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The variation among individual cells plays a significant role in many biological functions. Single-cell analysis is advantageous for gaining insight into intricate biochemical mechanisms rarely accessible when studying tissues as a whole. However, measurement on a unicellular scale is still challenging due to unicellular complex composition, minute substance quantities, and considerable differences in compound concentrations. Mass spectrometry has recently gained extensive attention in unicellular analytical fields due to its exceptional sensitivity, throughput, and compound identification abilities. At present, single-cell mass spectrometry primarily concentrates on the enhancement of ionization methods. The principal ionization approaches encompass nanoelectrospray ionization (nano-ESI), laser desorption ionization (LDI), secondary ion mass spectrometry (SIMS), and inductively coupled plasma (ICP). This article summarizes the most recent advancements in ionization techniques and explores their potential directions within the field of single-cell mass spectrometry.

Mass spectrometry imaging (MSI) has become an important analytical tool for the label‐free chemical imaging of diverse molecules in biological specimens. This minireview surveys some emerging methods in the context of factors that can lead to inaccurate information in MSI, chemical and spatial aberrations, along with their common sources. Matrix‐assisted laser desorption ionization, based on organic matrices, has become the most widely used MSI technique for biomolecules. However, due to inherent limitations associated with the use of organic matrices, for example, heterogeneous matrix‐analyte cocrystallization, and spectral interferences due to the matrix, laser desorption ionization (LDI) from inorganic and nanophotonic platforms has emerged as an alternative MSI modality with complementary advantages. In this review, inorganic and nanophotonic platforms for LDI‐MSI, their applications in imaging, notable merits, and limitations are described. [ABSTRACT FROM AUTHOR]

We herein report the optimization and application of silver cationization (Ag+) in combination with laser desorption ionization (LDI) ultrahigh-resolution mass spectrometry (UHR-MS) to determine the structures of the sulfur-containing compounds present in heavy crude oil. A number of sulfur-containing model compounds were used to optimize the positive-ion mode LDI-MS conditions in the presence of a silver-complexing agent. Under the optimized LDI conditions, sulfur-rich heavy oil fractions were treated with the silver salt, where Ag+ coordinated with the sulfur atoms to speciate the sulfur species. The obtained results suggested that benzothiophenic, naphtheno-non-aromatic sulfides, and non-aromatic thiols were the major components present in the analyzed oil sample. [ABSTRACT FROM AUTHOR]

The variation among individual cells plays a significant role in many biological functions. Single-cell analysis is advantageous for gaining insight into intricate biochemical mechanisms rarely accessible when studying tissues as a whole. However, measurement on a unicellular scale is still challenging due to unicellular complex composition, minute substance quantities, and considerable differences in compound concentrations. Mass spectrometry has recently gained extensive attention in unicellular analytical fields due to its exceptional sensitivity, throughput, and compound identification abilities. At present, single-cell mass spectrometry primarily concentrates on the enhancement of ionization methods. The principal ionization approaches encompass nanoelectrospray ionization (nano-ESI), laser desorption ionization (LDI), secondary ion mass spectrometry (SIMS), and inductively coupled plasma (ICP). This article summarizes the most recent advancements in ionization techniques and explores their potential directions within the field of single-cell mass spectrometry., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Zeng, Xia, Yin, Cheng, Xue, Tan, Gong and Ye.)

It has been known for about sixty years that proton and heavy ion therapy is a very powerful radiation procedure for treating tumors. It has an innate ability to irradiate tumors with greater doses and spatial selectivity compared with electron and photon therapy and, hence, is a tissue sparing procedure. For more than twenty years, powerful lasers have generated high energy beams of protons and heavy ions and it has, therefore, frequently been speculated that lasers could be used as an alternative to radiofrequency (RF) accelerators to produce the particle beams necessary for cancer therapy. The present paper reviews the progress made towards laser driven hadron cancer therapy and what has still to be accomplished to realize its inherent enormous potential.

Anisotropy at the nanoscale fascinates researchers in various areas of science and technology. Well-known applications of anisotropic nanoparticles include biosensors and catalysis. However, utilization of gold nanostars in analytical chemistry is limited to surface enhanced Raman spectroscopy. LDI-MS assisted with gold nanostars has not been addressed for low molecular weight compounds. Herein, we report LDI-MS performance of phospholipids at nanomolar concentrations with application of gold nanostars for the first time. Intense signals of molecular ions were detected as metal adduct ions with relatively low fragmentation and signals of interferences in low-mass region. Nanostars were characterized with utilization of electron microscopic, X-Ray powder diffraction and dynamic light scattering techniques. The results showed that gold nanostars can serve as a bright perspective for new inorganic matrices in LDI-MS of low molecular weight compounds. [Display omitted] • LDI-MS performance of gold nanostars was reported for the first time. • Gold nanostars as inorganic matrix allowed registration of phospholipids at nanomolar level. • The study shows a bright perspective for future utilization of gold nanostars in LDI-MS. [ABSTRACT FROM AUTHOR]

