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The steric effect is one of the most widely used concepts for chemical understanding in publications and textbooks, yet a well-accepted formulation of this effect is still elusive. Experimentally, this concept was quantified by the acid-catalyzed hydrolysis of esters, yielding the so-called Taft steric parameter. Theoretically, we recently proposed a density-based scheme to quantify the effect from density functional theory. In this work, we directly compare these two schemes, one from theory and the other from experiment. To this end, we first establish the ester hydrolysis mechanism with multiple water molecules explicitly considered and then apply the energetic span model to represent the hydrolysis barrier height between the two schemes. Our results show that the barrier height of the reaction series is strongly correlated with both Taft steric parameters from experiment and steric quantification from theory. We also obtained strong correlations with steric potential, steric force, and steric charge from our theoretical scheme. Strong correlations with a few information-theoretic quantities are additionally unveiled. To the best of our knowledge, this is the first time in the literature that such a direct comparison between theoretical and experimental results is made. These results also suggest that our proposed two-water three-step mechanism for ester hydrolysis is effective, and our theoretical quantification of the steric effect is valid, robust, and experimentally comparable. In our view, this work should have satisfactorily addressed the issue of how the steric effect can be formulated and quantified, and thus it lays the groundwork for future applications.

While high-pressure chemistry has a well-established history, methods to simulate pressure at the single-molecule level have been somewhat lacking. The current work aims at comparing two static models (XP-PCM and GOSTSHYP) to apply isotropic pressure to single molecules, focusing on the equilibrium bond length and electric dipole moment of diatomic molecules. Numerical challenges arising in the potential energy surface using the XP-PCM method were examined, and a pragmatic approach was followed to mitigate these. The definition of the cavity was scrutinized, and two approaches to retrieve the isotropic character that could potentially be lost when using the standard methodology were suggested. Subsequently, equilibrium bond lengths under pressure were evaluated, showing reasonable agreement between GOSTSHYP and XP-PCM, but some discrepancies persist. A Taylor series analysis introduced elsewhere was then applied to rationalize the observed trends in terms of the bond surface. Finally, the dipole moment was shown to be highly sensitive to the cavity definition, and qualitative agreement necessitates the use of our adapted procedure.

Tribolium castaneum is a challenging pest of stored products, causing significant economic losses. The present study explored the efficacy of Coridothymus capitatus essential oil and its primary constituent, carvacrol, as eco-friendly alternatives for managing this pest. To evaluate their insecticidal potential, repellency, fumigant toxicity, and antifeedant properties, progeny inhibition assays were performed. Carvacrol exhibited superior repellency compared to the essential oil, achieving a 92% repellency rate at 2 mg/cm 2 . Both compounds demonstrated significant fumigant toxicity against T. castaneum , with LC 50 values of 168.47 and 106.5 μL/L for the essential oil and carvacrol, respectively, after 24 h. Carvacrol also outperformed the essential oil in antifeedant activity, inducing an 80.7% feeding deterrence at 1.17 mg/g. Moreover, both treatments effectively suppressed the development of the pest's progeny. These results collectively underscore the potent insecticidal properties of C. capitatus essential oil and carvacrol, particularly carvacrol, as promising candidates for the sustainable management of T. castaneum in stored product protection.

The type of experimental model for the in vitro testing of drug formulations efficiency represents an important tool in cancer biology, with great attention being granted to three-dimensional (3D) cultures as these offer a closer approximation of the clinical sensitivity of drugs. In this study, the effects induced by carboxyl-functionalized single-walled carbon nanotubes complexed with cisplatin (SWCNT-COOH-CDDP) and free components (SWCNT-COOH and CDDP) were compared between conventional 2D- and 3D-spheroid cultures of human breast cancer cells. The 2D and 3D breast cancer cultures were exposed to various doses of SWCNT-COOH (0.25-2 μg/mL), CDDP (0.158-1.26 μg/mL) and the same doses of SWNCT-COOH-CDDP complex for 24 and 48 h. The anti-tumor activity, including modulation of cell viability, oxidative stress, proliferation, apoptosis, and invasion potential, was explored by spectrophotometric and fluorometric methods, immunoblotting, optical and fluorescence microscopy. The SWCNT-COOH-CDDP complex proved to have high anti-cancer efficiency on 2D and 3D cultures by inhibiting cell proliferation and activating cell death. A dose of 0.632 μg/mL complex triggered different pathways of apoptosis in 2D and 3D cultures, by intrinsic, extrinsic, and reticulum endoplasmic pathways. Overall, the 2D cultures showed higher susceptibility to the action of complex compared to 3D cultures and SWCNT-COOH-CDDP proved enhanced anti-tumoral activity compared to free CDDP., (© 2024. The Author(s).)

Carbon dots (CQD) have received significant attention as a novel ratiometric fluorescent pH nanoprobe, owing to their favorable optical properties and excellent biocompatibility. Despite their appealing features, the precise mechanism behind the pH-sensitive photoluminescence of CQDs remains to be fully understood. This study endeavors to unravel the mechanism underlying the pH-responsive ratiometric fluorescence in dual-emission CQDs, synthesized through a one-step hydrothermal method using o-phenylenediamine and oxalic acid as precursors. The resultant CQDs exhibit inherent dual-emission at wavelengths of 383 nm and 566 nm, with the ratiometric fluorescence response tailored by the ratio of precursors, providing a robust tool for pH sensing across a range of 2 to 6. Detailed characterizations, including chemical, morphological, and optical analyses, alongside theoretical insights from time-dependent density functional theory (TD-DFT), elucidate the mechanism underlying the pH-dependent luminescence, attributed to the electron cloud transmission between amide and adjacent carboxyl groups on the CQD surface. The superior performance of these CQDs in real-time pH monitoring is demonstrated through their application in glucose oxidase-catalyzed reactions, showcasing their potential as efficient, reliable nanoprobes for biomedical research and diagnostic applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

With the increasing shortage of water resources and the aggravation of water pollution, solar-driven interfacial steam generation (SISG) technology has garnered considerable attention because of its low energy consumption, simple operation, and environmental friendliness. The popular multi-layer SISG evaporator is composed of two basic structures: a photothermal layer and a support layer. Herein, the support layer underlies the photothermal layer and carries out thermal management, supports the photothermal layer, and transports water to the evaporation interface to improve the stability of the evaporator. While most research focuses on the photothermal layer, the support layer is typically viewed as a supporting object for the photothermal layer. This review focuses on the support layer, which is relatively neglected in evaporator development. It summarizes existing progress in the field of multi-layer interface evaporators, based on various polymers and biomaterials, along with their advantages and disadvantages. Specifically, mainly polymer-based support layers are reviewed, including polymer foams, gels, and their corresponding functional materials, while biomaterial support layers, including natural plants, carbonized biomaterials, and other innovation biomaterials are not. Additionally, the corresponding structure design strategies for the support layer were also involved. It was found that the selection and optimal design of the substrate also played an important role in the efficient operation of the whole steam generation system. Their evolution and refinement are vital for advancing the sustainability and effectiveness of interfacial evaporation technology. The corresponding potential future research direction and application prospects of support layer materials are carefully presented to enable effective responses to global water challenges.

