Chemistry and Materials Science

Abstract: Whether copper fundamentally alters Mo-centered redox thermodynamics or mainly tunes hydrogen adsorption in Ni–Mo electrocatalysts under alkaline hydrogen evolution reaction (HER) conditions remains unresolved. Density functional theory calculations combined with a field-corrected computational hydrogen electrode framework are used to evaluate the thermodynamic stability of H₃Mo, H₃MoOH, H₂Mo(OH)₂, and MoO(OH)₃ on Cu(111) and Ni(111) and to construct surface Pourbaix diagrams under electrochemical conditions. The results show that substrate identity reorganizes the redox stabilization hierarchy of these Mo intermediates. Across the examined conditions, at least one of H3Mo, H3MoOH, or MoO(OH)₃ is thermodynamically favored over H₂Mo(OH)₂ on both surfaces. However, only Cu(111) exhibits measurable pH-dependent free-energy shifts, reaching 0.28 eV on the reversible hydrogen electrode scale. The magnitude of this electrostatic modulation is comparable to the intrinsic substrate-dependent relative Gibbs free-energy differences, suggesting that Cu reshapes Mo redox thermodynamics rather than merely weakening hydrogen binding strength. Electronic structure and vibrational analyses further show that Cu(111) preferentially weakens Mo–O interactions, whereas Ni(111) more strongly perturbs Mo–H bonding in hydrogen-rich complexes. Overall, these results establish that substrate identity governs the electrostatic modulation of Mo redox thermodynamics under alkaline HER conditions and provide a mechanistic insight into substrate effects relevant to Cu-containing Ni–Mo systems.

Abstract: The Fenton reaction remains one of the most widely investigated advanced oxidation processes for wastewater treatment due to its ability to generate highly reactive oxygen species capable of degrading persistent organic pollutants. However, classical homoge-neous Fenton systems suffer from significant limitations, including narrow pH applica-bility, iron sludge generation, and poor catalyst reusability. In response, extensive research has been devoted to the development of heterogeneous and advanced Fenton-like catalysts that address these challenges while improving catalytic efficiency and operational stabil-ity. This review provides a comprehensive analysis of the evolution of Fenton catalysis, from classical homogeneous systems to modern advanced materials, including nanostructured catalysts, carbon-based Fe–N–C systems, metal–organic frameworks, and single-atom catalysts. Particular emphasis is placed on key performance parameters such as catalytic activity, manufacturability, stability, and catalyst lifespan. A critical comparison of these systems highlights the trade-offs between activity, cost, and scalability, demonstrating that the most advanced catalysts do not necessarily offer the best practical performance. A dedicated life cycle assessment perspective is included, focusing on catalyst lifespan, reuse efficiency, and iron leaching, providing quantitative insights into long-term sus-tainability. The analysis reveals that while advanced catalysts significantly improve cu-mulative catalytic output, their environmental and economic viability depends on synthe-sis complexity and durability under realistic conditions. Finally, current challenges and future directions are discussed, including the need for scalable synthesis methods, improved mechanistic understanding, and integration into hybrid treatment systems. This review aims to bridge the gap between fundamental re-search and practical application, offering guidance for the design of next-generation sus-tainable Fenton catalysts for wastewater treatment.

Abstract:

The viscosity stability of the polymer solution is one of the challenges in enhancing oil recovery and zwitterionic copolymer presents excellent viscosity stability and emulsification performance, enabling effective control the oil/water interface mobility and enhancing oil recovery. Herein, a zwitterionic copolymer (P(AM/AMBS/MAPTAC)) containing sulfonic acid group and quaternary amine group was synthesized by segmentation initiation with AM, AMBS and MAPTAC as monomers. The chemical structure of P(AM/AMBS/MAPTAC) was confirmed by FTIR and ¹H NMR. The M_w value of (P(AM/AMBS/MAPTAC)) was 9.91×10⁶, and the apparent viscosity of the solution of 2000 mg/L solution was 24.92 mP·s at 60 ℃ in the 5000 mg/L salt solution. P(AM/AMBS/MAPTAC) with the sulfonic acid group and the quaternary amine group exhibits outstanding salt tolerance and shear resistance. When the salinity was 10000 mg/L and the shear rate was 300 s^-1, the apparent viscosity and the viscosity reduction rates for the P(AM/AMBS/MAPTAC) solution were 23.45 mP·s and 69.23 %, respectively. Moreover, P(AM/AMBS/MAPTAC) exhibited higher emulsion property and higher oil-water interface thickness than HPAM and SPAM because of the synergistic effect of sulfonic acid and quaternary amine groups in the P(AM/AMBS/MAPTAC) molecule. The polymer flooding and the alkali-surfactant-polymer flooding formed by P(AM/AMBS/MAPTAC) had high chemical oil recovery and the oil displacement efficiency was higher than HPAM and SPAM in the polymer flooding and the alkali-surfactant-polymer flooding systems.

