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Tissue- and sex-specific lipidomic analysis of Schistosoma mansoni using high-resolution atmospheric pressure scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging
摘要： Schistosomes are human pathogens causing the neglected tropical disease schistosomiasis, which occurs worldwide in (sub-)tropical regions. This infectious disease is often associated with poverty, and more than 700 million people are at risk of infection. Exploitation of novel habitats and limited therapeutic options brought schistosomes into research focus. Schistosomes are the only trematodes that have evolved separate sexes. They are covered by their metabolically active tegument, a surface area representing the interface between male and female in their permanent mating contact but also between parasite and host. The tegument comprises, besides others, numerous specific lipid compounds. Limited information is available on the exact lipid composition and its spatial distribution. We used atmospheric-pressure scanning microprobe matrix-assisted laser desorption/ionization (AP-SMALDI) mass spectrometry imaging (MSI) to characterize the Schistosoma mansoni tegument surface in comparison to tissue sections of whole worms or couples. We found that phosphatidylcholines (PC) and specific phosphatidylethanolamines (PE) are significantly more abundant inside the worm body compared to the tegument. On the other hand, the latter was found to be enriched in sphingomyelins (SM), phosphatidylserines (PS), lysophosphatidylcholines (LPC), and specific PE species. We further investigated lipid classes concerning number of carbon atoms in fatty acyl chains as well as the degree of unsaturation and found pronounced differences between the tegument and whole-worm body. Furthermore, differences between male and female teguments were found. The lipid composition of S. mansoni tissues has been investigated in an untargeted, spatially resolved manner for the first time.
关键词： mass spectrometry imaging,phosphatidylserines,phosphatidylethanolamines,sphingomyelins,lipidomic analysis,Schistosoma mansoni,tegument,phosphatidylcholines,lysophosphatidylcholines
更新于2025-09-23 15:21:01
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Supervised Non-negative Matrix Factorization Methods for MALDI Imaging Applications
摘要： Motivation: Non-negative matrix factorization (NMF) is a common tool for obtaining low-rank approximations of non-negative data matrices and has been widely used in machine learning, e.g., for supporting feature extraction in high-dimensional classification tasks. In its classical form NMF is an unsupervised method, i.e. the class labels of the training data are not used when computing the NMF. However, incorporating the classification labels into the NMF algorithms allows to specifically guide them towards the extraction of data patterns relevant for discriminating the respective classes. This approach is particularly suited for the analysis of mass spectrometry imaging (MSI) data in clinical applications, such as tumor typing and classification, which are amongst the most challenging tasks in pathology. Thus, we investigate algorithms for extracting tumor specific spectral patterns from MSI data by NMF methods. Results: In this paper, we incorporate a priori class labels into the NMF cost functional by adding appropriate supervised penalty terms. Numerical experiments on a MALDI imaging dataset confirm that the novel supervised NMF methods lead to significantly better classification accuracy and stability as compared to other standard approaches.
关键词： MALDI imaging,tumor typing,Non-negative matrix factorization,mass spectrometry imaging,supervised learning
更新于2025-09-23 15:21:01
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Insights into the Synthesis Mechanism of Ag <sub/>29</sub> Nanoclusters
摘要： The current understanding of the synthesis mechanisms of noble metal clusters is limited, in particular for Ag clusters. Here, we present a detailed investigation into the synthesis process of atomically monodisperse Ag29 clusters, prepared via reduction of AgNO3 in the presence of dithiolate ligands. Using optical spectroscopy, mass spectrometry and X-ray spectroscopy, it was determined that the synthesis involves a rapid nucleation and growth to species with up to a few hundred Ag atoms. From these larger species, Ag29 clusters are formed and their concentration increases steadily over time. Oxygen plays an important role in the etching of large particles to Ag29. No other stable Ag cluster species are observed at any point during the synthesis.