The electrochemical conversion of glycerol into high-value chemicals through the selective glycerol oxidation reaction (GOR) holds importance in utilizing the surplus platform chemical component of glycerol. Nevertheless, it is still very limited in producing three-carbon chain (C 3 ) chemicals, especially glyceric acid/glycerate, through the direct oxidation of its primary hydroxyl group. Herein, Pd microstructure electrodeposited on the Ni foam support (Pd/NF) is designed and fabricated to achieve a highly efficient GOR, exhibiting a superior current density of ca. 120 mA cm -2 at 0.8 V vs. reversible hydrogen electrode (RHE), and high selectivity of glycerate at ca. 70%. The Faradaic efficiency of C 3 chemicals from GOR can still be maintained at ca. 80% after 20 continuous electrolysis runs, and the conversion rate of glycerol can reach 95% after 10-h electrolysis. It is also clarified that the dual-component interfaces constructed by the adjacent Pd and Ni sites are responsible for this highly efficient GOR. Specifically, Ni sites can effectively strengthen the generative capacity of the active adsorbed hydroxyl (OH ad ) species, which can steadily immigrate to the Pd sites, so that the surface adsorbed glycerol species are quickly oxidized into C 3 chemicals, rather than breaking the C-C bond of glycerol; thus, neither form the C 2 /C 1 species. This study may yield fresh perspectives on the electrocatalytic conversion of glycerol into high-value C 3 chemicals, such as glyceric acid/glycerate.

Endometrial cancer is the most common malignant tumor of the female reproductive system. It develops in the mucous membrane lining the inside of the uterine body-the endometrium, through the abnormal and continuous growth of cancer cells originating from the uterine mucosa. In recent years, there has been a significant increase in the number of cases in European countries. Photodynamic therapy (PDT) is an innovative and dynamically developing medical procedure, useful in the treatment of cancer and non-cancer tissue conditions. The PDT reaction involves the activation of a photosensitizing substance with visible light, which in turn leads to the formation of free oxygen radicals, which contribute to the destruction of the cell. PDT is minimally invasive, has few side effects, and preserves organ anatomy and function. Both diagnostics and photodynamic therapy as modern methods of treatment are becoming more and more popular in many research units around the world. They are most often practiced and tested in in vitro experimental conditions. In clinical practice, the use of PDT is rare. Comprehensive cooperation between scientists contributes to taking steps towards obtaining new, synthetic photosensitizers, directing their physicochemical properties, and showing the impact on a given organism. This review examines the evidence for the potential and usefulness of PDT in the treatment of endometrial cancer. This review highlights that PDT is gaining popularity and is becoming a promising field of medical research.

Gliomas account for 24% of all the primary brain and Central Nervous System (CNS) tumors. These tumors are diverse in cellular origin, genetic profile, and morphology but collectively have one of the most dismal prognoses of all cancers. Work is constantly underway to discover a new effective form of glioma therapy. Photodynamic therapy (PDT) may be one of them. It involves the local or systemic application of a photosensitive compound-a photosensitizer (PS)-which accumulates in the affected tissues. Photosensitizer molecules absorb light of the appropriate wavelength, initiating the activation processes leading to the formation of reactive oxygen species and the selective destruction of inappropriate cells. Research focusing on the effective use of PDT in glioma therapy is already underway with promising results. In our work, we provide detailed insights into the molecular changes in glioma after photodynamic therapy. We describe a number of molecules that may contribute to the resistance of glioma cells to PDT, such as the adenosine triphosphate (ATP)-binding cassette efflux transporter G2, glutathione, ferrochelatase, heme oxygenase, and hypoxia-inducible factor 1. We identify molecular targets that can be used to improve the photosensitizer delivery to glioma cells, such as the epithelial growth factor receptor, neuropilin-1, low-density lipoprotein receptor, and neuropeptide Y receptors. We note that PDT can increase the expression of some molecules that reduce the effectiveness of therapy, such as Vascular endothelial growth factor (VEGF), glutamate, and nitric oxide. However, the scientific literature lacks clear data on the effects of PDT on many of the molecules described, and the available reports are often contradictory. In our work, we highlight the gaps in this knowledge and point to directions for further research that may enhance the efficacy of PDT in the treatment of glioma.

The optimization of hydrogel structure is crucial for adsorption capacity, mechanical stability, and reusability. Herein, a chitosan and laponite-XLS co-doped poly(acrylic acid-co-acrylamide) hydrogel (CXAA) with honeycomb-like porous structures is synthesized by cooperative cross-linking of 2-hydroxypropyltrimethyl ammonium chloride chitosan (HACC) and laponite-XLS in reticular frameworks of acrylic acid (AAc) and acrylamide (AM). The CXAA exhibits extraordinary mechanical performances including tough tensile strength (3.36 MPa) and elasticity (2756 %), which facilitates recycling in practical adsorption treatment and broadens potential applications. Since the regular porous structures can fully expose numerous adsorption sites and electronegative natures within polymer materials, CXAA displays efficient and selective adsorption properties for cationic dyes like methylene blue (MB) and malachite green (MG) from mixed pollutants and can reach record-high values (MB = 6886 mg g -1 , MG = 11,381 mg g -1 ) compared with previously reported adsorbents. Therefore, CXAA exhibits promising potential for separating cationic and anionic dyes by their charge disparities. Mechanism studies show that the synergistic effects of HACC, laponite-XLS, and functional groups in monomers promote highly efficient adsorption. Besides, the adsorption capacity of CXAA remains stable even after undergoing five cycles of regeneration. The results confirm that CXAA is a promising adsorbent for effectively removing organic dyes in wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Ethylene glycol (EG) is one of the most attractive platform molecules derived from biomass and waste plastics. Thus, the selective electrooxidation of ethylene glycol (EGOR) into value-added chemicals (especially glycolic acid (GA)) can promote its recycling and upgrading. However, the understanding of the EG-to-GA process on Pt-group metal (PGM) electrodes is far limited now. It has been shown that the Pt and Pd electrodes could show considerable EGOR activity but not Rh and Ir electrodes. Meanwhile, EGOR mainly produces the glycolate, oxalate, and formate on Pt and Pd electrodes, whereas it can obtain minute amounts of glycolate and oxalate on Rh and Ir electrodes. Impressively, the selectivity of glycolate on Pt and Pd electrodes can be over 85% (apparent Faradaic efficiency) in alkaline media, although the stability should be further improved through interfacial tuning and/or engineering. This work might deepen the fundamental understanding of the EGOR process on the nature of PGM electrodes.

