Search Results (114)

As a potential strategic resource of critical metals, deep-sea cobalt-rich crusts represent one of the most promising metal reservoirs within oceanic seamount systems, and their metallogenic mechanism constitutes a frontier topic in deep-sea geoscience research. This review focuses on the cobalt-rich crusts from the Magellan Seamount region in the northwestern Pacific and synthesizes existing geological, mineralogical, and geochemical studies to systematically elucidate their mineralization processes and metal enrichment mechanisms from a microstructural perspective, with particular emphasis on cobalt enrichment and its controlling factors. Based on published observations and experimental evidence, the formation of cobalt-rich crusts is divided into three stages: (1) Mn/Fe colloid formation—At the chemical interface between oxygen-rich bottom water and the oxygen minimum zone (OMZ), Mn²⁺ and Fe²⁺ are oxidized to form hydrated oxide colloids such as δ-MnO₂ and Fe(OH)₃. (2) Key metal adsorption—Colloidal particles adsorb metal ions such as Co²⁺, Ni²⁺, and Cu²⁺ through surface complexation and oxidation–substitution reactions, among which Co²⁺ is further oxidized to Co³⁺ and stably incorporated into MnO₆ octahedral vacancies. (3) Colloid deposition and mineralization—Mn–Fe colloids aggregate, dehydrate, and cement on the exposed seamount bedrock surface to form layered cobalt-rich crusts. This process is dominated by the Fe/Mn redox cycle, representing a continuous evolution from colloidal reactions to solid-phase mineral formation. Biological processes play a crucial catalytic role in the microstructural evolution of the crusts. Mn-oxidizing bacteria and extracellular polymeric substances (EPS) accelerate Mn oxidation, regulate mineral-oriented growth, and enhance particle cementation, thereby significantly improving the oxidation and adsorption efficiency of metal ions. Tectonic and paleoceanographic evolution, seamount topography, and the circulation of Antarctic Bottom Water jointly control the metallogenic environment and metal sources, while crystal defects, redox gradients, and biological activity collectively drive metal enrichment. This review establishes a conceptual framework of a multi-level metallogenic model linking macroscopic oceanic circulation and geological evolution with microscopic chemical and biological processes, providing a theoretical basis for the exploration, prediction, and sustainable development of potential cobalt-rich crust deposits. Full article

This work aimed to synthesize new derivatives of 2-hydrazinylpyridine-3-carbonitrile and to investigate their biological activity as safeners for the 2,4-D herbicide. The new 2-hydrazinylnicotinonitriles were obtained in high yields (up to quantitative) under mild conditions (25 °C, dioxane) by treating 4,6-diaryl-2-bromo-3-cyanopyridines with hydrazine hydrate. The latter were synthesized by brominating 2-(3-oxo-1,3-diarylpropyl)malononitriles, the Michael adducts, which are readily available from 1,3-diarylpropenones (chalcones) and malononitrile. An unusual side product of the bromination/carbocyclization was isolated and characterized; it consisted of co-crystals of 3-benzoyl-4-hydroxy-4-phenyl-2,6-di-(p-tolyl)cyclohexane-1,1-dicarbonitrile and 3-benzoyl-5-bromo-4-hydroxy-4-phenyl-2,6-di-(p-tolyl)cyclohexane-1,1-dicarbonitrile at a ~4:6 ratio. The new 2-hydrazinylnicotinonitriles react with halogen-containing aromatic aldehydes to form the corresponding hydrazones. The biological activity of the new nicotinonitriles was examined for their function as 2,4-D antidotes. It was found that, under laboratory conditions, eight of the synthesized compounds exhibited a notable antidote effect against 2,4-D on sunflower seedlings. Full article

