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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 314: 124175, 2024 Jun 05.
Article En | MEDLINE | ID: mdl-38565051

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+.


Copper , Fluorescent Dyes , Humans , Copper/analysis , Fluorescent Dyes/chemistry , Spectrometry, Fluorescence , Ions/analysis , Food
2.
Luminescence ; 39(5): e4739, 2024 May.
Article En | MEDLINE | ID: mdl-38685743

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.


Copper , Fluorescent Dyes , Schiff Bases , Schiff Bases/chemistry , Copper/chemistry , Copper/analysis , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Density Functional Theory , Spectrometry, Fluorescence , Molecular Structure , Ferric Compounds/chemistry , Ferric Compounds/analysis , Heterocyclic Compounds/chemistry , Heterocyclic Compounds/analysis , Humans , Ions/analysis
3.
Int J Biol Macromol ; 267(Pt 2): 131416, 2024 May.
Article En | MEDLINE | ID: mdl-38582486

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 Dyes , Lignin , Nanofibers , Rhodamines , Wastewater , Water Pollutants, Chemical , Rhodamines/chemistry , Lignin/chemistry , Lignin/analysis , Wastewater/chemistry , Wastewater/analysis , Nanofibers/chemistry , Fluorescent Dyes/chemistry , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Colorimetry/methods , Metals, Heavy/analysis , Metals, Heavy/chemistry , Nanocomposites/chemistry , Ions/analysis , Limit of Detection , Polyvinyl Alcohol/chemistry
4.
J Chromatogr A ; 1722: 464903, 2024 May 10.
Article En | MEDLINE | ID: mdl-38615559

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.


Ion Mobility Spectrometry , Ion Mobility Spectrometry/methods , Models, Theoretical , Ions/chemistry , Ions/analysis
5.
ACS Sens ; 9(4): 1622-1643, 2024 Apr 26.
Article En | MEDLINE | ID: mdl-38587931

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.


Luminescent Proteins , Metals , Humans , Metals/chemistry , Luminescent Proteins/chemistry , Animals , Calcium/analysis , Biosensing Techniques/methods , Fluorescent Dyes/chemistry , Ions/chemistry , Ions/analysis
6.
Environ Sci Pollut Res Int ; 31(20): 29631-29643, 2024 Apr.
Article En | MEDLINE | ID: mdl-38581634

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.


Environmental Monitoring , Ions , Rivers , Seasons , Water Pollutants, Chemical , China , Rivers/chemistry , Ions/analysis , Water Pollutants, Chemical/analysis , Water Quality , Principal Component Analysis
7.
Carbohydr Polym ; 334: 122043, 2024 Jun 15.
Article En | MEDLINE | ID: mdl-38553239

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.


Artocarpus , Pectins , Artocarpus/chemistry , Food Packaging , Fruit/chemistry , Ions/analysis , Pectins/chemistry , Seeds
8.
Environ Pollut ; 348: 123834, 2024 May 01.
Article En | MEDLINE | ID: mdl-38518971

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.


Air Pollutants , Microbiota , Seasons , Seoul , Environmental Monitoring , Air Microbiology , Particulate Matter/analysis , Air Pollutants/analysis , Bacteria , Ions/analysis , Water/analysis
9.
Colloids Surf B Biointerfaces ; 237: 113840, 2024 May.
Article En | MEDLINE | ID: mdl-38508085

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.


DNA , Saline Solution , Saline Solution/analysis , Cell Membrane/chemistry , Ions/analysis , DNA/analysis , Plasmids , Unilamellar Liposomes/chemistry
10.
Nature ; 627(8005): 905-914, 2024 Mar.
Article En | MEDLINE | ID: mdl-38448589

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.


Bacteriophages , Capsid , DNA, Viral , Genome, Viral , Virion , Virus Assembly , Bacteriophages/chemistry , Bacteriophages/genetics , Bacteriophages/growth & development , Bacteriophages/metabolism , Capsid/chemistry , Capsid/metabolism , Capsid Proteins/chemistry , Capsid Proteins/metabolism , Diffusion , DNA, Viral/chemistry , DNA, Viral/genetics , DNA, Viral/metabolism , Ions/analysis , Ions/chemistry , Ions/metabolism , Static Electricity , Virion/chemistry , Virion/genetics , Virion/metabolism , Virus Assembly/genetics , Water/analysis , Water/chemistry , Water/metabolism
11.
Talanta ; 273: 125900, 2024 Jun 01.
Article En | MEDLINE | ID: mdl-38490021

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.


