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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 124989, 2025 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-39154403

RESUMO

A newly developed 2H5MA-MOF sensor by covalently linking NH2-MIL-53(Al) with 2'-Hydroxy-5'-methylacetophenon, designed for highly sensitive and selective detection of Cd2+ ions using fluorometric methods. Detailed structural and morphological analyses confirmed the sensor's unique properties. It demonstrated an impressive linear detection range from 0 to 2 ppm, with an exceptionally low detection limit of 5.77 × 10-2 ppm and a quantification limit of 1.75 × 10-1 ppm, indicating its high sensitivity (R2 = 0.9996). The sensor also responded quickly, detecting Cd2+ within just 30 s at pH 4. We successfully tested it on real samples of tap water and human blood plasma, achieving recovery rates between 96 % and 104 %. The accuracy of these findings was further validated by comparison with ICP-OES. Overall, the 2H5MA-MOF sensor shows great potential for fast, ultra-sensitive, and reliable detection of Cd2+ ions, making it a promising tool for environmental and biomedical applications.


Assuntos
Cádmio , Água Potável , Limite de Detecção , Estruturas Metalorgânicas , Cádmio/sangue , Cádmio/análise , Humanos , Estruturas Metalorgânicas/química , Água Potável/análise , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/sangue , Íons/sangue , Concentração de Íons de Hidrogênio
2.
Mol Med Rep ; 30(5)2024 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-39301641

RESUMO

Copper, a vital trace element, is indispensable for the maintenance of physiological functioning, particularly in the cardiac system. Unlike other forms of cell death such as iron death and apoptosis, copper­induced cell death has gained increasing recognition as a significant process influencing the development of cardiovascular diseases. The present review highlights the significance of maintaining copper homeostasis in addressing cardiovascular diseases. This review delves into the crucial roles of copper in physiology, including the metabolic pathways and its absorption, transport and excretion. It provides detailed insights into the mechanisms underlying cardiovascular diseases resulting from both excess and deficient copper levels. Additionally, it summarizes strategies for treating copper imbalances through approaches such as copper chelators and ion carriers while discussing their limitations and future prospects.


Assuntos
Doenças Cardiovasculares , Cobre , Humanos , Doenças Cardiovasculares/metabolismo , Cobre/metabolismo , Animais , Homeostase , Quelantes/uso terapêutico , Íons/metabolismo
3.
Anal Chim Acta ; 1325: 343135, 2024 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-39244297

RESUMO

BACKGROUND: Mass spectrometry (MS)-based proteomics is a powerful tool for identifying and quantifying proteins. However, chimeric spectra caused by the fragmentation of multiple precursors within the same isolation window impair the accuracy of peptide identification and isobaric mass tag-based quantification. While there have been advances in computational deconvolution of chimeric spectra and methods to further separate the peptides by ion mobility or through MSn, the use of narrower isolation windows to decrease the fraction of chimeric species remains to be fully explored. RESULTS: We present results obtained on a SCIEX TripleTOF instrument where the quadrupole was optimized and tuned for precursor isolation at 0.1 Da (FWHH). Using a three-proteome model (trypsin digest of protein lysates from yeast, human and E. coli) and 8-plex iTRAQ labeling to document the interference effect, we investigated the impact of co-fragmentation on spectral purity, identification accuracy and quantification accuracy. The narrow quadrupole isolation window significantly improved the spectral purity and reduced the interference of non-target precursors on quantification accuracy. The high-resolution isolation strategy also reduced the number of false identifications caused by chimeric spectra. While these improvements came at the cost of sensitivity loss, combining high-resolution isolation with other advanced techniques, including ion mobility, may result in improved accuracy in identification and quantification. SIGNIFICANCE: Compared to standard-resolution quadrupole isolation (0.7 Da), high-resolution quadrupole isolation (0.1 Da) significantly improved the spectral purity and quantification accuracy while reducing the number of potential false identifications caused by chimeric spectra, thus showing excellent potential for further development to analyze clinical proteomics samples, for which high accuracy is essential.


