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1.
FEMS Microbiol Ecol ; 100(8)2024 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-38955392

RESUMO

Guaymas Basin, located in the Gulf of California, is a hydrothermally active marginal basin. Due to steep geothermal gradients and localized heating by sill intrusions, microbial substrates like short-chain fatty acids and hydrocarbons are abiotically produced from sedimentary organic matter at comparatively shallow depths. We analyzed the effect of hydrocarbons on uptake of hydrocarbons by microorganisms via nano-scale secondary ion mass spectrometry (NanoSIMS) and microbial sulfate reduction rates (SRR), using samples from two drill sites sampled by IODP Expedition 385 (U1545C and U1546D). These sites are in close proximity of each other (ca. 1 km) and have very similar sedimentology. Site U1546D experienced the intrusion of a sill that has since then thermally equilibrated with the surrounding sediment. Both sites currently have an identical geothermal gradient, despite their different thermal history. The localized heating by the sill led to thermal cracking of sedimentary organic matter and formation of potentially bioavailable organic substrates. There were low levels of hydrocarbon and nitrogen uptake in some samples from both sites, mostly in surficial samples. Hydrocarbon and methane additions stimulated SRR in near-seafloor samples from Site U1545C, while samples from Site U1546D reacted positively only on methane. Our data indicate the potential of microorganisms to metabolize hydrocarbons even in the deep subsurface of Guaymas Basin.


Assuntos
Sedimentos Geológicos , Hidrocarbonetos , Sedimentos Geológicos/microbiologia , Hidrocarbonetos/metabolismo , Bactérias/metabolismo , Bactérias/genética , Sulfatos/metabolismo , Metano/metabolismo , Espectrometria de Massa de Íon Secundário , Água do Mar/microbiologia , Nitrogênio/metabolismo
2.
J Hazard Mater ; 477: 135278, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-39047566

RESUMO

Human hair has become a promising non-invasive matrix in assessing exposure to environmental organic pollutants (OPs). However, exogenous contaminants, which were absorbed into the hair via sweat, sebum, and air particles/dust, could contribute to OP levels in hair and interfere with the precise exposure assessment. So far, the microscopic mechanisms underlying the absorption of exogenous OPs into hair remain inadequately understood. This study focused on the in-situ investigation of the diffusion processes of exogenous OPs into the hair structure using secondary ion mass spectrometry (SIMS) and isotopic tracer techniques. Results showed that the relative signal intensities of deuterium-labeled tris(1,3-dichloro-2-propyl) phosphate (TDCPP), 1-hydroxypyrene (1-OH-Pry), and bisphenol A (BPA) in the hair cortex were notably elevated after a 6-hour exposure. Diffusion coefficients of contaminants were related to their molecular weight, and absorption volumes to their water solubility and molecular structures. Exposure duration and solvent influenced the rate of diffusion and absorption volumes. The distribution of deuterium-labeled molecules in exposed hair samples after washing with two different solvents (acetone or water) was similar to that before washing. Our findings revealed the diffusion of OPs in hair cross-sections, indicating exogenous contributions to contaminants that are biologically incorporated into the hair.


Assuntos
Poluentes Ambientais , Cabelo , Espectrometria de Massa de Íon Secundário , Humanos , Cabelo/química , Poluentes Ambientais/química , Poluentes Ambientais/análise , Compostos Benzidrílicos/análise , Compostos Benzidrílicos/química , Fenóis/análise , Fenóis/química , Feminino , Compostos Orgânicos/análise , Compostos Orgânicos/química , Adulto , Monitoramento Ambiental/métodos , Difusão
3.
Sci Rep ; 14(1): 14980, 2024 07 01.
Artigo em Inglês | MEDLINE | ID: mdl-38951137

