighter as the NaOH increased. n the a* coordinate, all the samples had a reddish colour and, in the b* coordinate, all the samples had a yellowish colour. About light and water fastness, all the samples lost colour, but in the water test it was not noticeable.

Abstract: Multifunctional self-healing supramolecular structural toughened resins, formulated to counteract the insulating properties of epoxy polymers and integrating auto-repair mechanisms, are morphologically and spectroscopically characterized using Tunneling Atomic Force Microscopy (TUNA) and Fourier-transform infrared spectroscopy (FT-IR), respectively. Specifically, the multifunctional resin comprises self-healing molecular fillers and electrically conductive carbon nanotubes (CNTs) embedded in the matrix. The selected self-healing molecules can form non-covalent bonds with the hydroxyl (OH) and carbonyl (C=O) groups of the toughened epoxy matrix through their H-bonding donor and acceptor sites. FT-IR analysis has been conducted to evaluate the interactions that the barbiturate acid derivatives, serving as self-healing fillers, can form with the constituent parts of the toughened epoxy blend. Tunneling Atomic Force Microscopy (TUNA) highlights the morphological characteristics of CNTs, their dispersion within the polymeric matrix, and their affinity for the globular rubber domains. The TUNA technique maps the samples' electrical conductivity at micro and nanoscale spatial domains. Detecting electrical currents reveals supramolecular networks, determined by hydrogen bonds, within the samples, showcasing the morphological features of the sample containing an embedded conductive nanofiller in the hosting matrix.

Abstract: A series of p-substituted pyridinium catalysts were investigated as sustainable organic catalysts for carbon dioxide utilization under ambient conditions. Dimethylaminopyridine hydroiodide (DMAP·HI) was found to be a superior catalyst for cyclic carbonate synthesis from epoxide and CO2 without solvents or additives. Mechanistic studies indicated that DMAP played a pivotal role as a nucleophile toward carbon dioxide during the cyclic carbonate formation. The organic catalyst could be recycled without any significant loss of catalytic activity, and was successfully applied for the multigram-scale synthesis of cyclic carbonate at mild temperature under atmospheric carbon dioxide.

Abstract: Concrete-filled steel columns are increasingly recognised for their enhanced structural performance. This study investigates an innovative shear connector design with screw connectors as an alternative to conventional connection types. From push-out testing, the shear capacity of screw connectors in composite columns comprising cold-formed steel sigma sections and concrete infill was evaluated. Experimental push-out testing demonstrated the effectiveness of theoretical equations in estimating the shear strength of screw connections. The comparison indicates that established design methods provide reasonable predictions, supporting their applicability in practical scenarios. Theoretical equations in the literature for estimating shear strength were tested for suitability and gave comparable results. De-assembling of tested specimens showed that a concrete failure was the prominent mode of ultimate condition. Shear screws offer a novel design alternative to conventional shear connection methods. They demonstrate significant potential for structural applications when integrated with advanced composite column sections, such as the four-sigma built-up CFS sections. The study highlights screw connectors as a cost-effective, sustainable, and practical solution for innovative composite column designs, offering significant potential for construction and maintenance efficiency.

Abstract: Objective: This study aimed to evaluate the effects of different surface treatments—no treatment, sandblasting, hydrofluoric acid etching, and their combination—on the shear bond strength of 3D-printed composite resin discs bonded with Panavia V5 cement. Methods: 3D-printed composite resin discs received surface treatments and were bonded to Vita Mark II ceramic rods using Panavia V5 cement. Shear bond strength tests were conducted following 24-hour water storage at 37°C. Data were analyzed using one-way ANOVA and post-hoc Tukey tests (p < 0.05). Results: Hydrofluoric acid etching, alone or combined with sandblasting, significantly improved bond strength compared to no treatment (p < 0.01) and sandblasting alone (p < 0.05). The highest bond strength (40.73 ± 11.53 MPa) was found in the combination group, with no significant difference from hydrofluoric acid etching alone (p = 0.887). Conclusion: Hydrofluoric acid etching, with or without sandblasting, was the most effective surface treatment for enhancing bond strength in 3D-printed composite resins. Sandblasting alone showed no significant improvement compared to untreated surfaces.

