Search Results (1,812)

Understanding the reaction pathway of aldehyde deformylation catalyzed by natural enzymes has shown significance in developing synthetic methodologies and new catalysts in organic, biochemical, and medicinal chemistry. However, unlike other well-rationalized chemical processes catalyzed by cytochrome P450 (Cyt P450) superfamilies, the detailed mechanism of the P450-catalyzed aldehyde deformylation is still controversial. Challenges lie in establishing synthetic models to decipher the reaction pathways, which normally are homogeneous systems for precisely mimicking the structure of the active sites in P450s. Herein, we report a heterogeneous Cyt P450 aromatase mimic based on a porphyrinic metal–organic framework (MOF) PCN-224. Through post-metalation of iron(II) triflate with the porphyrin unit, a five-coordinated Fe^II(Porp) compound could be afforded and isolated inside the resulting PCN-224(Fe) to mimic the heme active site in P450. This MOF-based P450 mimic could efficiently catalyze the oxidative deformylation of aldehydes to the corresponding ketones under room temperature using O₂ as the sole oxidant and triethylamine as the electron source, analogous to the NADPH reductase. The catalyst could be completely recovered after the catalytic reaction without undergoing structural decomposition or compromising its reactivity, representing it as one of the most valid mimics of P450 aromatase from both the structural and functional aspects. A mechanistic study reveals a strong correlation between the catalytic activity and the C^α-H bond dissociation energy of the aldehyde substrates, which, in conjunction with various trapping experiments, confirms an unconventional mechanism initiated by hydrogen atom abstraction. Full article

Quinazolinones, a class of nitrogen-containing heterocyclic compounds, occupy a crucial position in medicinal chemistry and materials science due to their significant application potential. In recent years, the catalytic asymmetric synthesis of axially chiral quinazolinones has emerged as a prominent research area, driven by their prospective applications in the development of bioactive molecules, design of chiral ligands, and fabrication of functional materials. This review comprehensively summarizes recent advancements in the catalytic asymmetric synthesis of axially chiral quinazolinones, with a particular focus on the construction strategies for the three major structural types: the C–N axis, N–N axis, and C–C axis. Key synthetic methodologies, including atroposelective halogenation, kinetic resolution, condensation–oxidation, and photoredox deracemization, are discussed in detail. In addition, the review provides an in-depth analysis of the applications of various catalytic systems, such as peptide catalysis, enzymatic catalysis, metal catalysis, chiral phosphoric acid catalysis, and others. Despite the substantial progress made thus far, several challenges remain, including the expansion of the substrate scope, enhanced control over stereoselectivity, and further exploration of practical applications, such as drug discovery and asymmetric catalysis. These insights are expected to guide future research towards the development of novel synthetic strategies, the diversification of structural variants, and a comprehensive understanding of their biological activities and catalytic functions. Ultimately, this will foster the continued growth and evolution of this rapidly advancing field. Full article

Coordination compounds, characterized by the coordination of metal ions with ligands, represent a pivotal area of research in chemistry due to their diverse structures and versatile applications. This review delves into the synthesis, characterization, biological evaluation, and practical applications of these compounds. A variety of synthetic methodologies (traditional solution-based techniques) are discussed to highlight advancements in the field. Investigations into the structural, electronic, and spectral properties of coordination compounds are emphasized to provide insights into their functional attributes. The biological evaluation section focuses on their roles in antimicrobial, anticancer, and enzyme-inhibitory activities, underscoring their potential in therapeutic development. Attention is paid to nanoparticles, which are increasingly used for the treatment of oncological diseases. The metal complexes have been shown to have antibacterial, antifungal, antiviral, antioxidant, and antiproliferative properties. Additionally, the review explores their applications across domains such as catalysis, illustrating their multifaceted utility. By synthesizing recent findings and trends, this article aims to bridge the gap between fundamental chemistry and applied sciences, paving the way for innovative uses of coordination compounds in both biological and industrial contexts. Full article

Polyethylene imine (PEI) is a synthetic water-soluble and nitrogen-rich polymer with an ethylene amine repeating unit. It exists in a linear or branched forms and finds applications in various areas. PEI is often chemically modified by crosslinking reactions using molecular and polymeric crosslinkers (e.g., trichlorotriazine, epichlorohydrin, ethylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, etc.) to increase its stability and reduce its water solubility. PEI (pristine/crosslinked) has a strong affinity for metal cations (e.g., Cu²⁺, Au³⁺, Pb²⁺, etc.), where the nitrogen atoms interact with the metal ions, and hence is suitable to remove metals from water with high efficiency. A thin film of crosslinked PEI on substrates can be prepared and finds diverse applications such as in removing metals and dyes, and biofouling prevention in the marine environment. The copper ion, as an example, can be stored (adsorbed) in a thin film of crosslinked PEI on a carbon cloth substrate, which can be released to water by passing an electric current through the film or with an acid treatment. It has also been reported that crosslinked PEI and composite materials can be used for the adsorption of dyes and gases such as CO₂ and SO₂ from the environment. The performance of pristine/composite/crosslinked PEI in gas, metal ion, and dye adsorption is affected by several factors. The focus of this review is to discuss the different reactions used to crosslink PEI and review the properties of the crosslinked materials and their applications. Studies have shown that the properties of the crosslinked PEI and hence its success in capturing metal ions, dyes, and CO₂ is dependent not only on the type of crosslinker but also on the degree of crosslinking. Full article

