Effects Of Ligands Research Articles

D-Band Engineering in Pd-Based Nanowire Networks for Further Enhancement in Ethanol Electrooxidation Reaction.

The development of highly efficient electrocatalysts for the ethanol oxidation reaction (EOR) is essential for the commercialization of direct ethanol fuel cells, yet challenges remain. In this study, a one-pot solution-phase method to synthesize Pd nanowire networks (NNWs) with very high surface-to-volume ratio having numerous twin and grain boundaries is developed. Using the same method, the Pd lattice is further engineered by introducing Ag and Cu atoms to produce AgPd, and CuPd alloy structure which significantly shifts the Pd d-band center upward and downward, respectively due to strain and ligand effects. Theoretical analysis employing density functional theory (DFT) demonstrates that such modification of the d-band center significantly influences the adsorption energies of reactants on the catalytic surface. Owing to their notably high surface-to-volume ratio and the presence of multiple twin and grain boundaries, Pd NNWs demonstrate significantly enhanced electrocatalytic activity toward EOR, ≈7.2 times greater than that of commercial Pd/C. Remarkably, compared to Pd NNWs, AgPd, and CuPd NNWs display enlarged and reduced electrocatalytic activity toward EOR, respectively. Specifically, Ag4Pd7 NNWs achieve a remarkable mass activity of 9.00Amgpd -1 for EOR, which is 13.6 times higher than commercial Pd/C.

Hydrogen Absorption in Palladium‐Based Nanocrystals for Electrocatalysis Investigation

AbstractHydrogen absorption in transition metals has received enormous attention for applications such as the hydrogen storage, sensing and corrosion. In particular, the Pd‐H system is a simple and classical metal hydride system that serves as a platform for a deeper understanding of hydrogen behavior. In the past few years, Pd‐H has been reported as electrocatalyst in multiple reactions, whereas the impact of hydrogen absorption/desorption in electrocatalytic applications remains unclear. Therefore, in this concept, factors influencing the hydrogen adsorption/desorption of palladium in the gas phase, such as facet engineering, ligand effects, and alloying effects, are summarized. Subsequently, in the context of electrocatalysis, factors affecting electrochemical hydrogen adsorption/desorption are outlined. Particularly, prospects for the further investigation of electrochemical hydrogen adsorption/desorption in catalysis are discussed.

Aliquat 336 in Solvent Extraction Chemistry of Metallic ReO4− Anions

A study of the liquid–liquid extraction of ReO4− anions from hydrochloric acid solutions using the ionic liquid Aliquat 336 (QCl: trialkyl(C8–C10)methylammonium chloride) via the well-known method of slope analysis along with the determination of the process parameters is presented. This study employs CCl4, CHCl3 and C6H12 as diluents. This study was carried out at room temperature (22 ± 2) °C and an aqueous/organic volumetric ratio of unity. The ligand effect on the complexation properties of ReO4− is quantitatively assessed in different organic media. The organic extract in chloroform media is examined through 1H, 13C and 15N NMR analysis as well as the HRMS technique and UV-Vis spectroscopy in order to view the anion exchange and ligand coordination in the organic phase solution. Final conclusions are given highlighting the role of the molecular diluent in complexation processes and selectivity involving ionic liquid ligands and various metal s-, p-, d- and f-cations. ReO4− ions have shown one of the best solvent extraction behaviors compared to other ions. For instance, the Aliquat 336 derivative bearing Cl− functions shows strongly enhanced extraction as well as pronounced separation abilities towards ReO4−.

Dimerization of Fe(III) Ion in an Aqueous Medium: Mechanistic Modelling and Effects of Ligands.

