A thiazole-based colorimetric and photoluminescent chemosensors for As3+ ions detection: Density functional theory, test strips, real samples, and bioimaging applications.

A Schiff-base Ethyl (E)-2-(3-((2-carbamothioylhydrazono)methyl)-4-hydroxyphenyl)-4-methylthiazole-5-carboxylate (TZTS) dual functional colorimetric and photoluminescent chemosensor which includes thiazole and thiosemicarbazide has been synthesized to detect arsenic (As3+) ions selectively in DMSO: H2O (7:3, v/v) solvent system. The molecular structure of the probe was characterized via FT-IR, 1H, and 13C NMR & HRMS analysis. Interestingly, the probe exhibits a remarkable and specific colorimetric and photoluminescence response to As3+ ions when exposed to various metal cations. The absorption spectral changes of TZTS were observed upon the addition of As3+ ions, with a naked eye detectable color change from colorless to yellow color. Additionally, the chemosensor (TZTS) exhibited a new absorption band at 412 nm and emission enhancements in photoluminescence at 528 nm after adding As3+ ions. The limit of detection (LOD) for As3+ ions was calculated to be 16.5 and 7.19 × 10-9 M by the UV-visible and photoluminescent titration methods, respectively. The underlying mechanism and experimental observations have been comprehensively elucidated through techniques such as Job's plot, Benesi-Hildebrand studies, and density functional theory (DFT) calculations. For practical application, the efficient determination of As3+ ions were accomplished using a spike and recovery approach applied to real water samples. In addition, the developed probe was successfully employed in test strip applications, allowing for the naked-eye detection of arsenic ions. Moreover, fluorescence imaging experiments of As3+ ions in the breast cancer cell line (MCF-7) demonstrated their practical applications in biological systems. Consequently, these findings highlight the significant potential of the TZTS sensor for detecting As3+ ions in environmental analysis systems.

Theoretical and experimental study on the effect of scanning speed on FAIMS peaks.

High-Field Asymmetric Ion Mobility Spectrometry (FAIMS) is a technique for ion separation and detection based on ion mobility variation under high electronic field. While compensation voltage scanning speed is a fundamental parameter in FAIMS, its impact on spectra remains unclear. In this work, a function referred to as F-EMG is introduced to describe the impact of compensation voltage scanning speed on FAIMS spectra, and the properties of the function are studied. Theoretical analysis emphasizes the impact of the scanning speed on peak height, position, and symmetry, as well as the capability of the F-EMG function to progressively approach Gaussian function at lower scanning speeds. Furthermore, the function indicates that spectra obtained in positive and negative scanning modes exhibits symmetry. An experimental validation, conducted with a custom FAIMS setup and analyzing hydrogen sulfide, ethylbenzene, toluene, styrene, benzene and ammonia, confirms the model's influence on peak features, fitting accuracy, and exhibits a closer alignment with the Gaussian function at lower scanning speeds. Additionally, the experimental data indicate that the spectra show symmetry in positive and negative scanning models. This work not only improves understanding of FAIMS spectral analysis but also introduces a robust method for enhancing data accuracy across varying scanning speeds.

Construction of a novel flavonol fluorescent probe for copper (II) ion detection and its application in actual samples.

Copper is an essential trace element in the human body, and its level is directly related to many diseases. While the source of copper in human body is mainly intake from food, then the detection of copper ions (Cu2+) in food becomes crucial. Here, we synthesized a novel probe (E)-3-hydroxy-2-styryl-4H-benzo[h]chromen-4-one (NSHF) and explored the binding ability of NSHF for Cu2+ using nuclear magnetic resonance hydrogen spectroscopy (1H NMR), high-resolution mass spectrometry (HRMS), Job's plot method and density functional theory (DFT). NSHF shows the advantages of fast response time, good selectivity and high sensitivity for Cu2+. The fluorescence intensity ratio (F/F0) of NSHF shows a good linear relationship with the concentration of Cu2+ and the detection limit is 0.061 µM. NSHF was successfully applied to the detection of Cu2+ in real samples. In addition, a simple and convenient Cu2+ detection platform was constructed by combining NSHF with a smartphone and a UV lamp, which can realize the rapid detection of Cu2+. This work provides an effective tool for the real-time detection of Cu2+.

Heterocyclic fluorescent Schiff base chemosensors for the detection of Fe(III) and Cu(II) ions.

