Solution Synthesis and Light-Emitting Applications of One-Dimensional Lead-Free Cerium(III) Metal Halides.

Combining rare earth elements with the halide perovskite structure offers valuable insights into designing nonlead (Pb) luminescent materials. However, most of these compositions tend to form zero-dimensional (0D) networks of metal-halide polyhedra, with higher-dimensional (1D, 2D, and 3D) structures receiving relatively less exploration. Herein, we present synthesis and optical properties of Cs3CeCl6·3H2O, characterized by its unique 1D crystal structure. The conduction band minimum of Cs3CeCl6·3H2O becomes less localized as a result of the increased structural dimension, making it possible for the materials to achieve an efficient electrical injection. For both Cs3CeCl6·3H2O single crystals and nanocrystals, we also observed remarkable luminescence with near-unity photoluminescence quantum yield and exceptional phase stability. Cs3CeCl6·3H2O single crystals demonstrate an X-ray scintillation light yield of 31900 photons/MeV, higher than that of commercial LuAG:Ce (22000 photons/MeV); electrically driven light-emitting diodes fabricated with Cs3CeCl6·3H2O nanocrystals yield the characteristic emission of Ce3+, indicating their potential use in next-generation violet-light-emitting devices.

A novel isatin Schiff based cerium complex: synthesis, characterization, antimicrobial activity and molecular docking studies.

In this work, a novel isatin-Schiff base L2 had been synthesized through a simple reaction between isatin and 2-amino-5-methylthio-1,3,4-thiadiazole. The produced Schiff base L2 was then subjected to a hydrothermal reaction with cerium chloride to produce the cerium (III)-Schiff base complex C2. Several spectroscopic methods, including mass spectra, FT-IR, elemental analysis, UV-vis, 13C-NMR, 1H-NMR, Thermogravimetric Analysis, HR-TEM, and FE-SEM/EDX, were used to completely characterize the produced L2 and C2. A computer simulation was performed using the MOE software program to find out the probable biological resistance of studied compounds against the proteins in some types of bacteria or fungi. To investigate the interaction between the ligand and its complex, we conducted molecular docking simulations using the molecular operating environment (MOE). The docking simulation findings revealed that the complex displayed greater efficacy and demonstrated a stronger affinity for Avr2 effector protein from the fungal plant pathogen Fusarium oxysporum (code 5OD4) than the original ligand. The antibacterial activity of the ligand and its Ce3+ complex were applied in vitro tests against different microorganism. The study showed that the complex was found to be more effective than the ligand.

Effect of Modified Bioceramic Mineral Trioxide Aggregate Cement with Mesoporous Nanoparticles on Human Gingival Fibroblasts.

The ion doping of mesoporous silica nanoparticles (MSNs) has played an important role in revolutionizing several materials applied in medicine and dentistry by enhancing their antibacterial and regenerative properties. Mineral trioxide aggregate (MTA) is a dental material widely used in vital pulp therapies with high success rates. The aim of this study was to investigate the effect of the modification of MTA with cerium (Ce)- or calcium (Ca)-doped MSNs on the biological behavior of human gingival fibroblasts (hGFs). MSNs were synthesized via sol-gel, doped with Ce and Ca ions, and mixed with MTA at three ratios each. Powder specimens were characterized using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Biocompatibility was evaluated using a 3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide (MTT) assay following hGFs' incubation in serial dilutions of material eluates. Antioxidant status was evaluated using Cayman's antioxidant assay after incubating hGFs with material disc specimens, and cell attachment following dehydration fixation was observed through SEM. Material characterization confirmed the presence of mesoporous structures. Biological behavior and antioxidant capacity were enhanced in all cases with a statistically significant increase in CeMTA 50.50. The application of modified MTA with cerium-doped MSNs offers a promising strategy for vital pulp therapies.

Bacteroid cerium oxide particles promote macrophage polarization to achieve early vascularization and subsequent osseointegration around implants.

