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1.
Anal Chem ; 96(19): 7697-7705, 2024 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-38697043

RESUMO

Dual/multimodal imaging strategies are increasingly recognized for their potential to provide comprehensive diagnostic insights in cancer imaging by harnessing complementary data. This study presents an innovative probe that capitalizes on the synergistic benefits of afterglow luminescence and magnetic resonance imaging (MRI), effectively eliminating autofluorescence interference and delivering a superior signal-to-noise ratio. Additionally, it facilitates deep tissue penetration and enables noninvasive imaging. Despite the advantages, only a limited number of probes have demonstrated the capability to simultaneously enhance afterglow luminescence and achieve high-resolution MRI and afterglow imaging. Herein, we introduce a cutting-edge imaging platform based on semiconducting polymer nanoparticles (PFODBT) integrated with NaYF4@NaGdF4 (Y@Gd@PFO-SPNs), which can directly amplify afterglow luminescence and generate MRI and afterglow signals in tumor tissues. The proposed mechanism involves lanthanide nanoparticles producing singlet oxygen (1O2) upon white light irradiation, which subsequently oxidizes PFODBT, thereby intensifying afterglow luminescence. This innovative platform paves the way for the development of high signal-to-background ratio imaging modalities, promising noninvasive diagnostics for cancer.


Assuntos
Elementos da Série dos Lantanídeos , Imageamento por Ressonância Magnética , Nanopartículas , Polímeros , Semicondutores , Imageamento por Ressonância Magnética/métodos , Animais , Elementos da Série dos Lantanídeos/química , Polímeros/química , Nanopartículas/química , Camundongos , Humanos , Gadolínio/química , Luminescência , Oxigênio Singlete/química , Ítrio/química , Fluoretos/química , Camundongos Nus
2.
ACS Nano ; 18(18): 11837-11848, 2024 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-38654614

RESUMO

A noninvasive strategy for in situ diagnosis and precise treatment of bacterial biofilm infections is highly anticipated but still a great challenge. Currently, no in vivo biofilm-targeted theranostic agent is available. Herein, we fabricated intelligent theranostic alginate lyase (Aly)-NaNdF4 nanohybrids with a 220 nm sunflower-like structure (NaNdF4@DMS-Aly) through an enrichment-encapsulating strategy, which exhibited excellent photothermal conversion efficiency and the second near-infrared (NIR-II) luminescence. Benefiting from the site-specific targeting and biofilm-responsive Aly release from NaNdF4@DMS-Aly, we not only enabled noninvasive diagnosis but also realized Aly-photothermal synergistic therapy and real-time evaluation of therapeutic effect in mice models with Pseudomonas aeruginosa biofilm-induced pulmonary infection. Furthermore, such nanobiohybrids with a sheddable siliceous shell are capable of delaying the NaNdF4 dissolution and biodegradation upon accomplishing the therapy, which is highly beneficial for the biosafety of theranostic agents.


Assuntos
Biofilmes , Elementos da Série dos Lantanídeos , Pseudomonas aeruginosa , Nanomedicina Teranóstica , Biofilmes/efeitos dos fármacos , Animais , Camundongos , Pseudomonas aeruginosa/efeitos dos fármacos , Elementos da Série dos Lantanídeos/química , Elementos da Série dos Lantanídeos/farmacologia , Infecções por Pseudomonas/tratamento farmacológico , Infecções por Pseudomonas/microbiologia , Antibacterianos/farmacologia , Antibacterianos/química , Humanos , Terapia Fototérmica , Camundongos Endogâmicos BALB C
3.
Anal Methods ; 16(16): 2556-2568, 2024 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-38592494