Aqueous iron solutions generally undergo spontaneous hydrolysis followed by aggregation resulting in the precipitation of nanocrystalline oxyhydroxide minerals. The mechanism of nucleation of such multinuclear oxyhydroxide clusters are unclear due to limited experimental evidence. Here, we investigate the mechanistic pathway of dimerization of Fe(III) ions using density functional theory (DFT) in aqueous medium considering effects of other ligands. Two hydrolyzed monomeric Fe(III) ions in aqueous medium may react to form two closely related binuclear products, the m-oxo and the dihydroxo Fe2 dimer. Our studies indicate that the water molecules in the second coordination sphere and those co-ordinated to the Fe(III) ion, both participate in the dimerization process. The proposed mechanism effectively explains the formation of dihydroxo and μ-oxo Fe2 dimers with interconversion possibilities, for the first time. Results show, with only water molecules present in the second co-ordination sphere, dihydroxo Fe2 dimer is the thermodynamically and kinetically favored product with a low activation free energy. We calculated the step-wise reaction free energies of dimerization in the presence of nitrate ions in the first and second coordination sphere of Fe(III) ion separately, which shows that with nitrate ions in the second co-ordination sphere, the μ-oxo Fe2 dimer formation iskinetically favored.

Bimetallic Cu@Ru Core-Shell Structures with Ligand Effects for Endo-Exogenous Stimulation-Mediated Dynamic Oncotherapy.

Dynamic therapies, which induce reactive oxygen species (ROS) production in situ through endogenous and exogenous stimulation, are emerging as attractive options for tumor treatment. However, the complexity of the tumor substantially limits the efficacy of individual stimulus-triggered dynamic therapy. Herein, bimetallic copper and ruthenium (Cu@Ru) core-shell nanoparticles are applied for endo-exogenous stimulation-triggered dynamic therapy. The electronic structure of Cu@Ru is regulated through the ligand effects to improve the adsorption level for small molecules, such as water and oxygen. The core-shell heterojunction interface can rapidly separate electron-hole pairs generated by ultrasound and light stimulation, which initiate reactions with adsorbed small molecules, thus enhancing ROS generation. This synergistically complements tumor treatment together with ROS from endogenous stimulation. In vitro and in vivo experiments demonstrate that Cu@Ru nanoparticles can induce tumor cell apoptosis and ferroptosis through generated ROS. This study provides a new paradigm for endo-exogenous stimulation-based synergistic tumor treatment.

Electron-induced deposition using Fe(CO)4MA and Fe(CO)5 - effect of MA ligand and process conditions.

The electron-induced decomposition of Fe(CO)4MA (MA = methyl acrylate), which is a potential new precursor for focused electron beam-induced deposition (FEBID), was investigated by surface science experiments under UHV conditions. Auger electron spectroscopy was used to monitor deposit formation. The comparison between Fe(CO)4MA and Fe(CO)5 revealed the effect of the modified ligand architecture on the deposit formation in electron irradiation experiments that mimic FEBID and cryo-FEBID processes. Electron-stimulated desorption and post-irradiation thermal desorption spectrometry were used to obtain insight into the fate of the ligands upon electron irradiation. As a key finding, the deposits obtained from Fe(CO)4MA and Fe(CO)5 were surprisingly similar, and the relative amount of carbon in deposits prepared from Fe(CO)4MA was considerably less than the amount of carbon in the MA ligand. This demonstrates that electron irradiation efficiently cleaves the neutral MA ligand from the precursor. In addition to deposit formation by electron irradiation, the thermal decomposition of Fe(CO)4MA and Fe(CO)5 on an Fe seed layer prepared by EBID was compared. While Fe(CO)5 sustains autocatalytic growth of the deposit, the MA ligand hinders the thermal decomposition in the case of Fe(CO)4MA. The heteroleptic precursor Fe(CO)4MA, thus, offers the possibility to suppress contributions of thermal reactions, which can compromise control over the deposit shape and size in FEBID processes.

Unveiling the Mechanistic Role of Chiral Palladacycles in Pd(II)-Catalyzed Enantioselective C(sp3)-H Functionalization.

