Search Results (481)

The poor stability of CsPbBr₃ perovskite nanocrystals (PNCs) caused by weak and dynamic ligand coordination severely limits their commercial applications. Herein, a dual-ligand synergistic modification strategy based on bromocarboxylic acids (BCAs) and oleylamine (OAm) was developed to mediate the surface structures and luminescent dynamics of CsPbBr₃ PNCs. The results reveal that carboxylate groups of BCA ligands modulate crystal growth, while its terminal Br atom forms a strong coordination with exposed Pb²⁺ on the PNCs surface, which can effectively passivate lead- and bromine-related defects. The synergistic protection of OAm ligands enhances the stability of PNCs via amino-halide electrostatic interactions and steric hindrance effects. Notably, based on the relatively dense surface coating of 4-bromobutyric acid (BBA) and OAm dual-ligands, the prepared CsPbBr₃ PNCs exhibit a high photoluminescence quantum yield (PLQY) of 85.2 ± 2.4% and remarkable storage stability, retaining 90.2 ± 1.7% of their initial PL intensity after being stored for 63 days under ambient conditions. Furthermore, a prototype white light-emitting diode (WLED) fabricated with these PNCs displays a wide color gamut covering 122.1% of the NTSC standard and a luminous efficacy of 64.6 lm/W. This work provides a facile and feasible ligand engineering strategy to obtain highly stable and emissive PNCs. Full article

Pharmaceutical residues are increasingly emerging in global drinking water sources, posing serious ecological and public health challenges by altering the physicochemical balance of aquatic systems. Among available purification approaches, adsorption remains one of the most promising techniques due to its simplicity, cost-effectiveness, and efficiency. In this work, a ternary nanocomposite of Cu- and ZnO-decorated carboxylated graphene oxide (Cu/ZnO@CGO) was synthesized and utilized for highly efficient and ultrafast removal of the antidiabetic drug metformin from aqueous environments. The adsorption mechanism arises from a synergistic combination of surface complexation on Cu nanoparticles, cation–π and π–π electron donor–acceptor interactions with the CGO aromatic structure, and hydrogen bonding through the amino groups of metformin and the oxygen-rich functional moieties of ZnO and CGO. The nanocomposite was thoroughly characterized using FTIR, XPS, XRD, SEM, HRTEM, and TGA analyses, confirming its well-defined hybrid structure. Unlike conventional single-phase or binary systems, the Cu/ZnO@CGO nanocomposite demonstrated remarkable cooperative effects that enhanced its performance through the integration of metal–ligand coordination, π–π stacking, cation–π forces, and hydrogen bonding. These interactions contributed to an outstanding adsorption capacity of 232.56 mg·g⁻¹ and an exceptionally fast equilibrium time of only 25 min. Moreover, the material maintained excellent reusability, with merely a 4.1% decline in efficiency after five regeneration cycles, and achieved almost complete removal of metformin (99.7 ± 3.4%) from several real water samples, namely river, tap, and bottled water. The unique structural design of Cu/ZnO@CGO prevents CGO aggregation and facilitates efficient contaminant capture even at trace concentrations, establishing it as a highly competitive and sustainable adsorbent for pharmaceutical wastewater treatment. Overall, this study highlights a novel and rationally engineered nanocomposite whose synergistic surface chemistry bridges adsorption and detoxification, providing valuable insight into the next generation of multifunctional graphene-based materials for environmental remediation. Full article

Spectrophotometric analysis of divalent Hg(II) using dithizone has been widely used. Yet, a number of analytical issues and concerns associated with this method remain to be addressed. We studied the effect of humic acids (Aldrich and Acros humic acids) and pH on Hg(II) analysis and clarified several analytical and operational issues. Our study shows that the humic acids lower the slopes of the Hg(II) calibrations and thus the sensitivity of the method. Nevertheless, the calibrations retain good linearity and thus still remain valid and useful in the presence of the humic acids at the tested levels of up to 100 ppm. The effect of the humic acids appears to be similar under both acidic and basic conditions. Our tests using cysteine (model agent for thiol group) and oxalate (carboxylic group) reveal the cause for the effect of the humic acids. The study shows that cysteine has the strongest effect on the Hg(II) analysis (largest calibration slope decreases), followed by humic acids and then oxalate. As for the pH effect, in the absence of the humic acids, basic conditions lead to lower sensitivity but still with good linearity at pH up to 9. Yet, the method fails to perform satisfactorily at pH ≥ 10. Our further extended study on the effect of ligands (chloride, hydroxyl, citrate, oxalate, and cysteine) confirms the effect and role of the thiol and carboxylic groups of humic acids in affecting the Hg(II) analysis. These ligands widely present in environmental samples can interfere with the Hg(II) analysis by lowering its sensitivity while still leaving its calibration linearity unaltered. Our operational study shows that the concentration of dithizone solution (dithizone in chloroform) should always be kept excessive and adjusted based on the level of Hg(II) analyzed to ensure complete complexation of Hg(II) with dithizone. Adoption of the dithizone solution used for the Hg(II) extraction, instead of chloroform, to zero the spectrophotometer proves to be useful and effective in minimizing analytical errors. The improved, refined method of spectrophotometric analysis of Hg(II) using dithizone can still serve as a useful analytical tool. Yet, a lack of due attention to and appropriate measures for handling the effect of humic acids and other ligands can result in analytical errors and research artifacts. This can consequently compromise the analytical validity of this method. Appropriate analytical calibrations should be conducted with the effect of humic acids or ligands in consideration, and only the specific calibration in the presence of the humic acid or ligand of concern at the relevant level(s) should be employed appropriately to calculate the results of the analytical unknowns. Full article