RESUMO

Polyethylene glycols (PEGs) are used in industrial, medical, health care, and personal care applications. The cycling and disposal of synthetic polymers like PEGs pose significant environmental concerns. Detecting and monitoring PEGs in the real world calls for immediate attention. This study unveils the efficacy of time-of-flight secondary ion mass spectrometry (ToF-SIMS) as a reliable approach for precise analysis and identification of reference PEGs and PEGs used in cosmetic products. By comparing SIMS spectra, we show remarkable sensitivity in pinpointing distinctive ion peaks inherent to various PEG compounds. Moreover, the employment of principal component analysis effectively discriminates compositions among different samples. Notably, the application of SIMS two-dimensional image analysis visually portrays the spatial distribution of various PEGs as reference materials. The same is observed in authentic cosmetic products. The application of ToF-SIMS underscores its potential in distinguishing PEGs within intricate environmental context. ToF-SIMS provides an effective solution to studying emerging environmental challenges, offering straightforward sample preparation and superior detection of synthetic organics in mass spectral analysis. These features show that SIMS can serve as a promising alternative for evaluation and assessment of PEGs in terms of the source, emission, and transport of anthropogenic organics.


Assuntos
Cosméticos , Polietilenoglicóis , Espectrometria de Massa de Íon Secundário , Cosméticos/análise , Cosméticos/química , Espectrometria de Massa de Íon Secundário/métodos , Polietilenoglicóis/química , Polietilenoglicóis/análise , Análise de Componente Principal
4.
J Oleo Sci ; 73(6): 825-837, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38825536

RESUMO

Hair is important to our appearance as well as to protect our heads. Human hair mainly consists of proteins (80-85%), melanin pigments (0-5%), water (10-13%), and lipids (1-6%). The physicochemical properties of hair have been studied for over 100 years. However, they are not yet thoroughly understood. In this review, recent progress and the latest findings are summarized from the following three perspectives: structural characteristics, delivery and distribution of active ingredients, and hair as a template. The structural characteristics of hair have been mainly investigated by microscopic and/or spectroscopic techniques such as atomic force microscopy integrated with infrared spectroscopy (AFM-IR) and rheological measurements. The distribution of active ingredients has been generally evaluated through techniques such as nanoscale secondary ion mass spectrometry (NanoSIMS). And finally, attempts to explore the potential of hair to be used as a substrate for flexible device fabrication will be introduced.


Assuntos
Cabelo , Cabelo/química , Humanos , Microscopia de Força Atômica , Melaninas , Fenômenos Químicos , Espectrometria de Massa de Íon Secundário/métodos , Reologia , Espectrofotometria Infravermelho/métodos , Lipídeos/análise , Lipídeos/química , Água , Proteínas/análise
5.
Methods Cell Biol ; 186: 213-231, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38705600

RESUMO

Advancements in multiplexed tissue imaging technologies are vital in shaping our understanding of tissue microenvironmental influences in disease contexts. These technologies now allow us to relate the phenotype of individual cells to their higher-order roles in tissue organization and function. Multiplexed Ion Beam Imaging (MIBI) is one of such technologies, which uses metal isotope-labeled antibodies and secondary ion mass spectrometry (SIMS) to image more than 40 protein markers simultaneously within a single tissue section. Here, we describe an optimized MIBI workflow for high-plex analysis of Formalin-Fixed Paraffin-Embedded (FFPE) tissues following antigen retrieval, metal isotope-conjugated antibody staining, imaging using the MIBI instrument, and subsequent data processing and analysis. While this workflow is focused on imaging human FFPE samples using the MIBI, this workflow can be easily extended to model systems, biological questions, and multiplexed imaging modalities.


Assuntos
Inclusão em Parafina , Humanos , Inclusão em Parafina/métodos , Espectrometria de Massa de Íon Secundário/métodos , Fixação de Tecidos/métodos , Processamento de Imagem Assistida por Computador/métodos , Formaldeído/química
6.
Aquat Toxicol ; 271: 106935, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38723468

