搜索结果：Inorganic Chemistry

Carbon is the element that makes up the major fraction of lipids and carbohydrates, which can be used for making biofuel. It is therefore important to provide enough carbon and also to follow the flow into particulate organic carbon and potential loss to dissolved organic forms of carbon. Here, we present methods for determining dissolved inorganic carbon, dissolved organic carbon, and particulate organic carbon.

Understanding how different C1 carbon sources participate in photocatalytic reduction is essential for clarifying carbon conversion pathways beyond conventional CO2-centric descriptions. Herein, polar chalcohalide photocatalysts SbSI and SbSeI are systematically investigated for the light-driven reduction of representative molecular and inorganic C1 carbon sources, including HCHO, HCOOH, CH3OH, NaHCO3, and CaCO3. Time-resolved product evolution, quantitative yields (μmol·g-1·h-1), and selectivity were determined using GC-TCD/FID and GC-MS. Across all systems, hydrogen evolution dominates the reaction network, methane is the primary carbon-containing product, and C2+ hydrocarbons appear as minor products, while CO and oxygen-containing organics are not detected. Molecular C1 substrates establish hydrogen-rich reaction environments that favor deep reduction and saturated hydrocarbon formation, whereas bicarbonate and carbonate sources exhibit reduced activity but enhanced formation of unsaturated C2+ hydrocarbons. These results establish a unified, experimentally driven framework for carbon-source-dependent photocatalytic reduction pathways over mixed-anion chalcohalide photocatalysts.

Phosphorus (P) is a macronutrient for all microalgal species, and the main form of uptake is orthophosphate (PO4). In this chapter we present a colorimetric method for determining the PO4 concentration and dissolved organic phosphorus (DOP) based on total phosphorus (TP) measurements. We also describe a method for determining particulate organic phosphorus (POP) based on the same principles.

Coordination-driven self-assembly offers a powerful toolkit for constructing sophisticated functional architectures. Rigid ligands are widely employed as building blocks in metallo-supramolecular chemistry due to their structural predictability during self-assembly. In contrast, flexible building blocks─though capable of offering greater structural diversity and stimuli-responsiveness─are rarely used, as their conformational freedom often complicates structural control. Consequently, the integration of flexible ligands into metallo-supramolecular systems remains underexplored. To address this challenge, we employ a postassembly ligand-exchange approach to construct a series of heteroleptic metallo-supramolecular cuboctahedra incorporating both rigid and flexible ligands. Investigations of chain length dependence reveal that flexible alkyl-diamine incorporation affects cage hydrodynamic size and stability, with optimal stability achieved at 8 units. This combined bottom-up and top-down synthetic approach offers a promising strategy for engineering complex architectures from flexible building blocks for further exploration of chemistry within a confined space.

The effects of anaerobic digestates on soil microbial communities have received increasing attention due to their potential impacts on soil health and antibiotic resistance. To date, no integrated analysis of rhizosphere bacterial community structure, antibiotic resistance genes (ARGs), and mobile genetic elements has been conducted in digestate-treated perennial ryegrass (Lolium perenne L.). We analyzed rhizosphere bacterial communities of this pasture using metabarcoding to study the effects of a manure-derived digestate on community structure and predicted functions. We also explored the association between digestate-enriched taxa and explanatory variables, including the abundance of two ARGs, class 1 integrons, and IncP-1ε plasmids. The greenhouse study included an unfertilized control and three fertilization treatments: digestate, inorganic fertilizer, and combined fertilizer (digestate + inorganic fertilizer). The results indicated a significant effect of the fertilizer type on bacterial communities and a stimulation of predicted functions related to genetic information processing by digestate and its combination. Digestate application resulted in the greatest differentiation in bacterial community structure relative to the unfertilized control and shifted communities toward amplicon sequence variants (ASVs) positively associated with class 1 integrons. Differential abundance analysis identified three ASVs and three genera (Arenimonas, Algoriphagus and Novosphingobium) that were significantly enriched under digestate treatment, relative to both urea and the unfertilized control. Our results demonstrate that anaerobic digestate application alters bacterial community structure and highlight the need for further studies to elucidate the potential adaptive role of class 1 integrons in rhizosphere microbiomes following digestate fertilization, including their contribution to antibiotic resistance.