RESUMO

A novel luminescence-based analytical methodology was established employing a europium(III) complex with 3-allyl-2-hydroxybenzohydrazide (HAZ) as the coordinating ligand for the quantification of gemifloxacin mesylate (GMF) in pharmaceutical preparations and human plasma samples spiked with the compound. The stoichiometry of the europium complex with HAZ was determined via the Job plot and exhibited a metal-to-ligand ratio of 1 : 2. The analytical procedure relies on a rapid and significant enhancement of luminescence by the Eu(AZ)2 complex when it interacts with gemifloxacin mesylate, which allowed for the rapid detection of 96 samples within approximately 2 minutes. The thermodynamic parameters of the complexation of GMF with Eu(AZ)2 were evaluated and showed that the complexation of GMF was spontaneous with a negative ΔG. The binding constant K was 4.27 × 105 L mol-1 and DFT calculations supported GMF binding and the formation of Eu(AZ)2-GMF without further ligand exchange. The calibration graph for the luminescence quantitation of GMF was linear over a wide concentration range of 0.11-16 µg mL-1 (2.26 × 10-7 to 3.30 × 10-5 mol L-1), with a limit of quantification (LOQ) of 110 ng mL-1 (230 nmol L-1) and a detection limit (LOD) of 40 ng mL-1 (82 nmol L-1). The proposed method showed good accuracy with an average recovery of 99% with relative standard deviations of less than 5% in spiking experiments, even in complex pharmaceutical dosage forms such as tablets and in human blood plasma. Herein, the ability of the suppression of the luminescence background by using the long lag times of the lanthanide probe in a time-resolved detection scheme provided reliable and precise results, which suggests its potential for use in further real or patient samples.


Assuntos
Európio , Gemifloxacina , Humanos , Gemifloxacina/química , Gemifloxacina/sangue , Európio/química , Medições Luminescentes/métodos , Limite de Detecção , Complexos de Coordenação/química , Complexos de Coordenação/sangue , Elementos da Série dos Lantanídeos/química , Naftiridinas/sangue , Naftiridinas/química
4.
Inorg Chem ; 63(17): 7560-7570, 2024 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-38610098

RESUMO

[Ln·DOTA]- complexes and systems derived therefrom are commonly used in MRI and optical bioimaging. These lanthanide(III) complexes are chiral, and, in solution, they are present in four forms, with two sets of enantiomers, with the ligand donors arranged in either a square antiprismatic, SAP, or twisted square antiprismatic geometry, TSAP. This complicated speciation is found in laboratory samples. To investigate speciation in biological media, when Ln·DOTA-like complexes interact with chiral biomolecules, six Eu·DOTA-monoamide complexes were prepared and investigated by using 1D and 2D 1H NMR. To emulate the chirality of biological media, the amide pendant arm was modified with one or two chiral centers. It is known that a chiral center on the DOTA scaffold significantly influences the properties of the system. Here, it was found that chirality much further away from the metal center changes the available conformational space and that both chiral centers and amide cis/trans isomerism may need to be considered─a fact that, for the optically enriched materials, led to the conclusion that eight chemically different forms may need to be considered, instead of the four forms necessary for DOTA. The results reported here clearly demonstrate the diverse speciation that must be considered when correlating an observation to a structure of a lanthanide(III) complex.


Assuntos
Complexos de Coordenação , Elementos da Série dos Lantanídeos , Imageamento por Ressonância Magnética , Elementos da Série dos Lantanídeos/química , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Complexos de Coordenação/farmacologia , Estereoisomerismo , Estrutura Molecular , Compostos Heterocíclicos com 1 Anel/química , Amidas/química , Meios de Contraste/química , Meios de Contraste/farmacologia
5.
Luminescence ; 39(4): e4740, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38618664

RESUMO

A lanthanide complex based on europium (Eu) and chelidamic acid was synthesized (Eu-CHE) and characterized. The complex Eu-CHE exhibited intense luminescence at 615 nm under excitation at 300 nm and was further investigated for highly sensitive turn-off detection of l-kynurenine (l-kyn), a cancer biomarker. The probe detected l-kyn linearly from 6 nM to 0.2 µM with a limit of detection and limit of quantification of 1.37 and 4.57 nM, respectively. The probe was investigated for selectivity towards l-kyn among co-existing amino acids and further extended for detecting l-kyn from human serum and urine samples. A low-cost paper strip-based sensing platform was also developed for the visual detection of l-kyn.