关键词： synthesis mechanism,Ag29 nanoclusters,optical spectroscopy,X-ray spectroscopy,mass spectrometry
更新于2025-09-23 15:21:01
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MALDI MS Imaging at Acquisition Rates Exceeding 100 Pixels per Second
摘要： The practicality of matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS) applied to molecular imaging of biological tissues is limited by the analysis speed. Typically, a relatively low speed of stop-and-go micromotion of XY stages is considered as a factor substantially reducing the rate with which fresh sample material can be supplied to the laser spot. The sample scan rate in our laboratory-built high-throughput imaging TOF mass spectrometer was significantly improved through the use of a galvanometer-based optical scanner performing fast laser spot repositioning on a target plate. The optical system incorporated into the ion source of our MALDI TOF mass spectrometer allowed focusing the laser beam via a modified grid into a 10-μm round spot. This permitted the acquisition of high-resolution MS images with a well-defined pixel size at acquisition rates exceeding 100 pixel/s. The influence of selected parameters on the total MS imaging time is discussed. The new scanning technique was employed to display the distribution of an antitumor agent in 3D colorectal adenocarcinoma cell aggregates; a single MS image comprising 100 × 100 pixels with 10-μm lateral resolution was recorded in approximately 70 s.
关键词： MSI,TOF,Mass spectrometry imaging,High throughput,Laser beam scanning,Colorectal adenocarcinoma,3D cell aggregates,Spheroids,Grid ion source,MALDI
更新于2025-09-23 15:21:01
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Unique Distribution of Diacyl-, Alkylacyl-, and Alkenylacyl-Phosphatidylcholine Species Visualized in Pork Chop Tissues by Matrix-Assisted Laser Desorption/Ionizationa??Mass Spectrometry Imaging
摘要： Phosphatidylcholine (PC) is the major phospholipid in meat and in?uences meat qualities, such as healthiness. PC is classi?ed into three groups based on the bond at the sn-1 position: Diacyl, alkylacyl, and alkenylacyl. To investigate their composition and distribution in pork tissues, including longissimus thoracis et lumborum (loin) spinalis muscles, intermuscular fat, and transparent tissues, we performed matrix-assisted laser desorption/ionization–mass spectrometry imaging (MALDI–MSI). Eleven diacyl-, seven alkylacyl-, and six alkenylacyl-PCs were identi?ed using liquid chromatography (LC)-tandem MS (MS/MS) analysis. Despite many alkylacyl- and alkenylacyl-PC species sharing identical m/z values, we were able to visualize these PC species using MALDI–MSI. Diacyl- and alkylacyl- and/or alkenylacyl-PC species showed unique distribution patterns in the tissues, suggesting that their distribution patterns were dependent on their fatty acid compositions. PCs are a major dietary source of choline in meat, and the amount was signi?cantly higher in the muscle tissues. Consumption of choline mitigates age-related memory decline and neurodegenerative diseases; therefore, the consumption of pork muscle tissues could help to mitigate these diseases. These results support the use of MALDI–MSI analysis for assessing the association between PC species and the quality parameters of meat.