Assuntos
Proteômica , Proteômica/métodos , Humanos , Íons/química , Escherichia coli/química , Saccharomyces cerevisiae/química , Peptídeos/química , Peptídeos/análise , Espectrometria de Massas/métodos
4.
Nat Commun ; 15(1): 7709, 2024 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-39231934

RESUMO

Electrospray ionization is widely used to generate vapor phase ions for analysis by mass spectrometry in proteomics research. However, only a small fraction of the analyte enters the mass spectrometer due to losses that are fundamentally linked to the use of a background gas to stimulate the generation of ions from electrosprayed droplets. Here we report a nanopore ion source that delivers ions directly into high vacuum from aqueous solutions. The ion source comprises a pulled quartz pipette with a sub-100 nm opening. Ions escape an electrified meniscus by ion evaporation and travel along collisionless trajectories to the ion detector. We measure mass spectra of 16 different amino acid ions, post-translationally modified variants of glutathione, and the peptide angiotensin II, showing that these analytes can be emitted as desolvated ions. The emitted current is composed of ions rather than charged droplets, and more than 90% of the current can be recovered in a distant collector.


Assuntos
Aminoácidos , Íons , Nanoporos , Peptídeos , Espectrometria de Massas por Ionização por Electrospray , Vácuo , Aminoácidos/química , Peptídeos/química , Espectrometria de Massas por Ionização por Electrospray/métodos , Proteômica/métodos , Angiotensina II/química
5.
Sci Rep ; 14(1): 20383, 2024 09 02.
Artigo em Inglês | MEDLINE | ID: mdl-39223199

RESUMO

Metal ion-DNA interactions play a crucial role in modulating the structure and function of genetic material in the natural environment. In this study, we report on the favorable electrochemical activity of holmium(III) (Ho3+) on a glassy carbon electrode (GCE) and its interaction with double-stranded DNA. The interaction between DNA and Ho3+ was investigated for the first time using cyclic voltammetry and differential pulse voltammetry. The electrochemical behavior of Ho3+ ions on a GCE exhibited a reversible electron transfer process, indicative of its redox activity. A linear correlation between the peak current and the square root of the scan rate was observed, suggesting a diffusion-controlled kinetic regime for the electrochemical process. Additionally, fluorescence and absorption spectroscopy were employed to confirm the binding of Ho3+ to DNA. Our findings demonstrate that, at pH 7.2, specific DNA bases and phosphate groups can interact with Ho3+ ions. Moreover, electrochemical measurements suggest that Ho3+ ions bind to DNA via a groove binding mode, with a calculated binding ratio of 1:1 between Ho3+ and DNA. Notably, under optimal conditions, an increase in the amount of DNA leads to a significant reduction in the current intensity of Ho3+ ions.


Assuntos
DNA , Técnicas Eletroquímicas , Eletrodos , Hólmio , Hólmio/química , DNA/química , Íons/química , Oxirredução , Carbono/química , Espectrometria de Fluorescência
6.
Sensors (Basel) ; 24(17)2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-39275538

RESUMO

Wearable sensors for sweat trace metal monitoring have the challenges of effective sweat collection and the real-time recording of detection signals. The existing detection technologies are implemented by generating enough sweat through exercise, which makes detecting trace metals in sweat cumbersome. Generally, it takes around 20 min to obtain enough sweat, resulting in dallied and prolonged detection signals that cannot reflect the endogenous fluctuations of the body. To solve these problems, we prepared a multifunctional hydrogel as an electrolyte and combined it with a flexible patch electrode to realize real-time monitoring of sweat Zn2+. Such hydrogel has magnetic and porous properties, and the porous structure of hydrogel enables a fast absorption of sweat, and the magnetic property of the addition of fabricated Fe3O4 NPs not only improves the conductivity but also ensures the adjustable internal structures of the hydrogel. Such a sensing platform for sweat Zn2+ monitoring shows a satisfied linear relationship in the concentration range of 0.16-16 µg/mL via differential pulsed anodic striping voltammetry (DPASV) and successfully detects the sweat Zn2+ of four volunteers during exercise and resting, displaying a promising path for commercial application.