Thermochemical energy storage (TCES) utilizes chemical reactions to store thermal energy, offering a promising solution for efficient energy management. However, a significant challenge in application of TCES materials, particularly with crystal-to-crystal chemical transformations, is the mechanical degradation of reactive particles during repeated cycles connected with the constant re-modeling of crystals due to consecutive hydration–dehydration steps. This degradation leads to increased pressure drops in packed beds due to swelling and fracturing of salt particles, complicating their practical application. To address this issue, this study investigates the effect of a polymeric network as stabilizing element within TCES particles to enhance mechanical stability. Using potassium carbonate hydrate (K₂CO₃·1.5H₂O) as a model thermochemical material and thermoplastic polymers for reinforcement, composite particles were developed to resist disintegration over multiple cycles. The incorporation of polymeric networks from polyamide (PA11), polyetherimide (PEI) and polyvinylidene fluoride (PVDF) resulted in improved mechanical properties at relatively high porosity, which contributes to higher hydration rate. The developed stabilization method is compatible with existing scalable particle production methods like tableting and compacting. Full article

Addressing the significant pressure for carbon emission reduction in the cement industry, the development of novel cement materials capable of achieving “in situ carbon sequestration” has become an important research focus. This study introduces nesquehonite (MgCO₃·3H₂O, NQ) as a functional admixture into the Portland cement system, systematically investigating its effects on the cement hydration process, the evolution of hydration products, and its carbon sequestration efficiency. Through designed penetration resistance tests and hydration tests with a high water-to-solid ratio, this research utilized X-ray diffraction analysis to determine the phase composition and content of hydration products at different ages. This was combined with scanning electron microscopy to observe microstructural evolution and Nano Measure software 1.2.5 for ettringite crystal size measurement, analyzing the impact of NQ on the early hydration process of P.I cement. The results indicate that the incorporation of NQ significantly alters the early hydration of P.I cement. The Mg²⁺ and CO₃²⁻ ions released upon its dissolution interact with Ca²⁺ and OH⁻ in the pore solution, effectively promoting the early precipitation of carbon sequestration products such as calcium carbonate and minor magnesium-containing carbonates. The addition of 10% NQ hindered the crystallization of Ca(OH)₂ before 6 h but promoted its formation after 24 h. Mechanical property tests revealed that a sample with an optimal 3% NQ dosage not only increased the paste’s penetration resistance but also enhanced the compressive strength of the 1-day hardened sample by 8.37% compared to the plain sample, without a decrease and even a slight increase at 28 days. This enhancement is closely related to the microstructural strengthening effect induced by the carbonation products. This study confirms the feasibility of using NQ to steer the cement hydration pathway towards a low-carbon direction, revealing its dual functionality in regulating hydration and sequestering carbon within cement-based materials. The findings provide a new theoretical basis and technical pathway for developing high-performance, low-carbon cement. Full article

Large amounts of wood waste fly ash (WWFA) are generated in bioenergy plants, yet their potential for reuse in construction materials remains underexplored. In this study, artificial lightweight aggregates (ALWAs) were produced by cold-bonded granulation of WWFA with hydrated lime, followed by carbonation curing (20 °C, 64% RH, 19% CO₂). The aggregates were evaluated according to EN 13055:2016 classification criteria, with testing performed following the relevant European standards, including EN 1097-3 and EN 1097-6 for density and water absorption, EN 1097-11 for crushing resistance, and EN 1367-7 for freeze–thaw resistance. All ALWAs met the lightweight aggregate classification, with bulk densities of 1010.9–1060.0 kg/m³ and crushing resistances up to 2.74 N/mm², exceeding that of lightweight expanded clay aggregate (LECA) (1.26 N/mm²). XRD confirmed CaCO₃ formation, SEM revealed binder- and w/m-dependent porosity and crystal morphology, and freeze–thaw resistance indicated suitability for non-structural applications. These results demonstrate that WWFA-based ALWAs are a sustainable alternative to natural aggregates, combining waste valorization with competitive performance. Full article

