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Fundamental understanding of chemical processes in extreme ultraviolet resist materials
摘要： New photoresists are needed to advance extreme ultraviolet (EUV) lithography. The tailored design of efficient photoresists is enabled by a fundamental understanding of EUV induced chemistry. Processes that occur in the resist film after absorption of an EUV photon are discussed, and a new approach to study these processes on a fundamental level is described. The processes of photoabsorption, electron emission, and molecular fragmentation were studied experimentally in the gas-phase on analogs of the monomer units employed in chemically amplified EUV resists. To demonstrate the dependence of the EUV absorption cross section on selective light harvesting substituents, halogenated methylphenols were characterized employing the following techniques. Photoelectron spectroscopy was utilized to investigate kinetic energies and yield of electrons emitted by a molecule. The emission of Auger electrons was detected following photoionization in the case of iodo-methylphenol. Mass-spectrometry was used to deduce the molecular fragmentation pathways following electron emission and atomic relaxation. To gain insight on the interaction of emitted electrons with neutral molecules in a condensed film, the fragmentation pattern of neutral gas-phase molecules, interacting with an electron beam, was studied and observed to be similar to EUV photon fragmentation. Below the ionization threshold, electrons were confirmed to dissociate iodo-methylphenol by resonant electron attachment.
关键词： photoabsorption,molecular fragmentation,electron emission,photoresists,mass-spectrometry,Auger electrons,photoelectron spectroscopy,EUV lithography,resonant electron attachment,halogenated methylphenols
更新于2025-09-23 15:21:01
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Preparation and comparison of Fe3O4@graphene oxide nanoclusters for analysis of glimepiride in urine by surface-assisted laser desorption/ionization time-of-flight mass spectrometry
摘要： Graphene oxide (GO) has the ability to absorb certain compounds, and it can be modified with functional groups for different purposes; for instance, iron oxide (IO) nanoparticles can be used to concentrate analyte by a magnet. Recently, many kinds of GO have been developed, such as single-layer GO (SLGO), two-to-four layers of GO (i.e., few-layer GO, FLGO2–4), and four-to-eight layers of GO (i.e., multi-layer GO, MLGO4–8). However, the abilities of these layered GO coated with IO nanoparticles have not been investigated. In this study, we conducted a novel analysis of glimepiride by using layered GO-coated magnetic clusters of IO nanoparticles that were synthesized through a simple and facile emulsion-solvent evaporation method. The methodology is based on (i) enrichment of glimepiride using the layered GO-coated magnetic clusters of IO nanoparticles (IO@SLGO, IO@FLGO2–4, and IO@MLGO4–8), and (ii) rapid determination using magnetic cluster–based surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOFMS). We found that IO@MLGO4–8, the magnetic cluster with the greatest number of GO layers, had the best limit of detection (28.6 pmol/μL for glimepiride). The number of GO layers played a significant role in increasing the sensitivity of the SALDI-MS, indicating that the size of GO in the magnetic clusters contributed to the desorption/ionization efficiency. To the best of our knowledge, this is the first study to enrich glimepiride using magnetic clusters of different GO types and to show that the glimepiride in HLB purified urine adsorbed by magnetic clusters can be analyzed by SALDI-TOFMS.
关键词： Mass spectrometry,Iron oxide,Glimepiride,Nanocluster,SALDI,Graphene oxide
更新于2025-09-23 15:21:01
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Simulation studies of the laser ablation ion source at the SHIPTRAP setup
摘要： A gas-filled miniature Radio-Frequency Quadrupole (mini-RFQ) was recently implemented into the SHIPTRAP laser ablation ion source to thermalize the laser-ablated ions and thus improve production efficiency as well as sample preparation. This source provides reference ions of various elements for online experiments with the SHIPTRAP mass spectrometer. In addition, it can be used to provide long-lived rare and radioactive isotopes available only in small sample sizes for high-precision mass measurements or to study systematic uncertainties. The performance of the laser ablation ion source was simulated using the COMSOL Multiphysics modeling software package. These studies indicate that a revised mechanical geometry and an optimized RF field improve the performance significantly.