The establishment of an osseointegration is crucial for the long-term stability and functionality of implant materials, and early angiogenesis is the key to successful osseointegration. However, the bioinertness of titanium implants affects osseointegration, limiting their clinical application. In this study, inspired by the rapid polarization of macrophages following the phagocytosis of bacteria, we developed bacteroid cerium oxide particles; these particles were composed of CeO2 and had a size similar to that of Bacillus (0.5 µ m). These particles were constructed on the implant surfaces using a hydrothermal method. In vitro experiments demonstrated that the particles effectively decreased the reactive oxygen species (ROS) levels in macrophages (RAW264.7). Furthermore, these particles exerted effects on M1 macrophage polarization, enhanced nitric oxide (NO) secretion to promote vascular regeneration, and facilitated rapid macrophage transition to the M2 phenotype. Subsequently, the particles facilitated human umbilical vein endothelial cell (HUVEC) migration. In vivo studies showed that these particles rapidly stimulated innate immune responses in animal models, leading to enhanced angiogenesis around the implant and improved osseointegration. In summary, the presence of bacteroid cerium oxide particles on the implant surface regulated and accelerated macrophage polarization, thereby enhancing angiogenesis during the immune response and improving peri-implant osseointegration.

CeO2-Based Frustrated Lewis Pairs via Defective Engineering: Formation Theory, Site Characterization, and Small Molecule Activation.

Activation of small molecules is considered to be a central concern in the theoretical investigation of environment- and energy-related catalytic conversions. Sub-nanostructured frustrated Lewis pairs (FLPs) have been an emerging research hotspot in recent years due to their advantages in small molecule activation. Although the progress of catalytic applications of FLPs is increasingly reported, the fundamental theories related to the structural formation, site regulation, and catalytic mechanism of FLPs have not yet been fully developed. Given this, it is attempted to demonstrate the underlying theory of FLPs formation, corresponding regulation methods, and its activation mechanism on small molecules using CeO2 as the representative metal oxide. Specifically, this paper presents three fundamental principles for constructing FLPs on CeO2 surfaces, and feasible engineering methods for the regulation of FLPs sites are presented. Furthermore, cases where typical small molecules (e.g., hydrogen, carbon dioxide, methane oxygen, etc.) are activated over FLPs are analyzed. Meanwhile, corresponding future challenges for the development of FLPs-centered theory are presented. The insights presented in this paper may contribute to the theories of FLPs, which can potentially provide inspiration for the development of broader environment- and energy-related catalysis involving small molecule activation.

Gradient Functional Layer Anode for Carbonate-Superstructured Solid Fuel Cells with Ethane Fuel.

Carbonate-superstructured solid fuel cells (CSSFCs) are an emerging type of fuel cells with high flexibility of fuels. However, using ethane fuel for solid fuel cells is a great challenge due to serious degradation of their anodes. Herein, this critical issue is solved by creating a novel gradient functional layer anode for CSSFCs. First, a finer-scale anode with a larger surface area is demonstrated to provide more active sites for the internal reforming reaction of ethane, achieving a 60% higher ethane conversion rate and 40% lower polarization resistance than conventional anodes. Second, incorporating a gradient functional layer into the anode results in an additional 50% enhancement in the peak power density of CSSFCs to a record high value (up to 241 mW cm-2) with dry ethane fuel at a low temperature of 550 °C, which is even comparable to the power density of conventional solid oxide fuel cells above 700 °C. Furthermore, the CSSFC with the gradient anode exhibits excellent durability for over 200 h. This finding provides a new strategy to develop efficient anodes for hydrocarbon fuels.

Influence of Oxygen Vacancies Introduced via Acceptor (Gadolinium) Doping to the Pseudocapacitive Properties of Nano-Sized Cerium Oxide.

The voluntary introduction of defects can be considered an effective strategy for enhancing the electrochemical properties of metal oxide electrodes. In this study, the enhanced pseudocapacitive properties of an acceptor (Gd) doped cerium oxide nanoparticle-a sustainable metal oxide with low environmental and human toxicity-are investigated in depth using ex situ X-ray photoemission spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Interestingly, with 15 at% Gd doping (15GDC), the specific capacitance of the nanoparticles measured at 1 A g-1 enhanced to 547.8 F g-1, which is fivefold higher than undoped CeO2 (98.7 F g-1 at 1 A g-1). The rate-dependent capacitance is also improved for 15GDC, which showed a 31.0% decrease in the specific capacitance upon a tenfold increase in the current density, while CeO2 showed a 49.9% decrease. The enhanced electrochemical properties are studied in depth via ex situ XPS and EIS analysis, which revealed that the oxygen vacancies at the surface of the nanoparticles played important roles in enhancing both the specific capacitance and the high-rate performance of 15GDC by acting as the active site for pseudocapacitive redox reaction and allowing fast diffusion of oxygen ions at the surface of 15GDC nanoparticles.