In this study, the potential protective role of Se(IV) against inorganic Hg-induced cytotoxicity was evaluated in the human neuroblastoma SH-SY5Y cell line using inductively coupled plasma mass spectrometry, both in conventional (ICP-MS) and single-cell (scICP-MS) modes. To this end, Se (25, 50, and 70 μmol Se L-1) was tested against equivalent concentrations of inorganic Hg (25, 50, and 70 μmol Hg L-1) under both co-exposure and pre-treatment conditions. Cell viability assessed using the MTT assay (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide), showed that Se (IV) at 25 and 50 μmol Se L-1 significantly attenuated Hg(II)-induced cytotoxicity, with pre-treatment demonstrating greater efficacy than co-exposure. Additionally, a chemical speciation model was applied to estimate the effective concentrations of Hg and Se available to cells relative to the nominal doses. scICP-MS measurements revealed heterogeneous Hg uptake among individual cells. Notably, co-exposure with 25 μmol Se L-1 reduced cellular Hg accumulation from 73 fg Hg cell-1 to 61 fg Hg cell-1, while pre-treatment further decreased it to 42 fg Hg cell-1. Overall, these findings suggest that selenium mitigates Hg-induced cytotoxicity primarily by reducing intracellular Hg accumulation, highlighting its modulatory role at the single-cell level. By integrating effective concentration modeling with single-cell metal quantification, this work highlights the importance of considering the bioavailable fraction of trace elements in toxicity assessments.

This review article provides an overview of selenium speciation using chromatographic and atomic techniques, based on a survey of relevant studies published in the 21st century. Selenium is an essential element, but the narrow range between deficiency and toxicity makes determining its various chemical forms in many samples fundamental. The total selenium content is insufficient to understand its behavior, as its various species exhibit distinct physicochemical and toxicological properties. In general, organic forms, such as selenomethionine (SeMet) and methylselenocysteine (MeSeCys), are less toxic and more bioavailable than inorganic species and are also associated with beneficial health effects, such as antioxidant activity and potential disease-prevention benefits. Therefore, selenium speciation analysis in various matrices is fundamental to understanding its toxicity, bioavailability, biotransformation, and bioaccumulation, since different chemical species exhibit distinct biological behaviors. Strategies combining chromatographic and atomic detection techniques have been explored for selenium speciation, leveraging separation resolution and detection sensitivity to achieve selective methods with low detection limits and applicability to complex matrices. The most used techniques for speciation include high-performance liquid chromatography (HPLC) and gas chromatography (GC), typically coupled to inductively coupled plasma mass spectrometry (ICP-MS) or other atomic detectors, such as atomic absorption spectroscopy (AAS) and atomic fluorescence spectroscopy (AFS). In addition to reviewing the literature on chromatography-atomic techniques combinations, sample preparation, separation methods, and detectors were discussed. Applications in food, biological, and environmental samples are presented, highlighting the importance of speciation for evaluating selenium toxicity and bioavailability. This review indicates that significant challenges remain due to low analyte concentrations, the risk of interconversion between species, and the emergence of new demands, such as analyzing complex matrices of food, supplements, and biological samples. This shows that Se speciation is a dynamic, continually evolving field essential to analytical chemistry and understanding the effects of selenium on health and the environment.

Calcium aluminate cement (CAC) is a suitable source of tetrahedral aluminum, which reacts with tetrahedral silicon from water glass (aqueous sodium or potassium silicate solution) in an exothermic reaction, forming inorganic polymer structures that are stable at high temperatures. All tetrahedrally configurated aluminum atoms of the various calcium aluminates tested, react with tetrahedral silicon groups to form -O-Si-O-Al-O- chains with an average Si/Al ratio near of 1. Octahedrally configurated aluminum, as in γ-Al2O3, does not react at room temperature. The sodium-to-silicate ratio of the silicate solution was measured to be 1:1, so most water glasses require activation with NaOH. The number of positive charges in the activated water glass (Na+ or K+ ions) corresponds to the negatively charged AlIV centers of the CACs, suggesting a sodium-to-aluminum ratio of 1:1. The polymer hardens at temperatures between 4 and 65 °C. The workability is identical to that of ordinary Portland cement (OPC) and enables concrete structures to be cast at room temperature without additional energy supply. The new polymer has the potential to completely replace OPC in all its applications, but can reduce annual CO2 emissions from OPC production worldwide from the current 8% to less than 2%.