Calcium carbonate (CaCO₃) is a dominant component of sedimentary rocks and biogenic structures, and is one of the most frequently studied inorganic compounds. It also plays a key role in preparing modern engineered materials. CaCO₃ has three well-known polymorphs, calcite, aragonite, and vaterite, and four solvatomorphs with diverse crystallographic arrangements, hydration states, reactivity, and stability. Its solvatomorphs include the variable water-containing amorphous calcium carbonate (ACC—CaCO₃·xH₂O) and the crystalline monohydrocalcite (MHC—CaCO₃·H₂O), calcium carbonate hexahydrate (ikaite—CaCO₃·6H₂O), and the recently reported hemihydrate (CCHH—CaCO₃·0.5H₂O). Here, we review the preparation, crystal structure, and properties of these solvatomorphs and discuss their mutual transformations. Full article

Pazufloxacin is a fluoroquinolone antibiotic synthesized by Toyama Chemical Co., Ltd. (Tokyo, Japan) in the 1990s. Up until now, the X-ray crystal structure of its mesylate salt had not been determined. The dissolution and recrystallization of pazufloxacin mesylate from different solvents afforded the salts pazufloxacinium mesylate (1), pazufloxacinium mesylate dihydrate (2), pazufloxacinium mesylate hydrate (3) and pazufloxacinium mesylate bis(peroxosolvate) (4), which were all crystallographically characterized. Molecular and crystal structures of these compounds, as well as their thermal behavior, were studied. For all compounds, single-crystal X-ray diffraction confirmed that a proton migrates from methanesulfonic acid to the amino group of pazufloxacin to form a salt. Dehydration of two hydrates occurs as a two-step single-crystal-to-powder process, leading to the formation of two metastable polymorphs of the anhydrous salt. In the solid state, the peroxosolvate compound is stable under ambient conditions for several months, thus making this drug–drug solid suitable for topical application. Full article

The aim of this study is an interdisciplinary assessment of the potential of cement pastes to permanently bind carbon dioxide (CO₂) under anaerobic digestion conditions, considering technological, microstructural, environmental, and economic aspects. The research focused on three types of Portland cement: CEM I 52.5N, CEM I 42.5R-1, and CEM I 42.5R-2, differing in phase composition and reactivity, which were evaluated in terms of their carbonation potential and resistance to chemically aggressive environments. The cement pastes were prepared with a water-to-cement ratio of 0.5 and subjected to 90-day exposure in two environments: a reference environment (tap water) and a fermentation environment (aqueous suspension of poultry manure simulating biogas reactor conditions). XRD, TG/DTA, SEM/EDS, and mercury intrusion porosimetry were applied to analyze CO₂ mineralization, phase changes, and microstructural evolution. XRD results revealed a significant increase in calcite content (e.g., for CEM I 52.5N from 5.9% to 41.1%) and the presence of vaterite (19.3%), indicating intense carbonation under organic conditions. TG/DTA analysis confirmed a reduction in portlandite and C-S-H phases, suggesting their transformation into stable carbonate forms. SEM observations and EDS analysis revealed well-developed calcite crystals and the dominance of Ca, C, and O, confirming effective CO₂ binding. In control samples, hydration products predominated without signs of mineralization. The highest sequestration potential was observed for CEM I 52.5N, while cements with higher C₃A content (e.g., CEM I 42.5R-2) exhibited lower chemical resistance. The results confirm that carbonation under fermentation conditions may serve as an effective tool for CO₂ emission management, contributing to improved durability of construction materials and generating measurable economic benefits in the context of climate policy and the EU ETS. The article highlights the need to integrate CO₂ sequestration technologies with emission management systems and life cycle assessment (LCA) of biogas infrastructure, supporting the transition toward a low-carbon economy. Full article

