Gold precursor salts are essential to modern catalysis, electronics, and chemical manufacturing, yet their production remains decoupled from sustainable resources. Here, we report a hydrogel that converts gold ions from electronic waste leachates into valence selective gold precursors without metallic intermediates. Through coordination and pH-programmed chemistry, the captured gold ions are converted into hydrogen tetrachloroaurate (HAuCl4.4H2O), hydrogen tetrabromoaurate (HAuBr4.3H2O), potassium dicyanoaurate (K[Au(CN)2]), and sodium bis(sulfito)aurate (Na3[Au(SO3)2]), representing Au(III) and Au(I) salts. The material demonstrates a gold absorption capacity of 837 mg/g and retains extraction efficiencies near 98% despite the presence of surplus competing metal ions. All gold precursors are acquired with quantitative yield and purity exceeding 99.9%, while the hydrogel maintains efficacy during numerous successive cycles. This work establishes a scalable route for transforming electronic waste into value-added gold feedstocks, advancing sustainable chemical manufacturing and circular materials design.
The review on Terminalia phillyreifolia, a valuable medicinal plant of the Combretaceae family in Asia, was provided, giving comprehensive descriptions in botanical background, geographic distribution, traditional applications, phytochemicals and pharmacological activities. Limitations of available research and potential perspective for later investigations on T. phillyreifolia were also clarified. Accordingly, a diverse array of natural compounds, categorised as phenolics, flavonoids, tannins, lignans, anthraquinones, xanthones, terpenoids, steroids, saponins, glycosides, cardiac glycosides, alkaloids, and amino acids, has been discovered in bark, stem (stem bark) and leaf, whose extracts were also acknowledged to be active in antioxidant, antimicrobial, antiviral, anti-diabetic, anti-inflammatory, antinociceptive, wound healing, cytotoxic effect on cancer cell lines, hepato-protective, antithrombotic, cardioprotective, antiplasmodial, and pro/antiangiogenic activities. However, the scarcity of isolated constituents, particularly from leaf, and the in-depth studies linking them with the reported biological/pharmacological activities have obscured T. phillyreifolia's values in modern medical applications.
Mn-based hybrids are emerging stimuli-responsive luminescent materials, whose response mechanism is generally based on chromic behavior induced by a transition from octahedral (Oh) to tetrahedral (Td) coordination. Upon a reversible phase transition driven by H2O/Cl- ligand exchange in an octahedral configuration (Oh to Oh), an alternative chromic mechanism is reported herein. Two zero-dimensional (0D) hybrid manganese chlorides, (C4H8N4)2[MnCl4(H2O)2]·2Cl (Mn-c) and (C4H8N4)2MnCl6 (Mn-r), were synthesized, featuring 4,6-diaminopyrimidinium cations and isolated Mn-centered octahedral motifs. Structural, spectroscopic, and theoretical analyses reveal that the cyan emission of Mn-c originates from the organic cations, whereas the red emission of Mn-r stems from Mn-centered d-d transitions. Interconversion between Mn-c and Mn-r can be triggered via the H2O/Cl- ligand exchange induced by heating (>108 °C) or by soaking in hydrochloric acid, resulting in a reversible phase transition and switchable photoluminescence (PL) behavior. Leveraging this reversible chromism, anticounterfeiting patterns were fabricated. This novel Oh-Oh phase transition and the related PL switching of 0D hybrid Mn-based halides provide a new platform for developing intelligent, multicolor-responsive luminescent materials.
The NH3-SCR reaction remains a key strategy for NOx removal, yet its efficiency is often limited by the unstable dispersion of active metal species and insufficient control over surface acid sites. Mesoporous materials offer a promising platform to overcome these challenges due to their large surface areas, tunable pore environments, and strong spatial confinement effects. In this work, we employ a ZrO2 surface-modification approach to tailor the pore-wall chemistry of mesoporous silica and construct a robust support for MnO2 nanoparticles. The ZrO2 layer enhances interfacial interactions, while the mesoporous confinement preserves the nano-size and uniform dispersion of MnO2. XRD, DRIFTS, DFT calculations, and kinetic analyses demonstrate that ZrO2-MnO2 coupling promotes reactant activation, oxygen migration, and stronger surface acidity, thereby markedly improving NH3-SCR activity. This study underscores the potential of engineered mesoporous structures in addressing fundamental limitations of NH3-SCR catalysis.