Assuntos
Hidrogéis , Suor , Dispositivos Eletrônicos Vestíveis , Zinco , Zinco/química , Suor/química , Humanos , Hidrogéis/química , Porosidade , Técnicas Biossensoriais/métodos , Técnicas Biossensoriais/instrumentação , Eletrodos , Íons/química , Técnicas Eletroquímicas/métodos , Técnicas Eletroquímicas/instrumentação
7.
Nano Lett ; 24(37): 11446-11453, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39225511

RESUMO

Cuproptosis, dependent on Cu overload, presents novel opportunities for cancer therapy. Cu-based nanomaterials have shown excellent advantages for the intracellular delivery of Cu. However, the biological process of Cu nanomaterials transporting Cu ions into cancer cells remains unclear. In this study, we tracked the Cu ion release process of copper nanowires (CuNWs) and copper nanoparticles (CuNPs) at the single-cell level. CuNWs with 5-µm length and CuNPs were found to be completely internalized by cancer cells. Interestingly, CuNWs escaped from the endolysosomal system, whereas CuNPs were mainly trapped in the lysosomes. This specific intracellular distribution of CuNWs led to cytoplasmic Cu ion overload, directly damaging mitochondria and inducing dihydrolipoamide S-acetyltransferase (DLAT) protein aggregation. Through these excessive Cu ions, CuNWs triggered more efficient cuproptosis than CuNPs to further increase cell death. Thus, CuNWs are more effective in delivering Cu ions than CuNPs, providing a novel perspective for designing cuproptosis-based functional nanomaterials for cancer therapy.


Assuntos
Cobre , Nanofios , Cobre/química , Cobre/farmacologia , Nanofios/química , Humanos , Nanopartículas Metálicas/química , Íons , Lisossomos/metabolismo , Lisossomos/efeitos dos fármacos , Mitocôndrias/metabolismo , Mitocôndrias/efeitos dos fármacos , Células HeLa , Linhagem Celular Tumoral
8.
Molecules ; 29(17)2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39275029

RESUMO

Although titanium and its alloys are widely used as dental implants, they cannot induce the formation of new bone around the implant, which is a basis for the functional integrity and long-term stability of implants. This study focused on the functionalization of the titanium/titanium oxide surface as the gold standard for dental implants, with electrospun composite fibers consisting of polyvinylpyrrolidone and Ca2+ ions. Polymer fibers as carriers of Ca2+ ions should gradually dissolve, releasing Ca2+ ions into the environment of the implant when it is immersed in a model electrolyte of artificial saliva. Scanning electron microscopy, energy dispersive X-ray spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy confirmed the successful formation of a porous network of composite fibers on the titanium/titanium oxide surface. The mechanism of the formation of the composite fibers was investigated in detail by quantum chemical calculations at the density functional theory level based on the simulation of possible molecular interactions between Ca2+ ions, polymer fibers and titanium substrate. During the 7-day immersion of the functionalized titanium in artificial saliva, the processes on the titanium/titanium oxide/composite fibers/artificial saliva interface were monitored by electrochemical impedance spectroscopy. It can be concluded from all the results that the composite fibers formed on titanium have application potential for the development of osteoinductive and thus more biocompatible dental implants.


Assuntos
Cálcio , Implantes Dentários , Titânio , Titânio/química , Cálcio/química , Cálcio/metabolismo , Povidona/química , Humanos , Íons/química , Espectroscopia de Infravermelho com Transformada de Fourier , Saliva Artificial/química , Materiais Biocompatíveis/química , Espectrometria por Raios X , Osteogênese/efeitos dos fármacos
9.
Molecules ; 29(17)2024 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-39275094

RESUMO

MiR-155 is a multifunctional microRNA involved in many biological processes. Since miR-155 is overexpressed in several pathologies, its detection deserves high interest in clinical diagnostics. Biosensing approaches often exploit the hybridization of miR-155 with its complementary strand. Molecular Dynamics (MD) simulations were applied to investigate the complex formed by miR-155 and its complementary strand in aqueous solution with Na+ and Cl- ions at ionic strengths in the 100-400 mM range, conditions commonly used in biosensing experiments. We found that the main structural properties of the duplex are preserved at all the investigated ionic strengths. The radial distribution functions of both Na+ and Cl- ions around the duplex show deviation from those of bulk with peaks whose relative intensity depends on the ionic strength. The number of ions monitored as a function of the distance from the duplex reveals a behavior reminiscent of the counterion condensation near the duplex surface. The occurrence of such a phenomenon could affect the Debye length with possible effects on the sensitivity in biosensing experiments.