Structural Heredity in Catalysis: CO2 Self-Selective CeO2 Nanocrystals for Efficient Photothermal CO2 Hydrogenation to Methane.

The chemical inertness of CO2 molecules makes their adsorption and activation on a catalyst surface one of the key challenges in recycling CO2 into chemical fuels. However, the traditional template synthesis and chemical modification strategies used to tackle this problem face severe structural collapse and modifier deactivation issues during the often-needed post-processing procedure. Herein, a CO2 self-selective hydrothermal growth strategy is proposed for the synthesis of CeO2 octahedral nanocrystals that participate in strong physicochemical interactions with CO2 molecules. The intense affinity for CO2 molecules persists during successive high-temperature treatments required for Ni deposition. This demonstrates the excellent structural heredity of the CO2 self-selective CeO2 nanocrystals, which leads to an outstanding photothermal CH4 productivity exceeding 9 mmol h-1 mcat -2 and an impressive selectivity of >99%. The excellent performance is correlated with the abundant oxygen vacancies and hydroxyl species on the CeO2 surface, which create many frustrated Lewis-pair active sites, and the strong interaction between Ni and CeO2 that promotes the dissociation of H2 molecules and the spillover of H atoms, thereby greatly benefitting the photothermal CO2 methanation reaction. This self-selective hydrothermal growth strategy represents a new pathway for the development of effective catalysts for targeted chemical reactions.

Gene-Engineered Cerium-Exosomes Mediate Atherosclerosis Therapy Through Remodeling of the Inflammatory Microenvironment and DNA Damage Repair.

The pro-inflammatory immune microenvironment in the localized lesion areas and the absence of DNA damage repair mechanisms in endothelial cells serve as essential accelerating factors in the development of atherosclerosis. The lack of targeted therapeutic strategies represents a significant limitation in the efficacy of therapeutic agents for atherosclerosis. In this study, Genetically engineered SNHG12-loaded cerium-macrophage exosomes (Ce-Exo) are designed as atherosclerosis-targeting agents. In vivo studies demonstrated that Ce-Exo exhibited multivalent targeting properties for macrophages, with a 4.1-fold higher atherosclerotic plaque-aggregation ability than that of the control drugs. This suggests that Ce-Exo has a higher homing capacity and deeper penetration into the atherosclerotic plaque. In apolipoprotein E-deficient mice, Ce-Exo found to effectively remodel the immune microenvironment in the lesion area, repair endothelial cell damage, and inhibit the development of atherosclerosis. This study provides a novel approach to the treatment of atherosclerosis and demonstrates the potential of cell-derived drug carriers in biomedicine.

Green, Safe, and Reliable Synthesis of Bimetallic MOF-808 Nanozymes With Enhanced Aqueous Stability and Reactivity for Biological Applications.

Bimetallic metal-organic frameworks (MOFs) are promising nanomaterials whose reactivity towards biomolecules remains challenging due to issues related to synthesis, stability, control over metal oxidation state, phase purity, and atomic level characterization. Here, these shortcomings are rationally addressed through development of a synthesis of mixed metal Zr/Ce-MOFs in aqueous environment, overcoming significant hurdles in the development of MOF nanozymes, sufficiently stable on biologically relevant conditions. Specifically, a green and safe synthesis of Zr/Ce-MOF-808 is reported in water/acetic acid mixture which affords remarkably water-stable materials with reliable nanozymatic reactivity, including MOFs with a high Ce content previously reported to be unstable in water. The new materials outperform analogous bimetallic MOF nanozymes, showcasing that rational synthesis modifications could impart outstanding improvements. Further, atomic-level characterization by X-ray Absorption Fine Structure (XAFS) and X-ray Diffraction (XRD) confirmed superior nanozymes arise from differences in the synthetic method, which results in aqueous stable materials, and Ce incorporation, which perturbs the ligand exchange dynamics of the material, and could ultimately be used to fine tune the intrinsic MOF reactivity. Similar rational strategies which leverage metals in a synergistic manner should enable other water-stable bimetallic MOF nanozymes able to surpass existing ones, laying the path for varied biotechnological applications.