Assuntos
Elementos da Série dos Lantanídeos , Neoplasias , Humanos , Cinurenina , Biomarcadores Tumorais , Neoplasias/diagnóstico , Aminoácidos , Európio
6.
Mikrochim Acta ; 191(4): 225, 2024 04 01.
Artigo em Inglês | MEDLINE | ID: mdl-38557876

RESUMO

An intelligent fluorescent nanoprobe (lignite-CDs-Eu) was constructed by an effective and facile method based on lignite-derived carbon dots (CDs) and lanthanide europium ions (Eu3+), which exhibited high sensitivity, low detection limit (13.35 nM) and visual color variation (from blue to red) under ultraviolet light towards tetracycline (TC) detection. Significantly, portable and economical sensors were developed using lignite-CDs-Eu immobilized fiber material of filter paper and wearable glove with the aid of color extracting and image processing application (APP) in the smartphone. Facile, fast and real-time visual detection of TC in food samples was realized. Moreover, logic gate circuit was also designed to achieve intelligent and semi-quantitative inspection of TC. To some extent, this study extended the cross-application of intelligent computer software in food analytical science, and provided a certain reference for the development of small portable detection sensors which were suitable for convenience and non-professional use in daily life.


Assuntos
Elementos da Série dos Lantanídeos , Tetraciclina , Antibacterianos , Európio , Carvão Mineral
7.
Biosens Bioelectron ; 257: 116330, 2024 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-38677022

RESUMO

Perfluorooctanoic acid (PFOA) poses a threat to the environment and human health due to its persistence, bioaccumulation, and reproductive toxicity. Herein, a lanthanide metal-organic framework (Ln-MOF)-based surface molecularly imprinted polymers (SMIPs) ratiometric fluorescence probe (Eu/Tb-MOF@MIPs) and a smartphone-assisted portable device were developed for the detection of PFOA with high selectivity in real water samples. The integration of Eu/Tb MOFs as carriers not only had highly stable multiple emission signals but also prevented deformation of the imprinting cavity of MIPs. Meanwhile, the MIPs layer preserved the fluorescence of Ln-MOF and provided selective cavities for improved specificity. Molecular dynamics (MD) was employed to simulate the polymerization process of MIPs, revealing that the formation of multiple recognition sites was attributed to the establishment of hydrogen bonds between functional monomers and templates. The probe showed a good linear relationship with PFOA concentration in the range of 0.02-2.8 µM, by giving the limit of detection (LOD) of 0.98 nM. Additionally, The red-green-blue (RGB) values analysis based on the smartphone-assisted portable device demonstrated a linear relationship of 0.1-2.8 µM PFOA with the LOD of 3.26 nM. The developed probe and portable device sensing platform exhibit substantial potential for on-site detecting PFOA in practical applications and provide a reliable strategy for the intelligent identification of important targets in water environmental samples.


Assuntos
Técnicas Biossensoriais , Caprilatos , Corantes Fluorescentes , Fluorocarbonos , Estruturas Metalorgânicas , Polímeros Molecularmente Impressos , Smartphone , Poluentes Químicos da Água , Estruturas Metalorgânicas/química , Caprilatos/análise , Caprilatos/química , Corantes Fluorescentes/química , Técnicas Biossensoriais/instrumentação , Fluorocarbonos/química , Fluorocarbonos/análise , Polímeros Molecularmente Impressos/química , Poluentes Químicos da Água/análise , Limite de Detecção , Elementos da Série dos Lantanídeos/química , Espectrometria de Fluorescência/métodos , Humanos
8.
Talanta ; 274: 126056, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38599123