Spectroscopic studies on domains and peptides of large proteins are complicated because of the tendency of short peptides to form oligomers in aquatic buffers, but conjugation of a peptide with a carrier protein may be helpful. In this study we approved that a fragment of SK30 peptide from phospholipase A2 domain of VP1 Parvovirus B19 capsid protein (residues: 144-159; 164; 171-183; sequence: SAVDSAARIHDFRYSQLAKLGINPYTHWTVADEELLKNIK) turns from random coil to alpha helix in the acidic medium only in case if it had been conjugated with BSA (through additional N-terminal Cys residue, turning it into CSK31 peptide, and SMCC linker) according to CD-spectroscopy results. In contrast, unconjugated SK30 peptide does not undergo such shift because it forms stable oligomers connected by intermolecular antiparallel beta sheet, according to IR-spectroscopy, CD-spectroscopy, blue native gel electrophoresis and centrifugal ultrafiltration, as, probably, the whole isolated phospholipase domain of VP1 protein does. However, being a part of the long VP1 capsid protein, phospholipase domain may change its fold during the acidification of the medium in the endolysosome by the way of the formation of contacts between protonated His153 and Asp175, promoting the shift from random coil to alpha helix in its N-terminal part. This study opens up a perspective of vaccine development, since rabbit polyclonal antibodies against the conjugate of CSK31 peptide with BSA, in which the structure of the second alpha helix from the phospholipase A2 domain should be reproduced, can bind epitopes of the complete recombinant unique part of VP1 Parvovirus B19 capsid (residues: 1-227)., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Over the past decades, medicine has made enormous progress, revolutionized by modern technologies and innovative therapeutic approaches. One of the most exciting branches of these developments is photodynamic therapy (PDT). Using a combination of light of a specific wavelength and specially designed photosensitizing substances, PDT offers new perspectives in the fight against cancer, bacterial infections, and other diseases that are resistant to traditional treatment methods. In today's world, where there is a growing problem of drug resistance, the search for alternative therapies is becoming more and more urgent. Imagine that we could destroy cancer cells or bacteria using light, without the need to use strong chemicals or antibiotics. This is what PDT promises. By activating photosensitizers using appropriately adjusted light, this therapy can induce the death of cancer or bacterial cells while minimizing damage to surrounding healthy tissues. In this work, we will explore this fascinating method, discovering its mechanisms of action, clinical applications, and development prospects. We will also analyze the latest research and patient testimonies to understand the potential of PDT for the future of medicine.

Background: Resistance to anti-tumor agents targeting the epidermal growth factor receptor (EGFR) reduces treatment response and requires the development of novel EGFR antagonists. Mutant epidermal growth factor (EGF) forms with reduced agonistic activity could be promising agents in cancer treatment., Methods: EGF D46G affinity to EGFR domain III was assessed with affinity chromatography. EGF D46G acute toxicity in Af albino mice at 320 and 3200 μg/kg subcutaneous doses was evaluated. EGF D46G activity in human epidermoid carcinoma cells at 10 ng/mL concentration in serum-free medium and in subcutaneous Ehrlich ascites carcinoma mice model at 320 μg/kg dose was studied., Results: The D46G substitution decreases the thermal stability of EGF complexes with EGFR domain III by decreasing the ability of the C-terminus to be released from the intermolecular β- sheet. However, with remaining binding sites for EGFR domain I, EGF D46G effectively competes with other EGF-like growth factors for binding to EGFR and does not demonstrate toxic effects in mice. EGF D46G inhibits the proliferation of human epidermoid carcinoma cells compared to native EGF. A single subcutaneous administration of EGF D46G along with Ehrlich carcinoma cells injection inhibits the proliferation of these cells and delays tumor formation for up to seven days., Conclusion: EGF D46G can be defined as a partial EGFR agonist as this mutant form demonstrates reduced agonistic activity compared to native EGF. The study emphasizes the role of the EGF C-terminus in establishing interactions with EGFR domain III, which are necessary for EGFR activation and subsequent proliferation of cells., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Our study explores the development of collagen membranes with integrated minocycline or irinotecan, targeting applications in tissue engineering and drug delivery systems. Type I collagen, extracted from bovine skin using advanced fibril-forming technology, was crosslinked with glutaraldehyde to create membranes. These membranes incorporated minocycline, an antibiotic, or irinotecan, a chemotherapeutic agent, in various concentrations. The membranes, varying in drug concentration, were studied by water absorption and enzymatic degradation tests, demonstrating a degree of permeability. We emphasize the advantages of local drug delivery for treating high-grade gliomas, highlighting the targeted approach's efficacy in reducing systemic adverse effects and enhancing drug bioavailability at the tumor site. The utilization of collagen membranes is proposed as a viable method for local drug delivery. Irinotecan's mechanism, a topoisomerase I inhibitor, and minocycline's broad antibacterial spectrum and inhibition of glial cell-induced membrane degradation are discussed. We critically examine the challenges posed by the systemic administration of chemotherapeutic agents, mainly due to the blood-brain barrier's restrictive nature, advocating for local delivery methods as a more effective alternative for glioblastoma treatment. These local delivery strategies, including collagen membranes, are posited as significant advancements in enhancing therapeutic outcomes for glioblastoma patients., Competing Interests: The authors declare no conflicts of interest.

Photodynamic therapy (PDT) is a promising cancer treatment method that uses photosensitizing (PS) compounds to selectively destroy tumor cells using laser light. This review discusses the main advantages of PDT, such as its low invasiveness, minimal systemic toxicity and low risk of complications. Special attention is paid to photosensitizers obtained by chemical synthesis. Three generations of photosensitizers are presented, starting with the first, based on porphyrins, through the second generation, including modified porphyrins, chlorins, 5-aminolevulinic acid (ALA) and its derivative hexyl aminolevulinate (HAL), to the third generation, which is based on the use of nanotechnology to increase the selectivity of therapy. In addition, current research trends are highlighted, including the search for new photosensitizers that can overcome the limitations of existing therapies, such as heavy-atom-free nonporphyrinoid photosensitizers, antibody-drug conjugates (ADCs) or photosensitizers with a near-infrared (NIR) absorption peak. Finally, the prospects for the development of PDTs are presented, taking into account advances in nanotechnology and biomedical engineering. The references include both older and newer works. In many cases, when writing about a given group of first- or second-generation photosensitizers, older publications are used because the properties of the compounds described therein have not changed over the years. Moreover, older articles provide information that serves as an introduction to a given group of drugs.

Photodynamic therapy (PDT) can not only directly eliminate cancer cells, but can also stimulate antitumor immune responses. It also affects the expression of immune checkpoints. The purpose of this review is to collect, analyze, and summarize recent news about PDT and immune checkpoints, along with their inhibitors, and to identify future research directions that may enhance the effectiveness of this approach. A search for research articles published between January 2023 and March 2024 was conducted in PubMed/MEDLINE. Eligibility criteria were as follows: (1) papers describing PDT and immune checkpoints, (2) only original research papers, (3) only papers describing new reports in the field of PDT and immune checkpoints, and (4) both in vitro and in vivo papers. Exclusion criteria included (1) papers written in a language other than Polish or English, (2) review papers, and (3) papers published before January 2023. 24 papers describing new data on PDT and immune checkpoints have been published since January 2023. These included information on the effects of PDT on immune checkpoints, and attempts to associate PDT with ICI and with other molecules to modulate immune checkpoints, improve the immunosuppressive environment of the tumor, and resolve PDT-related problems. They also focused on the development of new nanoparticles that can improve the delivery of photosensitizers and drugs selectively to the tumor. The effect of PDT on the level of immune checkpoints and the associated activity of the immune system has not been fully elucidated further, and reports in this area are divergent, indicating the complexity of the interaction between PDT and the immune system. PDT-based strategies have been shown to have a beneficial effect on the delivery of ICI to the tumor. The utility of PDT in enhancing the induction of the antitumor response by participating in the triggering of immunogenic cell death, the exposure of tumor antigens, and the release of various alarm signals that together promote the activation of dendritic cells and other components of the immune system has also been demonstrated, with the result that PDT can enhance the antitumor immune response induced by ICI therapy. PDT also enables multifaceted regulation of the tumor's immunosuppressive environment, as a result of which ICI therapy has the potential to achieve better antitumor efficacy. The current review has presented evidence of PDT's ability to modulate the level of immune checkpoints and the effectiveness of the association of PDT with ICIs and other molecules in inducing an effective immune response against cancer cells. However, these studies are at an early stage and many more observations need to be made to confirm their efficacy. The new research directions indicated may contribute to the development of further strategies.