Palladium-catalyzed enantioselective C(sp3)-H functionalization reactions has attracted considerable attention due to its ability for the synthesis of enantiomerically enriched molecules and stimulation of novel retrosynthetic disconnections. Understanding the reaction mechanism, especially the stereochemical process of the reaction, is crucial for the rational design of more efficient catalytic systems. Previously, we developed a Pd(II)/sulfoxide-2-hydroxypridine (SOHP) catalytic system for asymmetric C(sp3)-H functionalization reactions. In this study, we focused on unraveling the chemistry of chiral palladacycles involved in the Pd(II)-catalyzed enantioselective C(sp3)-H functionalization. We have isolated key palladacycle intermediates involved in the enantioselective β-C(sp3)-H arylation of carboxylic acids catalyzed by the Pd(II)/SOHP system. These palladacycles, exhibiting ligand-induced chirality, provided a significant opportunity to investigate the stereochemical process and the ligand effect in this asymmetric C-H functionalization. Our investigation provided direct evidence for the C-H palladation step as the enantioselectivity-determining step, which forms diastereomeric palladacycles that exhibited preservation of chirality in the functionalization step. DFT calculations provided insights into the chiral induction in palladacycle formation. This work highlights the value of chiral palladacycle chemistry in offering mechanistic insights into the Pd(II)-catalyzed asymmetric C(sp3)-H functionalization reactions.

Unveiling the Mechanistic Role of Chiral Palladacycles in Pd(II)‐Catalyzed Enantioselective C(sp3)‐H Functionalization

Palladium‐catalyzed enantioselective C(sp3)‐H functionalization reactions has attracted considerable attention due to its ability for the synthesis of enantiomerically enriched molecules and stimulation of novel retrosynthetic disconnections. Understanding the reaction mechanism, especially the stereochemical process of the reaction, is crucial for the rational design of more efficient catalytic systems. Previously, we developed a Pd(II)/sulfoxide‐2‐hydroxypridine (SOHP) catalytic system for asymmetric C(sp3)‐H functionalization reactions. In this study, we focused on unraveling the chemistry of chiral palladacycles involved in the Pd(II)‐catalyzed enantioselective C(sp3)‐H functionalization. We have isolated key palladacycle intermediates involved in the enantioselective β‐C(sp3)‐H arylation of carboxylic acids catalyzed by the Pd(II)/SOHP system. These palladacycles, exhibiting ligand‐induced chirality, provided a significant opportunity to investigate the stereochemical process and the ligand effect in this asymmetric C‐H functionalization. Our investigation provided direct evidence for the C‐H palladation step as the enantioselectivity‐determining step, which forms diastereomeric palladacycles that exhibited preservation of chirality in the functionalization step. DFT calculations provided insights into the chiral induction in palladacycle formation. This work highlights the value of chiral palladacycle chemistry in offering mechanistic insights into the Pd(II)‐catalyzed asymmetric C(sp3)‐H functionalization reactions.

Synthesis of phosphonic acid and amide functionalized core–shell magnetic composite and its mechanisms for synergistic adsorption of thorium from strongly acidic solution

To develop adsorbents for the preeminent extraction of thorium in strongly acidic solutions is very imperative, due to strong inorganic acids are frequently used in the fuel cycle of thorium. Herein, a robust core–shell magnetic nanocomposite Fe3O4@SiO2/P (MBA-VPA-AM) possessing phosphonic acid and amide was developed via distillation-precipitation copolymerization of N, N'-methylene diacrylamide (MBA), vinylphosphonic acid (VPA) with acrylamide (AM) employing Fe3O4 decorated by SiO2 (Fe3O4@SiO2) as magnetic core. Due to the synergistic effect of phosphonic acid and amide ligand, the sorbent could capture thorium from concentrated HNO3 media efficiently, and the maximum adsorption capacity (qmax) at 4 mol L−1 of HNO3 solution reached up to 232.5 mg g−1, superior to that of all magnetic sorbents reported previously. Furthermore, the sorbent displayed good selectivity towards thorium in the presence of competitive metal ions including La3+, Nd3+, and Ce3+. The excellent thorium sorption behavior in strong hydrogen nitrate solution was merely ascribed to the complexation of thorium with phosphonic acid ligand, and the amide ligand could not complex with thorium, evidenced by XPS, FT-IR and DFT method. However, the presence of amide ligand could enhance the hydrophilicity of the sorbent and the free movement degree of phosphonic acid ligand to a certain extent, both of which could help to promote the thorium sorption on the sorbent in strong HNO3 media. Besides, due to its core–shell structure and superparamagnetism, the sorbent not only exhibited excellent acidic resistance in strong acid medias, but could be magnetically recouped, which could avoid tedious centrifugation or filtration of traditional adsorbents. This work provides a novel strategy to develop magnetic sorbent for the preeminent entrapment of thorium from strong acid solutions.