Abstract: The therapeutic monoclonal antibody bevacizumab is typically purified using Protein-A affinity chromatography, a highly effective but costly method. As a lower-cost alternative, affinity-based precipitation has been described to purify antibodies. Therefore, in this work, a precipitation protocol was developed for bevacizumab purification using the branched peptide (Ac-PHQGQHIG-Ahx₃)2-K-Ahx₃-PHQGQHIG-NH₂, which contains the epitope PHQGQHIG responsible for interaction with bevacizumab. The peptide was synthesised by microwave-assisted solid-phase peptide synthesis employing LiCl as an additive to prevent aggregation and ensure high purity and yield. Three molecules of 6-aminohexanoic acid were introduced between each epitope branch as spacer arms to promote the formation of cyclic complexes. Bevacizumab purification from the cell-free culture broth was achieved through a fractional precipitation process. First, a negative precipitation step using (NH₄)₂SO₄ 1.18 M was performed to remove contaminants. Afterwards, 5 moles of peptide per mol of bevacizumab were added to the supernatant, together with additional (NH₄)₂SO₄ to reach a final concentration of 1.20 M. Under these conditions, bevacizumab was recovered in the precipitate with 98% purity and a yield of 73%. In addition to being recyclable, the peptide´s relative low production cost may enable the development of a single-use purification process, which would be particularly advantageous for biopharmaceutical manufacturing.

Abstract: Background/Objectives: Microbial resistance to antibiotics has become a major global public health problem, threatening the effectiveness of current therapeutic strategies. The present study seeks to investigate natural compounds originating from fungal sources for their ability to interfere with efflux pump–mediated resistance in multidrug-resistant (MDR) bacteria, with the overarching goal of uncovering new candidates for antimicrobial therapeutic development. A chemical investigation of the ethanol extract of Termitomyces clypeatus was carried out to isolate and identify its constituents. Methods: Structural elucidation of the isolated metabolites was achieved through 1D and 2D NMR spectroscopy supported by mass spectrometric data. The crude extract and the purified compounds were then evaluated for their antibacterial activities individually, in the presence of an efflux pump inhibitor, and in combination with three antibiotics, using standardized microdilution assays. Results: Chromatographic separation of the extract yielded eleven known compounds including three sphingolipids: (9Z,12Z)-N-(1,3,4-trihydroxyoctadecan-2-yl)octadeca-9,12-dienamide (1), 2-hydroxy-N-(1,3,4-trihydroxyoctadecan-2-yl)hexadecanamide (2), and cerebroside B (3); four steroids: ergosterol (4), cerevisterol (5), ergosterol peroxide (6), and 5α,6α-epoxy-(22E,24R)-ergosta-8(14),22-diene-3β,7α-diol (7); one alkaloid: piperine (8); one carbohydrate: D-mannitol (9); and two phthalates: dimethyl phthalate (10) and bis(2-ethylhexyl) terephthalate (11). GC–MS analysis led to the identification of eight fatty acid derivatives (12–19). Sub-fraction A, along with compounds 3, 4, and 8 exhibited notable antibacterial activity against some tested strains with MIC values of 64 μg/mL. These compounds were identified as substrates of bacterial efflux pumps, and their presence enhanced the antibacterial effects of ciprofloxacin, doxycycline, and amikacin. Conclusion: The findings of the present work indicate that Termitomyces clypeatus contains antibacterial compounds with potential therapeutic value, both as standalone agents and as adjuvants that enhance the activity of conventional antibiotics.