Water hyacinth plants (Eichhornia crassipes Mart.) collected from two South African rivers were analyzed in order to investigate their suitability for judging the presence of pharmaceuticals in the water. Thereby, a number of drugs, including amitriptyline, atenolol, citalopram, orphenadrine, lidocaine, telmisartan, and tramadol, could be detected. Particularly for the latter substance, relatively high concentrations (more than 5000 ng g -1 dry plant material) were detected in the water plants. Subsequently, the plant extracts were also screened for drug-derived transformation products, whereby a series of phase-one metabolites could be tentatively identified., (© 2024 The Author(s). Electrophoresis published by Wiley‐VCH GmbH.)

Appreciating reactivity in terms of physicochemical effects for chemical processes is one of the most important undertakings in chemistry. While transition state (TS) theory provides the framework enabling the reliable calculation of the barrier height for a given elementary step, analytical tools are necessary to gain insight into key factors governing the different processes during chemical reactions. In this contribution, we partition the potential energy surface of an elementary step along the intrinsic coordinate into three segments, the so-called Pre-TS, TS, and Post-TS regions, and then determine the most important factors dictating each segment. This analysis is based on the use of both reactivity descriptors from conceptual density functional theory and concepts from the information-theoretic approach in density functional theory. We found that in both Pre-TS and Post-TS regions, steric effects are the dominant factors, whereas in the TS region, it is the intrinsic electrophilic and nucleophilic propensity of the transition state structure that governs the reactivity. The wide applicability of our approach is shown by a validation for a total of 37 organic and inorganic reactions. This work thus, in our view, provides a novel perspective on how chemical reactivity can be quantified at different stages of chemical reactions., (© 2024 Wiley‐VCH GmbH.)

Tiliroside is a natural polyphenolic compound with a wide range of biological activity, and defatted strawberry seeds are its rich source. The goal of this study was to optimize accelerated solvent extraction (ASE) conditions, including temperature, solvent composition, and the number of extraction cycles, using Box-Behnken design to maximize the yield of tiliroside. UPLC-DAD-MS was applied to investigate the polyphenolic composition of the extracts, and preparative liquid chromatography (pLC) was used for isolation. All obtained mathematical models generally showed an increase in the efficiency of isolating polyphenolic compounds with an increase in temperature, ethanol content, and the number of extraction cycles. The optimal established ASE conditions for tiliroside were as follows: a temperature of 65 °C, 63% ethanol in water, and four extraction cycles. This allowed for the obtainment of a tiliroside-rich fraction, and the recovery of isolated tiliroside from plant material reached 243.2 mg from 100 g. Our study showed that ASE ensures the isolation of a tiliroside-rich fraction with high effectiveness. Furthermore, defatted strawberry seeds proved to be a convenient source of tiliroside because the matrix of accompanying components is relatively poor, which facilitates separation.

Chiral pyrrolidines are common structural motives in natural products as well as active pharmaceutical ingredients, explaining the need for methods for their enantioselective synthesis. While several, often metal-catalyzed, methods for their preparation do exist, the enantioselective synthesis of pyrrolidines containing quaternary stereocenters remains challenging. Herein, we report a Bro̷nsted acid-catalyzed intramolecular hydroamination that provides such pyrrolidines from simple starting materials in high yield and enantioselectivity. Key to an efficient reaction was the use of an electron-deficient protective group on nitrogen, the common nosyl-protecting group, to avoid deactivation of the Bro̷nsted acid by deprotonation. The reaction proceeds as a stereospecific anti -addition indicating a concerted reaction. Furthermore, kinetic studies show Michaelis-Menten behavior, suggesting the formation of a precomplex similar to those observed in enzymatic catalysis.

TiZrTaAg alloy is a remarkable material with exceptional properties, making it a unique choice among various industrial applications. In the present study, two types of bioactive coatings using MAPLE were obtained on a TiZrTaAg substrate. The base coating consisted in a mixture of chitosan and bioglass in which zinc oxide and graphene oxide were added. The samples were characterized in-depth through a varied choice of methods to provide a more complete picture of the two types of bioactive coating. The analysis included Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), ellipsometry, and micro-Raman. The Vickers hardness test was used to determine the hardness of the films and the penetration depth. Film adhesion forces were determined using atomic force microscopy (AFM). The corrosion rate was highlighted by polarization curves and by using electrochemical impedance spectroscopy (EIS). The performed tests revealed that the composite coatings improve the properties of the TiZrTaAg alloy, making them feasible for future use as scaffold materials or in implantology.

Spectroscopic properties are commonly used in the experimental evaluation of ground- and excited-state aromaticity in expanded porphyrins. Herein, we investigate if the defining photophysical properties still hold for a diverse set of hexaphyrins with varying redox states, topologies, peripheral substitutions, and core-modifications. By combining TD-DFT calculations with several aromaticity descriptors and chemical compound space maps, the intricate interplay between structural planarity, aromaticity, and absorption spectra is elucidated. Our results emphasize that the general assumption that antiaromatic porphyrinoids exhibit significantly attenuated absorption bands as compared to aromatic counterparts does not hold even for the unsubstituted hexaphyrin macrocycles. To connect the spectroscopic properties to the hexaphyrins' aromaticity behaviour, we analyzed chemical compound space maps defined by the various aromaticity indices. The intensity of the Q-band is not well described by the macrocyclic aromaticity. Instead, the degeneracy of the frontier molecular orbitals, the HOMO-LUMO gap, and the |ΔHOMO-ΔLUMO| 2 values appear to be better indicators to identify hexaphyrins with enhanced light-absorbing abilities in the near-infrared region. Regions with highly planar hexaphyrin structures, both aromatic and antiaromatic, are characterized by an intense B-band. Hence, we advise using a combination of global and local aromaticity descriptors rooted in different criteria to assess the aromaticity of expanded porphyrins instead of solely relying on the absorption spectra., (© 2024 Wiley-VCH GmbH.)

This study comprehensively analyzes the magnetically induced current density of polycyclic compounds labeled as "aromatic chameleons" since they can arrange their π-electrons to exhibit aromaticity in both the ground and the lowest triplet state. These compounds comprise benzenoid moieties fused to a central skeleton with 4n π-electrons and traditional magnetic descriptors are biased due to the superposition of local magnetic responses. In the S 0 state, our analysis reveals that the molecular constituent fragments preserve their (anti)aromatic features in agreement with two types of resonant structures: one associated with aromatic benzenoids and the other with a central antiaromatic ring. Regarding the T 1 state, a global and diatropic ring current is revealed. Our aromaticity study is complemented with advanced electronic and geometric descriptors to consider different aspects of aromaticity, particularly important in the evaluation of excited state aromaticity. Remarkably, these descriptors consistently align with the general features on the main delocalization pathways in polycyclic hydrocarbons consisting of fused 4n π-electron rings. Moreover, our study demonstrates an inverse correlation between the singlet-triplet energy difference and the antiaromatic character of the central ring in S 0 ., (© 2024 Wiley-VCH GmbH.)