Two new Schiff bases were synthesized from 1-(2,4-dihydroxyphenyl)ethanone and pyridine derivatives. Both compounds were characterized using infrared, UV-Vis., 1H NMR, 13C NMR and mass spectral studies. Density functional theory (DFT) calculations were performed for both the Schiff bases with 6-31G(d, p) as the basis set. Vibrational frequencies calculated using the theoretical method were in good agreement with the experimental values. Both the Schiff bases were highly fluorescent in nature. The cation-recognizing profile of the compounds was investigated in aqueous methanol medium. The Schiff base 4-(1-(pyridin-4-ylimino)ethyl)benzene-1,3-diol (PYEB) was found to interact with Fe(III) and Cu(II) ions, whereas the Schiff base 4,4'-((pyridine-2,3-diylbis(azanylylidene))bis(ethan-1-yl-1-ylidene))bis(benzene-1,3-diol) (PDEB) was found to detect Cu(II) ions. The mechanism of recognition was established as combined excited state intramolecular proton transfer (ESIPT)-chelation-enhanced fluorescence (CHEF) effect and chelation-enhanced quenching (CHEQ) process for the detection of Fe(III) and Cu(II) ions, respectively. The stability constant of the metal complexes formed during the sensing process was determined. The limit of detection for Fe(III) and Cu(II) ions with respect to Schiff base PYEB was found to be 1.64 × 10-6 and 2.16 × 10-7 M, respectively. With respect to Schiff base PDEB, the limit of detection for Cu(II) ion was found to be 4.54 × 10-4 M. The Cu(II) ion sensing property of the Schiff base PDEB was applied in bioimaging studies for the detection of HeLa cells.

A colorimetric and fluorescent probe of lignocellulose nanofiber composite modified with Rhodamine 6G derivative for reversible, selective and sensitive detection of metal ions in wastewater.

Heavy metal ions have extremely high toxicity. As the top of food chain, human beings certainly will accumulate them by ingesting food and participating other activities, which eventually result in the damage to our health. Therefore, it is very meaningful and necessary to design a simple, portable, stable and efficient material for heavy metal ions detection. Based on the spirolactam Rhodamine 6G (SRh6G) fluorescent probe, we prepared two types of nanocomposite materials (membrane and aerogel) by vacuum filtration and freeze-drying methods with lignocellulose nanofiber (CNF) as a carrier, polyvinyl alcohol (PVA) and glutaraldehyde (GA) as the cross-linkers. Then the microstructure, chemical composition, wetting property, fluorescence intensity and selectivity of as-prepared SRh6G/PVA/CNF would be characterized and analyzed. Results showed that SRh6G/PVA/CNF nanocomposites would turn red in color under strong acidic environment and produced orange fluorescence under ultraviolet light. Besides, they were also to detect Al3+, Cu2+, Hg2+, Fe3+ and Ag+ through color and fluorescence variations. We had further tested its sensitivity, selectivity, adsorption, fluorescence limits of detection (LOD) to Fe3+ and Cu2+. The test towards real water samples (hospital wastewater, Songhua River and tap water) proved that SRh6G/PVA/CNF nanocomposites could detect the polluted water with low concentrations of Fe3+ and Cu2+. In addition, SRh6G/PVA/CNF nanocomposites have excellent mechanical property, repeatability, superhydrophilicity and underwater superoleophobicity, which may offer a theoretical reference for the assembly strategy and detection application of cellulose-based fluorescent probe.

Fluorescent Protein-Based Sensors for Detecting Essential Metal Ions across the Tree of Life.

Genetically encoded fluorescent metal ion sensors are powerful tools for elucidating metal dynamics in living systems. Over the last 25 years since the first examples of genetically encoded fluorescent protein-based calcium indicators, this toolbox of probes has expanded to include other essential and non-essential metal ions. Collectively, these tools have illuminated fundamental aspects of metal homeostasis and trafficking that are crucial to fields ranging from neurobiology to human nutrition. Despite these advances, much of the application of metal ion sensors remains limited to mammalian cells and tissues and a limited number of essential metals. Applications beyond mammalian systems and in vivo applications in living organisms have primarily used genetically encoded calcium ion sensors. The aim of this Perspective is to provide, with the support of historical and recent literature, an updated and critical view of the design and use of fluorescent protein-based sensors for detecting essential metal ions in various organisms. We highlight the historical progress and achievements with calcium sensors and discuss more recent advances and opportunities for the detection of other essential metal ions. We also discuss outstanding challenges in the field and directions for future studies, including detecting a wider variety of metal ions, developing and implementing a broader spectral range of sensors for multiplexing experiments, and applying sensors to a wider range of single- and multi-species biological systems.