Assuntos
MicroRNAs , Simulação de Dinâmica Molecular , Sódio , MicroRNAs/química , MicroRNAs/genética , Concentração Osmolar , Sódio/química , Cloretos/química , Íons/química , Conformação de Ácido Nucleico
10.
Environ Sci Technol ; 58(37): 16525-16534, 2024 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-39235261

RESUMO

The reaction of dissolved Pb2+ with calcite surfaces at near-equilibrium conditions involves adsorption of Pb2+ and precipitation of secondary heteroepitaxial Pb-carbonate minerals. A more complex behavior is observed under far-from-equilibrium conditions, including strong inhibition of calcite dissolution, development of microtopography, and near-surface incorporation of multiple monolayers (ML) of Pb2+ without precipitation of secondary phases [where 1 ML ≡ 1 Ca/20.2 Å2, the crystallographic site density of the calcite (104) lattice plane]. However, the mechanistic controls governing far-from-equilibrium reactivity are not well understood. Here, we observe the interfacial incorporation of dissolved Pb2+ during the dissolution of calcite (104) surfaces at pH ∼ 3.7 in a flow-through reaction cell, revealing the formation of a ∼1 nm thick Pb-rich calcite layer with a total Pb coverage of ∼1.4 ML. These observations of the sorbed Pb distribution used resonant anomalous X-ray reflectivity, X-ray fluorescence, and nanoinfrared atomic force microscopy. We propose that this altered surface layer represents a novel sorption mode that is stabilized by conditions of sustained disequilibrium. This behavior may significantly impact the transport of dissolved metals during disequilibrium processes occurring in acid mine drainage and subsurface CO2 injection and, if appropriately accounted for, could improve the predictive capability of geochemical reactive-transport models.


Assuntos
Carbonato de Cálcio , Chumbo , Chumbo/química , Carbonato de Cálcio/química , Adsorção , Propriedades de Superfície , Íons
11.
BMC Oral Health ; 24(1): 1089, 2024 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-39277736

RESUMO

BACKGROUND: To predict the long-term performance of restorative materials in the oral environment, it is important to evaluate their resistance to chemical and mechanical degradation and to know the toxic potential of the type and amount of ions eluted from the filling material. In this study, home bleaching was applied to dental materials with different contents and it was aimed to determine the type and amount of ions released from these materials. METHODS: In this study, amalgam, posterior composite resin, anterior composite resin, bulk fill composite resin, indirect composite resin, hybrid ceramic and all-ceramic were used as restorative materials. 10 specimens of each material were prepared according to the manufacturer's instructions. Each material group was divided into two subgroups as the bleached group and the control group. After bleaching, all specimens were stored in 1 ml of 75% ethanol/water solution. Solutions were renewed after 1, 14 and 28 days. The type and amount of ions released from the materials were determined using Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). Data were analyzed using the Friedman, Wilcoxon Signed Ranks, and Mann-Whitney U tests (α = 0.05). RESULTS: It was determined that the amount of ions release from the restorative materials decreased over time (p < 0.05). According to the results of the Mann-Whitney U test, there was no difference between the bleaching and control groups in most of the restorative materials (p > 0.05). CONCLUSION: Within the limits of this study, home bleaching system does not have a significant effect on ion release from restorative materials.