RESUMO

Early diagnosis is paramount for enhancing survival rates and prognosis in the context of malignant diseases. Hepatocellular carcinoma (HCC), the second leading cause of cancer-related deaths worldwide, poses significant challenges for its early detection. In this study, we present an innovative approach which contributed to the early diagnosis of HCC. By lanthanide encoding signal amplification to map glycan-linkages at the single-cell level, the minute quantities of "soft" glycan-linkages on single cell surface were converted into "hard" elemental tags through the use of an MS2 signal amplifier. Harnessing the power of lanthanides encoded within MS2, we achieve nearly three orders of magnitude signal amplification. These encoded tags are subsequently quantified using single-cell inductively coupled plasma mass spectrometry (SC-ICP-MS). Linear discriminant analysis (LDA) identifies seven specific glycan-linkages (α-2,3-Sia, α-Gal, α-1,2-Fuc, α-1,6-Fuc, α-2,6-Sia, α-GalNAc, and Gal-ß-1,3-GalNAc) as biomarkers. Our methodology is initially validated at the cellular level with 100% accuracy in discriminating between hepatic carcinoma HepG2 cells and their normal HL7702 cells. We apply this approach to quantify and classify glycan-linkages on the surfaces of 55 clinical surgical HCC specimens. Leveraging these seven glycan-linkages as biomarkers, we achieve precise differentiation between 8 normal hepatic specimens, 40 early HCC specimens, and 7 colorectal metastasis HCC specimens. This pioneering work represents the first instance of employing single-cell glycan-linkages as biomarkers promising for the early diagnosis of HCC with a remarkable 100% predictive accuracy rate, which holds immense potential for enhancing the feasibility and precision of HCC diagnosis in clinical practice.


Assuntos
Carcinoma Hepatocelular , Elementos da Série dos Lantanídeos , Neoplasias Hepáticas , Espectrometria de Massas , Polissacarídeos , Análise de Célula Única , Carcinoma Hepatocelular/diagnóstico , Humanos , Neoplasias Hepáticas/diagnóstico , Polissacarídeos/análise , Polissacarídeos/química , Elementos da Série dos Lantanídeos/química , Espectrometria de Massas/métodos , Análise de Célula Única/métodos , Detecção Precoce de Câncer/métodos , Células Hep G2 , Biomarcadores Tumorais/análise
9.
Biosensors (Basel) ; 14(3)2024 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-38534223

RESUMO

Electrospun nanofibers possess a large surface area and a three-dimensional porous network that makes them a perfect material for embedding functional nanoparticles for diverse applications. Herein, we report the trends in embedding upconversion nanoparticles (UCNPs) in polymeric nanofibers for making an advanced miniaturized (bio)analytical device. UCNPs have the benefits of several optical properties, like near-infrared excitation, anti-Stokes emission over a wide range from UV to NIR, narrow emission bands, an extended lifespan, and photostability. The luminescence of UCNPs can be regulated using different lanthanide elements and can be used for sensing and tracking physical processes in biological systems. We foresee that a UCNP-based nanofiber sensing platform will open opportunities in developing cost-effective, miniaturized, portable and user-friendly point-of-care sensing device for monitoring (bio)analytical processes. Major challenges in developing microfluidic (bio)analytical systems based on UCNPs@nanofibers have been reviewed and presented.


Assuntos
Técnicas Biossensoriais , Elementos da Série dos Lantanídeos , Nanofibras , Nanopartículas , Luminescência , Polímeros
10.
Nat Commun ; 15(1): 2341, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38491065

RESUMO

Nanothermometers enable the detection of temperature changes at the microscopic scale, which is crucial for elucidating biological mechanisms and guiding treatment strategies. However, temperature monitoring of micron-scale structures in vivo using luminescent nanothermometers remains challenging, primarily due to the severe scattering effect of biological tissue that compromises the imaging resolution. Herein, a lanthanide luminescence nanothermometer with a working wavelength beyond 1500 nm is developed to achieve high-resolution temperature imaging in vivo. The energy transfer between lanthanide ions (Er3+ and Yb3+) and H2O molecules, called the environment quenching assisted downshifting process, is utilized to establish temperature-sensitive emissions at 1550 and 980 nm. Using an optimized thin active shell doped with Yb3+ ions, the nanothermometer's thermal sensitivity and the 1550 nm emission intensity are enhanced by modulating the environment quenching assisted downshifting process. Consequently, minimally invasive temperature imaging of the cerebrovascular system in mice with an imaging resolution of nearly 200 µm is achieved using the nanothermometer. This work points to a method for high-resolution temperature imaging of micron-level structures in vivo, potentially giving insights into research in temperature sensing, disease diagnosis, and treatment development.