Spatio-seasonal patterns and sources of major ions in the Longjiang River catchment, Southern China.

River water quality is closely related to the major ion sources and hydrological conditions. However, there is a limited cognition about the geochemical sources and the seasonal variations of major ions. Thus, in this study, a total of 90 water samples were collected from the Longjiang River and its three tributaries in the dry and wet seasons. The samples were analyzed, including major ion concentrations and physicochemical parameters. Statistical analysis, such as correlation analysis and principal component analysis (PCA), was employed to investigate the spatial and seasonal variations in major ion composition and their respective sources. Our study revealed that the predominant major ions in the studied samples are Ca2+, Mg2+, HCO - 3, and SO2 - 4. Most of ions exhibited notable spatial disparities attributable to variations in geological settings and human activities. Regions characterized by igneous rock outcrops tend to exhibit higher levels of K+ and Na+, while areas with higher population densities in the middle and downstream segments show elevated concentrations of Cl-, NO - 3, SO2 - 4, Na+, and K+. The observed peak SO2 - 4 levels may be attributed to active mining operations. Most parameters displayed higher values in flood season than those in dry season due to dilution effects. Stoichiometric analysis indicated that carbonate weathering inputs contribute to over 85% of the mean total cation concentrations in the water, followed by contributions from silicates, atmospheric deposition, and anthropogenic inputs. On the whole, although the water quality remains non-polluted and is suitable for drinking and irrigation purposes, the enrichment of SO2 - 4 and NO - 3 may contribute to water eutrophication. Caution is warranted during the dry season due to reduced water flow resulting from dam interceptions and limited dilution capacity, potentially leading to elevated pollutant concentrations. Taken together, our results provided a scientific basis for water quality managements of monsoon rivers.

A fluorescent chemosensor for selective detection of chromium (III) ions in environmentally and biologically relevant samples.

A simple single step one pot multicomponent reaction was performed to synthesize N-(tert-butyl)-2-(furan-2-yl)imidazo[1,2-a]pyridine-3-amine (TBFIPA). The synthesized TBFIPA was subjected to library of cations to study its ability for selective and sensitive detection of specific metal ions. Selective detection of chromium ions by TBFIPA were found from the significant hypsochromic shift (335 nm â†’ 285 nm) in the UV-Visible spectra. The fluorescent TBFIPA displays complete quenching of fluorescence under UV lamp (365 nm) only in the presence of chromium without the interference of common metal ions. Binding constant (ka) obtained from Benesi-Hildebrand plot is 0.21 × 105 M-1, limit of detection (LOD) and limit of quantification (LOQ) of TBFIPA toward Cr3+ ions are 4.70 × 10-7 M and 1.56 × 10-7 M, respectively. The mechanism proposed during complex formation were supported by stoichiometric Job continuous variation plot, 1H NMR titration and ESI-MS spectroscopic data. All the experimental confirmation for complex formation were corroborated with theoretical DFT studies optimized using RB3LYP/6-31G(d) basis set. The selectivity and sensitivity of TBFIPA toward Cr3+ ions are found suitable to design a user-friendly silica based portable test kit. Alongside, TBFIPA was successfully utilized for imaging onion epidermal cells. Furthermore, the results obtained for biological, environmental, and industrial samples provided solid evidence to estimate chromium ions using TBFIPA in these real samples.

Innovative assembled optode device for enhanced in-situ ceric ions (Ce4+) evaluation and preconcentration in its real human, foods, water, and alloy samples.