Objectives: Drug-drug cocrystals with improved properties can be used to facilitate the development of synergistic therapeutic combinations. The goal of the present study is to obtain novel drug-drug cocrystals involving two anti-glioma agents, temozolomide (TMZ) and myricetin (MYR). Methods: The novel TMZ-MYR cocrystal was prepared via slurry and solvent evaporation techniques and characterized by X-ray diffraction, thermal analysis, infrared spectroscopy, and dynamic vapor sorption measurements. The stability, compaction, and dissolution properties were also evaluated. Results: Crystal structure analysis revealed that the cocrystal lattice contains two TMZ molecules, one MYR molecule, and four water molecules, which are linked by hydrogen bonding interactions to produce a three-dimensional network. The cocrystal hydrate exhibited favorable stability and tabletability compared to pure TMZ. A dissolution study showed that the maximum solubility of MYR in the cocrystal (176.4 μg/mL) was approximately 6.6 times higher than that of pure MYR·H₂O (26.9 μg/mL), while the solubility of TMZ from the cocrystal (786.7 µg/mL) was remarkably lower than that of pure TMZ (7519.8 µg/mL). The solubility difference between MYR and TMZ was diminished from ~280-fold to ~4.5-fold. Conclusions: Overall, the TMZ-MYR cocrystal optimizes the stability and tabletability of TMZ and the dissolution behavior of both drugs, offering a promising approach for synergistic anti-glioma therapy with improved clinical potential. Full article

Soil stabilizers are environmentally friendly engineering materials that enable efficient utilization of local soil-water resources. The application of nano-modified stabilizers to reinforce loess can effectively enhance the microscopic interfacial structure and improve the macroscopic mechanical properties of soil. This study employed nano-SiO₂ and nano-CaCO₃ to modify cement-based soil stabilizers, investigating the enhancement mechanisms of nanomaterials on stabilizer performance through compressive and flexural strength tests combined with microscopic analyses, including SEM, XRD, and FT-IR. The key findings are as follows: (1) Comparative analysis of mortar specimen strength under identical conditions revealed that nano-SiO₂ generally demonstrated superior mechanical enhancement compared to nano-CaCO₃ across various curing ages (1–3% dosage). At 1% dosage, the compressive strength of both modified stabilizers increased with curing duration. Early-stage strength differences (3 days) remained below 3% but showed a significant divergence with prolonged curing: nano-SiO₂ groups exhibited 10.3%, 11.3%, and 7.2% higher compressive strengths than nano-CaCO₃ at 7, 14, and 28 days, respectively. (2) The strength enhancement effect of nano-SiO₂ on MBER soil stabilizer followed a parabolic trend within 1–3% dosage range, peaking at 2.5% with over 15% strength improvement. (3) The exceptional performance of nano-SiO₂ originates from its high reactivity and ultrafine particle characteristics, which induce nano-catalytic hydration effects and demonstrate strong pozzolanic activity. These properties accelerate hydration processes while promoting the formation of interlocking C-S-H gels and hexagonal prismatic AFt crystals, ultimately creating a robust three-dimensional network that optimizes interfacial structure and significantly enhances strength characteristics across curing periods. These findings provide scientific support for the performance optimization of soil stabilizers and their sustainable applications in eco-construction practices. Full article

Objectives: Drug–drug cocrystallization represents a promising approach for the development of novel combination drugs with improved physicochemical and biopharmaceutical properties. The aim of the present research is to prepare novel drug-drug cocrystalline forms of antiepileptic drug carbamazepine (CBZ) with sulfacetamide (SCTM). Methods: The novel CBZ cocrystal methanol solvate and cocrystal hydrate were prepared via solvent evaporation technique and characterized by single crystal X-ray diffraction, differential scanning calorimetry and thermogravimetric analysis. Results: Single-crystal X-ray diffraction and thermal analysis revealed that the multicomponent solids are isostructural, wherein the solvent molecule does not play a structure-forming role. To optimize the synthesis of [CBZ+SCTM+H₂O] (1:1:0.7), the binary and ternary phase diagrams were constructed in acetonitrile at 25 °C. A thorough investigation of the cocrystal hydrate behavior in aqueous solution showed that the pH of the dissolution medium exerted a significant effect on the stability and solubility of [CBZ+SCTM+H₂O] (1:1:0.7). According to the dissolution and diffusion experiments in a buffer solution pH 6.5, the cocrystal hydrate characterized an enhanced dissolution rate and flux of CBZ. Pharmacokinetic studies in rabbits showed that the novel cocrystal hydrate exhibited a comparable bioavailability to the parent CBZ. Conclusions: Overall, this work reports the preparation of a novel CBZ drug-drug cocrystal hydrate, which can be considered as an alternative CBZ solid form for oral usage, possessing additive pharmacological effect. Full article