RESUMO

Blood lipid-lowering agents, such as Pravastatin, are among the most frequently used pharmaceuticals released into the aquatic environment. Although their effects on humans are very well understood, their consequences on freshwater organisms are not well known, especially in chronic exposure conditions. Gammarus fossarum is commonly used as sentinel species in ecotoxicology because of its sensitivity to a wide range of environmental contaminants and the availability of standardized bioassays. Moreover, there is an increased interest in linking molecular changes in sentinel species, such as gammarids, to observed toxic effects. Here, we performed a reproductive toxicity assay on females exposed to different concentrations of pravastatin (30; 300; 3,000 and 30,000 ng L-1) during two successive reproductive cycles and we applied ToF-SIMS imaging to evaluate the effect of pravastatin on lipid homeostasis in gammarids. Reproductive bioassay showed that pravastatin could affect oocyte development in Gammarus fossarum inducing embryotoxicity in the second reproductive cycle. Mass spectrometry imaging highlighted the disruption in vitamin E production in the oocytes of exposed female gammarids at the second reproductive cycle, while limited alterations were observed in other lipid classes, regarding both production and tissue distribution. The results demonstrated the interest of applying spatially resolved lipidomics by mass spectrometry imaging to assess the molecular effects induced by long-term exposure to environmental pharmaceutical residues in sentinel species.


Assuntos
Anfípodes , Pravastatina , Reprodução , Poluentes Químicos da Água , Animais , Pravastatina/toxicidade , Poluentes Químicos da Água/toxicidade , Feminino , Anfípodes/efeitos dos fármacos , Reprodução/efeitos dos fármacos , Espectrometria de Massa de Íon Secundário , Oócitos/efeitos dos fármacos , Vitamina E
7.
Environ Pollut ; 355: 124197, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38782163

RESUMO

The presence and accumulation of both, plastics and antibiotics in soils may lead to the colonization, selection, and propagation of soil bacteria with certain metabolic traits, e.g., antibiotic resistance, in the plastisphere. However, the impact of plastic-antibiotic tandem on the soil ecosystem functioning, particularly on microbial function and metabolism remains currently unexplored. Herein, we investigated the competence of soil bacteria to colonize plastics and degrade 13C-labeled sulfamethoxazole (SMX). Using single-cell imaging, isotope tracers, soil respiration and SMX mineralization bulk measurements we show that microbial colonization of polyethylene (PE) and polystyrene (PS) surfaces takes place within the first 30 days of incubation. Morphologically diverse microorganisms were colonizing both plastic types, with a slight preference for PE substrate. CARD-FISH bacterial cell counts on PE and PS surfaces formed under SMX amendment ranged from 5.36 × 103 to 2.06 × 104, and 2.06 × 103 to 3.43 × 103 hybridized cells mm-2, respectively. Nano-scale Secondary Ion Mass Spectrometry measurements show that 13C enrichment was highest at 130 days with values up to 1.29 atom%, similar to those of the 13CO2 pool (up to 1.26 atom%, or 22.55 ‰). Independent Mann-Whitney U test showed a significant difference between the control plastisphere samples incubated without SMX and those in 13C-SMX incubations (P < 0.001). Our results provide direct evidence demonstrating, at single-cell level, the capacity of bacterial colonizers of plastics to assimilate 13C-SMX from contaminated soils. These findings expand our knowledge on the role of soil-seeded plastisphere microbiota in the ecological functioning of soils impacted by anthropogenic stressors.


Assuntos
Microbiologia do Solo , Poluentes do Solo , Solo , Sulfametoxazol , Sulfametoxazol/metabolismo , Poluentes do Solo/metabolismo , Solo/química , Análise de Célula Única , Bactérias/metabolismo , Isótopos de Carbono , Plásticos/metabolismo , Antibacterianos , Espectrometria de Massa de Íon Secundário
8.
Food Chem ; 452: 139556, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-38744133

RESUMO

This study explores the molecular interactions and structural changes in κ-carrageenan crosslinked with isovanillin to create a biocomposite material suitable for hard capsule and bio-degradable packaging applications. Proton Nuclear Magnetic Resonance (1H NMR) spectroscopy revealed chemical changes in the conjugate molecule, indicating improved electronegativity due to intermolecular hydrogen bonding between κ-carrageenan and isovanillin. Time-of-flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis revealed enhanced ion intensity due to intermolecular interactions, particularly between sulphate and hydrogen ions. X-ray Photoelectron Spectroscopy (XPS) study demonstrated that κ-carrageenan and isovanillin form stronger hydrogen bonds, with a shift in binding energy indicating higher electronegativity. These findings shed light on the molecular mechanisms that underpin the formation of the biocomposite material, as well as its potential for use in hard capsule and biodegradable packaging materials, addressing the need for sustainable alternatives in the pharmaceutical and packaging industries while also contributing to environmental conservation.