Cerium (Ce) are the most widely distributed rare earth element. However, humans exposed to Ce through inhalation have been reported to experience heat sensitivity, itching, and heightened taste and odour perception. The present study aims to develop an optical sensor device with a short response time and high selectivity for Ce amongst other ions in various environments. The potential applicability of a 6-hydroxy-5-((4-hydroxy-2-methylphenyl)diazenyl)pyrimidine-2,4(1H,3H)-dione (HHMDPD) assembled ligand as aceric ion (Ce4+)-selective caption optode was examined. After generating an ion pair with Tetra-n-octylammonium bromide (TOABr) and immobilizing on a tri-acetyl cellulose (TAC) membrane, the solubility of the HHMDPD ligand is improved. The constructed optode membrane reacts with Ce4+ by turning its orange colour to violet in Thiel buffer (pH of 5.5), which can be detected spectrophotometrically at λmax 667 nm. The measurement linearity was in the range of 0.70 - 18.7 × 10-6 mol/L of Ce4+ concentration with detection and quantification limits of 0.23 × 10-6 and 0.70 × 10-6 mol/L, respectively. Whatever the Ce4+ concentration in its real samples, the response time of the constructed device was 5.0 min. Additionally, it recorded repeatability and reproducibility with a %RSD of 1.37 and 2.55, respectively (n = 3). The proposed optode device exhibited complete reversibility, for multiple measurements, which could be easily achieved with the aid of a solution of HCl, 0.01 mol/L. The applicability of the proposed device has been effectively extended to analyze synthetic mixes corresponding to different Ce4+ real human, foods, water, and magnesium-based Ce4+ alloys.

A computational and experimental study of cis-trans isomeric pesticides based on collision-induced dissociation of high-resolution mass spectrometry.

RATIONALE: Pesticide isomers are widely available in agricultural production and may vary widely in biological activity, potency, and toxicity. Chromatographic and mass spectrometric analysis of pesticide isomers is challenging due to structural similarities. METHODS: Based on liquid chromatography time-of-flight mass spectrometry, identification of cis-trans isomeric pesticides was achieved through retention time, characteristic fragment ions, and relative abundance ratio. Furthermore, theoretical and basic research has been conducted on the differences in characteristic fragment ions and their relative abundance ratios of cis-trans isomers. On the one hand, the cleavage pathways of six cis-trans isomers were elucidated through collision-induced dissociation to explain different fragment ions of the isomers. On the other hand, for those with the same fragment ions but different abundance ratios, energy-resolved mass spectrometry combined with computational chemical density functional theory in terms of kinetics, thermodynamics, and bond lengths was employed to explain the reasons for the differences in characteristic fragment ions and their abundance ratios. RESULTS: A high-resolution mass spectrometry method was developed for the separation and analysis of cis-trans isomers of pesticides in traditional Chinese medicine Radix Codonopsis, and six pesticide isomers were distinguished by retention time, product ions, and relative abundance ratios. The limits of quantification of the six pesticides were up to 10 µg/kg, and the linear ranges of them were 10-200 µg/kg, with coefficients of determination (R2) > 0.99, which demonstrated the good linearity of the six pesticides. The recoveries of the pesticides at spiked concentrations of 10, 20, and 100 µg/kg reached 70-120% with relative standard deviations ≤20%. CONCLUSIONS: It was demonstrated that the application of the method was well suited for accurate qualitative and quantitative analysis for isomers with different structures, which could avoid false-negative results caused by ignoring other isomers effectively.

Implications of PM2.5 chemical composition in modulating microbial community dynamics during spring in Seoul.

Particulate matter with an aerodynamic diameter of 2.5 µm or less (PM2.5) harbors a diverse microbial community. To assess the ecological dynamics and potential health risks associated with airborne microorganisms, it is crucial to understand the factors influencing microbial communities within PM2.5. This study investigated the influence of abiotic parameters, including air pollutants, PM2.5 chemical composition (water-soluble ions and organics), and meteorological variables, on microbial communities in PM2.5 samples collected in Seoul during the spring season. Results revealed a significant correlation between air pollutants and water-soluble ions of PM2.5 with microbial α-diversity indices. Additionally, air pollutants exerted a dominant effect on the microbial community structure, with stronger correlations observed for fungi than bacteria, whereas meteorological variables including temperature, pressure, wind speed, and humidity exerted a limited influence on fungal α-diversity. Furthermore, the results revealed specific water-soluble ions, such as SO42-, NO3-, and NH4+, as important factors influencing fungal α-diversity, whereas K+ negatively correlated with both microbial α-diversity. Moreover, PM2.5 microbial diversity was affected by organic compounds within PM2.5, with fatty acids exhibited a positive correlation with fungal diversity, while dicarboxylic acids exhibited a negative correlation with it. Furthermore, network analysis revealed direct links between air pollutants and dominant bacterial and fungal genera. The air pollutants exhibited a strong correlation with bacterial genera, such as Arthrospira and Clostridium, and fungal genera, including Aureobasidium and Cladosporium. These results will contribute to our understanding of the ecological dynamics of airborne microorganisms and provide insights into the potential risks associated with PM2.5 exposure.