In this work, we synthesized and confirmed the structure of several alkaloid N-oxides using mass spectrometry and Fourier-transform infrared spectroscopy. We also investigated their reduction mechanisms using voltammetry. For the first time, we obtained alkaloid N-oxides using an oxidation reaction with potassium peroxymonosulfate as an oxidant. The structure was established based on the obtained fragmentation mass spectra recorded by LC-Q-ToF-MS. In the FT-IR spectra of the alkaloid N-oxides, characteristic signals of N-O group vibrations were recorded (bands in the range of 928 cm⁻ 1 to 971 cm⁻ 1 ), confirming the presence of this functional group. Electrochemical reduction studies demonstrated the reduction of alkaloid N-oxides at mercury-based electrodes back to the original form of the alkaloid. For the first time, the products of the electrochemical reduction of alkaloid N-oxides were detected by mass spectrometry. The findings provide insights into the structural characteristics and reduction behaviors of alkaloid N-oxides, offering implications for pharmacological and biochemical applications. This research contributes to a better understanding of alkaloid metabolism and degradation processes, with potential implications for drug development and environmental science.

The study carried out systematic research on the influence of selected oxysterols on cells viability, phospholipidosis and the level of secreted extracellular vesicles. Three oxidized cholesterol derivatives, namely 7α-hydroxycholesterol (7α-OH), 7- ketocholesterol (7-K) and 24(S)-hydroxycholesterol (24(S)-OH) were tested in three different concentrations: 50 μM, 100 μM and 200 μM for 24 h incubation with A549 lung cancer cell line. All the studied oxysterols were found to alter cells viability. The lowest survival rate of the cells was observed after 24 h of 7-K treatment, slightly better for 7α-OH while cells incubated with 24(S)-OH had the best survival rate among the oxysterols used. 7-K increased phospholipids accumulation in cells, however, most noticeable effect was noticed for 24(S)-OH. Changes in the level of extracellular vesicles secreted in cells culture after the treatment with oxysterols were also observed. It was found that all oxysterols used increased the level of secreted vesicles, both exosomes and ectosomes. The strongest effect was noticed for 24(S)-OH. Taken together, these results suggest that 7-K is the most potent inducer of cancer cell death, while 7α-OH is slightly less potent in this respect. The lower cytotoxic effect of 24(S)-OH correlates with greater phospholipids accumulation, extracellular vesicles production and better cells survival., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Multistress effects lead to unpredicted consequences in aquatic ecotoxicology and are extremely concerning. The goal of this study was to trace how specific effects of the antibiotic salinomycin (Sal) and microplastics (MP) on the bivalve molluscs are manifested in the combined environmentally relevant exposures. Unio tumidus specimens were treated with Sal (0.6 μg L -1 ), MP (1 mg L -1 , 2 μm size), and both at 18 °C (Mix) and 25 °C (MixT) for 14 days. The redox stress and apoptotic enzyme responses and the balance of Zn/Cu in the digestive gland were analyzed. The shared signs of stress included a decrease in NAD + /NADH and Zn/Cu ratios and lysosomal integrity and an increase in Zn-metallothioneins and cholinesterase levels. MP caused a decrease in the glutathione (GSH) concentration and redox state, total antioxidant capacity, and Zn levels. MP and Mix induced coordinated apoptotic/autophagy activities, increasing caspase-3 and cathepsin D (CtD) total and extralysosomal levels. Sal activated caspase-3 only and increased by five times Cu level in the tissue. Due to the discriminant analysis, the cumulative effect was evident in the combined exposure at 18 °C. However, under heating, the levels of NAD + , NADH, GSH, GSH/GSSG and metallothionein-related thiols were decreased, and coordination of the cytosolic and lysosomal death stimuli was distorted, confirming that heating and pollution could exert unexpected synergistic effects on aquatic life., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

The extension of conceptual density-functional theory (conceptual DFT) to include external electromagnetic fields in chemical systems is utilised to investigate the effects of strong magnetic fields on the electronic charge distribution and its consequences on the reactivity of π-systems. Formaldehyde, H 2 CO, is considered as a prototypical example and current-density-functional theory (current-DFT) calculations are used to evaluate the electric dipole moment together with two principal local conceptual DFT descriptors, the electron density and the Fukui functions, which provide insight into how H 2 CO behaves chemically in a magnetic field. In particular, the symmetry properties of these quantities are analysed on the basis of group, representation, and corepresentation theories using a recently developed automatic program for symbolic symmetry analysis, QSYM 2 . This allows us to leverage the simple symmetry constraints on the macroscopic electric dipole moment components to make profound predictions on the more nuanced symmetry transformation properties of the microscopic frontier molecular orbitals (MOs), electron densities, and Fukui functions. This is especially useful for complex-valued MOs in magnetic fields whose detailed symmetry analyses lead us to define the new concepts of modular and phasal symmetry breaking . Through these concepts, the deep connection between the vanishing constraints on the electric dipole moment components and the symmetry of electron densities and Fukui functions can be formalised, and the inability of the magnetic field in all three principal orientations considered to induce asymmetry with respect to the molecular plane of H 2 CO can be understood from a molecular perspective. Furthermore, the detailed forms of the Fukui functions reveal a remarkable reversal in the direction of the dipole moment along the CO bond in the presence of a parallel or perpendicular magnetic field, the origin of which can be attributed to the mixing between the frontier MOs due to their subduced symmetries in magnetic fields. The findings in this work are also discussed in the wider context of a long-standing debate on the possibility to create enantioselectivity by external fields.

Resulting from the solubility reduction of elemental sulfur during the development of high sulfur gas formations, sulfur deposition often occurs to reduce the gas production and threaten the safety of gas wells. Understanding the dissolution mechanism of elemental sulfur in natural gas is essential to reduce the risk caused by sulfur deposition. Because of the harsh conditions in the high-sulfur formations, it remains challenging to in situ characterize the dissolution-precipitation processes, making deficient the knowledge of sulfur dissolution mechanism. The dissolution of sulfur allotropes (S N , N = 2, 4, 6 and 8) in H 2 S, the main solvent of sulfur in natural gas, is studied in this work by means of first-principles calculations and molecular dynamics simulations. While S 6 and S 8 undergo physical interaction with H 2 S under the conditions corresponding to those at 1-6 km stratigraphic depths, S 2 and S 4 react with H 2 S and form stable polysulfides. Unravelling the mechanism would be helpful for understanding and controlling the sulfur deposition in high-sulfur gas development., Competing Interests: The authors declare no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

The new hydrazine 5 H -dibenzo[ b , f ]azepin-5-amine (2) reacts with P- and Si-electrophiles via deprotonation to afford P(III)-, P(V)-, and TMS-hydrazides 3-8 and with carbonyl electrophiles via acid-free condensation to the N -substituted hydrazones 9-12 that are potential N -alkene ligands. While β-ketohydrazone 9 and α-dihydrazone 10 react with [Mes(Cu)] 4 , [Cu(NCCCH 3 ) 4 ] 2 PF 6 , and FeCl 2 (THF) 1.5 to afford complexes devoid of alkene interaction, [Cu(OTf)] 2 ·C 6 H 6 reacts with the α-keto hydrazone 11 or with N , N dimethyl-hydrazone 12 to form the neutral dimeric Cu(I) complex 18 with bridging Cu(I)-alkene interactions or the tetrahedral cationic complex 19 in which 12 binds as a bidentate hydrazone-alkene ligand, respectively. The surprising stability of the alkene coordination in complexes 18 and 19 prevents substitutions with, e.g. , PPh 3 .