Assuntos
Carragenina , Embalagem de Alimentos , Espectroscopia de Ressonância Magnética , Espectroscopia Fotoeletrônica , Espectrometria de Massa de Íon Secundário , Carragenina/química , Embalagem de Alimentos/instrumentação , Ligação de Hidrogênio , Embalagem de Medicamentos , Benzaldeídos
9.
J Mass Spectrom ; 59(5): e5016, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38625003

RESUMO

The use of mass spectrometry (MS) to acquire molecular images of biological tissues and other substrates has developed into an indispensable analytical tool over the past 25 years. Imaging mass spectrometry technologies are widely used today to study the in situ spatial distributions for a variety of analytes. Early MS images were acquired using secondary ion mass spectrometry and matrix-assisted laser desorption/ionization. Researchers have also designed and developed other ionization techniques in recent years to probe surfaces and generate MS images, including desorption electrospray ionization (DESI), nanoDESI, laser ablation electrospray ionization, and infrared matrix-assisted laser desorption electrospray ionization. Investigators now have a plethora of ionization techniques to select from when performing imaging mass spectrometry experiments. This brief perspective will highlight the utility and relative figures of merit of these techniques within the context of their use in imaging mass spectrometry.


Assuntos
Espectrometria de Massa de Íon Secundário , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz
10.
Environ Microbiol ; 26(4): e16625, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38653479

RESUMO

Diatoms can survive long periods in dark, anoxic sediments by forming resting spores or resting cells. These have been considered dormant until recently when resting cells of Skeletonema marinoi were shown to assimilate nitrate and ammonium from the ambient environment in dark, anoxic conditions. Here, we show that resting cells of S. marinoi can also perform dissimilatory nitrate reduction to ammonium (DNRA), in dark, anoxic conditions. Transmission electron microscope analyses showed that chloroplasts were compacted, and few large mitochondria had visible cristae within resting cells. Using secondary ion mass spectrometry and isotope ratio mass spectrometry combined with stable isotopic tracers, we measured assimilatory and dissimilatory processes carried out by resting cells of S. marinoi under dark, anoxic conditions. Nitrate was both respired by DNRA and assimilated into biomass by resting cells. Cells assimilated nitrogen from urea and carbon from acetate, both of which are sources of dissolved organic matter produced in sediments. Carbon and nitrogen assimilation rates corresponded to turnover rates of cellular carbon and nitrogen content ranging between 469 and 10,000 years. Hence, diatom resting cells can sustain their cells in dark, anoxic sediments by slowly assimilating and respiring substrates from the ambient environment.


Assuntos
Compostos de Amônio , Diatomáceas , Nitratos , Oxirredução , Nitratos/metabolismo , Compostos de Amônio/metabolismo , Diatomáceas/metabolismo , Anaerobiose , Escuridão , Compostos Orgânicos/metabolismo , Espectrometria de Massa de Íon Secundário , Sedimentos Geológicos/microbiologia , Carbono/metabolismo , Nitrogênio/metabolismo
11.
Talanta ; 272: 125762, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38394748