Abstract Wrk2-02: Modelling the effects of cell-cell interactions in the tumor microenvironment from single cell variability

Abstract Multicellular programs underly emergent phenotypes in health and disease. Yet, deciphering the functional effects of interactions amongst cell types remains a major challenge. Cells typically send messages to their microenvironment by emitting ligands, which bind to complimentary receptors on the surfaced of target cells; then triggering a change in the behavior of the target cell. Complimentary ligand-receptor-pairs are well annotated and methods have been developed to infer cell-cell interactions from single cell expression data based on their mutual expression. However, these methods do not assess the effect of ligand-receptor-mediated interactions on the microenvironment. Thus, we developed ContactTracing – a fundamentally new, systems level approach that exploits inter- and intra-sample variability to infer ligand effects on gene expression in target (receptor-expressing) cells without prior knowledge of downstream signaling (Nature, 2023). Foundational work towards benchmarking and validation of this method was performed in isogenic breast cancer models distinguished by tumor cell-intrinsic rates of chromosome missegregation (a cellular process called chromosomal instability, or CIN). Through this, we identified tumor ligands emanating from an endoplasmic reticulum (ER)-stress response as potential mediators of immune suppression in chromosomally unstable tumors. Indeed, CIN-induced chronic STING activation led to rapid interferon-selective desensitization and a switch to ER-stress-dependent transcription. Moreover, inhibition of chronic STING - or key mediators of its unfolded protein response to ER-stress - suppressed metastasis in syngeneic models of melanoma, breast and colorectal cancer; validating this innovative methodology and identifying a targetable mediator of cancer metastasis. Citation Format: A. Laughney. Modelling the effects of cell-cell interactions in the tumor microenvironment from single cell variability [abstract]. In: Proceedings of the 2023 San Antonio Breast Cancer Symposium; 2023 Dec 5-9; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2024;84(9 Suppl):Abstract nr Wrk2-02.

Synthesis, Characterization and Evaluation of the Antimicrobial and Herbicidal Activities of Some Transition Metal Ions Complexes with the Tranexamic Acid.

New tranexamic acid (TXA) complexes of ferric(III), cobalt(II), nickel(II), copper(II) and zirconium(IV) were synthesized and characterized by elemental analysis (CHN), conductimetric (Λ), magnetic susceptibility investigations (μeff), Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (1H NMR), ultraviolet visible (UV-vis.), optical band gap energy (Eg) and thermal studies (TG/DTG and DTA). TXA complexes were established in 1:2 (metal: ligand) stoichiometric ratio according to CHN data. Based on FT-IR and 1H NMR data the disappeared of the carboxylic proton supported the deprotonating of TXA and linked to metal ions via the carboxylate group's oxygen atom as a bidentate ligand. UV-visible spectra and magnetic moment demonstrated that all chelates have geometric octahedral structures. Eg values indicated that our complexes are more electro conductive. DTA revealed presence of water molecules in inner and outer spheres of the complexes. DTA results showed that endothermic and exothermic peaks were identified in the degradation mechanisms. The ligand and metal complexes were investigated for their antimicrobial and herbicidal efficacy. The Co(II) and Ni(II) complexes showed antimicrobial activity against some tested species. The obtained results showed a promising herbicidal effect of TXA ligand and its metal complexes particularly copper and zirconium against the three tested plants.