关键词： Penning traps,Surface ionization ion source,Mass spectrometry,Laser ablation ion source
更新于2025-09-23 15:21:01
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Highly selective two-step laser ionization schemes for the analysis of actinide mixtures
摘要： Resonance ionization mass spectroscopy has proven to be a very efficient and selective method for the spatially resolved ultratrace determination of actinide contaminations, and the analysis of specific element and isotopic distributions on surfaces and environment particles. We report on the identification of highly element-selective optical excitation schemes identified for this purpose, with a particular focus on the precise determination of the isobaric ratios of 235U to 239Pu as well as 243Am to 241Pu. The chosen two-step ionization schemes were characterized with respect to their element selectivity on synthetic multi-element actinide mixtures, with an element ratio Pu : Am : U of 1 : 10 : 104, a composition which is typical, e.g., for spent nuclear reactor fuels.
关键词： Mass spectrometry,Actinides,Laser spectroscopy,Multi-element mixture,Isotope ratio
更新于2025-09-23 15:21:01
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Hanging drop cathode-atmospheric pressure glow discharge as a new method of sample introduction for inductively coupled plasma-optical emission spectrometry
摘要： This work reports the use of hanging drop cathode-atmospheric pressure glow discharge (HDC-APGD) as a new method of sample introduction for inductively coupled plasma-optical emission spectrometry (ICP-OES). The developed arrangement was characterized by a low sample uptake (0.56 mL min?1) and the fact that the entire sample solution volume was consumed by the discharge. This resulted in a very high transport efficiency of analytes from the sample solution into the ICP torch (usually > 80%). Under the optimal operating conditions of HDC-APGD, intensities of emission lines of studied elements were, on average, 2 times higher as compared to those obtained with conventional pneumatic nebulization (PN). Moreover, in the case of I and Y, the observed signal enhancements were even higher, i.e., 6.2 and 6.1 times, respectively. It was also shown that in the case of B and some elements that are known to form different volatile species (Ag, Bi, Cd, Hg, Os, Pb, and Se), the presence of low molecular weight organic compounds in the sample solution, i.e., CH3OH, C2H5OH, HCOOH, CH3COOH, or HCHO, resulted in the additional enhancement of their signals. It was especially evident in the case of Hg for which a 8.6-fold signal enhancement in the presence of HCOOH was noticed. The system presented herein was distinguished from other competitive APGD-type discharges because it could be successfully used for the determination of a vast group of elements, including alkali metals, alkaline earth metals, transition metals, and non-metals.
关键词： Atmospheric pressure glow discharge,Hanging drop cathode,Inductively coupled plasma,Optical emission spectrometry,Sample introduction
更新于2025-09-23 15:21:01
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Reference Module in Chemistry, Molecular Sciences and Chemical Engineering || SPECTROPHOTOMETRY/Diode Array ☆
摘要： Diode array spectrometry represents a particular approach for characterizing the result of the interaction between electromagnetic radiation and the sample, based on simultaneous measurement of light intensity over small spectral intervals having equal width. This is achieved through the following sequential stages, as schematically shown in Figs. 1 and 2D: a. interaction between the polychromatic beam and the sample; b. spatial dispersion of the transmitted (eventually reflected or emitted) radiation according to wavelength on multiple channels of equal widths, by means of a fixed optical element; c. imaging the dispersed radiation in a focal plane; and d. (quasi)simultaneous sampling of the dispersed radiation interval using photosensitive detectors, precisely positioned in the focal plane.
关键词： photodiode principle,Diode array spectrometry,concave diffraction gratings,spectrophotometry,instrumentation
更新于2025-09-23 15:21:01
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Analysis of High-Purity Germanium Dioxide by Inductively Coupled Plasma Atomic Emission Spectrometry with Reaction Distillation of the Matrix
摘要： A combined method of analysis of high-purity germanium dioxide by atomic emission spectrometry with matrix preseparation and trace element preconcentration was developed. The matrix was separated in an autoclave of a MARS 5 microwave system without the contact of samples with an acid solution. The method allows the determination of the following 50 analytes with the limits of detection 10–8–10–5 wt %: Ag, Al, As, Au, B, Ba, Be, Cd, Ce, Co, Cr, Cu, Dy, Er, Eu, Fe, Ga, Gd, Hf, Hg, Ho, In, La, Li, Lu, Mg, Mn, Na, Nb, Nd, Ni, P, Pb, Pr, Re, Sb, Sc, Sm, Sn, Sr, Ta, Tb, Te, Ti, Tm, W, Y, Yb, Zn, and Zr.