RESUMO

Membrane lipids have been known to influence multiple signalling and cellular processes. Dysregulation of lipids at the neuronal membrane is connected to a significant alteration of the brain function and morphology, leading to brain diseases and neurodegeneration. Understanding the lipid composition and turnover of neuronal membrane will provide a significant insight into the molecular events underlying the regulatory effects of these biomolecules in a neuronal system. In this study, we aimed to characterize the composition and turnover of the plasma membrane lipids in human neural progenitor cells (NPCs) at an early differentiation stage into midbrain neurons using ToF-SIMS imaging. Lipid composition of the native plasma membrane was explored, followed by an examination of the lipid turnover using different isotopically labelled lipid precursors, including 13C-choline, 13C-lauric acid, 15N-linoleic, and 13C-stearic. Our results showed that differentiating NPCs contain a high abundance of ceramides, glycerophosphoserines, neutral glycosphingolipids, diradylglycerols, and glycerophosphocholines at the plasma membrane. In addition, different precursors were found to incorporate into different membrane lipids which are specific for the short- or long-carbon chains, and the unsaturation or saturation stage of the precursors. The lipid structure of neuronal membrane reflects the differentiation status of NPCs, and it can be altered significantly using a particular lipid precursor. Our study illustrates a potential of ToF-SIMS imaging to study native plasma membrane lipids and elucidate complex cellular processes by providing molecular -rich information at a single cell level.


Assuntos
Lipídeos de Membrana , Espectrometria de Massa de Íon Secundário , Humanos , Espectrometria de Massa de Íon Secundário/métodos , Membrana Celular , Membranas , Células-Tronco
12.
Caries Res ; 58(4): 407-420, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38330936

RESUMO

INTRODUCTION: The aim of this in vitro study was to assess the suitability of high-resolution time-of-flight secondary ion mass spectrometry (ToF-SIMS) for visualizing cross-sectional changes in human enamel microstructure and chemical composition during treatment and remineralization cycling of artificially generated caries lesions underneath an artificial plaque. METHODS: Treatments consisted of exposure to twice daily toothpaste/water slurries prepared from 0, 1,100, and 5,000 µg/g fluoride (F) NaF/silica toothpastes. In addition, treatments with slurries prepared from 1,100 µg/g F SnF2/silica toothpastes were done using 44Ca in the remineralization solution to allow for differentiation of newly formed mineral and exploration of incorporated metal dopants using ToF-SIMS. Complementary microhardness, scanning electron microscopy, and high-resolution transmission electron microscopy (HR-TEM) investigations were performed on enamel cross sections. RESULTS: HR-TEM was used for the first time to determine the change in crystallinity during remineralization revealing distinct microstructural zones within one lesion. Chemical mapping using ToF-SIMS demonstrated that the distribution of F, while observed primarily in the new mineral phase, was widespread throughout the lesion with 44Ca substantially limited to the remineralizing mineral. Both penetrated the inter-rod spaces of the sound enamel illustrating how acid damage propagates into the native mineral as the caries lesion deepens. HR-TEM examination revealed different regions within the lesion characterized by distinct micro- and ultrastructures. Importantly, HR-TEM revealed a return of crystallinity following remineralization. F dose-response observations verified the ability of these high-resolution techniques to differentiate remineralization efficacy. CONCLUSION: The collective results provided new insights such as the visualization of F or calcium penetration pathways, as well as new tools to study the caries process.


Assuntos
Esmalte Dentário , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Espectrometria de Massa de Íon Secundário , Remineralização Dentária , Remineralização Dentária/métodos , Esmalte Dentário/ultraestrutura , Esmalte Dentário/química , Espectrometria de Massa de Íon Secundário/métodos , Humanos , Cremes Dentais/uso terapêutico , Cremes Dentais/química , Fluoreto de Sódio/uso terapêutico , Dureza , Cálcio/análise , Cariostáticos/uso terapêutico , Cárie Dentária/diagnóstico por imagem , Cárie Dentária/patologia , Fluoretos de Estanho/uso terapêutico , Fluoretos , Dióxido de Silício , Cristalização
13.
Biointerphases ; 19(1)2024 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-38341772