Gasification Reaction on CeO2(111) and Effects on the Structural and Electronic Properties of Adsorption Molecules

AbstractProducing hydrogen (H2) from biomass gasification offers exceptional benefits regarding renewable energy sources, zero‐carbon emission, cost‐effective processes, and high efficiency. The addition of catalysts to biomass gasification could accelerate the process and minimize the formation of coke. However, the catalyst deactivation caused by carbon deposition, poisoning, and sintering is still a significant problem in the gasification process. Therefore, achieving sustainable exploitation of the renewable natural resource of biomass requires substantial development and optimization of the present gasification process. The efficiency of gasification might decrease because of such a process. In this study, CeO2(111) is chosen to investigate the analysis of adsorption molecules during catalytic gasification using the density functional theory method. Three catalyst models, CeO2(111), Zr‐CeO2(111), and Ni‐CeO2(111), have been studied in this work in terms of structural, electronic, and adsorption molecule properties. The structural and electronic properties of the modified catalyst model show the ligand and strain effect on the alloy, with the addition of Zr and Ni as second metals promoting the adsorption capability. Searching for active sites is also carried out by adsorption of selected atoms and molecules and used as a preliminary study to find possible active sites for gasification reactions. The Zr‐CeO2(111) and Ni‐CeO2 catalysts exhibit better adsorption ability on atomics and molecules. The Zr and Ni metals are suitable second metal candidates for the catalyst to proceed with the gasification reaction and simultaneously reduce carbon deposition, poisoning, and sintering problems.

Mechanistic Insights into Rare-Earth-Catalyzed Alternating Copolymerization through C-H Polyaddition of Functionalized Organic Compounds to Unconjugated Dienes.

Density functional theory (DFT) calculations have been conducted to elucidate the detailed mechanisms of yttrium-catalyzed C-H polyaddition of 1,4-dimethoxybenzene (DMB) to 1,4-divinylbenzene (DVB). It was computationally determined that DMB not only serves as a substrate but also performs a crucial role as a ligand, stabilizing the catalytically active species and promoting alkene insertion. Side pathways involving Cβ-H activation and C═C continuous insertion were excluded due to steric and electronic factors, respectively, explaining why the reaction occurred efficiently and selectively to give perfectly alternating DMB-DVB polymers. Interestingly, the theoretical prediction of the reactivity of N,N-dimethyl-1,4-phenylenediamine and 2,2'-biethyl-4,4'-bipyridine reveals significant differences in the coordination effects of these substrates, leading to distinct mechanisms, primarily influenced by their steric effects. These findings shed new light on the previously overlooked role of substrate ligand effects in rare-earth-catalyzed step-growth copolymerization reactions.

Synthesis and Photophysical Properties of Silver(I) Coordination Polymers Bridged by Dimethylpyrazine: Comparison of Emissive Excited States between Silver(I) and Copper(I) Congeners.

Highly luminescent silver(I) coordination polymers [Ag2X2(PPh3)2(Me2pyz)]n (X = I, Br, Cl; Me2pyz: 2,5-dimethylpyrazine) were prepared together with copper congeners [Cu2X2(PPh3)2(Me2pyz)]n (X = I, Br). All the complexes showed thermally activated delayed fluorescence from the charge-transfer states in the visible region, from blue to red. The isomorphous relationship among the complexes allowed a detailed discussion of the effect of halogenido ligands and crystal packing on their luminescence energy. The relaxation in the emissive excited states (ESs) was determined to be more remarkable in silver complexes than in copper complexes despite their isomorphous structures, and the electronic effect of halogenido ligands was comparable to the effect of relaxation in emissive ESs.