This work reports the development of epoxy-based biocomposites via the valorization of coconut fiber, with tailored thermal and mechanical properties obtained by varying the reinforcement and curing system. An organosolv process was used to extract lignin from natural coconut fiber (NCF) using a 90% v/v aqueous acetic acid solution combined with 2% v/v HCl at 110 °C for 1 h, yielding organosolv coconut fiber lignin (OCFL) and modified coconut fiber (MCF). The polymeric matrix was composed of diglycidyl ether of bisphenol A containing 0 or 50 wt% OCFL, while NCF and MCF were used as reinforcements. The biocomposites were prepared with a matrix-to-reinforcement mass ratio of 80:20 and cured with either a protic or an aprotic ionic liquid, specifically 10 wt% [HMIM][HSO4] at 180 °C or 10 wt% [BMIM][PF6] at 220 °C for 1 h. The biocomposites were characterized by thermogravimetry, constant-pressure calorimetry, gel content, water absorption, chemical resistance, scanning electron microscopy and dynamic mechanical analysis. The results show that the thermal, thermos-oxidative, chemical, and mechanical properties of the biocomposites can be modulated by controlling the type of reinforcement, the lignin content in the matrix, and the curing ionic liquid. The valorization of coconut solid residues through a sustainable organosolv-based route thus enables the design of thermosetting materials with high glass transition temperatures, high gel content, and self-extinguishing behavior suitable for high-performance applications, with potential to partially replace petroleum-derived materials in selected sectors of the chemical industry.
Viscoelastic hydrogels crosslinked by dynamic bonds hold great promise for mimicking the matrix dynamics of native tissues in cell culture and tissue engineering. Yet, their application in light-based bioprinting remains largely unexplored due to the incompatibility between reversible bond formation and photocrosslinking. This study addresses this key challenge by presenting a new class of photocrosslinkable, hydrazone-based bioinks developed from two modified polymers (Gel-A-DAAM and Gel-C-DAAM). These polymers are designed to enable reversible bond formation within hydrogel networks by attaching polymerizable groups to the polymer backbone via modular hydrazone conjugation chemistry. The resulting materials exhibit distinct mechanical properties depending on their hydrazide substituent, swelling medium, incubation temperature, and incubation time. Storage moduli of produced hydrogels vary between 0.08 - 1.2 kPa, which spans multiple scales of physiologically relevant tissue environments. The novel bioinks are suitable for droplet-based bioprinting followed by light-based crosslinking, and support cell spreading of human fibroblasts. Notably, the morphology of encapsulated cells varies with different hydrazide substituents, highlighting the potential of the developed bioink system to systematically investigate cell-matrix interactions. The combination of biological tunability and printability positions this system as a promising platform for fabricating next-generation tissue-mimetic constructs using advanced bioprinting technologies.
Iridium-based nanomaterials have shown great potential for development in electrochemiluminescence (ECL) analysis, in response to the bottlenecks of traditional ECL materials in terms of stability and surface engineering. In this study, novel iridium nanoclusters (Ir NCs) were synthesized and first applied in ECL, enabling efficient anodic ECL signal output. During synthesis, N,N-dimethylformamide served as a mild ligand, offering a controllable reduction environment and suitable thermal annealing conditions. This coordination effect achieved the surface functionalization of Ir NCs, successfully preparing Ir NCs with a uniform size and a stable structure. The target analyte cytokeratin 19 fragment 21-1 drove the DNA walker to perform cyclic catalytic walking at the biosensing interface, continuously introducing Ir NCs-labeled DNA strands through strand growth reactions. This process achieved significant cascade amplification of the ECL signal. This biosensor showed a good linear relationship within the concentration range of 100 fg/mL to 100 ng/mL, with a detection limit as low as 42 fg/mL. This study demonstrates good application potential in the early screening and clinical diagnosis of diseases.