关键词： mass spectrometry imaging (MSI),lipid distribution,phosphatidylcholines,liquid chromatography-tandem mass spectrometry (LC-MS/MS),pork,matrix-assisted laser desorption/ionization (MALDI)
更新于2025-09-23 15:19:57
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Detecting Laser-Volatilized Salts with a Miniature 100-GHz Spectrometer
摘要： Rotational transitions are unique identi?ers of molecular species, including isotopologues. This article describes the rotational detections of two laser-volatilized salts, NaCl and KCl, made with a miniature Fourier transform millimeter-wave (FTmmW) cavity spectrometer that could one day be used to measure solid composition in the ?eld or in space. The two salts are relevant targets for icy moons in the outer solar system, and in principle, other molecular solids could be analyzed with the FTmmW instrument. By coupling the spectrometer to a collisionally cooling laser ablation source, (a) we demonstrate that the FTmmW instrument is sensitive enough to detect ablation products, and (b) we use the small size of the FTmmW cavity to measure ablation product signal along the carrier gas beam. We ?nd that for 532 nm nanosecond pulses, ablated molecules are widely dispersed in the carrier-gas jet. In addition to the miniature spectrometer results, we present several complementary measurements intended to characterize the laser ablation process. For pulse energies between 10 and 30 mJ, the ablation product yield increases linearly, reaching approximately 1012 salt molecules per 30 mJ pulse. Using mass spectrometry, we observe Li+, Na+, and K+ in the plumes of ablated NaCl, KCl, and LiCl, which implies dissociation of the volatilized material. We do not observe salt ions (e.g., NaCl+). However, with 800 nm femtosecond laser pulses, the triatomic ion clusters Li2Cl+, Na2Cl+, and K2Cl+ are produced. Finally, we observe incomplete volatilization with the nanosecond pulses: some of the ejecta are liquid droplets. The insights about ablation plume physics gleaned from these experiments should guide future implementations of the laser-volatilization technique.
关键词： KCl,Fourier transform millimeter-wave,FTmmW,rotational transitions,NaCl,mass spectrometry,outer solar system,icy moons,laser-volatilized salts,laser ablation
更新于2025-09-23 15:19:57
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Evaluating the influence of laser wavelength and detection stage geometry on optical detection efficiency in a single-particle mass spectrometer
摘要： Single-particle mass spectrometry (SPMS) is a useful tool for the online study of aerosols with the ability to measure size-resolved chemical composition with a temporal resolution relevant to atmospheric processes. In SPMS, optical particle detection is used for the effective temporal alignment of an ablation laser pulse with the presence of a particle in the ion source, and it gives the option of aerodynamic sizing by measuring the offset of particle arrival times between two detection stages. The efficiency of the optical detection stage has a strong influence on the overall instrument performance. A custom detection laser system consisting of a high-powered fibre-coupled Nd:YAG solid-state laser with a collimated beam was implemented in the detection stage of a laser ablation aerosol particle time-of-flight (LAAP-TOF) single-particle mass spectrometer without major modifications to instrument geometry. The use of a collimated laser beam permitted the construction of a numerical model that predicts the effects of detection laser wavelength, output power, beam focussing characteristics, light collection angle, particle size, and refractive index on the effective detection radius (R) of the detection laser beam. We compare the model predictions with an ambient data set acquired during the Ice in Clouds Experiment – Dust (ICE-D) project. The new laser system resulted in an order-of-magnitude improvement in instrument sensitivity to spherical particles in the size range 500–800 nm compared to a focussed 405 nm laser diode system. The model demonstrates that the limit of detection in terms of particle size is determined by the scattering cross section (Csca) as predicted by Mie theory. In addition, if light is collected over a narrow collection angle, oscillations in the magnitude of Csca with respect to particle diameter result in a variation in R, resulting in large particle-size-dependent variation in detection efficiency across the particle transmission range. This detection bias is imposed on the aerodynamic size distributions measured by the instrument and accounts for some of the detection bias towards sea salt particles in the ambient data set.