Abstract: Chiral-plasmonic hybrid nanostructures have emerged as a promising class of materials with the potential to revolutionize sensing and optical computing applications. These hybrid systems combine the unique optical properties of plasmonic materials with the distinct chiroptical responses of chiral structures, leading to enhanced control over light-matter interactions. This paper explores the design, fabrication, and functionalization of chiral-plasmonic nanostructures with a focus on controlled optical binding-an approach that allows precise manipulation of light at the nanoscale. By leveraging the interplay between plasmonic resonances and chirality, we demonstrate how these hybrid systems can be utilized for high-sensitivity sensing applications, such as biosensing and environmental monitoring. Additionally, we discuss their potential in optical computing, where controlled optical binding can facilitate efficient data processing and transmission in next-generation photonic circuits. This work highlights the promising future of chiral-plasmonic hybrid nanostructures in advancing both sensing technologies and optical computing paradigms.

Abstract: The manipulation of optical forces at the nanoscale has significant implications for nanophotonics, optical trapping, and advanced material design. This study explores the enhancement of optical repulsion in nano-dimers by optimizing the surrounding background media and leveraging wave engineering techniques. By systematically tailoring the refractive index and electromagnetic properties of the medium, we demonstrate an increase in the repulsive optical forces between coupled nanoparticles. Additionally, we investigate the role of structured light fields, including phase and polarization engineering, in modulating these interactions. Our findings provide insights into the fundamental mechanisms governing optical repulsion and open new avenues for designing non-contact optical manipulation strategies with potential applications in optical tweezers, nanofabrication, and biomedical engineering.

Abstract: This study explores the use of gypsum waste from civil construction as a partial replacement for cement in soil-cement formulations, aiming to produce eco-friendly bricks aligned with circular economy principles. Formulations were prepared using a 1:8 cement-to-soil ratio, with gypsum replacing cement in proportions ranging from 5% to 40%. The raw materials were characterized in terms of their chemical composition, crystalline phases, plasticity, and thermal profile. The formulations, molded by uniaxial pressing into cilindrical bodies and cured for 7 or 28 days, were tested for crystalline phases, compressive strength, water absorption, durability, and microstructure. Water absorption remained below 20% for all samples, with an average value of 16.20%. Compressive strength after 7 days decreased slightly with increasing gypsum content, from 16.36 MPa (0% gypsum) to 13.74 MPa (40% gypsum), still meeting the quality standard. After 28 days of curing, the formulation containing 10% gypsum achieved the highest strength (26.7 MPa), surpassing the reference sample without gypsum (25.2 MPa). Mass loss due to water immersion remained within acceptable limits for formulations containing up to 20% gypsum. Notably, samples with 5% and 10% gypsum exhibited superior mechanical performance, while samples with 20% gypsum showed comparable results to the reference. These findings suggest that replacing up to 20% of cement with gypsum waste is a viable and sustainable alternative, promoting circular economy practices and reducing the environmental impact of construction waste.

Abstract: This study investigates the use of peptide-based hydrogels as scaffolds for the encapsula-tion and delivery of Peptide Nucleic Acids (PNAs) in drug delivery applications. Ultra-short aromatic peptide-based hydrogels (HGs), such as Fmoc-FF (Nα-fluorenyl methox-ycarbonyl-diphenylalanine), provide an ideal platform for encapsulating biomolecules due to their biocompatibility, self-assembling nature, and ability to form stable, nanostructured networks. The functionalization of these hydrogels with Fmoc-FFX tripep-tides—where X is cysteine (C) or lysine (K)—enhances their ability to interact with PNA sequences. Model four-bases PNA, functionalized with cysteine (C) or glutamic acid (E) residues at the C-terminus, facilitate covalent or electrostatic interactions with the hydro-gel matrix, improving encapsulation efficiency and stabilizing the PNAs. We systemati-cally optimized the composition and ratios of hydrogel components and PNAs to enhance encapsulation efficiency, structural stability, and controlled release profiles. The resulting hydrogels were thoroughly characterized using High-Performance Liquid Chromatog-raphy (HPLC), Electrospray Ionization Mass Spectrometry (ESI-MS), Circular Dichroism (CD), rheology, Fourier-Transform Infrared (FT-IR) spectroscopy, Scanning Electron Mi-croscopy (SEM), Proton Nuclear Magnetic Resonance (¹H-NMR), as well as optical and fluorescence microscopy. Our results demonstrate the potential of these hydrogels as highly effective platforms for stabilizing and delivering PNAs, offering promising pro-spects for the development of innovative nucleic acid-based therapies.