The effect of intra spinal administration of cerium oxide nanoparticles on central pain mechanism: An experimental study.

This study investigated Cerium oxide nanoparticles (CeONPs) effect on central neuropathic pain (CNP). The compressive method of spinal cord injury (SCI) model was used for pain induction. Three groups were formed by a random allocation of 24 rats. In the treatment group, CeONPs were injected above and below the lesion site immediately after inducing SCI. pain symptoms were evaluated using acetone, Radian Heat, and Von Frey tests weekly for six weeks. Finally, we counted fibroblasts using H&E staining. We evaluated the expression of Cx43, GAD65 and HDAC2 proteins using the western blot method. The analysis of results was done by PRISM software. At the end of the study, we found that CeONPs reduced pain symptoms to levels similar to those observed in normal animals. CeONPs also increased the expression of GAD65 and Cx43 proteins but did not affect HDAC2 inhibition. CeONPs probably have a pain-relieving effect on chronic pain by potentially preserving GAD65 and Cx43 protein expression and hindering fibroblast infiltration.

Examination of the PET in vivo generator 134Ce as a theranostic match for 225Ac.

PURPOSE: The radionuclide pair cerium-134/lanthanum-134 (134Ce/134La) was recently proposed as a suitable diagnostic counterpart for the therapeutic alpha-emitter actinium-225 (225Ac). The unique properties of 134Ce offer perspectives for developing innovative in vivo investigations that are not possible with 225Ac. In this work, 225Ac- and 134Ce-labelled tracers were directly compared using internalizing and slow-internalizing cancer models to evaluate their in vivo comparability, progeny meandering, and potential as a matched theranostic pair for clinical translation. Despite being an excellent chemical match, 134Ce/134La has limitations to the setting of quantitative positron emission tomography imaging. METHODS: The precursor PSMA-617 and a macropa-based tetrazine-conjugate (mcp-PEG8-Tz) were radiolabelled with 225Ac or 134Ce and compared in vitro and in vivo using standard (radio)chemical methods. Employing biodistribution studies and positron emission tomography (PET) imaging in athymic nude mice, the radiolabelled PSMA-617 tracers were evaluated in a PC3/PIP (PC3 engineered to express a high level of prostate-specific membrane antigen) prostate cancer mouse model. The 225Ac and 134Ce-labelled mcp-PEG8-Tz were investigated in a BxPC-3 pancreatic tumour model harnessing the pretargeting strategy based on a trans-cyclooctene-modified 5B1 monoclonal antibody. RESULTS: In vitro and in vivo studies with both 225Ac and 134Ce-labelled tracers led to comparable results, confirming the matching pharmacokinetics of this theranostic pair. However, PET imaging of the 134Ce-labelled precursors indicated that quantification is highly dependent on tracer internalization due to the redistribution of 134Ce's PET-compatible daughter 134La. Consequently, radiotracers based on internalizing vectors like PSMA-617 are suited for this theranostic pair, while slow-internalizing 225Ac-labelled tracers are not quantitatively represented by 134Ce PET imaging. CONCLUSION: When employing slow-internalizing vectors, 134Ce might not be an ideal match for 225Ac due to the underestimation of tumour uptake caused by the in vivo redistribution of 134La. However, this same characteristic makes it possible to estimate the redistribution of 225Ac's progeny noninvasively. In future studies, this unique PET in vivo generator will further be harnessed to study tracer internalization, trafficking of receptors, and the progression of the tumour microenvironment.

Cerium Oxide Catalyzed Disproportionation of Hydrogen Peroxide: A Closer Look at the Reaction Intermediate.