Assuntos
Elementos da Série dos Lantanídeos , Animais , Camundongos , Elementos da Série dos Lantanídeos/química , Temperatura , Luminescência , Diagnóstico por Imagem , Íons
11.
Anal Chem ; 96(11): 4430-4436, 2024 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-38447029

RESUMO

Traditional single-molecule fluorescence in situ hybridization (smFISH) methods for RNA detection often face sensitivity challenges due to the low fluorescence intensity of the probe. Also, short-lived autofluorescence complicates obtaining clear signals from tissue sections. In response, we have developed an smFISH probe using highly grafted lanthanide complexes to address both concentration quenching and autofluorescence background. Our approach involves an oligo PCR incorporating azide-dUTP, enabling conjugation with lanthanide complexes. This method has proven to be stable, convenient, and cost-effective. Notably, for the mRNA detection in SKBR3 cells, the lanthanide probe group exhibited 2.5 times higher luminescence intensity and detected 3 times more signal points in cells compared with the Cy3 group. Furthermore, we successfully applied the probe to image HER2 mRNA molecules in breast cancer FFPE tissue sections, achieving a 2.7-fold improvement in sensitivity compared to Cy3-based probes. These results emphasize the potential of time-resolved smFISH as a highly sensitive method for nucleic acid detection, free of background fluorescence interference.


Assuntos
Elementos da Série dos Lantanídeos , Hibridização in Situ Fluorescente/métodos , RNA/análise , RNA Mensageiro/genética , Diagnóstico por Imagem
12.
Int J Biol Macromol ; 265(Pt 2): 131011, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38518947

RESUMO

Preserving fish meat poses a significant challenge due to its high protein and low fat content. This study introduces a novel approach that utilizes a common type of lanthanide metal-organic frameworks (Ln-MOFs), EuMOFs, in combination with 5-fluorescein isothiocyanate (FITC) and methylcellulose (MC) to develop fluorescent sensor arrays for real-time monitoring the freshness of fish meat. The EuMOF-FITC/MC fluorescence films were characterized with excellent fluorescence response, ideal morphology, good mechanical properties, and improved hydrophobicity. The efficacy of the fluorescence sensor array was evaluated by testing various concentrations of spoilage gases (such as ammonia, dimethylamine, and trimethylamine) within a 20-min timeframe using a smartphone-based camera obscura device. This sensor array enables the real-time monitoring of fish freshness, with the ability to preliminarily identify the freshness status of mackerel meat with the naked eye. Furthermore, the study employed four convolutional neural network (CNN) models to enhance the performance of freshness assessment, all of which achieved accuracy levels exceeding 93 %. Notably, the ResNext-101 model demonstrated a particularly high accuracy of 98.97 %. These results highlight the potential of the EuMOF-based fluorescence sensor array, in conjunction with the CNN model, as a reliable and accurate method for real-time monitoring the freshness of fish meat.


Assuntos
Aprendizado Profundo , Isotiocianatos , Elementos da Série dos Lantanídeos , Animais , Fluoresceína-5-Isotiocianato , Peixes , Corantes , Fluoresceína
13.
Acta Crystallogr D Struct Biol ; 80(Pt 4): 289-298, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38512071

RESUMO

Lanthanide ions have ideal chemical properties for catalysis, such as hard Lewis acidity, fast ligand-exchange kinetics, high coordination-number preferences and low geometric requirements for coordination. As a result, many small-molecule lanthanide catalysts have been described in the literature. Yet, despite the ability of enzymes to catalyse highly stereoselective reactions under gentle conditions, very few lanthanoenzymes have been investigated. In this work, the mononuclear binding of europium(III) and gadolinium(III) to the active site of a mutant of the model enzyme phosphotriesterase are described using X-ray crystallography at 1.78 and 1.61 Šresolution, respectively. It is also shown that despite coordinating a single non-natural metal cation, the PTE-R18 mutant is still able to maintain esterase activity.