As metal-containing resists attract increasing research interest in high-resolution lithography, gaining insights into the photochemical mechanisms, particularly in relation to the ligand functionality, is actively demanded. In this work, a controlled pair of organotin carboxylates with analogous structures but different functional groups has been designed and synthesized as deep-ultraviolet (DUV) resists. Both resists demonstrate 90 nm half-pitch resolution and the capability of pattern transfer on carbon-based hard-mask layers. Through various characterizations and comparison of the controlled pair, we propose two competitive reaction paths for the organotin system with olefin groups, which regulate the lithographic sensitivity and dissolution contrast. Our findings highlight the structural adjustability of organotin carboxylates and their potential application as high-resolution and etch-durable DUV resists. Full article

Metallic biomaterials play essential roles in modern medical devices, but their long-term performance depends critically on protein adsorption and subsequent cellular responses at material interfaces. This review examines the molecular mechanisms governing these interactions and discusses surface modification strategies for controlling biocompatibility. The physicochemical properties of oxide layers formed on metal surfaces—including Lewis acid-base chemistry, surface charge, surface free energy, and permittivity—collectively determine protein adsorption behavior. Titanium surfaces promote stable protein adsorption through strong coordination bonds with carboxylate groups, while stainless steel surfaces show complex formation with proteins that can lead to metal ion release. Surface modification strategies can be systematically categorized based on two key parameters: effective ligand density (σ_eff) and effective mechanical response (E_eff). Direct control approaches include protein immobilization, self-assembled monolayers, and ionic modifications. The most promising strategies involve coupled control of both parameters through hierarchical surface architectures and three-dimensional modifications. Despite advances in understanding molecular-level interactions, substantial challenges remain in bridging the gap between surface chemistry and tissue-level biological performance. Future developments must address three-dimensional interfacial interactions and develop systems-level approaches integrating multiple scales of biological organization to enable rational design of next-generation metallic biomaterials. Full article

Siderophores are low-molecular-weight chelating agents secreted by microorganisms under iron-limiting conditions, playing a crucial role in metal bioavailability and microbial survival. In this study, siderophores produced by Glutamicibacter sp. strain Al-Teq-24-F2, isolated from plant-associated samples, were characterized through a combination of spectroscopic and analytical methods. ESI-MS analysis of the crude extract revealed several abundant ions between 175 and 800 m/z, suggesting a mixture of secondary metabolites. After chromatographic purification, FT-IR and NMR analyses indicated the presence of amide, hydroxyl, and carboxylate functional groups. Integrating these data allowed for the proposal of a siderophore structure with a molecular weight of 438.25 Da. Thermogravimetric analysis showed thermal stability below 115 °C. During Fe (III) complexation, the zeta potential shifted from −21.15 mV to +42 mV, confirming strong interaction between the ligand and the metal. UV–Vis and fluorescence spectroscopy displayed characteristic bathochromic and hypochromic shifts, together with pronounced fluorescence quenching upon iron binding. These findings provide new insight into the structural and physicochemical properties of siderophores produced by Glutamicibacter sp. and highlight their potential applications in biosensing and metal chelation processes. Full article