Assuntos
Peróxido de Carbamida , Resinas Compostas , Amálgama Dentário , Materiais Dentários , Restauração Dentária Permanente , Teste de Materiais , Peróxidos , Clareadores Dentários , Ureia , Peróxido de Carbamida/farmacologia , Peróxidos/química , Resinas Compostas/química , Clareadores Dentários/química , Amálgama Dentário/química , Ureia/análogos & derivados , Ureia/química , Restauração Dentária Permanente/métodos , Materiais Dentários/química , Íons , Cerâmica/química , Humanos , Fatores de Tempo
12.
Luminescence ; 39(9): e4874, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39252570

RESUMO

The capped CdS-ZnS quantum dots (QDs) were synthesized with various thiol capping agents of glycolic acid (TGA), mercaptosuccinic acid (MSA), and L-cysteine (LCY) and used as fluorescence probe for determination of Cu (II) ions. The method of two-level three-factor full-factorial experiment design was used to achieve the best optical fluorescence emission. Results revealed that Cu (II) ions can effectively quench the emission of QDs, and the fluorescence intensity is linearly decreased with increasing Cu (II) ion concentration. The limit of detection for CdS-ZnS@ QDs capped with TGA, MSA, and LCY was obtained at 1.15 × 10-7, 1.32 × 10-7, and 2.19 × 10-7 mol L-1, respectively, with linear dynamic range of 3.13 × 10-6 to 1.41 × 10-4 mol L-1. Luminescence quantum yields of CdS-ZnS@LCY, CdS-ZnS@MSA, and CdS-ZnS@TGA were obtained at 4.17, 1.92, and 2.47, respectively. Results indicated that no significant quenching occurred in the presence of the other metal ions. The binding constant (Kb) of capped CdS-ZnS@ QDs with Cu2+ and the other metal ions was also investigated and discussed. The Kb value for Cu2+ was obtained considerably more than that the other ions. This work presents a new and sensitive method for determination of Cu2+ ion.


Assuntos
Compostos de Cádmio , Cobre , Corantes Fluorescentes , Pontos Quânticos , Compostos de Sulfidrila , Sulfetos , Propriedades de Superfície , Compostos de Zinco , Pontos Quânticos/química , Cobre/química , Cobre/análise , Sulfetos/química , Compostos de Zinco/química , Compostos de Cádmio/química , Compostos de Sulfidrila/química , Compostos de Sulfidrila/análise , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Espectrometria de Fluorescência , Fluorescência , Íons/química , Íons/análise
13.
J Mater Sci Mater Med ; 35(1): 54, 2024 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-39251504

RESUMO

Both silicon (Si) and zinc (Zn) ions are essential elements to bone health and their mechanisms for promoting osteogenesis have aroused the extensive attention of researchers. Thereinto, the mechanism by which dual ions promote osteogenic differentiation remains to be elucidated. Herein, the effects of Si and Zn ions on the cytological behaviors of mBMSCs were firstly studied. Then, the molecular mechanism of Si-Zn dual ions regulating the osteogenic differentiation of mBMSCs was investigated via transcriptome sequencing technology. In the single-ion system, Si ion at the concentration of 1.5 mM (Si-1.5) had better comprehensive effects of cell proliferation, ALP activity and osteogenesis-related gene expression levels (ALP, Runx2, OCN, Col-I and BSP); Zn ion at the concentration of 50 µM (Zn-50) demonstrated better combining effects of cell proliferation, ALP activity and same osteogenic genes expression levels. In the dual-ion system, the Si (1.5 mM)-Zn (50 µM) group (Si1.5-Zn50) synthetically enhanced ALP activity and osteogenesis genes compared with single-ion groups. Analysis of the transcriptome sequencing results showed that Si ion had a certain effect on promoting the osteogenic differentiation of mBMSCs; Zn ion had a stronger effect of contributing to a better osteogenic differentiation of mBMSCs than that of Si ion; the Si-Zn dual ions had a synergistic enhancement on conducting to the osteogenic differentiation of mBMSCs compared to single ion (Si or Zn). This study offers a blueprint for exploring the regulation mechanism of osteogenic differentiation by dual ions.