Abstract: In this study, extracts of metallurgical slags of the former lead plant in Shymkent and Zhezkent Mining and Processing Plant are used as a liquid mineral fertilizer for growing corn. Slag extraction was carried out by the method of chemical leaching with potassium sulfate and ammonia solution in hydrogen peroxide medium. Macro- and microelement analysis of extracts from slag was carried out. Among the obtained extracts, the slag extract of the second slag store of the former lead plant is the least toxic and the richest in macro- and microelements (27.605 Са 2+; 5.959 Mg2+; 423.751 Cu2+; 86.649 Zn2+; 5.567 Fe2+,3+; 22.652 Mn mg/L). The studied solution was diluted in the ratio of extract: distilled water 1:10 for the extract based on potassium sulfate and 1:200 for the extract based on ammonia and used to evaluate the initial development of seeds and yield of corn. Germination of seed corn and its development after 90 days did not differ from the control variant. The concentration of potentially toxic elements in the dry mass of the plant does not exceed the permissible concentration. The results showed the potential of safe application of this fertilizer in agriculture and rational utilization of industrial waste.

Abstract: Today, interest in natural remedies for biocontrol of crop pests is paramount. Punica granatum L. (pomegranate) is studied worldwide to obtain interesting bioactive compounds. Its anti-parasitic activity is associated with the presence of alkaloids in its roots. In this work, we explored the possibility of obtaining from P. granatum roots pelletierine-like alkaloids, which were extracted, characterized, isolated and used for the biocontrol of pests such as Spodoptera littoralis, Myzus persicae, Rhopalosiphum padi and Meloidogyne javanica. Two different extracts were obtained, characterised and quantified by GC-MS and LC-ESI-HRMS. In vitro assays of nematicidal activity were performed comparing the extracts with isopelletierine and pseudopelletierine as pure molecules. The results of these assays showed a difference in activity between iso- and pseudopelletierine, especially in terms of the nematocidal effect against M. javanica with isopelletierine being more active than pseudopelletierine. This leads us to conclude that only extracts from P. granatum roots with a high concentration of isopelletierine alkaloid can be used in effective pest control products.

Abstract: As the key enzyme catalyzing the final step in the biosynthesis of heme and chlorophyll, protoporphyrinogen oxidase (PPO) has become a crucial target for herbicide development. To date, more than 40 PPO-inhibiting herbicides have been developed, exhibiting multiple advantageous characteristics: they combine high efficacy with environmental friendliness, feature low effective concentrations, rapid action, long-lasting effects, and excellent control of both monocotyledonous and dicotyledonous weeds. In recent years, significant progress has been made in the structural biology of PPO—five crystal structures from tobacco, humans, and various bacteria have been resolved, most of which are presented as enzyme-inhibitor complexes. Although the development of such herbicides spans over five decades, novel PPO inhibitors still hold broad potential for innovation due to the resistance of early applied PPOs. This review systematically summarizes the three-dimensional structures of PPO from different sources, the interaction mechanisms between the enzyme and inhibitors, studies on quantitative structure-activity relationships of inhibitors, and outlines molecular design directions for the next generation of PPO inhibitors.

Abstract: This work demonstrates an efficient and reproducible method for the covalent biofunctionalization of epoxy solder mask surfaces on printed circuit boards (PCBs) produced using a conventional manufacturing process, enabling the implementation of capacitive biosensors without the need for any additional PCB fabrication steps and thereby supporting low-cost biosensing applications. Surface activation was achieved using 600 mM 3-mercaptopropionic acid (3-MPA) and 600 mM EDC/NHS, followed by immobilization of 600 µM bovine serum albumin (BSA) as a model protein, achieving spatial variability below 10%. This methodology can be directly applied to other proteins by simply substituting the biomolecule of interest. ATR-FTIR analysis confirmed successful chemical modification through the appearance of characteristic carboxyl and amide bands, while BCA assays verified effective protein attachment. The sensing performance of the functionalized surface was evaluated using electrochemical impedance spectroscopy on interdigitated PCB-based electrodes. A clear decrease in the impedance module was observed at 1 MHz after BSA immobilization and subsequent anti-BSA binding with a variation of 2826 ± 235 Ω and 4214 ± 239 Ω respectively (p < 0.001). Remarkably, anti-BSA was detected at concentrations as low as 10 ppb. These results highlight not only the strong biochemical activity and stability of the modified solder mask surface, but also its potential for scalable, robust, and cost-effective PCB-integrated biosensors for clinical biomarker detection and point-of-care diagnostics, as well as other widespread diagnostic and sensing applications.