This research introduces a novel synthetic method for introducing highly luminescent silver nanoclusters (AgNCs). The technique relies on coffee Arabica seed extraction (CSE), which is the focus of this study. Our developed and manufactured ecologically friendly approach has enhanced the selectivity of AgNCs for Hg(II) ions. The coffee extract was employed in the synthesis process to stabilize and enhance the quantity of AgNCs generated. Various advanced techniques were used to characterize the AgNCs precisely in their prepared condition concerning size, surface modification, and composition. The fluorescence quenching of the AgNCs was the mechanism via which the CSE-AgNCs reacted to the principal metal ions in the experiment. Using this sensing methodology, a very accurate and selective sensing method is provided for Hg(II) in the dynamic range of 0.117 µM to 1.4 µM, with a limit of detection (LOD) equal to 35.21 nM. Comparative research was conducted to determine how selective CSE-AgNCs are for Hg(II) ions compared to other ions. Consequently, a notable degree of selectivity of AgNCs towards these Hg(II) metal ions was achieved, allowing the sensitive detection of Hg(II) metal ions, even their interfering metal ions, in the environment. AgNCs can detect Hg(II) at acceptable values within the nanomolar range. Based on their characteristics, Hg(II) ions were detected in real samples using CSE-AgNCs. Full article

Slaughterhouses generate a huge amount of highly polluted wastewater; if left untreated, this effluent could seriously threaten the environment and human health. In the present study, Ag₂O/Ba/TiO₂ nanocomposite was synthesized using the precipitation method, and its efficacy was investigated for the remediation of real slaughterhouse wastewater (SWW) under visible light. Its performance was assessed for the inactivation of bacterial strains identified in SWW and for the degradation of total organic solids, volatile solids, fixed solids, and heavy metals. The results indicated an excellent photocatalytic performance of the synthesized Ag₂O/Ba/TiO₂ nanocomposites, confirmed by 87.3% volatile solids, 30% total organic solids, and 40% fixed solids removal from SWW. The zone of inhibition runs from 4 to 9 mm, and the nanocomposites have demonstrated outstanding bacterial inactivation activity in this range. It has been shown that the synthetic Ag₂O/Ba/TiO₂ nanocomposites can function as an effective photocatalyst for the remediation of SWW and other waste products produced by various industries worldwide. Full article

Enantioselective transition metal catalysis is undoubtedly a cornerstone at the frontier of chemistry, attracting intense interest from both academia and the pharmaceutical industry. Central to this field is the strategic utilization of noncovalent interactions (NCIs), including hydrogen bonding, ion pairing, and π-system engagements, which not only drive asymmetric synthesis but also enable precise stereochemical control in transition metal-catalyzed transformations. Recent breakthroughs have unveiled a new generation of rationally designed ligands that exploit ligand–substrate noncovalent interactions, emerging as indispensable tools for stereocontrolled synthesis and setting new paradigms in ligand engineering. These advancements establish a transformative framework for ligand engineering, bridging fundamental mechanistic insights with practical synthetic utility. In this review, the judicious design concepts and syntheses of novel ligands from the past five years were highlighted and their synthetic applications in asymmetric catalysis were detailed. Full article