Pyridines , Zinc , Zinc/chemistry , Pyrimidines , Ions/analysis , Adenosine Triphosphate , Fluorescent Dyes/chemistry , Spectrometry, Fluorescence
12.
Rapid Commun Mass Spectrom ; 38(10): e9736, 2024 May 30.
Article En | MEDLINE | ID: mdl-38533576

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.


Pesticide Residues , Pesticides , Pesticides/analysis , Gas Chromatography-Mass Spectrometry/methods , Tandem Mass Spectrometry/methods , Isomerism , Ions/analysis , Pesticide Residues/analysis
13.
Environ Sci Technol ; 58(9): 4092-4103, 2024 Mar 05.
Article En | MEDLINE | ID: mdl-38373958

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.


Air Pollutants , Humans , Pregnancy , Female , Child , Air Pollutants/toxicity , Air Pollutants/analysis , Water , Particulate Matter/toxicity , Particulate Matter/analysis , Birth Weight , Environmental Monitoring , Ions/analysis , China
14.
Environ Res ; 248: 118393, 2024 May 01.
Article En | MEDLINE | ID: mdl-38309564

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.


Soil Pollutants , Solanum nigrum , Solanum , Cadmium/analysis , Dissolved Organic Matter , Soil/chemistry , Biodegradation, Environmental , Soil Pollutants/analysis , Minerals/analysis , Ions/analysis , Plant Roots/chemistry , Calcium/analysis , Hydrogen-Ion Concentration
15.
J Am Soc Mass Spectrom ; 35(3): 603-612, 2024 Mar 06.
Article En | MEDLINE | ID: mdl-38391322

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.


Diterpenes, Kaurane , Diterpenes , Glucosides , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Chromatography, Liquid , Liquid Chromatography-Mass Spectrometry , Diterpenes/analysis , Glycosides , Plant Extracts/chemistry , Sugars/analysis , Ions/analysis , Plant Leaves/chemistry
16.
Spectrochim Acta A Mol Biomol Spectrosc ; 311: 123999, 2024 Apr 15.
Article En | MEDLINE | ID: mdl-38340449

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.


Cosmetics , Mercury , Rhodamines/chemistry , Mercury/analysis , Water/chemistry , Fluorescent Dyes/chemistry , Solubility , Ions/analysis , Cosmetics/analysis , Spectrometry, Fluorescence
17.
Int J Biol Macromol ; 261(Pt 2): 129922, 2024 Mar.
Article En | MEDLINE | ID: mdl-38309403

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.


Gelatin , Tanning , Aluminum/analysis , Zirconium , Ions/analysis , Industrial Waste/analysis
18.
Mikrochim Acta ; 191(1): 77, 2024 01 05.
Article En | MEDLINE | ID: mdl-38177621

Sweat is easily accessible from the human skin's surface. It is secreted by the eccrine glands and contains a wealth of physiological information, including metabolites and electrolytes like glucose and Na ions. Sweat is a particularly useful biofluid because of its easy and non-invasive access, unlike other biofluids, like blood. On the other hand, nanomaterials have started to show promise operation as a competitive substitute for biosensors and molecular sensors throughout the last 10 years. Among the most synthetic nanomaterials that are studied, applied, and discussed, carbon nanomaterials are special. They are desirable candidates for sensor applications because of their many intrinsic electrical, magnetic, and optical characteristics; their chemical diversity and simplicity of manipulation; their biocompatibility; and their effectiveness as a chemically resistant platform. Carbon nanofibers (CNFs), carbon dots (CDs), carbon nanotubes (CNTs), and graphene have been intensively investigated as molecular sensors or as components that can be integrated into devices. In this review, we summarize recent advances in the use of carbon nanomaterials as sweat sensors and consider how they can be utilized to detect a diverse range of analytes in sweat, such as glucose, ions, lactate, cortisol, uric acid, and pH.