In this report, we present the dual activation models for transient directing group-directed and amino-self-directed Pd-catalyzed α-aminophosphonate side-chain C(sp 3 )-H arylation. Both strategies showed facile, efficient, and single regioselectivity in the reaction between free α-aminophosphonates and aryl iodides. Furthermore, the modification of amino and late-stage functionalization of the C(sp 3 )-P bond from products indicates potential applications for α-aminophosphonates.

Cancer therapy, especially for tumors near sensitive areas, demands precise treatment. This review explores photodynamic therapy (PDT), a method leveraging photosensitizers (PS), specific wavelength light, and oxygen to target cancer effectively. Recent advancements affirm PDT's efficacy, utilizing ROS generation to induce cancer cell death. With a history spanning over decades, PDT's dynamic evolution has expanded its application across dermatology, oncology, and dentistry. This review aims to dissect PDT's principles, from its inception to contemporary medical applications, highlighting its role in modern cancer treatment strategies., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Aebisher, Rogóż, Myśliwiec, Dynarowicz, Wiench, Cieślar, Kawczyk-Krupka and Bartusik-Aebisher.)

Plastic materials are ubiquitous and raise concerns about their impact on health and the environment. To address these concerns, it is crucial to characterize the structural, size, and textural properties of plastics throughout their lifecycle from production to degradation. Raman spectroscopy appears as a valuable tool for this purpose, offering speed, robustness, and sensitivity to nanoscale and amorphous particles. In order to be properly used for plastics, the Raman response of reference materials needs to be carefully assessed, with the literature on such assessments being scarce. This study addresses this gap by using theoretical calculations to generate ab initio spectra for polystyrene, a reference material. The aim is to explain the origins of the spectral peaks and their consistency across various compositions and structures using linear ordered polymeric and finite amorphous models. The CRYSTAL package is employed to obtain full Raman spectra based on a careful benchmark of computational settings. While some peaks are present across all spectra and can serve for calibration, others exhibit structure-dependent behavior, enabling polymer identification. We conclude that Raman spectroscopy is a well-suited technique for plastics characterization provided that a careful analysis of signal origin is conducted to fully interpret the spectra and deploy applications.

Metallic lithium (Li) is highly desirable for Li battery anodes due to its unique advantages. However, the growth of Li dendrites poses challenges for commercialization. To address this issue, researchers have proposed various three-dimensional (3D) current collectors. In this study, the selective modification of a 3D Cu foam scaffold with lithiophilic elements was explored to induce controlled Li deposition. The Cu foam was selectively modified with Ag and Sn to create uniform Cu foam (U-Cu) and gradient lithiophilic Cu foam (G-Cu) structures. Density Functional Theory (DFT) calculations revealed that Ag exhibited a stronger binding energy with Li compared to Sn, indicating superior Li induction capabilities. Electrochemical testing demonstrated that the half cell with the G-Cu@Ag electrode exhibited excellent cycling stability, maintaining 550 cycles with an average Coulombic efficiency (CE) of 97.35%. This performance surpassed that of both Cu foam and G-Cu@Sn. The gradient modification of the current collectors improved the utilization of the 3D scaffold and prevented Li accumulation at the top of the scaffold. Overall, the selective modification of the 3D Cu foam scaffold with lithiophilic elements, particularly Ag, offers promising prospects for mitigating Li dendrite growth and enhancing the performance of Li batteries., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

A microneedle transdermal drug delivery system simultaneously avoids systemic toxicity of oral administration and low efficiency of traditional transdermal administration, which is of great significance for acne vulgaris therapy. Herein, eugenol-loaded hyaluronic acid-based dissolving microneedles (E@P-EO-HA MNs) with antibacterial and anti-inflammatory activities are developed for acne vulgaris therapy via eugenol transdermal delivery integrated with photothermal therapy. E@P-EO-HA MNs are pyramid-shaped with a sharp tip and a hollow cavity structure, which possess sufficient mechanical strength to penetrate the stratum corneum of the skin and achieve transdermal delivery, in addition to excellent in vivo biocompatibility. Significantly, E@P-EO-HA MNs show effective photothermal therapy to destroy sebaceous glands and achieve antibacterial activity against deep-seated Propionibacterium acnes ( P. acnes ) under near-infrared-light irradiation. Moreover, cavity-loaded eugenol is released from rapidly dissolved microneedle bodies to play a sustained antibacterial and anti-inflammatory therapy on the P. acnes infectious wound. E@P-EO-HA MNs based on a synergistic therapeutic strategy combining photothermal therapy and eugenol transdermal administration can significantly alleviate inflammatory response and ultimately facilitate the repair of acne vulgaris. Overall, E@P-EO-HA MNs are expected to be clinically applied as a functional minimally invasive transdermal delivery strategy for superficial skin diseases therapy in skin tissue engineering.

A method for generation of S VI sulfones from β-sulfinyl esters (S IV ) under transition-metal-free non-oxidative mild conditions is presented. Various sulfones have been achieved with moderate to excellent yields. The advantage of using β-sulfinyl esters as masked aryl sulfinates has also been exemplified using brominated substrates. Oxygen isotope-labeling experiments indicated that the oxygen atoms incorporated into the sulfone product come from the sulfoxide of the β-sulfinyl ester. Successive β-elimination/ O -addition/sulfinate esterification/β-elimination processes are proposed for the mechanism of generating S VI from S IV .