RESUMO

In-source fragmentation (ISF) poses a significant challenge in secondary ion mass spectrometry (SIMS). These fragment ions increase the spectral complexity and can lead to incorrect annotation of fragments as intact species. The presence of salt that is ubiquitous in biological samples can influence the fragmentation and ionization of analytes in a significant manner, but their influences on SIMS have not been well characterized. To elucidate the effect of substrates and salt on ISF in SIMS, we have employed experimental SIMS in combination with atomistic simulations of a sphingolipid on a gold surface with various NaCl concentrations as a model system. Our results revealed that a combination of bond dissociation energy and binding energy between N-palmitoyl-sphingomyelin and a gold surface is a good predictor of fragment ion intensities in the absence of salt. However, ion-fragment interactions play a significant role in determining fragment yields in the presence of salt. Additionally, the charge distribution on fragment species may be a major contributor to the varying effects of salt on fragmentation. This study demonstrates that atomistic modeling can help predict ionization potential when salts are present, providing insights for more accurate interpretations of complex biological spectra.


Assuntos
Cloreto de Sódio , Espectrometria de Massa de Íon Secundário , Seguimentos , Espectrometria de Massa de Íon Secundário/métodos , Íons/química
14.
Eur J Pharm Biopharm ; 196: 114181, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38224755

RESUMO

Hyperpigmentation, a prevalent dermatological condition characterized by melanin overproduction, poses treatment challenges due to the hydrophilicity of alpha-arbutin, a widely utilized tyrosinase inhibitor. This study investigates the efficacy of dissolving microneedles (DMNs) in augmenting skin permeation for alpha-arbutin delivery to the targeted epidermal site. Porcine full-thickness skin was employed in a 24-hour Franz cell study, commencing with the assessment of commercial alpha-arbutin-containing products. Solid steel microneedles (CMNs) from Dermapen® were utilized as both pre- and post-treatment modalities to evaluate the influence of different applications on alpha-arbutin delivery. Additionally, alpha-arbutin-loaded polyvinylpyrrolidone-co-vinyl acetate (PVPVA) DMNs, containing 2 % w/w alpha-arbutin, were fabricated and examined for their permeation-enhancing capabilities. HPLC analysis and 3D Orbitrap Secondary Ion Mass Spectrometry (OrbiSIMS) were employed to quantify and visualize alpha-arbutin in various Franz cell components. Results indicate that alpha-arbutin permeation to the skin was restricted (less than 1 %) without microneedle application and significantly increased by 6-fold (4-5 %) with post-treatment CMNs and DMNs, but not with pre-treatment CMNs. Notably, DMNs exhibited a more sustainable and robust capacity than post-treatment CMNs. OrbiSIMS imaging analysis revealed that DMNs visually enhance skin permeation of alpha-arbutin by delivering the compound to the basal layer of the targeted skin location. Overall, this study underscores the potential of DMNs as a promising delivery system for promoting targeted intradermal delivery of alpha-arbutin, providing a comprehensive exploration of various methodologies to identify innovative and improved microneedle approaches for alpha-arbutin permeation.


Assuntos
Arbutina , Nevo Pigmentado , Neoplasias Cutâneas , Espectrometria de Massa de Íon Secundário , Suínos , Animais , Administração Cutânea , Pele , Epiderme , Polímeros , Agulhas , Sistemas de Liberação de Medicamentos/métodos
15.
Analyst ; 149(3): 846-858, 2024 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-38167886