Assuntos
Elementos da Série dos Lantanídeos , Metaloproteínas , Hidrolases de Triester Fosfórico , Hidrolases de Triester Fosfórico/química , Hidrolases de Triester Fosfórico/metabolismo , Domínio Catalítico , Gadolínio , Európio , Cátions
14.
ACS Appl Bio Mater ; 7(4): 2460-2471, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38517347

RESUMO

Here, we demonstrate a label-free dual optical response strategy for the detection of cytochrome c (Cyt c) with ultrahigh sensitivity using highly luminescent lanthanides containing inorganic-organic hybrid nanotubular sensor arrays. These sensor arrays are formed by the sequential incorporation of the photosensitizers 2,3-dihydroxynaphthalene (DHN) or 1,10-phenanthroline (Phen), and trivalent lanthanide terbium ions (Tb3+) into sodium lithocholate (NaLC) nanotube templates. Our sensing platform relies on the detection and quantification of Cyt c in solution by providing dual photoluminescence quenching responses from the nanotubular hybrid arrays in the presence of Cyt c. The large quenching of the sensitized Tb3+ emission within the DHN/Phen-Tb3+-NaLC nanotubular sensor arrays caused by the strong binding of the photosensitizers to Cyt c provides an important signal response for the selective detection of Cyt c. This long-lived lanthanide emission response-based sensing strategy can be highly advantageous for the detection of Cyt c in a cellular environment eliminating background fluorescence and scattering signals through time-gated measurements. The DHN containing nanotubular sensor arrays (DHN-NaLC and DHN-Tb3+-NaLC) provide an additional quenching response characterized by a unique spectral valley splitting with quantized quenching dip on the DHN fluorescence emission. This spectral quenching dip resulting from efficient FRET between the protein bound DHN photosensitizer and the heme group of Cyt c serves as an important means for specific detection and quantification of Cyt c in the concentration range of 0-30 µM with a low detection limit of around 20 nM.


Assuntos
Elementos da Série dos Lantanídeos , Elementos da Série dos Lantanídeos/química , Citocromos c , Fármacos Fotossensibilizantes , Térbio/química , Luminescência
15.
Anal Chem ; 96(11): 4612-4622, 2024 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-38462905

RESUMO

The iron nanozyme-based colorimetric method, which is widely applied for biosubstrate detection in in vitro diagnosis (IVD), faces some limitations. The optimal catalytic conditions of iron nanozymes necessitate a strong acidic environment, high temperature, and other restrictive factors; additionally, the colorimetric results are highly influenced by optical interferences. To address these challenges, iron nanozymes doped with various transition elements were efficiently prepared in this study, and notably, the manganese-modified one displayed a high catalytic activity owing to its electron transfer property. Furthermore, the introduction of lanthanide ions into the catalytic reactions, specifically the neodymium ion, significantly boosted the generation efficiency of hydroxyl radicals; importantly, this enhancement extended to a wide range of pH levels and temperatures, amplifying the detection signal. Moreover, the nanozyme's superparamagnetic characteristic was also employed to perform a logical optical and magnetic resonance dual-modality detection for substrates, effectively eliminating background optical interference and ensuring a reliable verification of the signal's authenticity. Based on this magnetic signal, the integration of natural glucose oxidase with the nanozyme resulted in a notable 61.5% increase in detection sensitivity, surpassing the capabilities of the traditional colorimetric approach. Consequently, the incorporation of lanthanide ions into the magnetic nanozyme enables the effective identification of physiological biomarkers through the dual-modality signal. This not only guarantees enhanced sensitivity but also demonstrates significant potential for future applications.


Assuntos
Elementos da Série dos Lantanídeos , Imageamento por Ressonância Magnética , Ferro , Espectroscopia de Ressonância Magnética , Íons/química , Colorimetria/métodos , Peróxido de Hidrogênio
16.
Molecules ; 29(6)2024 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-38542988