Industrial growth is generating alarming amounts of oily wastewater. Because these contaminants don't degrade readily, they threaten ecosystems and human health. Consequently, identifying efficient and cost-effective materials for separating oil from water, particularly for stable emulsions, is a critical environmental challenge that must be addressed. Organic-inorganic hybrid materials are considered among the most promising options for developing membranes. In this study, a novel gyroid-shaped 3D polyamide-graphite-MoS2 membrane (PGM@gyroid-3D membrane) was fabricated via selective laser sintering. The composition, structure, morphology, and thermal stability of the fabricated PGM@gyroid-3D membrane were characterized using multiple techniques to elucidate its properties. It was observed that graphene and MoS2 are uniformly spread on the polyamide surface. The surface exhibits low roughness and crystalline topography. The FTIR results confirm the successful creation of the PGM@gyroid-3D membrane. Tensile, compressive, and flexural tests were performed to evaluate and compare the effects of laser power on specimens fabricated from composite powder and pure PA-12. The separation efficiency of the PGM@gyroid-3D membrane for the tested oils was admirable, suggesting that this membrane is a good candidate for industrial oil-contaminated water treatment.

This chapter will thoroughly examine how the landscape of skin cancer therapeutics is changing with a particular focus on the fact that nanotechnology has resulted in a transformative advancement in drug delivery systems. It starts by providing a summary of the epidemiology of skin cancer, and the treatment difficulties that are associated with conventional modalities, including surgery, radiotherapy, and topical chemotherapy, and their shortcomings. The wide variety of nanocarriers, including lipid-based systems, polymeric nanoparticles, micelles, dendrimers, and inorganic platforms like gold nanoparticles and quantum dots, are then discussed along with their physicochemical properties, the mechanism of improved drug solubility, stability, bioavailability, and targeted activity. The hybrid and stimuli-sensitive delivery systems that are intended to be delivered on the site of action in response to internal (pH, redox, enzyme) or exterior (light, temperature, magnetic field) stimuli receive particular attention. The efforts to optimize therapeutic utility and reduce toxicity in the off-target tissues through enhanced permeability and retention (EPR) impact and ligand-based targeting are among the passive and active tumor targeting mechanisms that are taken into consideration.The chapter ends with a discussion on the recent research, combination therapies, theranostics, and future on clinical translation of nanotechnology-based methods in managing skin cancer.

Persistent and mobile chemicals (PMs) threaten groundwater quality and drinking water safety, yet many remain undetected because analytical methods insufficiently address highly polar and ionic substances, while regulatory frameworks lack monitoring requirements for these compound classes. Here, we developed a supercritical fluid chromatography-high-resolution mass spectrometry-based smart-screen approach that integrates three key prioritisation strategies: (i) sampling site prioritisation, (ii) suspect-level prioritisation through tiered suspect lists, and (iii) candidate prioritisation using stepwise scoring. Additionally, the method achieved the sensitive identification and reliable quantification of PMs in groundwater, with a median limit of quantification of 6.8 ng/L, stable recoveries (75%), and low matrix effects (-12%) across diverse groundwater types. Prioritisation reduced 599 groundwater wells to 10 representative sites, yielding an 8.6-fold reduction in analytical workload while maintaining chemical diversity. The tiered suspect lists and stepwise scoring strategies improved confirmation efficiency and facilitated the detection of substances of high environmental relevance. Collectively, 34 PMs were detected across six substance groups including polar per- and polyfluoroalkyl substances, polyfluorinated inorganic species, transformation products, and amide or ether solvents at concentrations of 0.1-22,300 ng/L. Among these, 16 substances were newly detected in ambient groundwater and four were reported for the first time in any environmental compartment. Several substances (e.g. 2-phenylpropane-2-sulphonic acid) are not classified as persistent under EU regulation on registration, evaluation, authorisation and restriction of chemicals (REACH) yet occur ubiquitously in groundwater, suggesting an underestimation of PMs under aquifer conditions. These findings advance monitoring of PMs, supporting their regulation for groundwater and drinking water protection.

Enhancing cycling reversibility in high-energy-density lithium metal batteries necessitates precise management of electrolyte-derived electrochemical reactions at electrodes and interphases, yet recently developed localized high-concentration electrolytes suffer from limited tunability of these reactions for the non-solvation-participating nature of oxygen-proximal fluorinated diluents. Here we address this issue by synthesizing an oxygen-distal fluorinated di-2,2,3,3-tetrafluoropropoxyethane diluent whose molecular skeleton is strategically edited to position fluorine atoms distal to oxygen centers that attenuate electron-withdrawing effects at Li+-coordination sites, enabling: enhanced diluent/anion participation and reduced volatile solvents in solvation shells; atypical H-F bonding between diluent and solvent toward enhanced oxidation resistance; and promotion of diluent and salt-derived highly stable inorganic-rich interphase formation. This electrolyte achieves 99.8% Li plating/stripping Coulombic efficiency, 450 stable cycles in 4.5 V high-voltage Li || LiNi0.8Mn0.1Co0.1O2 cells, and 5.9-Ah, 504.6 Wh kg-1 (based on mass of all components including packaging) pouch cells that exhibits 0.053% per-cycle capacity decay. This work introduces oxygen-distal fluorination as a potential molecular skeleton editing strategy for stable energy-dense lithium metal batteries.