The replacement of ionizable functional groups that are predominantly charged at physiological pH with neutral bioisosteres is a common strategy in medicinal chemistry; however, its impact on binding affinity is often context-dependent. Here, we investigated a series of amide derivatives of a glycomimetic E-selectin ligand, in which the carboxylate group of the lead compound is substituted with a range of amide and isosteric analogs. Despite the expected loss of the salt-bridge interaction with Arg97, several amides retained or even improved the binding affinity. Co-crystal structures revealed conserved binding poses across the series, with consistent interactions involving the carbonyl oxygen of the amide and the key residues Tyr48 and Arg97. High-level quantum chemical calculations ruled out a direct correlation between carbonyl partial charges and affinity. Instead, a moderate correlation was observed between ligand binding and the out-of-plane pyramidality of the amide nitrogen, suggesting a favorable steric adaptation within the binding site. Molecular dynamics (MD) simulations revealed that high-affinity ligands exhibit enhanced solution-phase pre-organization toward the bioactive conformation, likely reducing the entropic penalty upon binding. Further analysis of protein–ligand complexes using Molecular mechanics/Generalized born surface area (MM-GB/SA) decomposition suggested minor lipophilic contributions from amide substituents. Taken together, this work underscores the importance of geometric and conformational descriptors, beyond classical electrostatics, in driving affinity in glycomimetic ligand design and provides new insights into the nuanced role of amides as carboxylate isosteres in protein–ligand recognition. Full article

Thiourea and structurally related urea derivatives are widely recognised for their ability to transport anions through hydrogen bonding interactions. The strength of these interactions correlates with the electronegativity of the ligand and the acidity of the NH hydrogens involved. Thiourea, being more acidic than urea, exhibits partial deprotonation in the presence of certain anions such as organic carboxylates, fluoride, and bromide, while remaining resistant to deprotonation by chloride. This behaviour suggests a degree of selectivity toward chloride ions. Additionally, while carbamide-containing molecules tend to aggregate—potentially reducing their ion-binding efficiency—thiourea derivatives show reduced aggregation, preserving their binding capabilities. In this study, we report the synthesis and characterisation of 21 novel thiourea derivatives obtained by reacting 2-aminobenzoylamino acid esters with various substituted phenyl isothiocyanates. Seven similar thiourea-containing molecules were made as a comparison—without the amino acids—by reacting aniline with the different phenyl isothiocyanates. The reaction kinetics were found to be influenced primarily by the electronic nature of the substituents on the phenyl ring. Electron-withdrawing groups (EWGs), such as para-nitro, 3,5-bis(trifluoromethyl), and fluorine, accelerated the reaction, while electron-donating groups (EDGs), such as para-methoxy, slowed it down. Interestingly, the nature of the amino acid precursors had no significant impact on reaction time; however, reactions with aniline proceeded the fastest. Solvent choice also played a role: reactions in N,N-dimethylformamide (DMF) proceeded faster than in acetone, although with reduced yields. Consequently, reaction conditions were optimised to balance time efficiency and product yield. To evaluate the chloride ion-binding properties of the synthesised compounds, ¹H NMR titration experiments were conducted in deuterated dimethyl sulfoxide (DMSO-d₆). The association constants (K_a) derived from these studies revealed a clear correlation with the electronic nature of the substituents. Compounds bearing EWGs exhibited enhanced chloride binding, while those with EDGs showed diminished binding affinity. Surprisingly, the presence of amino acid moieties led to a decrease in K_a values, despite the electron-withdrawing nature of the amide groups. This suggests that steric or conformational factors may play a role in modulating binding strength. Overall, the synthesised thiourea derivatives demonstrate mild, reversible chloride ion-binding behaviour, making them promising candidates for further development as selective anion receptors. The insights gained from this study contribute to a deeper understanding of structure–activity relationships in anion-binding systems and may inform the design of future supramolecular architectures with tailored ion recognition properties. Full article

The development of stable and sensitive fluorescent sensors for metal ion detection remains a challenge in materials chemistry. Although hydrogen-bonded organic frameworks (HOFs) have shown great potential in luminescent applications, their practical use is often limited by structural instability. In this work, we present a novel charge-assisted HOF, termed FDU-HOF-21 ([H(NH₂Bpy)]₂(TPE)), constructed from a tetraphenylethylene (TPE)-based carboxylic acid ligand (H₄TCPE) and 2,2′-bipyridine-5,5′-diamine (NH₂Bpy). Single-crystal X-ray diffraction (SCXRD) reveals a stable three-dimensional framework stabilized by an extensive hydrogen-bonding network and reinforced by charge-assisted hydrogen bonds (CAHBs), and it exhibits exceptional stability across various solvents and pH conditions. Moreover, FDU-HOF-21 serves as a highly sensitive and selective fluorescent turn-on sensor for Al³⁺ ions, with a lowest limit of detection (LOD) of 1.7 × 10⁻⁶ M. Characterization and time-dependent density functional theory (TDDFT) calculations reveal that the fluorescence enhancement originates from the suppression of non-radiative decay likely due to the reduction in intermolecular charge transfer (Inter-CT) during the emission process, coupled with the restricted intramolecular rotation upon Al³⁺ chelation. Full article