RESUMO

Magnetic nanoparticles (MNPs), either paramagnetic or superparamagnetic depending on their composition and size, have been thoroughly studied as magnetic resonance imaging (MRI) contrast agents using in vitro and in vivo biomedical preclinical studies, while some are clinically used. Their magnetic properties responsible in some cases for high magnetization values, together with large surface area-to-volume ratios and the possibility of surface functionalization, have been used in MRI-based diagnostic and theranostics applications. MNPs are usually used as positive (T1) or negative (T2) MRI contrast agents, causing brightening or darkening of selected regions in MRI images, respectively. This review focusses on recent developments and optimization of MNPs containing Gd, Mn, Fe and other lanthanide ions which may function as dual-mode T1-T2 MRI contrast agents (DMCAs). They induce positive or negative contrast in the same MRI scanner upon changing its operational mode between T1-weighted and T2-weighted pulse sequences. The type of contrast they induce depends critically on their r2/r1 relaxivity ratio, which for DMCAs should be in the 2-10 range of values. After briefly discussing the basic principles of paramagnetic relaxation in MNPs, in this review, the basic strategies for the rational design of DMCAs are presented and typical examples are discussed, including in vivo preclinical applications: (1) the use of NPs with a single type of contrast material, Gd- or Mn-based NPs or superparamagnetic NPs with appropriate size and magnetization to provide T2 and T1 contrast; and (2) inclusion of both types of T1 and T2 contrast materials in the same nanoplatform by changing their relative positions.


Assuntos
Elementos da Série dos Lantanídeos , Nanopartículas de Magnetita , Meios de Contraste , Imageamento por Ressonância Magnética/métodos , Gadolínio
17.
Environ Monit Assess ; 196(4): 399, 2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38532156

RESUMO

Plankton plays a very crucial role in bioaccumulation and transfer of metals in the marine food web and represents a suitable bioindicator of the occurrence of trace and rare earth elements in the ecosystem. Trace elements and REEs were analyzed by ICP-MS in phytoplankton samples from the northwestern Mediterranean Sea. Metal concentrations in phytoplankton were found strongly influenced by seasons and depth of collection (- 30 m, - 50 m). Principal component analysis (PCA) has shown that Al, As, Cr, Cu, Ga, and Sn concentrations were related to summer and autumn in samples collected at 30 m depth, while Fe, Mn, Ni, V, and Zn levels related strongly with summer and spring at 50 m depth. Fe, Al, and Zn were the most represented elements in all samples (mean values respectively in the ranges 4.2-8.2, 9.6-13, and 1.0-4.4 mg kg-1) according to their widespread presence in the environment and in the earth crust. Principal component analysis (PCA) performed on REEs showed that mostly all lanthanides' concentrations strongly correlate with summer and autumn seasons (- 30 m depth); the highest ∑REE concentration (75 µg kg-1) was found in winter. Phytoplankton REE normalized profile was comparable to those of other marine biota collected in the same area according to the suitability of lanthanides as geological tracers.


Assuntos
Elementos da Série dos Lantanídeos , Metais Terras Raras , Oligoelementos , Ecossistema , Fitoplâncton , Monitoramento Ambiental , Metais Terras Raras/análise , Oligoelementos/análise , Elementos da Série dos Lantanídeos/análise , Itália
18.
Int J Biol Macromol ; 264(Pt 2): 130768, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38467228

RESUMO

Lanthanide luminescent hydrogels have broad application prospects in various fields. However, most of lanthanide hydrogels possess relatively simple functions, which is not conducive to practical applications. Therefore, it is becoming increasingly urgent to develop multifunctional hydrogels. Herein, a multifunctional chitosan-based lanthanide luminescent hydrogel with ultra-stretchability, multi-adhesion, excellent self-healing, emission color tunability, and good antibacterial ability was prepared by a simple one-step free radical polymerization. In this work, our designed lanthanide complexes [Ln(4-VDPA)3] contain three reaction sites, which can be copolymerized with N-[tris(hydroxymethyl) methyl] acrylamide (THMA), acrylamide (AM), and diacryloyl poly(ethylene glycol) (DPEG) to form the first chemical crosslinking network, while hydroxypropyltrimethyl ammonium chloride chitosan (HACC) interacts with the hydroxyl and amino groups derived from the chemical crosslinking network through hydrogen bonds to form the second physical crosslinking network. The structure of the double network as well as the dynamic hydrogen bond and lanthanide coordination endow the hydrogel with excellent stretchability, adhesion and self-healing properties. Moreover, the introduction of lanthanide complexes and chitosan makes the hydrogel exhibit outstanding luminescence and antibacterial performances. This research not only realizes the simple synthesis of multifunctional luminescent hydrogels, but also provides a new idea for the fabrication of biomass-based hydrogels as intelligent and sustainable materials.