关键词： LAAP-TOF,aerosol,single-particle mass spectrometry,Mie theory,laser wavelength,detection stage geometry,optical detection efficiency
更新于2025-09-23 15:19:57
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Co Incorporated Mesoporous Carbon Material Assisted Laser Desorption/Ionization Ion Source as an on-line Interface of in vivo Microdialysis Coupled with Mass Spectrometry
摘要： The combination of microdialysis and mass spectrometry (MS) provides the potential for rapidly monitoring diverse metabolites in vivo. Unfortunately, the high concentration of salt in biological microdialysates hindered the sensitive and on-line detection of these small molecular compounds. In this study, we synthesized Co incorporated mesoporous carbon material (Co-NC), and developed Co-NC assisted laser desorption/ionization (LDI) ion source as an on-line interface of in vivo microdialysis coupled with MS for direct analysis of diverse metabolites in microdialysates. The Co-NC could be used as matrix for surface assisted laser desorption/ionization mass spectrometry (SALDI MS) analysis of small molecular compounds, even under high concentration of salt conditions. The Co-NC possessed the adsorption ability for small molecular compounds, and it was believed that the adsorption ability of Co-NC might separate the analytes from the salt in microdialysates at a microscopic level, which might facilitate the desorption and ionization of the analytes and finally improved the salt-tolerance ability as matrix. Furthermore, the Co-NC assisted LDI ion source as a novel interface of in vivo microdialysis coupled with MS has been applied to the on-line monitoring of liver metabolites from the CCl4-induced liver injury rat model for the first time.
关键词： microdialysis,Co incorporated mesoporous carbon material,metabolites,mass spectrometry,laser desorption/ionization,salt-tolerance
更新于2025-09-23 15:19:57
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Coal Discrimination Analysis Using Tandem Laser-Induced Breakdown Spectroscopy and Laser Ablation Inductively Coupled Plasma Time-of-Flight Mass Spectrometry
摘要： The contribution and impact of combined laser ablation inductively coupled plasma time of flight mass spectrometry (LA-ICP-TOF-MS) and laser induced breakdown spectroscopy (LIBS) were evaluated for the discrimination analysis of different coal samples. This Tandem approach allows simultaneous determination of major and minor elements (C, H, Si, Ca, Al, Mg, etc), and trace elements (V, Ba, Pb, U, etc.) in the coal. The research focused on coal classification strategies based on principle component analysis (PCA) combined with K-means clustering, partial least squares discrimination analysis (PLS-DA), and support vector machine (SVM) for analytical performance. Correlation analyses performed from TOF mass and LIBS emission spectra from the coal samples showed that most major, minor, and trace elements emissions had negative correlation with the volatile content. Suitable variables for the classification models were determined from these data. The individual TOF data, LIBS data, and the combined data of TOF and LIBS, respectively, as the input for different models were analyzed and compared. In all cases, the results obtained with the combined TOF and LIBS data were found to be superior to those obtained with the individual TOF or LIBS data. The nonlinear SVM model combined with TOF and LIBS data provided the best coal classification performance, with a classification accuracy of up to 98%.
关键词： Principal component analysis,Support vector machine,Partial least squares discrimination analysis,Laser-induced breakdown spectroscopy,K-means clustering,Coal discrimination,Laser ablation inductively coupled plasma time of flight mass spectrometry
更新于2025-09-23 15:19:57
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Direct Ultraviolet Laser-Induced Reduction of Disulfide Bonds in Insulin and Vasopressin
摘要： Ultraviolet (UV) light has been shown to induce reduction of disulfide bonds in solution. The photoreduction is proposed to be a result of electron donation from excited Tyr or Trp residues. In this work, a powerful UV femtosecond laser was used to generate photoreduced products, while the hypothesis of Tyr/Trp mediation was studied with spectroscopy and mass spectrometry. With limited irradiation times of 3 min or less at 280 nm, the laser-induced reduction in arginine vasopressin and human insulin led to significant yields of ～3% stable reduced product. The photogenerated thiols required acidic pH for stabilization, while neutral pH primarily caused scrambling and trisulfide formation. Interestingly, there was no direct evidence that Tyr/Trp mediation was a required criterion for the photoreduction of disulfide bonds. Intermolecular electron transfer remained a possibility for insulin but was ruled out for vasopressin. We propose that an additional mechanism should be increasingly considered in UV light-induced reduction of disulfide bonds in solution, in which a single UV photon is directly absorbed by the disulfide bond.
关键词： mass spectrometry,photoreduction,disulfide bonds,Tyr/Trp mediation,femtosecond laser,Ultraviolet light
更新于2025-09-23 15:19:57