The challenge of drug resistance in bacteria caused by the over use of biotics is increasing during the therapy process, which has attracted great attentions of the clinicians and scientists around the world. Recently, photodynamic therapy (PDT) triggered by photosensitizer (PS) has become a promising treatment method because of its high efficacy, easy operation, and low side effect. Herein, the poly-l-lysine (PLL) modified metal-organic framework (MOF) nanoparticles, ZIF/PLL-CIP/CUR, were synthesized to allow both reactive oxygen species (ROS) responsive drug release and photodynamic effect for synergistic therapy against drug resistant bacterial infections. The PLL was modified on the shell of the zeolite imidazole framework (ZIF) by the ROS-responsive thioketal linker for controllable CIP release. CUR were encapsulated in ZIF as the photosensitizer for blue light mediated photodynamic effect to produce singlet oxygen ( 1 O 2 ) and superoxide anion radical (O 2 - ) for efficient inhibition towards methicillin-resistant Staphylococcus aureus (MRSA). The charge conversion from negative charge (-4.6 mV) to positive charge (2.6 mV) was observed at pH 7.4 and pH 5.5, and 70.9 % CIP was found released at pH 5.5 in the presence of H 2 O 2 , which suggests the good biosafety at physiological pH and ROS-responsive drug release of the as-prepared nanoparticle in the bacterial microenvironment. The as-prepared nanoparticles could effectively kill MRSA and disrupt bacterial biofilm by combination of chemo- and photodynamic therapy. In mice model, the as-prepared nanoparticles exhibited excellent biosafety and synergistic effect with 98.81 % healing rate in treatment of MRSA infection, which is considered as a promising candidate in combating drug resistant bacterial infection., Competing Interests: Declaration of competing interest All authors have read and approved this version of the article, and due care has been taken to ensure the integrity of the work. No part of this manuscript has published or submitted elsewhere. No conflict of interest exits in the submission of this manuscript., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Lipids, together with lipoprotein particles, are the cause of atherosclerosis, which is a pathology of the cardiovascular system. In addition, it affects inflammatory processes and affects the vessels and heart. In pharmaceutical answer to this, statins are considered a first-stage treatment method to block cholesterol synthesis. Many times, additional drugs are also used with this method to lower lipid concentrations in order to achieve certain values of low-density lipoprotein (LDL) cholesterol. Recent advances in photodynamic therapy (PDT) as a new cancer treatment have gained the therapy much attention as a minimally invasive and highly selective method. Photodynamic therapy has been proven more effective than chemotherapy, radiotherapy, and immunotherapy alone in numerous studies. Consequently, photodynamic therapy research has expanded in many fields of medicine due to its increased therapeutic effects and reduced side effects. Currently, PDT is the most commonly used therapy for treating age-related macular degeneration, as well as inflammatory diseases, and skin infections. The effectiveness of photodynamic therapy against a number of pathogens has also been demonstrated in various studies. Also, PDT has been used in the treatment of cardiovascular diseases, such as atherosclerosis and hyperplasia of the arterial intima. This review evaluates the effectiveness and usefulness of photodynamic therapy in cardiovascular diseases. According to the analysis, photodynamic therapy is a promising approach for treating cardiovascular diseases and may lead to new clinical trials and management standards. Our review addresses the used therapeutic strategies and also describes new therapeutic strategies to reduce the cardiovascular burden that is induced by lipids.

Metal-organic framework (MOF) materials have unique structure and fantastic properties for wide-ranging applications. Pilot studies highlighted the toxicity and potential threats of MOF materials to the environment. In this study, we revealed the phytotoxicity of MOF-74(Co) nanoparticles (NPs) and their inhibitory effects on the photosynthesis of pea seedlings ( Pisum sativum L.). MOF-74(Co) NPs have limited influences on the germination of pea seeds, but distinct environmental effects of MOF-74(Co) NPs were found in pea seedlings. The root length of pea seedlings, fresh weight and dry weight decreased by 50.0%, 29.2% and 36.4%, respectively, compared with the control group, when the material concentration was greater than 100 mg L -1 . The net photosynthetic rate decreased by 48% and the intercellular CO 2 concentration increased by 183% upon exposure to MOF-74(Co) NPs. Mechanistically, MOF-74(Co) exposure led to Co uptake in pea seedlings; the increases were 223% for the root, 267% for the stem and 6562% for the leaves, respectively, when the MOF-74(Co) NP concentration was 10 mg L -1 . The released Co ions from MOF-74(Co) NPs caused oxidative damage to leaves and induced damage to the acceptor side of photosynthesis system II. Our results indicated that the environmental toxicity of MOF materials was largely regulated by the metal centers. MOF materials with nontoxic metal elements are desirable for future applications.

Ethylenediamine (EDA) is a crucial chemical raw material and fine chemical intermediate. Compared with the industrial approach of ammonolysis of 1,2-dichloroethane, the catalytic amination of ethylene glycol (EG) is an economical and environmentally benign route that will be the future trend for EDA synthesis. Herein, we systemically review the recent progress in direct and indirect catalytic conversion of EG to EDA. Furthermore, different types of catalysts are discussed: (i) supported metal and multimetallic catalysts, (ii) solid acid catalysts, and (iii) other active catalysts (e.g., ionic liquids and metal complexes). Finally, we conclude with the frontiers and future prospects of the catalytic synthesis of EDA from EG and monoethanolamine, providing readers a snapshot of this field., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

This work presents the synthesis of CoSb 3 one-dimensional (1D) thermoelectric nanomaterials using electrodeposition under galvanostatic conditions and polycarbonate membranes as a template (50 nm diameter pores). Cyclic voltammetry measurements have been performed to get preliminary information on the electrochemical reduction process of the involved species. Different current density values in the range 1-4 mA cm -2 have been applied, leading to the formation of nanowires (NWs) and micro- and nanomushroom caps, as evidenced by the scanning electron microscopy and scanning transmission electron microscopy investigations. Through fine-tuning of the current density the desired Co/Sb atomic ratio could be achieved. Energy-dispersive X-ray spectroscopy analysis showed the formation of CoSb 3 at 1.4 mA cm -2 , and it has also been confirmed by high-resolution transmission electron microscopy and micro-Raman spectroscopy. In this work, we present for the first time the fabrication of a CoSb 3 -Co x Sb y heterojunction on the same NW exhibiting Sb-rich and Co-rich alloy segments, prepared by electrodeposition from the same electrolyte by simply varying the applied current density.

Atopic dermatitis (AD) is an abnormal inflammatory response in the skin to food, environmental IgE, or non-IgE allergens. This disease belongs to a group of inflammatory diseases that affect both children and adults. In highly developed countries, AD is diagnosed twice as often in children than in adults, which may possibly be connected to increased urbanization. The immune system's pathomechanisms of AD involve humoral mechanisms with IgE, cellular T lymphocytes, dendritic cells occurring in the dermis, Langerhans cells occurring in the epidermis, and other cells infiltrating the site of inflammation (eosinophils, macrophages, mast cells, neutrophils, and basophils). Cytokines are small proteins that affect the interaction and communication between cells. This review characterizes cytokines and potential aspects of the treatment of atopic dermatitis, as well as new strategies that are currently being developed, including targeting cytokines and their receptors.

The development of highly efficient electrocatalysts for complete oxidation of ethylene glycol (EG) in direct EG fuel cells is of decisive importance to hold higher energy efficiency. Despite some achievements, their progress, especially electrocatalytic selectivity to complete oxidated C 1 products, is remarkably slower than expected. In this work, we developed a facile aqueous synthesis of Ir-doped CuPd single-crystalline mesoporous nanotetrahedrons (Ir-CuPd SMTs) as high-performance electrocatalyst for promoting oxidation cleavage of C-C bond in alkaline EG oxidation reaction (EGOR) electrocatalysis. The synthesis relied on precise reduction/co-nucleation and epitaxial growth of Ir, Cu and Pd precursors with cetyltrimethylammonium chloride as the mesopore-forming surfactant and extra Br - as the facet-selective agent under ambient conditions. The products featured concave nanotetrahedron morphology enclosed by well-defined (111) facets, single-crystalline and mesoporous structure radiated from the center, and uniform elemental composition without any phase separation. Ir-CuPd SMTs disclosed remarkably enhanced electrocatalytic activity and excellent stability as well as superior selectivity of C 1 products for alkaline EGOR electrocatalysis. Detailed mechanism studies demonstrated that performance improvement came from structural and compositional synergies, which kinetically accelerated transports of electrons/reactants within active sites of penetrated mesopores and facilitated oxidation cleavage of high-energy-barrier C-C bond of EG for desired C 1 products. More interestingly, Ir-CuPd SMTs performed well in coupled electrocatalysis of anode EGOR and cathode nitrate reduction, highlighting its high potential as bifunctional electrocatalyst in various applications., (© 2024 Wiley‐VCH GmbH.)