To address clinical bottlenecks of traditional antipsychotic drugs, including delayed onset of action, significant peripheral side effects, and poor patient compliance, nanodelivery systems offer a feasible approach through their unique physicochemical properties to improve drug solubility, optimize in vivo transport, and enhance blood-brain barrier (BBB) penetration efficiency. This review focuses on the application potential and translational value of nanodelivery systems in psychiatric disorders. We systematically summarize recent advances in the construction strategies of mainstream nanocarriers, including lipid‑based, polymer‑based, inorganic nanomaterials, Metal-Organic Frameworks (MOFs), and Extracellular Vesicles (EVs), as well as commonly used nanoparticle preparation and characterization techniques. We briefly discuss key challenges facing nanoformulations, such as long‑term safety, large‑scale production, and batch‑to‑batch consistency, and highlight future directions driven by artificial intelligence and precision medicine. This review aims to provide insights for the rational design of nanodelivery systems for psychiatric disorders and to advance the development of precision psychiatry.

The rational use of carbohydrate polymers as functional matrices for integrating inorganic and organic components remains a key challenge in developing sustainable multifunctional materials. Here, a process-oriented, bio-inspired strategy for fabricating a chitosan-centred multifunctional composite coating is presented. This approach uniquely combines plasma-assisted activation of the silk surface, chitosan immobilisation, and subsequent controlled in situ generation of TiO2 nanoparticles in the presence of curcumin, a naturally derived polyphenolic compound. The resulting chitosan/TiO2/curcumin composite system simultaneously imparts antibacterial, UV-shielding, and photocatalytic self-cleaning functions to the silk. Chitosan provides strong antimicrobial activity, maintaining robust bio-barrier antibacterial protection in the composite system and achieving over 99.5% inhibition of Staphylococcus aureus and Escherichia coli growth. Curcumin acts as a TiO2 photosensitiser and charge-transfer mediator, suppressing electron-hole recombination and enabling efficient visible-light-driven photocatalytic activity, as confirmed by accelerated Rhodamine B dye degradation and effective coffee stain removal. Complementary UV absorption by TiO2 (UV-B) and curcumin (UV-A) delivers broad-spectrum UV protection with a UV protection factor of 32.1. Overall, this work demonstrates a distinct carbohydrate polymer-driven fabrication paradigm for engineering high-performance textiles with integrated multifunctional protective properties.

Zero-dimensional (0D) lead-free metal halides are promising luminescent materials, yet their emission origins remain unclear. Using hybrid-functional first-principles calculations, we clarify the photophysical mechanisms in pristine and ns2/nd10-doped Cs2ZnX4 (X = Cl, Br). We reveal that experimentally observed emissions stem not from self-trapped excitons or isolated dopants but from intrinsic point defects and strongly interacting defect-dopant complexes. In pristine hosts, intrinsic luminescence arises from ligand-to-metal charge-transfer transitions involving halogen vacancies (VCl•, and VBr•). For high-valent ns2 dopants, emissions originate from localized s ↔ p transitions within highly coordinated dopant-interstitial complexes, such as (SbZn + Cli)×. Notably, isovalent Sn2+ exhibits a flat, dual-minima excited-state adiabatic potential energy surface, explaining its anomalous cooling-induced red shift. For nd10 dopants, emissive centers include simple substitutional defects and vacancy-assisted complexes, specifically, the (CuZn + VBr)× complex in Cu-doped systems and the (AgZn + 2VBr)• complex responsible for thermochromic luminescence in Ag-doped systems. Ultimately, this defect-chemistry-driven model demonstrates that abundant intrinsic defects and their coupling with dopants govern the luminescence of 0D zinc-based halides, offering insights for designing high-performance, stable lead-free materials.