Assuntos
Quitosana , Elementos da Série dos Lantanídeos , Prunella , Hidrogéis , Luminescência , Acrilamida , Antibacterianos/farmacologia , Aderências Teciduais
19.
Chemosphere ; 353: 141509, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38403125

RESUMO

The release of lanthanides (Ln) into the environment has increased in recent decades due to their expanding applications in society. Studying their toxicity in aquatic ecosystems is urgent and challenging, with contradictory evidence presented in the literature. This study compared the biodistribution of La and Gd in Daphnia magna exposed to sub-chronic conditions and developed the first Toxicokinetic-Toxicodynamic (TKTD) model for these lanthanides with this model crustacean. D. magna were initially exposed for 7 days to concentrations close to the LC50 of La (2.10 mg L-1) and Gd (1.70 mg L-1). After exposure, half of the live daphnids were introduced in a clean media to allow depuration over 24 h, while the other organisms were directly prepared for synchrotron imaging measurements. Synchrotron X-ray fluorescence analysis revealed that metal distribution in the organisms was similar for both La and Gd, predominantly localized in the intestinal tract, even after the depuration process. These results indicate that ingested metal can adversely affect organisms under sub-chronic exposure conditions, highlighting the importance of using nominal concentrations as a more suitable indicator of metal bioavailability for risk assessment. The General Unified Threshold Model of Survival (GUTS) TKTD framework, in its reduced form (GUTS-RED), was developed for La and Gd using dissolved and nominal concentrations. D. magna were exposed for 7 days to concentrations from 0.5 to 5 mg L-1 of La or Gd and mortality monitored daily. The mechanistic model revealed a faster toxicokinetics for La than Gd and a higher toxicity for Gd than La in the organism. This study confirmed, despite similar chemical properties, the variation in both toxicity and toxicokinetics between these two metals.


Assuntos
Elementos da Série dos Lantanídeos , Poluentes Químicos da Água , Animais , Daphnia magna , Raios X , Daphnia , Ecossistema , Síncrotrons , Distribuição Tecidual , Imagem Óptica , Poluentes Químicos da Água/toxicidade
20.
Sci Total Environ ; 922: 171115, 2024 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-38401730

RESUMO

In the current context of water environmental monitoring and pollution control, there's a crucial need for rapid and simple methods to detect multi-pollutant. We herein report an easy one-step hydrothermal synthesis method to produce Eu-based metal-organic frameworks (Eu MOFs), which was used as a fluorescent probe to detect the aquatic environmental pollutants of ciprofloxacin (CIP) and aluminum ions (Al3+). This fluorescent sensor enabled the cascade detection of CIP and Al3+ through fluorescence enhancement and ratio fluorescence response, respectively. The introduction of CIP significantly turned on the characteristic fluorescence of Eu MOFs at 595 nm and 616 nm through the "antenna effect". Based on this, the sensor enables quantitative detection of CIP within a linear range of 0-120 µM with a LOD as low as 50.421 nM. In the presence of Al3+, the fluorescence emission of Eu MOFs-CIP was sharply turned off due to strong Al3+ coordination with CIP, while the blue fluorescence emission of CIP was remarkably enhanced. And thus allowing ratio fluorescence quantitative detection of Al3+ (LOD = 2.681 µM). The introduction of CIP and Al3+ in cascade resulted in distinct fluorescence color changes from colorless to red and eventually to blue, exhibiting pronounced fluorescence characteristics. This observable phenomenon enables the visual detection of CIP and Al3+ in both aqueous phase and paper test strips. By combining the analysis of fluorescence chromaticity with the use of a smartphone, the fluorescence color of test papers allows for simple quantitative determination, which provides a convenient and accessible approach for quantifying CIP and Al3+ in water environments.


Assuntos
Poluentes Ambientais , Elementos da Série dos Lantanídeos , Ciprofloxacina , Espectrometria de Fluorescência , Água , Corantes Fluorescentes
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