Kinetic resolution has been a cornerstone for accessing enantioenriched molecules, but its application in radical chemistry has remained elusive due to the high reactivity of radical intermediates. Here, we present a new approach enabling precise Kinetic resolution in radical addition processes, yielding enantioenriched products and recovered starting materials with high efficiency. Two examples are provided: the Kinetic resolution of Minisci reactions between N-heterobiaryls or biaryls and glycine-derived redox-active esters under visible light irradiation with a chiral Brønsted acid catalyst, achieving high yields and enantioselectivities. The second example involves the reductive coupling of aldehydes with N-heterobiaryl-based olefins, enabling efficient synthesis of axially chiral heterobiaryls featuring both axial and remote central chirality. This work represents a conceptual breakthrough in asymmetric radical reactions, inspiring future developments in radical transformations using accessible racemic feedstocks.
Biomolecular condensates are formed through liquid-liquid phase separation (LLPS). They are highly dynamic, membraneless compartments within cells. The liquid-to-solid transition (LST) of these condensates plays a central role in regulating cellular physiological functions, maintaining tissue structural stability, and driving disease progression. Engineering LST has emerged as a major research frontier, integrating biophysics, synthetic biology, and materials science. This review systematically outlines the molecular grammar governing LST, key engineering strategies for its spatiotemporal control, and emerging applications in designed biological systems. We further discuss current challenges and future directions for harnessing LST as a design principle in systems chemistry and synthetic biology.
Metal cluster-based metal-organic frameworks (MOFs) offer many classical MOF materials because of their better directionality and selectivity of coordination geometry. However, unlike the numerous substitutable organic ligands and metal ions in MOFs, precisely controlling the inorganic bridging species in the metal cluster remains a significant challenge. Here, we use a prefabricated fluoride-bridged lanthanide cluster as a precursor to unambiguously introduce fluoride bridges into a well-known UiO-66-type MOF with an fcu topology. This blueprint provides eight isoreticular coordination networks with bridging F- through organic ligand alterations of different lengths and functional groups. The characterization of the content and position of bridging F- proves the complete substitution of O-bridge with F-bridge. More importantly, the rapid and moderate reaction process allows for the synthesis of ten-gram scale at room temperature within 5 s. Compared with prototypical UiO-66, the bridging F- in the representative structure can promote C2H2 adsorption and conduct efficient C2H2/CO2 separation.
Despite their high specific capacity, O3-type layered oxides face challenges of structural instability and sluggish kinetics as cathode materials for sodium-ion batteries (SIBs). Herein, we report a targeted synergistic strategy involving dual-element (Cu2+/Ti4+) doping at the transition metal (TM) sites and Ca2+ introduction into the Na sites of O3-type NaNi1/3Fe1/3Mn1/3O2 (NFM) to address their inherent defects. This multi-site modification effectively stabilizes the crystal structure, alleviates the phase transition amplitude, suppresses irreversible oxygen loss even at high voltage (up to 4.2 V vs. Na+/Na), and enhances Na+ migration by reducing the migration barrier and interfacial impedance. As a result, the optimized cathode (CCT) delivers a high reversible capacity of 125.3 mAh g-1 with 76.9% capacity retention after 300 cycles (vs. 64.1% for NFM). Even at a high current density of 2000 mA g-1 (∼13 C), the CCT cathode cycled at 4.2 V delivers a remarkable capacity of 94.3 mAh g-1, demonstrating excellent rate capability. The CCT//HC full-cell demonstrates excellent performance, achieving a high initial capacity (123.5 mAh g-1) and outstanding cycling stability (76.2% capacity retention) over 300 cycles. This work underscores the efficacy of multi-site synergistic doping strategy in designing high-performance layered oxide cathodes for practical SIBs.