Mechanistic Origin of Ligand Effects on Exhaustive Functionalization During Pd-Catalyzed Cross-Coupling of Dihaloarenes

Mechanistic Origin of Ligand Effects on Exhaustive Functionalization During Pd-Catalyzed Cross-Coupling of Dihaloarenes

The effect of ligands on the size distribution of copper nanoclusters: Insights from molecular dynamics simulations.

Controlling the size distribution in the nucleation of copper particles is crucial for achieving nanocrystals with desired physical and chemical properties. However, their synthesis involves a complex system of solvents, ligands, and copper precursors with intertwining effects on the size of the nanoclusters. We combine molecular dynamics simulations and density functional theory calculations to provide insights into the nucleation mechanism in the presence of a triphenyl phosphite ligand. We identify the crucial role of the strength of the metal-phosphine interaction in inhibiting the cluster's growth. We demonstrate computationally several practical routes to fine-tune the interaction strength by modifying the side groups of the additive. Our work provides molecular insights into the complex nucleation process of protected copper nanocrystals, which can assist in controlling their size distribution and, eventually, their morphology.

Nickel(II) and Palladium(II) complexes with imine-based tridentate ligand: Synthesis, spectral characterization, Antimicrobial, cytotoxicity and DFT studies

The organic compound (Z)-2-bromo-2-(5-bromo-2-hydroxy-3-methoxybenzylidene)-N-metylhydrazine-1-carbothioamide (L1H2) and its nickel(II) complex [Ni(L1)(PPh3)](1) and palladium(II) complex [Pd(L1)(PPh3)](2) were synthesized and characterized using various spectroscopic methods, including NMR,FT-IR, HRMS, and UV–Vis spectroscopy. Single-crystal X-ray diffraction analysis was used to determine the crystal structures of [Ni(L1)(PPh3)](1) and [Pd(L1) (PPh3)](2). The Hirshfeld surface analysis was used to study various interactions in the crystal structure of complexes. In addition, an energy framework computational analysis was also done to gain a further understanding of the structural details of the complexes. DFT-based calculations were done for the ligand and its associated metal complexes to establish the correlations between their structural characteristics and integral properties. Ligand and its complexes were evaluated for their antimicrobial effects. The antimicrobial effects of ligands and their complexes were assessed. It was found that both Ni(II) and Pd(II) complexes showed better antimicrobial activity.The minimum inhibitory concentration for the [Ni(L1)(PPh3)] complex ranges from 1.95–250 µM; for the [Pd(L1)(PPh3)] complex, it ranges from 3.5–250 µM; and for the ligand, it ranges from 62.5–250 µM against both bacterial and fungal strains. The synthesized compounds were tested for anti-proliferative assays against the HELA carcinoma cell line. The IC50 values obtained were 98.83 µM for the ligand, 83.09 µM for the Ni(II) complex, and 86.74 µM for the Pd(II) complex, suggesting Ni(II) complex a stronger anti-cancerous agent compared to the Pd(II) complex.Noteworthy, both complexes and standard drugs (ciprofloxacin and nystatin) showed non-cytotoxic behavior towards the normal HEK-293 cell line. The increased efficacy and selective cytotoxicity of the complexes highlight their potential as a candidate for further investigation and development into a potent therapeutic agent as an antimicrobial and anticancer agent.

Theoretical Investigation on Dialumenes toward Dihydrogen Activation: Mechanism and Ligand Effect.