Assuntos
Diferenciação Celular , Proliferação de Células , Íons , Células-Tronco Mesenquimais , Osteogênese , RNA Mensageiro , Silício , Zinco , Osteogênese/efeitos dos fármacos , Osteogênese/genética , Silício/química , Silício/farmacologia , Diferenciação Celular/efeitos dos fármacos , Zinco/química , Zinco/farmacologia , Proliferação de Células/efeitos dos fármacos , Células-Tronco Mesenquimais/efeitos dos fármacos , Células-Tronco Mesenquimais/citologia , Células-Tronco Mesenquimais/metabolismo , Animais , RNA Mensageiro/genética , RNA Mensageiro/metabolismo , Transcriptoma/efeitos dos fármacos , Células Cultivadas , Perfilação da Expressão Gênica/métodos , Análise de Sequência de RNA
14.
PeerJ ; 12: e17796, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39247553

RESUMO

Benggangs are a special type of soil erosion in the hilly granite regions of the tropical and subtropical areas of Southern China. They cause severe soil and water loss, which can severely deteriorate soil quality and threat to the local ecological environment. Soils (red soil, sandy soil and detritus soil) were collected from collapsing wall of a typical Benggang in Changting County of Fujian Province, and their physicochemical and mineralogical properties were analyzed. Five different monovalent cations were used to saturate the soil samples to examine the specific ion effects on the shear strength and clay surface properties. Red soil had a higher clay content, plastic limit, liquid limit and shear strength than sandy soil and detritus soil. The studied soils mainly consisted of kaolinite, hydroxy-interlayer vermiculite, illite and gibbsite clay minerals. The soils saturated with K+, NH4 +and Cs+ had greater cohesion than the Li+- and Na+-saturated soils, e.g., the cohesion of the red soil saturated with Li+, K+, NH4 + and Cs+ cations were 1.05, 1.23, 1.45 and 1.20 times larger than that of the Na+-saturated soil, respectively. While the internal friction angle was slightly different, which indicated that different monovalent cations affected the shear strength differently. K+-, NH4 +- and Cs+-saturated clay particles had higher zeta potentials and thinner shear plane thicknesses than Li+- and Na+-saturated clay particles and showed strong specific ion effects on the clay surface properties. The changes in clay surface properties strongly affected the soil mechanical properties. Soils saturated with K+, NH4 + and Cs+ could increase the shear strength, and then increase the stability of the collapsing wall, thus might decrease the erosion intensity of Benggang. The results provide a scientific basis for the interpretation of and practical treatment of Benggang.


Assuntos
Silicatos de Alumínio , Argila , Resistência ao Cisalhamento , Solo , Propriedades de Superfície , Solo/química , Argila/química , Silicatos de Alumínio/química , China , Íons , Caulim/química
15.
Luminescence ; 39(9): e4895, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39239921

RESUMO

Easy, economical, and swift detecting tools are very demanded for assaying various chemical species. The introduction of label-free paper-based read-out devices has significantly reached the demand of analytical science for target analytes assays. Herein, a facile, and disposable inexpensive paper-based sensing tool was fabricated for sensing As3+ ion using graphene quantum dots (GQDs) as a fluorescent reader. The CA-GQDs were synthesized using citric acid (CA) as a precursor via the pyrolysis method, further physisorbed on the cellulose substrate for sensing of As3+ via aggregation-based fluorescence "turn-off" mechanism. The linear range for quantitating As3+ ion is in the range of 0.05-50 µM with a detection limit of 10 nM. The practical application of the CA-GQDs-based analytical platform was verified by assaying As3+ ion in water samples. The CA-GQDs-embedded paper strip can be easily extended for assaying of As3+ ion, which meets the demand for monitoring of As3+ ion in real samples.


Assuntos
Celulose , Grafite , Papel , Pontos Quânticos , Grafite/química , Pontos Quânticos/química , Celulose/química , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Espectrometria de Fluorescência , Íons/análise , Íons/química , Limite de Detecção , Fluorescência
16.
J Phys Chem B ; 128(37): 8966-8973, 2024 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-39254719