Novel films of pectin extracted from ambarella fruit peel and jackfruit seed slimy sheath: Effect of ionic crosslinking on the properties of pectin film.

Here, we prepared ionically crosslinked films using pectin extracted from agro-wastes, specifically ambarella peels (AFP) and jackfruit seed slimy sheath (JFS). Physiochemical properties of pectins, including moisture content, molecular weight (Mw), degree of esterification (DE), and galacturonic acid (GA), were analyzed. Optimal extraction was determined, i.e., citric acid concentration 0.3 M, time 60 min, solid/liquid ratio 1:25, and temperature 90 °C for AFP or 85 °C for JFS. Pectin yields under these conditions were 29.67 % ± 0.35 % and 29.93 ± 0.49 %, respectively. AFP pectin revealed Mw, DE, and GA values of 533.20 kDa, 67.08 % ± 0.68 %, and 75.39 ± 0.82 %, while JFS pectin exhibited values of 859.94 kDa, 63.04 % ± 0.47 %, and 78.63 % ± 0.71 %, respectively. The pectin films crosslinked with Ca2+, Cu2+, Fe3+, or Zn2+ exhibited enhanced tensile strength and Young's modulus, along with reduced elongation at break, moisture content, water solubility, water vapor permeability, and oxygen permeability. Structural analyses indicated metal ions were effectively crosslinked with carboxyl groups of pectin. Notably, the Cu2+-crosslinked film demonstrated superior water resistance, mechanical properties, and exhibited the highest antioxidant and antibacterial activities among all tested films. Therefore, the pectin films represent a promising avenue to produce eco-friendly food packaging materials with excellent properties.

Giant vesicles form in physiological saline and encapsulate pDNA by the modified electroformation method.

Giant vesicles (GVs) are used to study the structures and functions of cells and cell membranes. Electroformation is the most commonly used method for GV preparation. However, the electroformation of GVs is hindered in highly concentrated ionic solutions, limiting their application as cell models for research under physiological conditions. In this study, giant multilayer vesicles were successfully generated in physiological saline using a modified electroformation device by adding an insulating layer between the two electrode plates. The influence of the electric frequency and strength on the electroformation of GVs in physiological saline was explored, and a possible mechanism for this improvement was assessed. It has been shown that an insulating layer between the two electrodes can improve the electroformation of GVs in physiological saline by increasing the electrical impedance, which is weakened by the saline solution, thereby restoring the reduced effective electric field strength. Furthermore, macromolecular plasmid DNA (pDNA) was successfully encapsulated in the electroformed GVs of the modified device. This modified electroformation method may be useful for generating eukaryotic cell models under physiological conditions.

The structure and physical properties of a packaged bacteriophage particle.

A string of nucleotides confined within a protein capsid contains all the instructions necessary to make a functional virus particle, a virion. Although the structure of the protein capsid is known for many virus species1,2, the three-dimensional organization of viral genomes has mostly eluded experimental probes3,4. Here we report all-atom structural models of an HK97 virion5, including its entire 39,732 base pair genome, obtained through multiresolution simulations. Mimicking the action of a packaging motor6, the genome was gradually loaded into the capsid. The structure of the packaged capsid was then refined through simulations of increasing resolution, which produced a 26 million atom model of the complete virion, including water and ions confined within the capsid. DNA packaging occurs through a loop extrusion mechanism7 that produces globally different configurations of the packaged genome and gives each viral particle individual traits. Multiple microsecond-long all-atom simulations characterized the effect of the packaged genome on capsid structure, internal pressure, electrostatics and diffusion of water, ions and DNA, and revealed the structural imprints of the capsid onto the genome. Our approach can be generalized to obtain complete all-atom structural models of other virus species, thereby potentially revealing new drug targets at the genome-capsid interface.

Pyridine appended pyrimidine bis hydrazone: Zn2+/ATP detection, bioimaging and functional properties of its dinuclear Zn(II) complex.