Herein, we report a computation study based on the density functional theory calculations to understand the mechanism and ligand effect of the base-stabilized dialumenes toward dihydrogen activation. Among all of the examined modes of dihydrogen activation using the base-stabilized dialumene, we found that the concerted 1,2-hydrogenation of the Al═Al double bond is kinetically more preferable. The concerted 1,2-hydrogenation of the Al═Al double bond adopts an electron-transfer model with certain asynchrony. That is, the initial electron donation from the H-H σ bonding orbital to the empty 3p orbital of the Al1 center is followed by the backdonation from the lone pair electron of the Al2 center to the H-H σ antibonding orbital. Combined with the energy decomposition analysis on the transition states of the concerted 1,2-hydrogenation of the Al═Al double bond and the topographic steric mapping analysis on the free dialumenes, we ascribe the higher reactivity of the aryl-substituted dialumene over the silyl-substituted analogue in dihydrogen activation to the stronger electron-withdrawing effect of the aryl group, which not only increases the flexibility of the Al═Al double bond but also enhances the Lewis acidity of the Al═Al core. Consequently, the aryl-substituted dialumene fragment suffers less geometric deformation, and the orbital interactions between the dialumene and dihydrogen moieties are more attractive during the 1,2-hydrogenation process. Moreover, our calculations also predict that the Al═Al double bond has a good tolerance with the stronger electron-withdrawing group (-CF3) and the weaker σ-donating N-heterocyclic carbene (NHC) analogue (e.g., triazol carbene and NHSi). The reactivity of the dialumene in dihydrogen activation can be further improved by introducing these groups as the supporting ligand and the stabilizing base on the Al═Al core, respectively.

Endocrine disruptors, aryl hydrocarbon receptor and cortisol secretion.

Endocrine disruptors exert a plethora of effects in endocrine tissues, from altered function to carcinogenesis. Given its lipophilic nature, the adrenal cortex represents an ideal target for endocrine disruptors and thus, possibly, xenobiotic-induced adrenocortical dysfunction. However, there is no clear understanding of the effect of endocrine disruptors on adrenal steroidogenesis, in particular as regards the aryl hydrocarbon receptor (AHR) pathway, one of the key mediators. The present review recapitulates available evidence on the effects of AHR ligands on adrenal steroidogenesis, with focus on cortisol secretion. Short-term exposure to AHR ligands most often induced a stress-like corticosteroid response followed by decreased responsiveness to stressors with long-term exposure. This was observed in several experimental models across species as well as in animals and humans in real-life settings. Prenatal exposure led to different effects according to sex of the offspring, as observed in murine models and in children from mothers in several countries. In vitro findings proved highly dependent on the experimental setting, with reduced cortisol response and steroidogenic enzyme synthesis mostly observed in fish and increased cortisol synthesis and secretion observed in murine and human adrenal cell lines. Of note, no AHR-binding element was detected in steroidogenic enzyme promoters, suggesting the involvement of additional factors. Ourreview provides evidence for the impact of AHR ligands on adrenocortical function and indicates further avenues of research to better clarify its effects.

Unveiling synergy of strain and ligand effects in metallic aerogel for electrocatalytic polyethylene terephthalate upcycling

Recently, there has been a notable surge in interest regarding reclaiming valuable chemicals from waste plastics. However, the energy-intensive conventional thermal catalysis does not align with the concept of sustainable development. Herein, we report a sustainable electrocatalytic approach allowing the selective synthesis of glycolic acid (GA) from waste polyethylene terephthalate (PET) over a Pd67Ag33 alloy catalyst under ambient conditions. Notably, Pd67Ag33 delivers a high mass activity of 9.7 A mgPd-1 for ethylene glycol oxidation reaction (EGOR) and GA Faradaic efficiency of 92.7 %, representing the most active catalyst for selective GA synthesis. In situ experiments and computational simulations uncover that ligand effect induced by Ag incorporation enhances the GA selectivity by facilitating carbonyl intermediates desorption, while the lattice mismatch-triggered tensile strain optimizes the adsorption of *OH species to boost reaction kinetics. This work unveils the synergistic of strain and ligand effect in alloy catalyst and provides guidance for the design of future catalysts for PET upcycling. We further investigate the versatility of Pd67Ag33 catalyst on CO2 reduction reaction (CO2RR) and assemble EGOR//CO2RR integrated electrolyzer, presenting a pioneering demonstration for reforming waste carbon resource (i.e., PET and CO2) into high-value chemicals.