Abstract: Novel aspects in drive train lubrication are coming into the focus of future technologies covering new materials, accompagnied by digital and ecological aspects. Cradle to cradle (C2C) and waste to cradle (W2C) are offering broad sources of chemicals derived from greens out of the bio-cycle, obtained by decentralized farming. This leads to the fact, that valuable raw materials are accessible from everywhere. Chemicals derived from the bio-life cycle are in tendence rich in oxygen (nitrogen) and as such polar with a general affinity to water with high degree of sustainability and superior CO2 footprint. Lubricants as been used today in contrast are derivatives of fossils with low oxygen content and low affinity to water, poor in sustainability and CO2 footprint. As all life cycle assessments are based on the current lubrication technology, the efforts are high (low technical readiness level) for assessing bio-life cycle based lubricants with respect to their suitability in the technical life cycle, based on test rigs. However, machine learning (ML) techniques could reveal the relevant chemical predictors that are needed to pass a life cycle test rig. Such predictors are available from numerous test rig results assessing traditional lubricants and could be taken for the prediction of the novel bio-life based chemicals. Such concepts have been published recently (Literature). Novel sensor concepts could assist by early predicting failures. As such, the use of ML is inevitable to predict their usefulness in drive train. Coatings may serve as adjuvants for novel C2C (W2C) based lubrication. So far, to open the gate for bio-life based C2C (W2C) chemistry brings up a stringent need for novel sensor concepts in junction with ML. The upcoming EV drive train technology is reaching out for non water based fluids with high heat capacity and thermal conductivity for the electrical segment on one side and low viscous lubricants for the mechanical part on the other. Novel, ML based technologies in C2C (W2C) chemistry could couple both parts into one, as a vision for decentralized sustainable and low CO2 footprint technologies.

Abstract: A new series of 6-arylaminoflavones was synthesized via the Buchwald-Hartwig cross-coupling reaction, aiming to functionalize the flavone core efficiently. Reaction optimization revealed that Pd₂(dba)₃/XantPhos with Cs₂CO₃ in toluene provided the best yields, with isolated yields ranging from 8% to 95%, depending on the arylamine structure. Steric hindrance and electron-withdrawing groups at the arylamine ring negatively impacted the reaction. Cytotoxicity assays indicated that specific substituents at the 6-position influenced biological activity, with trifluoromethyl- (13c) and chlorine-containing (13g) derivatives showing higher selectivity towards prostate cancer cells (PC3). These findings provide insights into the structure-activity relationship of 6-arylaminoflavones while contributing to the development of synthetic methodologies for functionalized flavones.

Abstract: Titanium dioxide manganese/multi-walled carbon nanotubes (MTiO₂/x-CNT) nanocomposites were successfully prepared using the sol-gel method by reaction specific amounts of CNT with titanium dioxide and manganese, aiming to shift the band edge toward longer wavelengths and provide more effective separation of electron-hole pairs. The MTiO₂ and MTiO₂/CNTs were then characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV–vis absorption spectra. The results confirm the successful synthesis and the presence of Mn and CNT in the nanocomposite. The photocatalytic performance was evaluated by investigating the removal of methylene blue as an example of organic pollutants. Among the various composites examined, the MTiO₂/CNT (5%) exhibited the best performance in removing MB, with a degradation rate exceeding 92% and a rate constant of 2.59 × 10⁻² min⁻¹. These results suggest that this compound could have potential applications in other fields.

Abstract: In this paper the modification of natural clinoptilolite and mordenite zeolites from Almaty using acid treatment is addressed for the purposes of improving adsorption performance and for drinking water purification. Structural chemical transformation was characterized by the use of XRD, FTIR, and SEM techniques. Acid treatment led to a partial dealumination that was responsible for the increase in number of surface defects and micropores, improvement in ion exchange capacity and selectivity toward heavy metals. Additionally, modifications greatly enhance the uptake capacities of Pb²⁺, Cd²⁺ and As³⁺. The clinoptilolite post-modification removal efficiencies reached 94%, 86%, and 84% respectively, while mordenite zeolites achieved 95%, 90%, and 87% removal efficiencies respectively. The enhancement of performance was related to the increase of surface area and active sites for ion exchange, verified from analysis of BET surface area. The use of different Bhatt and Kothari methods has revealed that adsorption processes followed Langmuir isotherm models for Pb²⁺ and Cd²⁺, whereas As³⁺ adsorption was better described by the Freundlich isotherm model. However, second-order kinetics indicate that chemisorption was the dominant mechanism. Such evidence indicates spontaneity and an endothermic process, as shown from thermodynamic studies. Results showed that modified zeolites indeed had a high degree of reusability, with over 80% of the adsorption capacity retained even after five cycles. Acid-modified zeolites can provide cheaper, greener methods of purification, generating only negligible secondary waste when compare to conventional methods of water purification, for example, activated carbon and membrane filtration. Results from this study proved that modified clinoptilolite and mordenite zeolites have the potential for sustainable heavy metal treatment in drinking water purification systems.