A pyridine functionalized pyrimidine-based system, H2P was successfully synthesized, characterized, and evaluated for its remarkable selective characteristics towards Zn2+ and ATP ions. The chemical sensing capabilities of H2P were demonstrated through absorption, fluorescence, and NMR spectroscopic techniques. The probe exhibited outstanding sensitivity when interacting with the ions, demonstrating relatively strong association constants and impressively low detection limits. The comprehensive binding mechanism of H2P with respect to Zn2+ and ATP ions was investigated using a combination of analytical methods, including Job's plot, NMR spectroscopy, mass spectrometry, and density functional theory (DFT) experiments. The interesting sensing ability of H2P for Zn2+/ATP ions was harnessed for live cell bioimaging and other diverse on-site detection purposes, including paper strips, cotton swabs, and applications involving mung bean sprouts. Further, the fluorescent probe demonstrated its effectiveness in detecting Zn2+ and ATP within live cells, indicating its significant potential in the realm of biological imaging applications. Moreover, the molecular configuration of the zinc complex (H2P-Zn2Cl4), derived from H2P, was elucidated using X-ray crystallography. This complex exhibited intriguing multifunctional attributes, encompassing its capability for detecting picric acid and for reversible acid/base sensing responses. The enhanced conducting behavior of the complex as well as its resistance properties were investigated by performing I-V characteristics and electrochemical impedance spectroscopic (EIS) experiments respectively.

New materials-based on gelatin coordinated with zirconium or aluminum for ecological retanning.

Ecological retanning agent is an effective way to solve the pollution source of leather manufacturing industry. In this study, the gelatin from chrome-containing leather shavings in the leather industry was used to realize sustainable leather post-tanning. The gelatin hydrolysate (GH) coordinated with Zr4+ or Al3+ to prepare eco-friendly retanning agents GH-Zr and GH-Al. The successful coordination between GH and metal ions was characterized by FTIR and XPS. The retanning agents were characterized by FTIR curve-fitting and circular dichroism spectroscopy. The results showed that the conformation of the secondary structure of the polypeptide became ordered and stable after coordinating with the metal ions. The particle size and weight average molecular weight of the retanning agents were ~1700 nm and ~2100, respectively, measured by nanoparticle size analyzer and gel permeation chromatography (GPC). The retanning agents were applied to retanning of chrome tanned leather and glutaraldehyde tanned leather. The abundant free amino from retanning agents can consume the free formaldehyde. Meanwhile, retanning agents can effectively improve the multiple binding sites, resulting in favorable thickening rate (>110 %) and excellent dye and fatliquor absorption rate with ~99.91 % and ~93.18 %. Thus, this strategy can provide a viable choice for solid leather waste and sustainable development of the leather industry.

Tradeoffs between pH, dissolved organic carbon, and mineral ions regulate cadmium uptake by Solanum hyperaccumulators in calcareous soil.

Soil solution pH and dissolved organic carbon (DOC) influence cadmium (Cd) uptake by hyperaccumulators but their tradeoff in calcareous soils is unclear. This study investigated the mechanisms of Solanum nigrum L. and Solanum alatum Moench in calcareous soil using a combination of concentration gradient experiments (0.6-100 mg Cd kg-1) and soil solution composition analysis. The results showed that the soil solution pH of S. nigrum remained stable despite Cd stress. On average, the soil solution pH of S. alatum was 0.23 units higher than that of S. nigrum, although pH decreased significantly under high Cd stress. In addition, the concentrations of potassium (K) and calcium (Ca) in the soil solution of S. nigrum increased and decreased under low and high levels of Cd stress, respectively. In S. alatum, the K and Ca concentrations in the soil solution generally increased with increasing Cd stress levels. Moreover, the level of DOC in the soil solution of both plants was higher under Cd stress compared to the control, and a gradually increasing trend with Cd stress level was observed in S. alatum. Consequently, the bioconcentration factors of the roots (2.62-19.35) and shoots (1.20-9.59) of both plants were >1, while the translocation factors were <1, showing an obstacle of Solanum hyperaccumulators in transferring Cd into their aboveground parts. Redundancy analysis revealed that the Cd concentration in S. nigrum roots was significantly negatively correlated with the soil solutions of K and Ca. In contrast, Cd concentrations in S. alatum roots and shoots were significantly positively correlated with soil solution DOC, K, and Ca but negatively correlated with pH. Our results suggest that calcareous soil neutralizes the acidity of released protons but does not affect cation exchange, inhibiting DOC in assisting the translocation of Cd within plants.