Composite grids serve as reinforcement in concrete structures, offering alternatives to conventional steel reinforcement. These grids can be fabricated from various materials, including synthetic polymers, metals, and natural fibers. This study explores the use of composite grids as lateral confinement of self-compacting concrete (SCC) cylinders and examines their impact on the failure mode under axial compression. In the experiment, the types of grids and mesh shapes used were plastic grids of diamond mesh (PGD) and regular mesh (PGT), metallic grids of diamond mesh (MGD) and square mesh (MGS), vegetable grids of Alfa fiber mesh, 10 × 10 mm (VGAF-1) and 20 × 20 mm (VGAF-2), and vegetable grids of date palm fibers (VGDF). The binder of SCC mixtures incorporated 10% marble powder as a partial replacement for ordinary Portland cement (OPC). SCC mixtures were tested in the fresh state by measuring the slump flow diameter, V-funnel flow time, L-box blocking ratio, and segregation index. Cylinders with a diameter of 160 mm and a height of 320 mm were made to assess the mechanical properties of hardened SCC mixtures under axial compression. The results indicate that most of the confined cylinders exhibited an increase in ductility compared to unconfined cylinders. Grid types MGD and PGD provided the best performance, with ductility increases of 100.33% and 96.45%, respectively. VGAF-2 cylinders had greater compressive strength than cylinders with other grid types. The findings revealed that the type and mesh shape of the grids affects the failure mode of confined cylinders, but has minimal influence on their modulus of elasticity. This study highlights the potential of lateral grid confinement as a technique for rehabilitating, strengthening, and reinforcing weaker structural concrete elements, thereby improving their mechanical properties and extending the service life of building structures. Full article

Synthetic cannabinoids (SCs), a class of widely abused new psychoactive substances, are characterized by their structural diversity and rapid evolution. Structure–affinity relationships are crucial for predicting pharmacological effects and potential toxicity. Traditional methods for affinity testing are often complex and less applicable to newly modified compounds. In contrast, Surface Plasmon Resonance (SPR) is a sensitive and label-free technology that detects molecular interactions by measuring refractive index changes on a metallic surface with the advantages of high sensitivity, low sample consumption, and high-throughput capability. In this study, we used SPR to determine the receptor affinity constants of 10 SCs, including some first-reported substances, and analyzed their structure–affinity relationships to validate the method’s reliability. The results showed that (1) indazole-based SCs exhibited stronger CB1 receptor affinity compared to their indole counterparts, (2) the head structure of p-fluorophenyl enhanced affinity relative to 5-fluoropentyl, (3) and the affinity rankings obtained from SPR experiments were consistent with those derived from traditional methods. These results collectively demonstrate the reliability and effectiveness of SPR in assessing CB1 receptor affinity and differentiating affinity differences among structurally similar analogs, with promising application prospects in drug research, particularly in the development and screening of therapeutic agents targeting cannabinoid receptors. Full article

Adsorption represents an effective strategy for water remediation applications, particularly when utilising eco-friendly materials in a circular economy framework. This approach offers significant advantages, including low cost, material availability, ease of operation, and high efficiency. Herein, the performance of cadmium ion adsorption onto hydroxyapatites, derived through a calcination-free process from shells of two mollusc species, Queen Scallop (Aequipecten opercularis) and Pacific Oyster (Magallana gigas), is examined. The phase and morphology of the synthesised adsorbents were investigated. The results showed that hydroxyapatites obtained from mollusc shells are characterised by high efficiency regarding cadmium removal from water, exhibiting rapid kinetics with equilibrium achieved within 5 min and high adsorption capacities up to 334.9 mg g⁻¹, much higher than many waste-based adsorbents reported in literature. Structural investigation revealed the presence of Cadmium Hydrogen Phosphate Hydrate in the hydroxyapatite derived from oyster shells loaded with Cd, indicating the formation of a solid solution. This finding suggests that the material not only has the capability to decontaminate but also to immobilise and store Cd. Overall, the results indicate that hydroxyapatites prepared via a synthetic route in mild conditions from waste shells are an economical and efficient sorbent for heavy metals encountered in wastewater. Full article

The 2-arylethylamine motif is very well-known in medicinal chemistry because of its interesting properties when it comes to interacting with the Central Neural System thanks to its ability to pass the blood–brain barrier. This nitrogen-containing family of compounds is of great interest in synthetic organic chemistry and, when it comes to its asymmetric synthesis, great challenges can be faced in order to obtain the chiral purity required in the drug industry. Thus, we provide a concise transition metal review presenting the recent advances in the synthesis of chiral 2-arylethylamines using transition metals as the main catalysts in the introduction of chirality. Both conventional and photocatalysis methods will be covered, considering the main transition metal used in the studies. Full article

2-(2′-aminophenyl)benzothiazole is a readily tunable fluorescent core with widespread applications in coordination chemistry, sensing, light-emitting processes, medicinal chemistry, and catalysis. This review provides an overview of the synthetic methodologies to access 2-(2′-aminophenyl)benzothiazole and its organic derivatives, including various phosphorous and silane pincer ligands. The luminescent properties will be discussed, with a special focus on ESIPT and AIE processes. The coordination of transition metals and lanthanides is presented, as well as their influence on biological and light-emitting properties. 2-(2′-aminophenyl)benzothiazole derivatives have also been employed as sensors for a range of cations and anions due to their various binding modes, as well as for bioimaging purposes. Recently, the first application in photocatalysis has emerged, showing one of the many openings for these organic building blocks in the future. Full article