Type 2 diabetes mellitus remains a critical metabolic disorder requiring novel therapeutic approaches. In this work, a library of 1-deazapurine derivatives was evaluated as α-glucosidase inhibitors through molecular docking with MOE software. The three top-ranked ligands—Methyl 6-(2-hydroxybenzoyl)-3-(2-phenylethyl)imidazo[4,5-b] pyridine-5-carboxylate (–6.1247 kcal/mol), 5-(furan-2-yl)-3-(4-methoxybenzyl)-2-phenyl-7- (trifluoromethyl)imidazo[4,5-b]pyridine (–5.7030 kcal/mol), and 3-[2-phenylethyl]-5-thio phen-2-yl-7-(trifluoromethyl)imidazo[4,5-b]pyridine (–5.5403 kcal/mol)—were further validated by molecular dynamics simulations. ADMET and drug-likeness predictions confirmed favourable pharmacokinetic behaviour, gastrointestinal absorption, and oral bioavailability. These findings highlight 1-deazapurines as promising scaffolds for developing new α-glucosidase inhibitors targeting type 2 diabetes. Full article

Two diruthenium(II,II) naphthyridine complexes coordinated with 4-trifluoromethylbenzoate (O₂CPh-4-CF₃) and 3,5-bis(trifluoromethyl)benzoate (O₂CPh-3,5-diCF₃) ligands, formulated as [Ru₂(npc)₂(O₂CPh-4-CF₃)₂] (4; npc = 1,8-naphthyridine-2-carboxylate) and [Ru₂(npc)₂(O₂CPh-3,5-diCF₃)₂] (5), respectively, were synthesized and structurally characterized. Single-crystal X-ray diffraction analysis revealed that both 4 and 5 form a direct metal–metal bond between the two Ru ions (2.2893(8) and 2.2896(7) Å, respectively) and adopt a paddlewheel-type structure in which two npc and two trifluoromethyl-substituted benzoate ligands are coordinated to a Ru₂⁴⁺ core with a cis-2:2 arrangement. The temperature dependence of the magnetic susceptibility measurements of 4 and 5 exhibited very large zero-field splitting (D = 242 and 246 cm⁻¹, respectively) of the triplet ground state of the Ru₂⁴⁺ core, similar to that of [Ru₂(npc)₂(O₂CPh)₂] (3; D = 238 cm⁻¹). Owing to the effects of the trifluoromethyl substituents, compared with 3, 4 and 5 showed (i) a significant blue shift of the absorption bands in the visible region and (ii) a positive shift of the redox potentials, with both shifts becoming more pronounced as the number of trifluoromethyl substituents increased. These experimental results are in good agreement with the electronic structure results obtained from density functional theory calculations. Full article

2-Oxazolines are five-membered heterocyclic compounds with significant biological properties. They also play an important role in organic synthesis, acting as chiral ligands and protecting groups for hydroxyamino acids and amino alcohols. Poly(2-oxazolines) are known coating materials, for example, in biomedicine. Classic synthetic methods of 2-oxazolines involve a dehydrative cyclisation reaction between amino alcohols and carboxylic acids, acid chlorides, nitriles, imidates, and aldehydes. However, the electrophilic intramolecular cyclization of unsaturated amides is becoming an increasingly important synthetic method for the preparation of 2-oxazolines. This brief review summarizes procedures for synthesizing oxazolines using the electrophilic intramolecular oxidative cyclisation of N-allyl and N-propargyl amides, as published between 2014 and 2024. It covers the synthesis of 5-halomethyl-, 5-trifluoromethyl-, 5-sulfonylmethyl-, 5-sulfenylmethyl-, 5-selenylmethyl-, 5-acetoxymethyl-, 5-hydroxymethyl-, 5-aminomethyl-, 5-alkilo-, and 5-alkylideneoxazolines. Full article