Tackling the water solubility dilemma of spiroring-closing rhodamine: Sulfone-functionalization enabling rational designing water-soluble probe for rapid visualizing mercury ions in cosmetics.

Rhodamine derivatives possessing spiroring-closing structures exhibit colorlessness, while the induction of spiroring-opening by metal ions results in notable color changes, rendering them as ideal platform for the development of functional probes with broad applications. However, the spiroring-closing form of rhodamine-based probes exhibits limited water solubility due to its neutral character, necessitating the incorporation of organic solvents to enhance solubility, which may adversely affect the natural system. Designing rhodamine probes with high solubility in both the zwitterionic and neutral form is of utmost importance and presents a significant challenge. This study presents a sulfone-rhodamine-based probe that exhibits good water solubility both in the spiroring opening and closing for detecting Hg2+. Upon the presence of Hg2+, the color undergoes a noticeable change from colorless to pink, with a response time of less than 1 min. probe 1 demonstrates an excellent linear relationship with Hg2+ concentrations within the range of 0-8 µM, and achieves a detection limit is 17.26 nM. The effectiveness of probe 1 was confirmed through the analysis of mercury ions in cosmetic products. Utilizing this probe, test paper strips have been developed to enhance the portability of Hg2+ detection naked eyes.

Exposure to Airborne PM2.5 Water-Soluble Inorganic Ions Induces a Wide Array of Reproductive Toxicity.

Water-soluble inorganic ions (WSIIs, primarily NH4+, SO42-, and NO3-) are major components in ambient PM2.5, but their reproductive toxicity remains largely unknown. An animal study was conducted where parental mice were exposed to PM2.5 WSIIs or clean air during preconception and the gestational period. After delivery, all maternal and offspring mice lived in a clean air environment. We assessed reproductive organs, gestation outcome, birth weight, and growth trajectory of the offspring mice. In parallel, we collected birth weight and placenta transcriptome data from 150 mother-infant pairs from the Rhode Island Child Health Study. We found that PM2.5 WSIIs induced a broad range of adverse reproductive outcomes in mice. PM2.5 NH4+, SO42-, and NO3- exposure reduced ovary weight by 24.22% (p = 0.005), 14.45% (p = 0.048), and 16.64% (p = 0.022) relative to the clean air controls. PM2.5 SO42- exposure reduced the weight of testicle by 5.24% (p = 0.025); further, mice in the PM2.5 SO42- exposure group had 1.81 (p = 0.027) fewer offspring than the control group. PM2.5 NH4+, SO42-, and NO3- exposure all led to lower birth than controls. In mice, 557 placenta genes were perturbed by exposure. Integrative analysis of mouse and human data suggested hypoxia response in placenta as an etiological mechanism underlying PM2.5 WSII exposure's reproductive toxicity.

Fine-Scale Characterization of Plant Diterpene Glycosides Using Energy-Resolved Untargeted LC-MS/MS Metabolomics Analysis.

Plant diterpene glycosides are essential for diverse physiological processes. Comprehensive structural characterization proved to be a challenge due to variations in glycosylation patterns, diverse aglycone structures, and the absence of comprehensive reference databases. In this study, a method for fine-scale characterization was proposed based on energy-resolved (ER) untargeted LC-MS/MS metabolomics analysis using steviol glycosides as a demonstration. Energy-dependent fragmentation patterns were unveiled by a series of model compounds. Distinct glycosylation sites were discerned by leveraging varying fragmentation energies for the precursor ions. The sugar moiety linkage at C19OOH (R1) exhibited facile and intact cleavage at low collision energies, while the sugar moiety at C13-OH (R2) demonstrated consecutive cleavage with increasing energy. Aglycone ions exhibited a higher relative intensity at NCE 50, with relative intensities ranging from 95% to 100%. Subsequently, aglycone candidates, R1 sugar composition, and R2 sugar sequence were deduced through ER-MS/MS analysis. The developed method was applied to Stevia rebaudiana leaves. A total of 91 diterpene glycosides were unambiguously identified, including 16 steviol glycosides with novel acetylglycosylation patterns. This method offers a rapid alternative for glycan analysis and the structural differentiation of isomers. The developed method enhances the understanding of diterpene glycosides in plants, providing a reliable tool for the in-depth characterization of complex metabolite profiles.