Abstract: Development of new polymers, that cannot be achieved by using conventional catalysts has been the central research objective, and copolymerization is an effective strategy to modify the materials’ (thermal, physical, mechanical and electronic) properties. Modified half-titanocenes, Cp’TiX2(Y) (Cp’ = cyclopentadienyl; X = Cl, Me etc.; Y = anionic donor such as phenoxide, ketimide, amidinate etc.), are known to be the effective catalysts. This review introduces several selected efforts for efficient synthesis of ethylene copolymers containing cyclic olefins, biobased conjugated dienes, disubstituted α-olefins including effect of cocatalysts. Moreover, here introduces analysis using XAS (X-ray absorption spectroscopy), which has been recognized as powerful method providing direct information of the catalytically active species, such as coordination numbers and the distances of the coordinated atoms as well as oxidation state and the geometry of the metal centre in catalyst solution.

Abstract: Aldolases are powerful biocatalysts for the stereoselective formation of carbon–carbon bonds and are widely used in the synthesis of chiral intermediates for pharmaceutical applications. Among them, 2-deoxyribose-5-phosphate aldolase (DERA) has been extensively exploited for the preparation of the conserved side chain of statins. In this work, we report a novel chemoenzymatic approach for the synthesis of nucleobase-substituted lactol products as potential precursors of new statin analogues. A C49M variant of DERA from Pectobacterium atrosepticum (PaDERA C49M) was employed to catalyze sequential aldol additions using aldehyde-functionalized nucleobases as non-natural electrophilic substrates. The formation of nucleobase-containing lactols was confirmed, demonstrating for the first time the acceptance of nucleobase-derived aldehydes in DERA-catalyzed aldol reactions. This strategy provides access to structurally novel statin side-chain precursors and expands the synthetic potential of DERA toward the generation of new classes of bioactive compounds.

Abstract: A series of Fe-ZSM-5 catalysts with varying Fe loadings were synthesized via a hydrothermal method. Their catalytic performance was evaluated for the selective catalytic reduction (SCR) of NOx with ammonia. The catalyst with a Fe:Al molar ratio of 1:1 demonstrated the highest NOx conversion (99.9%) and exhibited a broader operating temperature window (240–390°C) compared to catalysts with other Fe/Al ratios. Characterization by X-ray diffraction (XRD),scanning electron microscopy(SEM), and X-ray photoelectron spectroscopy(XPS) confirmed that the incorporation of iron ions preserved the high crystallinity and MFI structure of the ZSM-5 zeolite. NH3-temperature-programmed desorption (NH3-TPD) profiles revealed the presence of two distinct acid sites at approximately 250 °C and 400 °C.

Abstract:

The photocatalytic dehydrogenative coupling of methanol to produce the high-value-added chemical ethylene glycol (EG) has garnered widespread attention owing to its environmental benignity and mild reaction conditions. The ternary metal sulfide Zn₂In₂S₅(ZIS), by virtue of its unique stoichiometric ratio, demonstrates a high intrinsic selectivity for the activation of the α-C-H bond in methanol. However, pristine ZIS faces the challenge of rapid recombination of photogenerated electron-hole pairs, which severely restricts its photocatalytic efficiency. In this study, the conductive polymer polyaniline (PANI) was successfully coupled with the ZIS photocatalyst via a simple one-step hydrothermal polymerization method to fabricate a series of PANI/ZIS nanocomposite photocatalysts. Systematic evaluation results indicate that the optimal catalyst, 7.5%-PANI/ZIS, exhibits exceptional catalytic performance under visible light, achieving an ethylene glycol generation rate as high as 4.87 mmol/g/h, representing a 6.76-fold enhancement over pristine ZIS (0.72 mmol/g/h). The significant performance enhancement is attributed to the synergistic effects of PANI and ZIS, which formed Type-II heterojunction effectively promotes the separation and transport of photogenerated charges and significantly reduces the charge transfer resistance. This research provides new insights into interfacial engineering based on conductive polymers and is of significant scientific importance for the high-value utilization of C1 small molecules.