The development of stable, environmentally benign, and high-performance perovskite solar cells (PSCs) has increasingly focused on innovative inorganic absorber materials. In this study, we conduct a detailed evaluation of the optoelectronic and mechanical properties of Ca3AsBr3, a promising non-toxic halide perovskite, using density functional theory (DFT) alongside SCAPS-1D simulations. The DFT results indicate that Ca3AsBr3 possesses a direct bandgap of 1.66 eV, along with good mechanical stability and strong optical absorption, making it well-suited for photovoltaic applications. To further investigate device performance, four electron transport layers (ETLs)-WS2, SnS2, CdS, and TiO2 were incorporated into HTL-free FTO/ETL/Ca3AsBr3/Au architecture, allowing analysis of energy band alignment, defect tolerance, and overall efficiency. Among these configurations, the WS₂-based device demonstrated superior performance, achieving a power conversion efficiency (PCE) of 20.50%, with an open-circuit voltage (Voc) of 1.165 V, a short-circuit current density (Jsc) of 20.55 mA/cm², and a fill factor (FF) of 85.64%. Further simulation results highlight that an optimal absorber thickness of 1200 nm, along with reduced bulk and interface defect densities (≤ 10¹⁵ cm⁻³ and ≤ 10¹³ cm⁻²), plays a crucial role in minimizing non-radiative recombination losses and improving charge carrier collection. Overall, this work identifies Ca3AsBr3 as a viable eco-friendly absorber material and emphasizes the importance of ETL optimization in achieving efficient, stable, and scalable PSC devices.
A successful green biodiesel process was achieved through the full utilization of catalysts derived from waste. The catalysts in this study were composed of nano CaO (31.0 nm, calcined eggshell undergoing hydration-dehydration cycles) and MgAlOx mixed oxides (14.0 nm, derived from Mg-Al layered double hydroxide). Transesterification of waste cooking oil using only CaO resulted in 95.9 ± 0.8% biodiesel. Using a combination of CaO and MgAlOx in a mass ratio of 70:30 achieved an improved biodiesel yield of 97.8 ± 0.5% under optimal conditions (molar ratio of methanol to oil at 12:1, catalyst mass fraction of 3 wt%, temperature of 60 °C, duration of 45 min, and ultrasonic support). The recycled CaO/MgAlOx hybrid catalyst exhibits greater stability compared to pure CaO, achieving 91.4 ± 1.2% of its initial activity after five reuse cycles for the mixed catalyst, whereas pure CaO attains only 87.9 ± 1.5%. Feedstocks with elevated Free Fatty Acid (FFA) content can be transformed into biodiesel using the hybrid catalyst, yielding 96.9 ± 0.7% from waste cow fat. All produced biodiesels meet American Society for Testing and Materials (ASTM) D6751 and European Committee for Standardization (EN) 14,214 standards. All biodiesel-diesel blends with varying biodiesel ratios- B5 (5%), B10 (10%), and B20 (20%) meet ASTM D7467 standards; therefore, the biodiesel can be used in existing diesel engines. This demonstrates a circular economy approach where various waste products can be recycled into high-value biodiesel using sustainable catalysts under green conditions.
Prussian blue analogs (PBA) are promising sodium-ion battery (SIB) cathodes but are hindered by structural defects, lattice hydration, and unstable interfaces, which limit redox reversibility and cycling. This study combines synthesis control and binder engineering to address these issues. Using polyvinylpyrrolidone (PVP) and sodium citrate in N2 coprecipitation with freeze-drying, Na2-δMnHCF_PVP_SC_N2_FD achieved higher crystallinity, fewer defects, and reduced excess and loosely bound interstitial water content. The optimized material exhibited a capacity of 92.9 mAh g-1, outperforming vacuum-dried (65.5 mAh g-1, +42%) and freeze-dried (80.2 mAh g-1, +16%) samples. The overall water content decreased, and the capacity retention reached 83.8% after 100 cycles, which was higher than that of the nonoptimized electrode. In addition, when a poly(acrylic acid)-polyaniline (PAA:PANI = 1:2) hybrid binder was applied, the initial charging capacity increased compared to that of PAA alone. Capacities of 127.8 mAh g-1 at 0.01 A g-1 and 56.8 mAh g-1 at 2 A g-1 were achieved, and the capacity recovered to 88.6 mAh g-1 when the current density returned to 0.05 A g-1, corresponding to a retention of 82.34%. Although the recovery retention was lower than that of the PAA-only electrode, the PAA:PANI = 1:2 binder delivered the best overall rate performance by maintaining substantially higher capacities across the entire current density range. Long-term stability was also greatly improved, maintaining a capacity retention rate of 78.6 mAh g-1 even after 500 cycles, which is 41% higher than that of PAA alone. Thus, the synergies of defect-minimized synthesis and conductive binder chemistry can convert Na2-δMnHCF from a limited-performance PBA to a quantitatively validated high-performance cathode platform. This presents a path for next-generation sodium-ion cells with both durability and high-rate characteristics and provides a potentially generalizable framework for PBA design for sustainable large-scale energy storage.