Cerium oxide nanoparticles (CNPs) have recently gained increasing interest as redox enzyme-mimetics to scavenge the intracellular excess of reactive oxygen species, including hydrogen peroxide (H2 O2 ). Despite the extensive exploration, there remains a notable discrepancy regarding the interpretation of observed redshift of UV-Visible spectroscopy due to H2 O2 addition and the catalase-mimicking mechanism of CNPs. To address this question, we investigated the reaction mechanism by taking a closer look at the reaction intermediate during the catalase mimicking reaction. In this study, we present evidence demonstrating that in aqueous solutions, H2 O2 adsorption at CNP surface triggers the formation of stable intermediates known as cerium-peroxo (Ce-O2 2- ) and/or cerium-hydroperoxo (Ce-OOH- ) complexes as resolved by Raman scattering and UV-Visible spectroscopy. Polymer coating presents steric hinderance for H2 O2 accessibility to the solid-liquid interface limiting further intermediate formation. We demonstrate in depth that the catalytic reactivity of CNPs in the H2 O2 disproportionation reaction increases with the Ce(III)-fraction and decreases in the presence of polymer coatings. The developed approach using UV-Visible spectroscopy for the characterization of the surface peroxide species can potentially serve as a foundation for determining the catalytic reactivity of CNPs in the disproportionation of H2 O2 .

Synthesis of Ce(IV) Heteroleptic Double-Decker Complex with a New Helical Naphthalocyanine as a Potential Gearing Subunit.

This paper describes the synthesis of a cerium(IV)-based molecular gear composed of a thioether functionalized phthalocyanine anchoring ligand, and a helical naphthalocyanine rotating cogwheel functionalized with four carbazoles. The naphthalocyanine ligand 9 was obtained after eleven steps (overall yield of 0.2%) as a mixture of three geometrical isomers, two of which are chiral and exhibit high levels of steric hindrance, as shown by DFT calculations. Their attributions have been made using 1H-NMR based on their different symmetry groups. The ratio of isomers was also determined and the prochiral C4h naphthalocyanine shown to be the major compound (55%). Its heteroleptic complexation with cerium (IV) and the anchoring phthalocyanine ligand 10 gave the targeted molecular gear in a 16% yield.

Customizing Cerium Oxide Particle Synthesis with Hybrid Polyion Complex Templates for Enhanced Oxidation Performance in Photo-Fenton Processes.

Hybrid poly-ion complexes were synthesized through the complexation of a double hydrophilic copolymer with Ce(III) ions. These colloids act as reservoirs for cerium ions, enabling the synthesis of cerium-based Prussian blue nanoparticles with a cubic structure, a narrow size distribution around 100 nm, and good colloidal stability in water. Upon high-temperature calcination, these nanoparticles are transformed into a cerium/iron-based metal oxide catalyst (CeO2/Fe2O3). The resultant composite catalyst demonstrates superior performance in the photo-Fenton oxidation of methylene blue pollutants, achieving a conversion efficiency that rivals other metal-based oxides and cerium-based catalysts.

Redox-Neutral Multicatalytic Cerium Photoredox-Enabled Cleavage of O-H Bearing Substrates.

The need for synthetic methodologies capable of rapidly altering molecular structure are in high demand. Most existing methods to modify scaffolds rely on net exothermicity to drive the desired transformation. We sought to develop a general strategy for the cleavage of C-C bonds ß to hydroxyl groups independent of inherent substrate strain. To this end we have applied a multicatalytic cerium photoredox-based system capable of activating O-H bonds in lactols to deliver formate esters. The same system is also capable of effecting hydrodecarboxylation and hydrodecarbonylation reactions. Initial mechanistic probes demonstrate atomic chlorine (Cl⋅) is generated under the reaction conditions, but substrate activation through cerium-alkoxides or -carboxylates cannot be ruled out.

Electronic-Structure Interpretation: How Much Do We Understand Ce L3 XANES?