RESUMO

Lipid alterations in the brain are well-documented in disease and aging, but our understanding of their pathogenic implications remains incomplete. Recent technological advances in assessing lipid profiles have enabled us to intricately examine the spatiotemporal variations in lipid compositions within the complex brain characterized by diverse cell types and intricate neural networks. In this study, we coupled time-of-flight secondary ion mass spectrometry (ToF-SIMS) to an amyotrophic lateral sclerosis (ALS) Drosophila model, for the first time, to elucidate changes in the lipid landscape and investigate their potential role in the disease process, serving as a methodological and analytical complement to our prior approach that utilized matrix-assisted laser desorption/ionization mass spectrometry. The expansion of G4C2 repeats in the C9orf72 gene is the most prevalent genetic factor in ALS. Our findings indicate that expressing these repeats in fly brains elevates the levels of fatty acids, diacylglycerols, and ceramides during the early stages (day 5) of disease progression, preceding motor dysfunction. Using RNAi-based genetic screening targeting lipid regulators, we found that reducing fatty acid transport protein 1 (FATP1) and Acyl-CoA-binding protein (ACBP) alleviates the retinal degeneration caused by G4C2 repeat expression and also markedly restores the G4C2-dependent alterations in lipid profiles. Significantly, the expression of FATP1 and ACBP is upregulated in G4C2-expressing flies, suggesting their contribution to lipid dysregulation. Collectively, our novel use of ToF-SIMS with the ALS Drosophila model, alongside methodological and analytical improvements, successfully identifies crucial lipids and related genetic factors in ALS pathogenesis.


Assuntos
Esclerose Lateral Amiotrófica , Animais , Esclerose Lateral Amiotrófica/genética , Esclerose Lateral Amiotrófica/metabolismo , Drosophila , Espectrometria de Massa de Íon Secundário , Lipídeos
16.
Anal Chem ; 96(9): 3717-3721, 2024 03 05.
Artigo em Inglês | MEDLINE | ID: mdl-38262943

RESUMO

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has become a promising analytical tool for molecular profiling in biological applications. However, its ultrahigh vacuum environment and matrix effects hamper the absolute quantitation of solution samples. Herein, we present a rapid high-throughput platform for quantitative ToF-SIMS analysis of amino acids in matrix deposits formed from freeze-dried solution drops through ice sublimation on a parylene film microarray substrate. Droplets of the amino acid solutions, which were mixed with stable isotope-labeled phenylalanine (F*) of high concentration (10 mM), were loaded on wells of the microarray, then frozen and evaporated slowly below the freezing point, forming continuous solid-phase F* matrix deposits. The amino acids (≤500 µM), adequately well dispersed throughout the F* matrix deposits on each well, were quantitatively analyzed by ToF-SIMS in a rapid and high-throughput fashion. The lower limit of quantitation reached below 10 µM.


Assuntos
Aminoácidos , Espectrometria de Massa de Íon Secundário , Espectrometria de Massa de Íon Secundário/métodos , Congelamento , Fenilalanina , Análise em Microsséries
17.
Rapid Commun Mass Spectrom ; 38(2): e9658, 2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-38124172

RESUMO

RATIONALE: The use of secondary ion mass spectrometry (SIMS) to perform micrometer-scale in situ carbon isotope (δ13 C) analyses of shells of marine microfossils called planktic foraminifers holds promise to explore calcification and ecological processes. The potential of this technique, however, cannot be realized without comparison to traditional whole-shell δ13 C values measured by gas source mass spectrometry (GSMS). METHODS: Paired SIMS and GSMS δ13 C values measured from final chamber fragments of the same shell of the planktic foraminifer Orbulina universa are compared. The SIMS-GSMS δ13 C differences (Δ13 CSIMS-GSMS ) were determined via paired analysis of hydrogen peroxide-cleaned fragments of modern cultured specimens and of fossil specimens from deep-sea sediments that were either untreated, sonicated, and cleaned with hydrogen peroxide or vacuum roasted. After treatment, fragments were analyzed by a CAMECA IMS 1280 SIMS instrument and either a ThermoScientific MAT-253 or a Fisons Optima isotope ratio mass spectrometer (GSMS). RESULTS: Paired analyses of cleaned fragments of cultured specimens (n = 7) yield no SIMS-GSMS δ13 C difference. However, paired analyses of untreated (n = 18) and cleaned (n = 12) fragments of fossil shells yield average Δ13 CSIMS-GSMS values of 0.8‰ and 0.6‰ (±0.2‰, 2 SE), respectively, while vacuum roasting of fossil shell fragments (n = 11) removes the SIMS-GSMS δ13 C difference. CONCLUSIONS: The noted Δ13 CSIMS-GSMS values are most likely due to matrix effects causing sample-standard mismatch for SIMS analyses but may also be a combination of other factors such as SIMS measurement of chemically bound water. The volume of material analyzed via SIMS is ~105 times smaller than that analyzed by GSMS; hence, the extent to which these Δ13 CSIMS-GSMS values represent differences in analyte or instrument factors remains unclear.