Data on the interplay between muscle, bone, and adipose tissue metabolism in normal-weight children with Prader–Willi syndrome (PWS) undergoing growth hormone (GH) therapy and dietary interventions are limited. This study aimed to assess the myokine profile and explore the associations between myokines, bone markers, adipokines, and body composition in these patients. The study included 26 children with PWS and 26 age-matched healthy controls. Serum levels of irisin, myostatin (MSTN), fibroblast growth factor-2, insulin-like growth factor-I (IGF-I), IGF-binding protein-2, bone alkaline phosphatase (BALP), osteocalcin (OC), carboxylated OC (Gla-OC), periostin, soluble receptor activator of nuclear factor kappa-B ligand, tartrate-resistant acid phosphatase 5b, leptin/soluble leptin receptor, adiponectin, and proinsulin were measured using immunoenzymatic assays. Children with PWS had significantly lower lean mass (p = 0.047) and a higher fat mass/lean mass ratio (p < 0.001) than controls. Irisin levels were lower in the PWS group (p = 0.031), while MSTN levels were similar between the groups. In patients, irisin positively correlated with BALP (p = 0.025) and negatively correlated with Gla-OC (p = 0.041) and periostin (p = 0.005). MSTN was positively associated with proinsulin (p = 0.001) and negatively associated with lean mass (p = 0.015). OC concentration was lower in the PWS group and correlated positively with lean mass (p = 0.052). Children with PWS exhibit altered myokine, osteokine, and adipokine profiles, as well as differences in body composition. Reduced irisin and osteocalcin levels, along with the negative association between MSTN and lean mass, may impair muscle development and bone metabolism. These imbalances could also contribute to future metabolic disorders in patients with PWS. Full article

The Lower Cambrian Niutitang Formation was deposited precisely during the Cambrian Explosion period, a short-lived interval marked by drastic shifts in oceanic chemistry and climate. This stratigraphic sequence preserves a comprehensive record of early-ocean evolution and constitutes a world-class reservoir for rare and precious metals, widely termed the “poly-metallic enrichment layer”. Despite its metallogenic prominence, the genetic model for metal enrichment in the Niutitang Formation remains contentious. In this study, we employed inductively coupled plasma mass spectrometry (ICP-MS), carbon and sulfur analyzer, and X-ray fluorescence spectrometry (XRF) to quantify trace-metal abundances, redox-sensitive element distribution patterns, rare-earth element signatures, and total organic carbon contents. Results reveal that metal enrichment in the Niutitang Formation was governed by temporally distinct mechanisms. Member I records extreme enrichment in As, Ag, V, Re, Ba, Cr, Cs, Ga, Ge, Se and In. This anomaly was driven by the Great Oxidation Event and intensified upwelling that oxidized surface waters, elevated primary productivity and delivered abundant organic matter. Subsequent microbial sulfate reduction generated high H₂S concentrations, converting the water column to euxinic conditions. Basin restriction imposed persistent anoxia in bottom waters, establishing a pronounced redox stratification. Concurrent vigorous hydrothermal activity injected large metal fluxes, leading to efficient scavenging of the above metals at the sulfidic–anoxic interface. In Members II and III, basin restriction waned, permitting enhanced water-mass exchange and a concomitant shift from euxinic to anoxic–suboxic conditions. Hydrothermal metal fluxes declined, yet elevated organic-matter fluxes continued to sequester Ag, Mo, Ni, Sb, Re, Th, Ga, and Tl via carboxyl- and thiol-complexation. Thus, “organic ligand shuttling” superseded “sulfide precipitation” as the dominant enrichment mechanism. Collectively, the polymetallic enrichment in the Niutitang Formation reflects a hybrid model controlled by seawater redox gradients, episodic hydrothermal metal supply, and organic-complexation processes. Consequently, metal enrichment in Member I was primarily governed by the interplay between vigorous hydrothermal flux and a persistently sulfidic water column, whereas enrichment in Members II and III was dominated by organic-ligand complexation and fluctuations in the marine redox interface. This study clarifies the stage-dependent metal enrichment model of the Niutitang Formation and provides a theoretical basis for accurate prediction and efficient exploration of polymetallic resources in the region. Full article

Organophosphonates have manifold applications in the chemical industry, of which one of the most commonly used is 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC). It is widely used as a cement additive and may pose a potential risk of complexing radionuclides such as uranium in nuclear waste repositories. PBTC, in its fully deprotonated form, has four negatively charged groups, one phosphonate and three carboxylate groups, which makes it a superior ligand for metal ion complexation. In this study, for the first time, its complexation behavior towards hexavalent uranium, U(VI), in the pH range from 2 to 11, has been investigated using various spectroscopic methods. The structure-sensitive methods NMR, IR, and Raman spectroscopy were used to characterize the complex structure. The interpretation of the results was supported by density functional calculations. Over almost the entire pH range studied, U(VI) and PBTC form a chelate complex via the phosphonate and the geminal carboxylate group, highlighting the strong chelating ability of the ligand. UV-Vis spectroscopy combined with factor analysis was applied to determine the distribution of differently protonated chelate species and their stability constants. Time-resolved laser-induced luminescence spectroscopy (TRLFS) was additionally used as a complementary method. Full article