Abstract: Three alloys, two based on cobalt and one on nickel, containing 5 or 10 wt.%Al for their resistance to hot oxidation, and Ta and C for forming TaC carbides for they creep–resistance at high temperature, were synthesized by casting. They were subjected to the control of their as–cast microstructures and to oxidation tests at 1200°C for 50 hours in a thermobalance. The initial microstructures of the two low Al alloys, both containing 5 wt.%Al, are not significantly modified by the Al introduction by comparison to the more usual {25 to 30 wt.%Cr}–containing original alloys. In contrast, their oxidation behaviors are either catastrophic (Co alloy) or acceptable but not really alumina–forming. To improve the oxidation resistance of the Co alloy a version with 10 wt.%Al was additionally elaborated. Increasing the Al content improved significantly the oxidation behavior but also induced obvious modifications in the microstructure, with the appearance of the Co3Al intermetallic replacing almost a half of the volume fraction of the Co solid solution matrix. Except the 5wt.%Al cobalt alloy over which a thick double–structured scale made of CoO and of a mix of CoO and spinel formed, the 5wt.%Al nickel alloy and the 10wt.%Al cobalt alloy were covered a duplex external oxide scale with an outermost spinel oxide and an innermost alumina oxide, rather protective considering the parabolic constants but threatened by spallation even for the rather slow cooling. The responsibility of tantalum, the oxide of which seems deleterious for adherence, was pointed out.

Abstract: A novel poly(ionic liquid) nanofiber membrane (PIL NF) was synthesized by the cyclization of polyacrylonitrile (PAN) with piperazine, converting the nitrile groups into imidazoline units, followed by quaternization with 1-bromobutane. The resulting PIL NF was further functionalized by loading the photocatalyst, phosphomolybdic acid (PMo), via anion exchange, forming a new type of photocatalytic material, PM-PIL. Under visible light irradiation, the PM-PIL photocatalyst achieved an impressive methyl blue degradation rate of 98%. Additionally, the nanofiber membrane morphology facilitates the efficient recovery of the catalyst, with 98% of the initial degradation efficiency maintained after five photocatalytic cycles. This robust, highly efficient, and recyclable material provides a new approach for catalyst support. To the best of our knowledge, PM-PIL is the first reported photocatalyst of this kind. This cost-effective, functionalized membrane material utilizes solar light as an economical and clean energy source, offering promising potential for sustainable environmental applications.

Abstract: The main theme of present comprehensive review paper is the microwave-assisted heat-ing (MWH) developed in CNR SCITEC laboratories in Genoa. By modifying a domestic microwave, this technique has been used to prepare various innovative materials through synthesis, sintering, or heating (foaming or melting). These materials include inorganic compounds like superconductive magnesium diboride (MgB2), as well as organic and or-ganic-inorganic composite. The review highlights the significant improvements in en-ergy efficiency, time saving, material properties, and environmental sustainability achieved through these processes. Specific applications discussed include the rotational molding of polyethylene powders, sintering of hydroxyapatite-based scaffolds, and the preparation of cork composites for sound-absorbing panels, expanded polystyrene com-posites for building elements, and polyvinylidene fluoride piezoelectric compo-sites. Future potential applications and market demand for these technologies are also explored.

Abstract:

This study investigates the development of Ni-based catalysts for low-temperature dry methane reforming (DMR) at 550 °C. The catalysts were prepared by dispersing Ni on γ-Al₂O₃ modified with 9 wt% MgO and 1 wt% ZrO₂, while 10 wt% Ni–x wt% ZrO₂ promoters (0, 1, and 3 wt%) were introduced using the incipient wetness impregnation method. A Ni–NiO–ZrO₂ surface network was generated on the 10 wt% Ni–3 wt% ZrO₂ catalyst via an ammonia vapor–assisted impregnation route. The ZrO₂ promoter strengthened the metal–support interaction, which increased the total amount of reducible Ni while shifting the reduction to higher temperatures. This modification also promoted CO₂ activation relative to CH₄, thereby enhancing the RWGS pathway and lowering the H₂/CO ratio. In contrast, the Ni–NiO–ZrO₂ network formed through the ammonia-assisted method increased the concentration of surface-accessible Ni, reduced excessive coverage by ZrO₂, and significantly improved oxygen mobility. These features facilitated continuous oxygen transfer, enhanced coke oxidation, and ensured a more balanced activation of both reactants. Overall, the combined structural and functional synergies achieved through promoter optimization and the ammonia vapor–assisted preparation method resulted in superior catalytic activity and selectivity for DMR at 550 °C.