RESUMO

Magnesium (Mg2+) is the most abundant divalent cation in the cell and is essential to nearly every biochemical reaction involving adenosine triphosphate (ATP) and its lower energy counterpart, adenosine diphosphate (ADP). In this work, we examine the solution dynamics of ADP at different concentrations and record the changes thereof due to the presence of Mg2+ ions. Relaxation and diffusion experiments were performed on a range of ADP solutions with increasing magnesium concentration. The most significant changes of both relaxation and diffusion behaviors are observed when adding Mg2+ up to 0.5 ADP equivalent (eq), with most of the changes complete at 1 eq. Molecular dynamics simulations also show a significant structure introduced by Mg2+ with very stable pyramidal coordination with the phosphate oxygens. A more extended structure found in the presence of Mg2+ is consistent with the experimental slowing of diffusion and an increase in the spin-lattice relaxation rate. We do not observe direct evidence of aggregation in solution, although translational diffusion is slowed down significantly at higher concentrations (while solvent diffusion remains constant).


Assuntos
Difosfato de Adenosina , Magnésio , Simulação de Dinâmica Molecular , Magnésio/química , Difosfato de Adenosina/química , Difosfato de Adenosina/metabolismo , Espectroscopia de Ressonância Magnética , Difusão , Íons/química
17.
Int J Mol Sci ; 25(17)2024 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-39273086

RESUMO

The mode of coordination of copper(II) ions with dopamine (DA, L) in the binary, as well as ternary systems with Ado, AMP, ADP, and ATP (L') as second ligands, was studied with the use of experimental-potentiometric and spectroscopic (VIS, EPR, NMR, IR)-methods and computational-molecular modeling and DFT-studies. In the Cu(II)/DA system, depending on the pH value, the active centers of the ligand involved in the coordination with copper(II) ions changed from nitrogen and oxygen atoms (CuH(DA)3+, Cu(DA)2+), via nitrogen atoms (CuH2(DA)24+), to oxygen atoms at strongly alkaline pH (Cu(DA)22+). The introduction of L' into this system changed the mode of interaction of dopamine from oxygen atoms to the nitrogen atom in the hydroxocomplexes formed at high pH values. In the ternary systems, the ML'-L (non-covalent interaction) and ML'HxL, ML'L, and ML'L(OH)x species were found. In the Cu(II)/DA/AMP or ATP systems, mixed forms were formed up to a pH of around 9.0; above this pH, only Cu(II)/DA complexes occurred. In contrast to systems with AMP and ATP, ternary species with Ado and ADP occurred in the whole pH range at a high concentration, and moreover, binary complexes of Cu(II) ions with dopamine did not form in the detectable concentration.


Assuntos
Cobre , Dopamina , Cobre/química , Dopamina/química , Nucleotídeos/química , Nucleotídeos/metabolismo , Nucleosídeos/química , Concentração de Íons de Hidrogênio , Complexos de Coordenação/química , Íons/química , Ligantes , Modelos Moleculares
18.
Nat Commun ; 15(1): 7545, 2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-39215031

RESUMO

Two-pore domain K+ (K2P) channel activity was previously thought to be controlled primarily via a selectivity filter (SF) gate. However, recent crystal structures of TASK-1 and TASK-2 revealed a lower gate at the cytoplasmic pore entrance. Here, we report functional evidence of such a lower gate in the K2P channel K2P17.1 (TALK-2, TASK-4). We identified compounds (drugs and lipids) and mutations that opened the lower gate allowing the fast modification of pore cysteine residues. Surprisingly, stimuli that directly target the SF gate (i.e., pHe., Rb+ permeation, membrane depolarization) also opened the cytoplasmic gate. Reciprocally, opening of the lower gate reduced the electric work to open the SF via voltage driven ion binding. Therefore, it appears that the SF is so rigidly locked into the TALK-2 protein structure that changes in ion occupancy can pry open a distant lower gate and, vice versa, opening of the lower gate concurrently promote SF gate opening. This concept might extent to other K+ channels that contain two gates (e.g., voltage-gated K+ channels) for which such a positive gate coupling has been suggested, but so far not directly demonstrated.