Abstract: Lignin, a complex aromatic biopolymer abundant as waste in biorefineries and the pulp and paper industry, holds significant potential for valorization. This study presents the oxidative depolymerization of Lignoboost lignin (LB) using H2O2 under mild, solvent- and catalyst-free, inherently acidic conditions at temperatures from 50-70°C. The depolymerized LB was rich in aromatic dimers-trimers (68.6 wt.%) with high functionalization (2.75 mmol/g OHphen, 3.58 mmol/g OHcarb, 19.5 wt.% of H in -CH=CH-), and aliphatic dicarboxylic acids (53.4 wt.% of the monomers). Acidic conditions provided higher depolymerization and functionalization than alkaline conditions, alongside simplified product recovery. The process was also successfully applied to Kraft lignin (KL) from black liquor, demonstrating its versatility and robustness. The optimized conditions were scaled up (×25), improving efficiency and yielding a Mw and Đ of 464 g/mol and 1.3, respectively. As proof of concept, the scaled-up product underwent radical crosslinking, resulting in a new biopolymer with higher thermal stability than LB (54.2 wt.% residual mass at 600°C versus 36.1 wt.%). This green, scalable depolymerization process enhances lignin valorization, producing two high-value compounds—low molecular weight functionalized aromatics and dicarboxylic acids—that can be used independently or together, owing to their inherent capacity to form crosslinked networks.

Abstract: Childhood neuroblastoma (NB) is a malignant tumour that is a member of a class of embryonic tumours that have their origins in sympathoadrenal progenitor cells. There are five stages in the clinical NB staging system: 1, 2A, 2B, 3, 4S, and 4. For those diagnosed with stage 4 neuroblastoma (NBS4) the treatment options are limited with a survival rate of between 40 to 50%. Since 1975, more than 15 targets have been identified in the search for a treatment for high-risk NBS4. This article is concerned with the search for a multi-target drug treatment for high-risk NBS4 and focuses on four possible treatment targets that research has identified as having a role in the development of NBS4 and includes the inhibitors Histone Deacetylase (HDAC), Bromodomain (BRD), Hedgehog (HH), and Tropomyosin Kinase (TRK). Computer-aided drug design and molecular modelling have greatly assisted drug discovery in medicinal chemistry. Computational methods such as molecular docking, homology modelling, molecular dynamics, and quantitative structure-activity relationships (QSAR) are frequently used as part of the process for finding new therapeutic drug targets. Using these methods, 8 compounds (inhibitors) were identified as possible inhibitors for all four targets. Results revealed that all four targets BRD, HDAC, HH and TRK share similar amino acid sequencing that ranges from 80-100% offering the possibility of further testing for multi-target drug use. Two additional targets were also tested as part of this work, Retinoic Acid (RA) and c-Src (Csk) which showed similarity across their receptors of 80-100% but lower that 80% for the other four targets. The work for these two targets is the subject of a paper currently in progress.

Abstract: This study explores the development of aluminum doped MgV2O4 spinel cathodes for aqueous zinc-ion batteries (AZIBs), aiming to overcome the challenges of poor ion diffusion and structural instability. Al3+ ions were pre-inserted into the spinel structure using a sol-gel method, enhancing the material's structural stability and electrical conductivity. The Al3+ doping mitigates the electrostatic interactions between Zn2+ ions and the cathode, improving ion diffusion and facilitating efficient charge/discharge processes. The resulting Al-MgV2O4 cathode demonstrates excellent electrochemical performance, retaining a capacity of 254.3 mAh g−1 at an ultra-high current density of 10 A g−1 after 1000 cycles, with a capacity retention of 93.6%. At an ultra-high current density of 20 A g−1, the material retains 186.8 mAh g−1 after 2000 cycles, with a capacity retention of 90.2%, making it a promising candidate for high-rate energy storage applications.