Biological assemblies such as proteins adapt their helical morphology and function in response to external stimuli, yet controlled polymorphic transitions in synthetic chiral supramolecular analogues remain poorly understood. Herein, we demonstrate a strategy to achieve controlled chiral supramolecular polymorphism in water by coupling molecular design with external stimuli. An unsymmetrical oligo(phenyleneethynylene) derivative 1 bearing a pyridine unit, a hydrogen-bonding amide group, and chiral hydrophilic side chains self-assembles into three distinct chiral supramolecular polymorphs in water that are stable at different temperature regimes. At room temperature (RT), 1 self-assembles into short cylinders (AggI), which undergo a polymorphic transition to transient double helical fibers upon heating around the LCST (AggII, ≈ 325 K) and ultimately to irregular planar aggregates (AggIII) above the LCST. Remarkably, the polymorphic transitions are linked to the temperature-dependent conformation and degree of dehydration of the glycol chains. Although AggII exists only within a narrow temperature window in pristine water, it can be stabilized and isolated at RT through chemical stimuli such as co-solvents or metal salts that modulate the LCST. Our results establish LCST-coupled chirality as a powerful strategy to regulate thermoresponsive supramolecular polymorphism and offer potential strategies for the design of adaptive materials.
Controlling peroxymonosulfate (PMS) activation at the atomic scale is crucial for steering reactive oxygen species (ROS) pathways, yet design principles that selectively bias PMS chemistry toward interfacial radical states remain elusive. Herein, we report an asymmetric Fe-Te dual-atom pair (FeTe DAs/NC), in which a p-block metalloid electronically modulates an Fe center through pronounced p-d hybridization. This atomic asymmetry reconstructs the local electronic structure, strengthens PMS binding, and directs PMS activation toward the generation and retention of surface-bound hydroxyl radicals. Mechanistic studies reveal surface-bound hydroxyl radicals (•OH) as the dominant ROS, while singlet oxygen (1O2) plays a secondary role. As a result, FeTe DAs/NC achieves complete degradation of carbamazepine within 60 min, markedly outperforming Fe or Te single-atom analogs, together with excellent reactivity and cycling stability across different water matrices and pollutant systems. This work establishes atomic-scale asymmetry and metal-metalloid p-d coupling as an effective strategy for steering PMS activation chemistry toward long-lived interfacial radical states.
Understanding the mechanisms of nickel (Ni) uptake by hyperaccumulator plants is essential for advancing sustainable phytomanagement. In this study, saponite materials containing either isotopically natural or 61Ni-enriched Ni were synthesised and applied in RHIZOtest experiments with Odontarrhena chalcidica. The amendments were mixed with two ultramafic soils differing in Ni content, alongside a serpentinite control. Ni bioavailability and uptake were evaluated via elemental and isotopic analysis of plant digests and diffusive gradients in thin films (DGT). Stable isotope spiking with 61Ni allowed tracing of amendment-derived Ni uptake into plant tissues, even though total Ni mass fractions in planted versus unplanted soils did not indicate significant mobilisation during the 14-day growth period. Isotope pattern deconvolution (IPD) revealed clear shifts in Ni isotopic composition in both plant and DGT samples. Tracer uptake was more pronounced in the low Ni soil, with amendment-derived Ni (xamendment) contributing 19.3 ± 5.0% of total Ni in shoots, compared to 7.7 ± 1.8% in the high-Ni soil. In standard solutions containing 50 ng g-1 total Ni, isotope pattern shifts were still detectable at enrichment levels as low as 0.01% xspike (≈ 5 pg g-1 61Ni). The findings demonstrate the sensitivity of stable isotope spiking combined with IPD in the detection of subtle uptake processes, even in short-term experiments. This approach enables the differentiation of various Ni sources in soil-plant systems that would not be achievable with quantification alone, and can thereby provide new insights into how soil mineralogy influences uptake dynamics in metal-hyperaccumulating species.