Historically, cerium has been attractive for pharmaceutical and industrial applications. The cerium atom has the unique ability to cycle between two chemical states (Ce(III) and Ce(IV)) and drastically adjust its electronic configuration: [Xe] 4f15d16s2 in response to a chemical reaction. Understanding how electrons drive chemical reactions is an important topic. The most direct way of probing the chemical and electronic structure of materials is by X-ray absorption spectroscopy (XAS) or X-ray absorption near-edge structure (XANES) in high energy resolution fluorescence detection (HERFD) mode. Such measurements at the Ce L3 edge have the advantage of a high penetration depth, enabling in-situ reaction studies in a time-resolved manner and investigation of material production or material performance under specific conditions. But how much do we understand Ce L3 XANES? This article provides an overview of the information that can be extracted from experimental Ce L3 XAS/XANES/HERFD data. A collection of XANES data recorded on various cerium systems in HERFD mode is presented here together with detailed discussions on data analysis and the current status of spectral interpretation, including electronic structure calculations.

Synthesis, Structure and (Photo)Catalytic Behavior of Ce-MOFs Containing Perfluoroalkylcarboxylate Linkers: Experimental and Theoretical Insights.

Cerium-based Metal-Organic frameworks (Ce-MOFs) are attracting increasing interest due to their similar structural features to zirconium MOFs. The redox behavior of Ce(III/IV) adds a range of properties to the compounds. Recently, perfluorinated linkers have been used in the synthesis of MOFs to introduce new characteristic into the structure. We report the synthesis and structural characterization of Ce(IV)-based MOFs constructed using two perfluorinated alkyl linkers. Their structure, based on hexanuclear Ce6O4(OH)4 12+ clusters linked to each other by the dicarboxylate ions, has been solved ab-initio from X-ray powder diffraction data and refined by the Rietveld method. The crystallization kinetics and the MOF formation mechanism was also invesitigated by Synchrotron radiation with XAS spectroscopies (EXAFS and XANES). The MOFs present the same fcu cubic topology as observed in MOF-801 and UiO-66, and they showed good stability in water at different pH conditions. The electronic structure of these MOFs has been studied by DFT calculations in order to obtain insights into the density of states structure of the reported compounds, resulting in band gaps in the range of 2.8-3.1 eV. Their catalytic properties were tested both thermally and under visible light irradiation for the degradation of methyl orange (MO) dye.

Primary photophysical and photochemical processes for cerium ammonium nitrate (CAN) in acetonitrile.

Cerium ammonium nitrate (CAN) is an important photolytic source of NO3• radicals in aqueous nitric acid solutions and in acetonitrile. In this work we performed the study of primary photochemical processes for CAN in acetonitrile by means of ultrafast TA spectroscopy and quantum chemical calculations. Photoexcitation of CAN is followed by ultrafast (< 100 fs) intersystem crossing; the vibrationally cooled triplet state decays to pentacoordinated Ce(III) intermediate and NO3• radical with the characteristic time of ca. 40 ps. Quantum chemical (QM) calculations satisfactorily describe the UV-vis spectrum of the triplet state. An important feature of CAN photochemistry in CH3CN is the partial stabilization of the radical complex (RC) [(NH4)2CeIII(NO3)5…NO3•], which lifetime is ca. 2 µs. The possibility of the RC stabilization is supported by the QM calculations.

Atom Pairing Enhances Sulfur Resistance in Low-Temperature SCR via Upshifting the Lowest Unoccupied States of Cerium.

Environmentally benign cerium-based catalysts are promising alternatives to toxic vanadium-based catalysts for controlling NOx emissions via selective catalytic reduction (SCR), but conventional cerium-based catalysts unavoidably suffer from SO2 poisoning in low-temperature SCR. We develop a strongly sulfur-resistant Ce1+1/TiO2 catalyst by spatially confining Ce atom pairs to different anchoring sites of anatase TiO2(001) surfaces. Experimental results combined with theoretical calculations demonstrate that strong electronic interactions between the paired Ce atoms upshift the lowest unoccupied states to an energy level higher than the highest occupied molecular orbital (HOMO) of SO2 so as to be catalytically inert in SO2 oxidation but slightly lower than HOMO of NH3 so that Ce1+1/TiO2 has desired ability toward NH3 activation required for SCR. Hence, Ce1+1/TiO2 shows higher SCR activity and excellent stability in the presence of SO2 at low temperatures with respect to supported single Ce atoms. This work provides a general strategy to develop sulfur-resistant catalysts by tuning the electronic states of active sites for low-temperature SCR, which has implications for practical applications with energy-saving requirements.