关键词： high-purity germanium dioxide,matrix separation,limits of detection,atomic emission spectrometry,inductively coupled plasma,multielement analysis
更新于2025-09-23 15:21:01
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Raman spectroscopy coupled with ambient ionization mass spectrometry: A forensic laboratory investigation into rapid and simple dual instrumental analysis techniques
摘要： We present a laboratory experiment, developed around a pair of instrumental analysis techniques, Raman spectroscopy and ambient ionization mass spectrometry (MS), conducted by senior chemistry undergraduate students for bulk analysis of over-the-counter drugs using benchtop versions of the two instruments, as well as trace analysis of illicit drugs utilizing the corresponding portable instruments. The identification and confirmation of seized drugs is a routine operation in forensic laboratories that can be simplified using these two instrumental techniques in tandem. Bulk samples are readily analyzed using conventional Raman spectroscopy followed by paper cone spray ionization (PCSI) MS, while trace analysis is allowed by a simple single-substrate dual-analyzer method using surface enhanced Raman spectroscopy (SERS) from paper followed by paper spray ionization (PSI) MS. The introduction of these novel strategies to the students exposed them to potential career paths in forensic science by means of a hands-on experience that provided fundamental knowledge about this set of analytical methods, including intercomparisons of their performance, as well as practical issues like costs, regulations and databases. The use of portable instrumentation represents an additional learning experience for the students, considering that it is cutting-edge technology that is just now being transferred from academic to industrial labs and that it allows a valuable discussion of the advantages and disadvantages of bringing the laboratory to the field.
关键词： Mass spectrometry,Hands-on learning,Forensic analysis,Drugs of abuse,Paper cone spray ionization,Paper spray ionization,Paper surface enhanced Raman spectroscopy,Raman spectroscopy,Ambient ionization,Laboratory instruction
更新于2025-09-23 15:21:01
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High-Throughput Fingerprinting of Rhizobial Free Fatty Acids by Chemical Thin-Film Deposition and Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry
摘要： Fatty acids (FAs) represent an important class of metabolites, impacting on membrane building blocks and signaling compounds in cellular regulatory networks. In nature, prokaryotes are characterized with the most impressing FA structural diversity and the highest relative content of free fatty acids (FFAs). In this context, nitrogen-fixing bacteria (order Rhizobiales), the symbionts of legumes, are particularly interesting. Indeed, the FA profiles influence the structure of rhizobial nodulation factors, required for successful infection of plant root. Although FA patterns can be assessed by gas chromatography—(GC-) and liquid chromatography—mass spectrometry (LC-MS), sample preparation for these methods is time-consuming and quantification suffers from compromised sensitivity, low stability of derivatives and artifacts. In contrast, matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS) represents an excellent platform for high-efficient metabolite fingerprinting, also applicable to FFAs. Therefore, here we propose a simple and straightforward protocol for high-throughput relative quantification of FFAs in rhizobia by combination of Langmuir technology and MALDI-TOF-MS featuring a high sensitivity, accuracy and precision of quantification. We describe a step-by-step procedure comprising rhizobia culturing, pre-cleaning, extraction, sample preparation, mass spectrometric analysis, data processing and post-processing. As a case study, a comparison of the FFA metabolomes of two rhizobia species—Rhizobium leguminosarum and Sinorhizobium meliloti, demonstrates the analytical potential of the protocol.
关键词： bacteria,metabolic fingerprinting,matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS),barium monocarboxylates,free fatty acids (FFAs),chemical deposition technique,Langmuir film technology,rhizobia
更新于2025-09-23 15:21:01
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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