Polyaniline (PANI) constitutes a very propitious conductive polymer utilized in several biomedical, as well as environmental applications, including tissue engineering, catalysis, and photocatalysis, due to its unique properties. In this study, nano-PANI/N-TiO 2 and nano-PANI/Ag-TiO 2 photocatalytic composites were fabricated via aniline's oxidative polymerization, while the Ag-and N-chemically modified TiO 2 nanopowders were synthesized through the sol-gel approach. All produced materials were fully characterized. Through micro-Raman and FT-IR analysis, the co-existence of PANI and chemically modified TiO 2 particles was confirmed, while via XRD analysis the composites' average crystallite size was determined as ≈20 nm. The semi-crystal structure of polyaniline exhibits higher photocatalytic efficiency compared to that of other less crystalline forms. The spherical-shaped developed materials are innovative, stable (zeta potential in the range from -26 to -37 mV), and cost-effective, characterized by enhanced photocatalytic efficiency under visible light (energy band gaps ≈ 2 eV), and synthesized with relatively simple methods, with the possibility of recycling and reusing them in potential future applications in industry, in wastewater treatment as well as in biomedicine. Thus, the PANI-encapsulated Ag and N chemically modified TiO 2 nanocomposites exhibit high degradation efficiency towards Rhodamine B dye upon visible-light irradiation, presenting simultaneously high biocompatibility in different normal cell lines.

The transmission of lumpy skin disease (LSD) occurs through ticks, mosquitoes, and flies. The most effective way to combat LSD is to conduct large-scale vaccination, covering the entire cattle population with safe and effective vaccines, while introducing restrictions on the movement of livestock. The first and only LSD cases that occurred in Armenia happened in 2015,and they were controlled with the use of a once yearly heterologous sheep pox vaccine for cattle in high-risk areas. We have previously reported on the safety and immunogenicity of this vaccine in cattle, but information on the duration of immunity is lacking. Our aim was to determine the duration of immunity to the LSD virus (LSDV) in cattle when utilizing a heterologous sheep pox vaccine. We have evaluated antibodies in cattle blood prior to and post-vaccination (1, 6, and 11 months). We have utilized an enzyme-linked immunosorbent assay to follow the development and waning of LSDV antibodies in vaccinated cattle in two age groups: 1) young unvaccinated cattle ≤12 months of age and 2) adult cattle that had previously been vaccinated. Our results were consistent with our previous study in Armenia, showing a high level of population immunity, 80.0-83.3%, in both age groups at 1 month, with a significant ( p = 0.001) drop for young cattle at 6 months. Previously vaccinated adult cattle showed a longer duration of immunity at 11 months for this heterologous sheep pox vaccine. Based on these data, we advise that young cattle receive an additional booster vaccination 4-6 months after their first vaccination, and then yearly vaccinations in high-risk areas.

Livestock-polluted water is a pressing water environmental issue in plateau pastoral regions, necessitating the adoption of eco-friendly solutions. Despite periphyton being a promising alternative, its efficacy is limited by the prevalence of intense ultraviolet radiation, particularly ultraviolet-B (UVB), in these regions. Therefore, this study employs molecular tools and small-scale trials to explore the crucial role of indole-3-acetic acid (IAA) in modulating periphyton characteristics and mediating nutrient removal from livestock-polluted water under UVB exposure. The results revealed that IAA augments periphyton's resilience to UVB stress through several pathways, including increasing periphyton's biomass, producing more extracellular polymeric substances (EPS), and enhancing antioxidant enzyme activities and photosynthetic activity of periphyton. Moreover, IAA addition increased periphyton's bacterial diversity, reshaped bacterial community structure, enhanced community stability, and elevated the R 2 value of neutral processes in bacterial assembly from 0.257 to 0.651 under UVB. Practically, an IAA concentration of 50 mg/L was recommended. Small-scale trials confirmed the effectiveness of IAA in assisting UVB-stressed periphyton to remove nitrogen and phosphorus from livestock-polluted water, without the risk of nitrogen accumulation. These findings offer valuable insights into the protection of aquatic ecosystems in plateau pastoral regions based on periphyton property in an eco-friendly manner., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The development and application of lithium (Li) anode is hindered by volumetric variation, dendritic Li growth, and parasitic reactions. Herein, a dual-phase Li-barium (Ba) alloy with self-assembled microchannels array is synthesized through a one-step thermal fusion method to investigate the inhibition effect of lithiophilic composite porous array on Li dendrites. The Li-rich Li-Ba alloy (BaLi24) as composite Li electrode exhibits an ordered porous structure of BaLi 4 intermetallic compound after delithiation, which acts as a built-in 3D current collector during Li plating/striping process. Furthermore, the lithiophilic BaLi 4 alloy scaffold is a mixed conductor, featuring with Li + ions diffusion capability, which can efficiently transport the reduced Li to the interior of the electrode structure. This unique top-down growth mode can effectively prohibit Li dendrites growth and improve the space utilization of 3D electrode structure. The spin-polarized density functional theory (DFT) calculations suggest that the absorption capability of BaLi 4 benefits the deposition of Li metal. As a result, the cell performance with the dual-phase Li-Ba alloy anode is significantly improved., (© 2023 Wiley‐VCH GmbH.)

A combined computational and interpretational DFT study is performed to investigate the regioselectivity of B 18 and B 30 leapfrog boron sheets upon reaction with XH 3 -type electrophiles and nucleophiles (X = N, P, As, B, Al). The M062X, B3LYP, and B3LYP-D3 functionals are used combined with the 6-31+G(d,p) basis. The molecular electrostatic potential (MEP), Fukui functions, and the dual descriptor are employed to predict the local reactivity of B 18 and B 30 . Our results reveal that both clusters are hard and prefer to react with hard bases and acids, such as NH 3 and BH 3 . Further, these leapfrog B 6n clusters can play the role of catalysts as they break B-H and Al-H bonds of BH 3 and AlH 3 in s -BH 3 -B 6n and s -AlH 3 -B 6 n complexes, respectively. Leapfrog B 6 n -XH 3 complexes (X = B and Al) can be considered as an interaction between two electron-deficient systems. Therefore, the chemical reactivity between these systems cannot be interpreted in terms of the Hard-Soft-Acid-Base principle.

Recently, planar and neutral tricoordinated oxygen embedded in graphene has been imaged experimentally ( Nat. Commun. , 2019, 10 , 4570-4577). In this work, this unusual chemical species is studied utilizing a variety of state-of-the-art methods and combining periodic calculations with a fragmental approach. Several factors influencing the stability of trivalent oxygen are identified. A σ-donation and a π-backdonation mechanism between graphite and oxygen is established. π-Local aromaticity, with a delocalized 4c-2e bond involving the oxygen atom and the three nearest carbon atoms aids in the stabilization of this system. In addition, the framework in which the oxygen is embedded is crucial too to the stabilization, helping to delocalize the "extra" electron pair in the virtual orbitals. Based on the understanding gathered in this work, a set of organic molecules containing planar and neutral trivalent oxygen is theoretically proposed for the first time., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)