Assuntos
Ativação do Canal Iônico , Canais de Potássio de Domínios Poros em Tandem , Animais , Humanos , Citoplasma/metabolismo , Células HEK293 , Íons/metabolismo , Mutação , Canais de Potássio de Domínios Poros em Tandem/metabolismo , Canais de Potássio de Domínios Poros em Tandem/química , Canais de Potássio de Domínios Poros em Tandem/genética , Xenopus laevis
19.
Environ Geochem Health ; 46(9): 363, 2024 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-39126534

RESUMO

Fluoroquinolone antibiotics have been extensively used in clinical treatments for human and animal diseases. However, their long-term presence in the environment increases the risk of producing resistance genes and creates a potential threat to ecosystems and the health of humans and animals. Batch equilibrium experiments were utilized to investigate the adsorption and retention behavior and mechanism of the quinolone antibiotic enrofloxacin (ENR) in farmland soil in North China. The adsorption and desorption kinetics of ENR in soil were best fitted by pseudo-second-order model (R2 > 0.999). Both the adsorption and desorption processes of ENR in soil reached equilibrium in 1 h. The desorption amounts of ENR were significantly lower than the adsorption amounts, with the hysteresis coefficient (HI) being less than 0.7. The adsorption thermodynamic process of ENR followed the Linear and Freundlich models (0.965 < R2 < 0.985). Hydrophobic distribution and heterogeneous multimolecular layer adsorption were identified as critical factors in the adsorption process. The adsorption amount of ENR gradually decreased with increasing temperature and the initial concentration of ENR. The adsorption rate of ENR was above 80%, while the desorption rate remained below 15%, indicating strong retention ability. The adsorption rate of ENR in soil decreased with increasing pH, the adsorption rate reached 98.3% at pH 3.0 but only 31.5% at pH 11. The influence of coexisting ions on adsorption primarily depended on their properties, such as ion radius, ionic strength, and hydrolysis properties, and the inhibition of adsorption increased with increasing ionic strength. These findings contribute to understanding the fate and risk of veterinary antibiotics in loess soil in North China.


Assuntos
Antibacterianos , Enrofloxacina , Poluentes do Solo , Solo , Enrofloxacina/química , Adsorção , Poluentes do Solo/química , Concentração de Íons de Hidrogênio , Antibacterianos/química , Solo/química , China , Fazendas , Fluoroquinolonas/química , Cinética , Íons/química
20.
Environ Sci Pollut Res Int ; 31(39): 51222-51236, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39103586

RESUMO

Sulphidation of nZVI (S-nZVI) has shown to significantly improve the arsenic removal capacity of nZVI, concurrently modifying the sequestration mechanism. However, to better apply S-nZVI for groundwater arsenic remediation, the impact of groundwater coexisting ions on the efficacy of arsenic uptake by S-nZVI needs to be investigated. This present study evaluates the potential of S-nZVI to remove arsenic in the presence of typical groundwater coexisting ions such as Cl-, HA, HCO3-, PO43- and SO42- through batch adsorption experiments. Individually, PO43- and HA had a dominant inhibition effect, while SO42- promoted As(III) removal by S-nZVI. Conversely, for As(V) removal, HCO3- and SO42- impeded the removal process. X-ray spectroscopic investigation suggests that the coexisting ions can either compete with arsenic for the adsorption sites, influence the S-nZVI corrosion rates and/or generate distinct corrosion products, thereby interfering with arsenic removal by S-nZVI. To investigate the cumulative effects of these ions, a 25-1 Fractional Factorial Design of experiments was employed, wherein the concentration of all the ions were varied simultaneously in an optimized manner, and their impact on arsenic removal by S-nZVI was observed. Our results shows that when these ions are present concurrently, PO43-, SO42- and HA still exerted a dominant influence on As(III) removal, whereas HCO3- was the main ions affecting As(V) removal, although the combined influence of the ions was not merely a summation of their individual effects. Overall, the finding of our study might provide valuable insight for predicting the actual performance of S-nZVI in field-scale applications for the remediation of arsenic-contaminated groundwater.


Assuntos
Arsênio , Água Subterrânea , Ferro , Poluentes Químicos da Água , Água Subterrânea/química , Arsênio/química , Poluentes Químicos da Água/química , Ferro/química , Adsorção , Sulfetos/química , Íons , Purificação da Água/métodos
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