Organic luminescent radicals with efficient doublet emission can directly transfer electrons and energy to oxygen, enabling fluorescence-guided photodynamic therapy. However, their water insolubility and unclear oxygen interaction mechanisms limit their application. To address these challenges, we synthesized an amphiphilic organic radical (TTM-2PyPh) that forms self-assembled water-soluble nanoparticles (TTM-2PyPh_SA@NPs) with deep-red emission, serving as Type-I/II photosensitizers. Quantum chemistry calculations confirm an efficient electron transfer process between the radicals and oxygen. These nanoparticles self-assemble in vivo, target tumors, and produce reactive oxygen species more effectively than core-shell nanoparticles (TTM-2Py_CS@NPs), chlorin e6, and methylene blue. Additionally, TTM-2PyPh_SA@NPs demonstrate superior tumor eradication in vivo. This work advances the development of novel water-soluble radical-based photosensitizers for enhanced photodynamic therapy.
Nitrogen-doped carbon dots (CDs) were prepared from essential fluorescent amino acids, such as lysine (Lys), phenylalanine (Phe), tyrosine (Tyr), and tryptophan (Trp) by two routes, microwave and teflon-lined autoclave. The fluorescent properties of these amino acids were significantly improved in their corresponding CD forms, especially for those prepared via the hydrothermal process. A significantly high fluorescent intensity was measured in the emission range of 420-470 nm at the excitation wavelengths of 300-350 nm. While a negatively zeta potential value of - 9.8 ± 2.6 mV was obtained for Lys CDs suspension, the CDs of Phe, Tyr, and Trp afforded strong positive zeta potentials, + 24.0 ± 2.4, + 12.5 ± 3.1, and + 31.9 ± 3.8 mV, respectively. The Lys CDs were found not to be antimicrobial even at a 10 mg/mL concentration, which is likely due to their negative surface charge that weakens electrostatic interactions with negatively charged microbial membranes. Whereas the Phe, Tyr, and Trp CDs had a 2.5 mg/mL minimum inhibition concentration (MIC) against a Gram-negative bacterium, Klebsiella pneumoniae. The Phe CDs commenced the highest antibacterial effect against Bacillus subtilis (ATCC 6633) Gram-positive bacteria, but the lowest MIC value of 1.25 mg/mL was determined for Tyr CDs against Candida albicans (ATCC 10231) fungus. Furthermore, a UV light exposure, 30 min treatment of UV-A light with a 6.88 mW/cm2 irradiance value on amino acids CD exhibited improved photodynamic activity. The natural amino acid-derived CDs show great biocompatibility on L929 fibroblast cells with > 86% cell viability, for all formulations except Tyr CDs, retaining 78 ± 3% viability even at 1000 μg/mL concentration, and blood compatibility at 500 μg/mL concentration. Therefore, these CDs derived from fluorescent amino acids are photoactivated and are of excellent nanosized materials in a variety of biomedical in vitro and in vivo uses, including diagnostic, sensor, and therapeutic applications.
In this study, a novel HPMC/gelatin composite scaffold was prepared by incorporating 13-93B3 borate bioactive glass (BBG) microparticles and cerium oxide (CeO₂) submicrometric particles as a discrete phase, enabling higher ceria loadings without disrupting the bioactive glass chemistry. Composite hydrogel inks containing 5 wt% BBG microparticles and up to 20 wt% CeO₂ submicrometric particles were successfully extrusion-printed into porous scaffolds with interconnected pore architecture. CeO₂ incorporation preserved printability and mechanical strength while significantly enhancing scaffold deformation ability. Degradation behavior was tunable, with BBG microparticles reducing swelling and CeO₂ submicrometric particles modulating water uptake and pH evolution. BBG microparticles and CeO₂ submicrometric particles synergistically promoted apatite formation following 7 days of SBF incubation. In vitro studies using MC3T3-E1 pre-osteoblasts confirmed high cytocompatibility and Alizarin red study showed enhanced mineralization in CeO₂-containing scaffolds. Additionally, BBG and CeO₂ incorporated scaffolds exhibited strong antibacterial activity against Staphylococcus aureus and Escherichia coli. Overall, this multifunctional scaffold platform demonstrates promise for bone tissue engineering applications.