Assuntos
Peróxido de Hidrogênio , Espectrometria de Massa de Íon Secundário , Espectrometria de Massa de Íon Secundário/métodos , Isótopos de Carbono/análise , Gases
18.
Astrobiology ; 24(1): 61-83, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38109217

RESUMO

Laser desorption-ionization mass spectrometry (MS) shows great potential for in situ molecular analysis of planetary surfaces and microanalysis of space-returned samples or (micro)fossils. Coupled with pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) in ESA's ExoMars project, this technique could help assess further the origin of sulfur-bearing organic matter (OM) recently detected on Mars. To unravel this potential, we analyzed sulfurized microbial OM from ca. 150 million year-old carbonates with laser desorption-ionization mass spectrometry (single- and two-step: LDI-MS and L2MS), in comparison with time-of-flight secondary-ion mass spectrometry (ToF-SIMS), gas chromatography-mass spectrometry (GC-MS), and Py-GC-MS. We show that LDI-MS and L2MS readily detect sulfur-bearing moieties such as (alkyl)thiophenes and (alkyl)benzothiophenes. The mineral matrix, however, made the identification of sulfur-bearing molecules challenging in our L2MS experiment. The dominance of small aromatic hydrocarbons (≤14 carbons) in the LDI-MS and L2MS of the extracted soluble and insoluble OM and of the bulk rock is consistent with the low thermal maturity of the sediment and contrasts with the predominance of larger polycyclic aromatic structures commonly observed in meteorites with these techniques. We detected inorganic ions, in particular VO+, in demineralized OM that likely originate from geoporphyrins, which derive from chlorophylls during sediment diagenesis. Finally, insoluble OM yielded distinct compositions compared with extracted soluble OM, with a greater abundance of ions of mass-to-charge ratio (m/z) over 175 and additional N-moieties. This highlights the potential of laser-assisted MS to decipher the composition of macromolecular OM, in particular to investigate the preservation of biomacromolecules in microfossils. Studies comparing diverse biogenic and abiogenic OM are needed to further assess the use of this technique to search for biosignatures.


Assuntos
Carbonatos , Enxofre , Cromatografia Gasosa-Espectrometria de Massas/métodos , Espectrometria de Massa de Íon Secundário , Lasers , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos
19.
Biointerphases ; 18(6)2023 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-38108477

RESUMO

This Tutorial focuses on the use of secondary ion mass spectrometry for the analysis of cellular and tissue samples. The Tutorial aims to cover the considerations in sample preparation analytical set up and some specific aspects of data interpretation associated with such analysis.


Assuntos
Espectrometria de Massa de Íon Secundário
20.
In. Schiabel, Homero; Slaets, Annie France Frère; Costa, Luciano da Fontoura; Baffa Filho, Oswaldo; Marques, Paulo Mazzoncini de Azevedo. Anais do III Fórum Nacional de Ciência e Tecnologia em Saúde. Säo Carlos, s.n, 1996. p.515-516, graf.
Monografia em Português | LILACS | ID: lil-233846

RESUMO

A espectrometria de massa de íons secundários (SIMS) permite a detecção rápida de elementos estáveis ou radioativos, bem como o cálculo de seu percentual isotópico. Ademais, essa técnica possibilita a localização de radioisótipos, à níveis de traços, em amostras biológicas. Neste trabalho procurou-se estudar a utilização dessa metodologia na detecção de urânio natural à baixa concentração. Estudos sobre a preparação de amostras e limites de detecção foram também realizados.


Assuntos
Elementos Radioativos/análise , Urânio/metabolismo , Liberação Nociva de Radioativos , Espectrometria de Massa de Íon Secundário/métodos , Filme para Raios X/estatística & dados numéricos
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