To address the high carbon emissions and resource dependency associated with conventional ordinary Portland cement (OPC) production, this study systematically investigated the preparation processes, hydration mechanisms, and chemical properties of high-belite calcium sulfoaluminate (HBCSA) and calcium sulfoaluminate (CSA) cements based from industrial solid wastes. The results demonstrate that substituting natural raw materials (e.g., limestone and gypsum) with industrial solid wastes—including fly ash, phosphogypsum, steel slag, and red mud—not only reduces raw material costs but also mitigates land occupation and pollution caused by waste accumulation. Under optimized calcination regimes, clinkers containing key mineral phases (C₄A₃S⁻ and C₂S) were successfully synthesized. Hydration products, such as ettringite (AFt), aluminum hydroxide (AH₃), and C-S-H gel, were identified, where AFt crystals form a three-dimensional framework through disordered growth, whereas AH₃ and C-S-H fill the matrix to create a dense interfacial transition zone (ITZ), thereby increasing the mechanical strength. The incorporation of steel slag and granulated blast furnace slag was found to increase the setting time, with low reactivity contributing to reduced strength development in the hardened paste. In contrast, Solid-waste gypsum did not significantly differ from natural gypsum in stabilizing ettringite (AFt). Furthermore, this study clarified key roles of components in HBCSA/CSA systems; Fe₂O₃ serves as a flux but substitutes some Al₂O₃, reducing C₄A₃S⁻ content. CaSO₄ retards hydration while stabilizing strength via sustained AFt formation. CaCO₃ provides nucleation sites and CaO but risks AFt expansion, degrading strength. These insights enable optimized clinker designs balancing reactivity, stability, and strength. Full article

Salt lakes and the surrounding saline soils distributed across northwestern China and Inner Mongolia impose severe physicochemical corrosion on cement-based concrete. Understanding the corrosion products and mechanisms are crucial scientific and technological factors in ensuring the durability and service life of concrete structures in these regions. In this study, various analytical techniques—including X-ray diffraction, thermogravimetric–differential thermal analysis, X-ray fluorescence, and scanning electron microscopy coupled with energy-dispersive spectroscopy—were employed to systematically analyze the corrosion products of ordinary Portland cement (OPC) and high-performance concrete (HPC) specimens after eight years of field exposure in the Qarhan Salt Lake area of Qinghai. The study provided an in-depth understanding of the physicochemical corrosion mechanisms involved. The results showed that, after eight years of exposure, the corrosion products comprised both physical corrosion products (primarily sodium chloride crystals), and chemical corrosion products (associated with chloride, sulfate, and magnesium salt attacks). A strong correlation could be observed between the chemical corrosion products and the strength grade of the concrete. In C25 OPC, the detected corrosion products included gypsum, monosulfate-type calcium sulfoaluminate (AFm), Friedel’s salt, chloro-ettringite, brucite, magnesium oxychloride hydrate 318, calcium carbonate, potassium chloride, and sodium chloride. In C60 HPC, the identified corrosion products included Kuzel’s salt, Friedel’s salt, chloro-ettringite, brucite, calcium carbonate, potassium chloride, and sodium chloride. Among them, sulfate-induced corrosion led to the formation of gypsum and AFm, whereas chloride-induced corrosion resulted in chloro-ettringite and Friedel’s salt. Magnesium salt corrosion contributed to the formation of brucite and magnesium oxychloride hydrate 318, with Kuzel’s salt emerging as a co-corrosion product of chloride and sulfate attacks. Furthermore, a conversion phenomenon was evident between the sulfate and chloride corrosion products, which was closely linked to the internal chloride ion concentration in the concrete. As the chloride ion concentration increased, the transformation sequence of sulfate corrosion products occurred in the following order: AFm → Kuzel’s salt → Friedel’s salt → chloro-ettringite. There was a gradual increase in chloride ion content within these corrosion products. This investigation into concrete durability in salt-lake ecosystems offers technological guidance for infrastructure development and material specification in hyper-saline environments. Full article