Heavy metal pollution from anthropogenic sources poses significant risks to ecosystems and human health. Biosorption offers a sustainable removal method, but kinetics are poorly captured by traditional neural networks. This study introduces optimized Bidirectional Long Short-Term Memory (Bi-LSTM) networks for multivariate modeling of Ni(II) biosorption on Quercus crassipes acorn shells, trained using experimental (EKD), synthetic (SKD), and combined (CKD) datasets. A two-stage hyperparameter optimization with Optuna yielded models with R² above 0.995 and low RMSE in 5-fold cross-validation. Second-stage models showed high stability, with coefficient of variation (CoV) values below 10% for RMSE. Based on unseen kinetics, production models showed slightly lower performance (R² = 0.89–0.996): EKD1, EKD2, and CKD1 showed the most consistent performance across challenging conditions with R² values of 0.9617, 0.9769, and 0.9415, respectively; SKD models achieved strong results under standard conditions (kinetic 1, SKD1 R² = 0.9963). SHapley Additive exPlanations (SHAP) analysis identified contact time and initial Ni(II) concentration as key variables, with temperature, cation charge, and a salt interference code also contributing to model interpretability. These findings demonstrate that optimized Bi-LSTM networks offer a robust and interpretable data-driven solution for modeling Ni(II) removal under multivariate conditions, including the presence of salts. Full article

Carbon dots (CDs) are metal-free carbon-based nanoparticles. They possess excellent photoluminescent properties, various physical properties, good chemical stability, high water solubility, high biocompatibility, and tunable surface functionalities, suitable for biomedical applications. Their properties are subject to synthetic conditions such as pH, reaction time, temperature, precursor, and solvent. Until now, a large number of articles on the synthesis and biomedical applications of CDs using their photoluminescent properties have been reported. However, their research on magnetic properties and especially, diamagnetic chemical exchange saturation transfer (diaCEST) in magnetic resonance imaging (MRI) is very poor. The diaCEST MRI contrast agents are based on exchangeable protons of materials with bulk water protons and thus, different from conventional MRI contrast agents, which are based on enhancements of proton spin relaxations of bulk water and tissue. In this review, various syntheses, characterizations, magnetic properties, and potential applications of CDs as diaCEST MRI contrast agents are reviewed. Finally, future perspectives of CDs as the next-generation diaCEST MRI contrast agents are discussed. Full article

Synthetic non-metallic nanoparticles (NMNPs) such as carbon nanotubes (CNTs), carbon nanodots (CNDs), and cell-penetrating peptides (CPPs) have been explored to treat harmful algal blooms. However, their strain-specific algicidal activities have been rarely investigated. Here we determined their acute toxicity to nine freshwater cyanobacterial strains belonging to seven genera, including Microcystis aeruginosa UTEX 2386, M. aeruginosa UTEX 2385, M. aeruginosa LE3, Anabaena cylindrica PCC 7122, Aphanizomenon sp. NZ, Planktothrix agardhii SB 1810, Synechocystis sp. PCC 6803, Lyngbya sp. CCAP 1446/10, and Microcoleus autumnale CAWBG635 ATX. We prepared in-house three batches of CNDs using glucose (CND-G) or chloroform and methanol (CND-C/M) as the substrate and one batch of single-walled CNTs (SWCNTs). We also ordered a commercially synthesized CPP called γ-Zein-CADY. The axenic laboratory culture of each cyanobacterial strain was exposed to an NMNP at two dosage levels (high and low, with high = 2 × low) for 48 h, followed by measurement of five endpoints. The endpoints were optical density (OD) at 680 nm (OD₆₈₀) for chlorophyll-a estimation, OD at 750 nm (OD₇₅₀) for cell density, instantaneous pigment fluorescence emission (FE) after being excited with 450 nm blue light (FE₄₅₀) for chlorophyll-a or 620 nm red light (FE₆₂₀) for phycocyanin, and quantum yield (QY) for photosynthesis efficiency of photosystem II. The results indicate that the acute toxicity was strain-, NMNP type-, dosage-, and endpoint-dependent. The two benthic strains Microcoleus autumnale and Lyngbya sp. were more resistant to NMNP treatment than the other seven free-floating strains. SWCNTs and fraction A14 of CND-G were more toxic than CND-G and CND-C/M. The CPP was the least toxic. The high dose generally caused more severe impairment than the low dose. OD₇₅₀ and OD₆₈₀ were more sensitive than FE₄₅₀ and FE₆₂₀. QY was the least sensitive endpoint. The strain dependence of toxicity suggested the potential application of these NMNPs as a target-specific tool for mitigating harmful cyanobacterial blooms. Full article