In aquatic environments, the arsenic (As) mobilization from anoxic sediments is an important process affecting water quality and associated health risks, as sediment-bound As can serve as a persistent secondary source to overlying waters and groundwater systems. Dissimilatory arsenate reduction (DAsR) is a key microbial process releasing dissolved As(III), yet the role of inorganic electron donors in this pathway remains poorly constrained. Although hydrogen (H₂) is thermodynamically favorable for arsenate respiration, its role in arsenate reduction in natural sediments remains insufficiently resolved. In this study, hydrogen oxidation coupled to arsenate reduction (HOAsR) was investigated using sediments from an As-contaminated, mining-impacted river system. Microcosm incubations showed that H₂ amendment stimulated As(V) reduction under anoxic conditions. DNA-stable isotope probing combined with metagenomics identified Sulfuritalea, Dechloromonas, and a Moorellia-related lineage as putative HOAsR-associated populations. Corresponding metagenome-assembled genomes encoded both H₂ uptake [NiFe]-hydrogenases and the dissimilatory arsenate reductase gene (arrA). Comparative genome analysis further revealed that ∼75% of arrA-containing genomes harbor H₂ uptake [NiFe]-hydrogenases, suggesting that H₂ oxidation represents a phylogenetically widespread metabolic trait among DAsR bacteria. Analysis of public riverine metagenomes further indicated that HOAsR-associated genetic configurations are broadly distributed across sediment microbial communities. Together, these results indicated that HOAsR is a biologically plausible and geographically widespread potential pathway contributing to arsenic mobilization in anoxic sediments.

Chiral organic-inorganic hybrid metal halides (OIMHs) with intrinsic non-centrosymmetric structures have attracted considerable attention for their potential nonlinear optical (NLO) applications. However, compared to their achiral counterparts, the chirality-induced mechanism underlying their NLO effects remains unclear. This study reports for the first time a pair of Ge-based chiral OIMHs (R/S-MPz)Ge4I10 with a unique 2D [Ge4I10]2- layers, exhibiting a second-harmonic effect approximately five times greater than that of benchmark K2HPO4 (KDP). This represents the highest value achieved to date among reported chiral Ge-based OIMHs and far exceeds those observed in the organic R/S-MPz. First-principles calculations reveal that the unique [Ge4I10]2- layer, constructed by edge-shared [GeI6]4- octahedra induced by chirality, is crucial for the dominate NLO effect. By further enhancing the polarity of the organic component, this material achieves a gain record of ∼15×KDP. Our study not only expands the family of chiral Ge-based OIMHs but also elucidates the relationship between chiral motif and NLO property, providing a rational design strategy for chiral NLO materials.

Fluorine incorporation into mixed-anion inorganic solids is often limited by the thermodynamic stability of conventional solid fluorination reagents. LiF, the most used fluorine source in solid-state and mechanochemical synthesis, exhibits strong Li─F bonding that can hinder fluorine transfer and lead to residual LiF and coupled Li/F off-stoichiometry. Here, we investigate fluorinated graphite (CFx) as an alternative fluorine source for the mechanochemical synthesis of lithium metal oxyfluorides. Owing to the heterogeneous nature of C─F bonding in CFx, mechanochemical activation enables stepwise defluorination and effective fluorine transfer while decoupling fluorine delivery from lithium stoichiometry. Using disordered rock-salt Li2VO2F and Al-substituted Li2V1- xAlxO2F as model systems, we obtain the oxyfluoride active materials with no detectable residual CFx, as confirmed by combined X-ray and neutron diffraction, atomic pair distribution function analysis, and 1 9F solid-state NMR. Electrochemical measurements indicate improved fluorine incorporation relative to LiF-derived analogues, featured by more symmetric charge-discharge behavior and elevated redox potential. These results demonstrate that fluorinated graphite can serve as an effective fluorine source for mechanochemical oxyfluoride synthesis and provide insight into how heterogeneous C─F bonding environments influence fluorine transfer in the solid state.

The development of sustainable and highly sensitive diagnostic platforms is critical for rapid pathogen identification and effective disease management. Here, a green, magneto-electrochemical biosensing strategy is reported for the selective detection of Streptococcus pneumoniae based on pathogen-specific nuclease activity. Uniform organic-inorganic hybrid polyhedral oligomeric silsesquioxane (POSS) nanoparticles were synthesized via an ultrafast UV-initiated emulsion polymerization within 5 min using an eco-friendly approach. The nanoparticles were sequentially functionalized by in situ deposition of superparamagnetic iron oxide nanoparticles and biomimetic polydopamine coating, enabling robust and high-density immobilization of nuclease-responsive oligonucleotide probes. The resulting PDA@SPION/POSS nanohybrids exhibit controlled size, preserved structural integrity, and strong superparamagnetic behavior, allowing efficient magnetic manipulation and electrochemical signal transduction. Upon exposure to S. pneumoniae, nuclease-mediated probe cleavage produces a pronounced electrochemical response, enabling label-free detection over a wide dynamic range (102-10⁸ CFU mL⁻¹) with a detection limit of 102 CFU mL⁻¹. High selectivity against non-target bacteria highlights the specificity of the enzymatic recognition mechanism. This work establishes a sustainable and amplification-free biosensing platform with strong potential for rapid clinical diagnostics.