Nanostructures , Nanotubes, Carbon , Humans , Sweat/chemistry , Nanotubes, Carbon/chemistry , Nanostructures/chemistry , Ions/analysis , Glucose/analysis
19.
Environ Monit Assess ; 196(2): 179, 2024 Jan 20.
Article En | MEDLINE | ID: mdl-38244082

This study aims to investigate and understand the temporal and spatial movement of seawater intrusion into the coastal aquifers. Groundwater salinity increase has affected the entire eastern part of the study area and is primarily influenced by direct and reverse ion exchange reactions associated with intrusion and freshwater influx phases, which alternate over monsoons. To gain insights into the spatiotemporal dynamics of the seawater intrusion process, hydrochemical facies analysis utilizing the HFE-Diagram was employed. Additionally, the study considered the major ionic changes during both the monsoons. The HFE-Diagram analysis of hydrochemical facies revealed distinctions in the behaviour of each coastal aquifer concerning seawater intrusion-induced salinization. In PRM 2020, the data shows that approximately 65% of the samples fall under the freshening phase, while the remaining 35% were categorized as intrusion phase. Within the freshening phase, seven different hydrochemical facies were identified, including Na-Cl, Na-MixCl, MixNa-MixCl, Na-MixHCO3/MixSO4, MixNa-MixSO4, Na-HCO3, and MixCa-HCO3. In contrast, the intrusion phase had four facies: MixCaMixHCO3, MixNa-Cl, Ca-Cl, and Na-Cl. Especially, the Na-Cl facies (f1) within the freshening phase attributed for the largest percentage, contributing 30% of the samples. In POM 2021, the distribution of samples shifted slightly, with approximately 72.5% belonging to the freshening phase and 27.5% to the intrusion phase. Within the freshening phase of POM 2021, five hydrochemical facies were identified: Na-Cl, Na-MixCl, Na-MixHCO3/MixSO4, MixNa-MixSO4, and Na-HCO3. The intrusion phase of POM 2021 had three facies: MixNa-Cl, Na-Cl, and MixCa-Cl. Similar to PRM 2020, the Na-Cl facies (f1) remained the most predominant in the freshening phase, comprising 30% of the samples. The relation between total dissolved solids (TDS) and various ionic ratios, such as HCO3-/Cl-, Na+/Cl-, Ca2+/Cl-, Mg2+/Cl-, K+/Cl-, and SO42-/Cl-, clearly demonstrates the presence of seawater influence within the coastal aquifers of the study area.


Groundwater , Water Pollutants, Chemical , Humans , Facies , Environmental Monitoring , Groundwater/analysis , Seawater/analysis , India , Salinity , Ions/analysis , Sodium/analysis , Water Pollutants, Chemical/analysis
20.
Macromol Rapid Commun ; 45(8): e2300678, 2024 Apr.
Article En | MEDLINE | ID: mdl-38183637

Covalent organic frameworks (COFs) represent a new type of crystalline porous polymers that possess pre-designed skeletons, uniform nanopores, and ordered π structure. These attributes make them well-suited for the design of light-emitting materials. However, the majority of COFs exhibits poor luminescence due to aggregation-caused quenching (ACQ), resulting from the strong interaction between adjacent layers. To break the limitation, the building units with three methoxy groups on the walls are used to construct TM-OMe-EBTHz-COF, which suppresses the ACQ effects to improve light-emitting activity of COF. The TM-OMe-EBTHz-COF exhibits a notable emission of yellow-green luminescence in the solid state, with a remarkably high absolute quantum yield of 21.1%. The methoxy groups and hydrazine linkage form three coordination sites, contributing to excellent performance in metal ions sensing. The TM-OMe-EBTHz-COF demonstrates high sensitivity and selectivity to Fe3+ ion. Importantly, the low detection limit is below 150 nanomolar, ranking it among the best-performing Fe3+ sensor systems.


Iron , Metal-Organic Frameworks , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Iron/chemistry , Iron/analysis , Ions/chemistry , Ions/analysis , Polymers/chemistry , Polymers/chemical synthesis , Porosity , Molecular Structure , Luminescence , Limit of Detection , Particle Size , Surface Properties
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