Abstract: Surfactants are commonly employed in cleaning, cosmetic and pharmaceutical formula-tions due to their ability to lower surface tension and facilitate the formation of emulsions, foams, and dispersions. Recent research highlights the advantages of synergistic interac-tions between anionic and nonionic surfactants to improve overall performance. In this study the physicochemical properties and performance of binary mixtures of the anionic surfactant sodium lauryl sulfate (SLS) and the amphoteric surfactant lauryl dimethyl amine oxide (LDAO) at varying ratios (100% SLS, 90:10, 80:20, 70:30, 60:40, and 50:50) were investigated. Key parameters analysed included critical micelle concentration (CMC), surface tension (), foam volume and potential irritability, assessed via the Zein test. The results revealed a clear synergistic effect between SLS and LDAO: all mixtures showed reduced CMC and minimum surface tension compared to the individual surfac-tants, while exhibiting enhanced foam volume and stability. Regarding irritability, in-creasing LDAO content consistently led to decreased protein denaturation, indicating lower irritancy levels. Furthermore, the results obtained in the Zein test confirmed that mixtures induced less protein denaturation than the sum of their individual surfactant components, with formulations ranging from moderately to non-irritating. The results obtained indicate that the more stable mixed micelle systems (SLS+LDAO) might improve the performance of cleaning formulations (, CMC, foam) while reducing the irritability.

Abstract: Silica–chitosan hybrid composites containing up to 3.5 % chitosan were prepared via a reproducible and simple sol–gel route through the hydrolysis and condensation of tet-raethoxysilane (TEOS). The obtained gels were systematically characterized in terms of their textural, optical and thermal properties using UV–Vis spectroscopy, TG/DTA analysis, scanning electron microscopy (SEM), X-Ray diffraction and thermal conduc-tivity measurements. The bulk gel density was found to increase with chitosan content, indicating gradual compaction of the silica network and high sample homogeneity. These structural changes were accompanied by alterations in thermal stability, optical transparency, and heat transfer properties. DTA analysis revealed a broad exothermic feature, which may indicate a thermally induced process, such as partial carbonization. The resulting composites are suitable for various applications, including thermal insu-lation with controlled thermal conductivity, optical devices, biocompatible coatings, adsorbents for pollutant removal, controlled drug delivery, catalytic supports, and sensors. UV/Vis measurements display an intense absorption feature of the composites at 280 – 305 nm, which is promising for optical filter applications in combination with the increased mechanical stability due to chitosan addition.

Abstract: The petroleum industry faces intensifying challenges related to the depletion of easily accessible reservoirs and the growing energy demand, necessitating the adoption of ad-vanced chemical agents that can operate under extreme conditions. Cationic gemini sur-factants, characterized by their unique dimeric architecture consisting of two hydrophilic head groups and two hydrophobic tails, have emerged as superior alternatives to con-ventional monomeric surfactants due to their enhanced interfacial activity and physico-chemical resilience. This review provides a comprehensive analysis of the literature concerning the molecular structure, synthesis, and functional applications of cationic gemini surfactants across the entire oil value chain, from extraction to refining. The analysis reveals that gemini surfactants exhibit critical micelle concentrations signifi-cantly lower than their monomeric analogues and maintain stability in high-temperature and high-salinity environments. They demonstrate exceptional efficacy in enhanced oil recovery through ultra-low interfacial tension reduction and wettability alteration, while simultaneously serving as effective drag reducers, wax inhibitors, and dual-action bio-cidal corrosion inhibitors in transportation pipelines. Cationic gemini surfactants repre-sent a transformative class of multifunctional materials for the oil industry.