The dynamic evolution of alkalinity during hydration/carbonation of CO₂-conditioned cements results in the formation of polymorphic hydrated calcium silicates (C-S-H), whose differences in carbon sequestration capacity have not been systematically investigated. However, the micro-nano structures and carbon sequestration capacities of C-S-H are controlled by the dynamic effects of pore solution alkalinity and Ca/Si. Accordingly, different alkalinity and Ca/Si were set to simulate the cement hydration environment for the synthesis of C-S-H, and tests such as thermogravimetric and ²⁹Si nuclear magnetic resonance (NMR) were used to investigate the effects and mechanisms of initial alkalinity and Ca/Si on the morphology of the synthesized C-S-H, the CO₂ uptake. The results showed that the C-S-H synthesized at pH 7.2–12.0 and Ca/Si ratio of 1.0–2.3 was in flocculated and acicular forms, which were well crystallized and dominated by Q², while its CO₂ uptake was positively correlated with Ca/Si. On the contrary, the synthesized C-S-H was poorly crystallized under the conditions of pH increasing to 13.5 and Ca/Si ratios of 1.0–2.3. With the increase in Ca/Si, the synthesized C-S-H evolved from Q²-dominated foil to Q¹-dominated porous structure, and its CO₂ uptake was non-positively correlated with Ca/Si. This was mainly related to the average pore diameter of C-S-H and its silica-oxygen tetrahedral structure. This was mainly related to the average pore diameter of C-S-H and its silica-oxygen tetrahedral structure. Full article

Background: It is generally accepted that water as a plasticizer can decrease the glass transition temperatures (T_gs) of amorphous drugs and drug delivery systems, resulting in physical instabilities. However, a recent study has reported an anti-plasticizing effect of water on amorphous lidocaine (LID). In co-amorphous systems, LID might be used as a co-former to impair the plasticizing effect of water. Method: Flurbiprofen (FLB) was used to form a co-amorphous system with a mole fraction of LID of 0.8. The effect of water on the stability of co-amorphous FLB-LID upon hydration was investigated. The crystallization behaviors of anhydrous and hydrated co-amorphous FLB-LID systems were measured by an isothermal modulated differential scanning calorimetric (iMDSC) method. The relaxation times of the co-amorphous FLB-LID system upon hydration were measured by a broadband dielectric spectroscopy (BDS), and the differences in Gibbs free energy (ΔG) and entropy (ΔS) between the amorphous and crystalline phases were determined by differential scanning calorimetry (DSC). Results: It was found that the crystallization tendency of co-amorphous FLB-LID decreased with the addition of water. Molecular mobility and thermodynamic factors were both investigated to explain the difference in crystallization tendencies of co-amorphous FLB-LID upon hydration. Conclusions: The results of the study showed that LID could be used as an effective co-former to decrease the crystallization tendency of co-amorphous FLB-LID upon hydration by enhancing the entropic (ΔS) and thermodynamic activation barriers (TΔS)³/ΔG²) to crystallization. Full article