Marine microorganisms adapt to their habitat by structural modification of their membrane lipids. This concept is the basis of numerous molecular proxies used for paleoenvironmental reconstruction. Archaeal tetraether lipids from ubiquitous marine planktonic archaea are particularly abundant, well preserved in the sedimentary record and used in several molecular proxies. We here introduce the direct, extraction-free analysis of these compounds in intact sediment core sections using laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). LDI FTICR-MS can detect the target lipids in single submillimeter-sized spots on sediment sections, equivalent to a sample mass in the nanogram range, and could thus pave the way for biomarker-based reconstruction of past environments and ecosystems at subannual to decadal resolution. We demonstrate that ratios of selected archaeal tetraethers acquired by LDI FTICR-MS are highly correlated with values obtained by conventional liquid chromatography/MS protocols. The ratio of the major archaeal lipids, caldarchaeol and crenarchaeol, analyzed in a 6.2-cm intact section of Mediterranean sapropel S1 at 250-μm resolution (∼4-y temporal resolution), provides an unprecedented view of the fine-scale patchiness of sedimentary biomarker distributions and the processes involved in proxy signal formation. Temporal variations of this lipid ratio indicate a strong influence of the ∼200-y de Vries solar cycle on reconstructed sea surface temperatures with possible amplitudes of several degrees, and suggest signal amplification by a complex interplay of ecological and environmental factors. Laser-based biomarker analysis of geological samples has the potential to revolutionize molecular stratigraphic studies of paleoenvironments. [ABSTRACT FROM AUTHOR]

It has been known for about sixty years that proton and heavy ion therapy is a very powerful radiation procedure for treating tumors. It has an innate ability to irradiate tumors with greater doses and spatial selectivity compared with electron and photon therapy and, hence, is a tissue sparing procedure. For more than twenty years, powerful lasers have generated high energy beams of protons and heavy ions and it has, therefore, frequently been speculated that lasers could be used as an alternative to radiofrequency (RF) accelerators to produce the particle beams necessary for cancer therapy. The present paper reviews the progress made towards laser driven hadron cancer therapy and what has still to be accomplished to realize its inherent enormous potential. [ABSTRACT FROM AUTHOR]

Highlights: [•] Fullerene films are excited with infrared lasers and ions (positive and negative) are detected with time-of-flight mass spectrometry. [•] The mechanism of infrared desorption and ionization is investigated with different samples and IR wavelengths. [•] Tunable IR studies provide desorbed ion infrared spectra of C60, revealing new vibrational combination bands. [Copyright &y& Elsevier]

Nanomaterials have emerging importance in laser desorption ionization mass spectrometry (LDI-MS) with the ultimate objective being to overcome some of the most important limitations intrinsically related to the use of conventional organic matrices in matrix-assisted (MA) LDI-MS. This review provides a critical overview of the most recent literature on the use of gold nanomaterials as non-conventional desorption ionization promoters in LDI-MS, with particular emphasis on bioanalytical applications. Old seminal papers will also be discussed to provide a timeline of the most significant achievements in the field. Future prospects and research needs are also briefly discussed. [ABSTRACT FROM AUTHOR]

Silver nanofractals (Ag-NFs) have been electrosynthesized and characterized by means of morphological and spectroscopic analytical techniques. In particular, X-ray photoelectron spectroscopy has been used to assess the nanomaterial surface chemical state. Ag-NFs show interesting perspectives in bioanalytical applications, particularly as non-conventional desorption and ionization promoters in laser desorption ionization mass spectrometry. [ABSTRACT FROM AUTHOR]

Abstract: An ion trap time-of-flight (IT-TOF) mass spectrometer has been developed for online analysis of organic aerosol. Airborne particles are focused through an aerodynamic lens assembly and deposited onto a stainless steel collection probe inserted through a hole in the ring electrode of an ion trap. The collected sample is desorbed and ionized with a pulsed 355-nm Nd:YAG laser beam within the ion trap cavity. Ions are collisionally cooled to the center of the trap prior to extraction into a reflectron time-of-flight mass analyzer. Relative to a previous version of the instrument without an ion trap, incorporation of the ion trap increases the sensitivity and resolution of ions that are formed directly at the probe surface and permits post-ionization with electrons to be performed. Online analysis of perylene and C60 test aerosols were performed by one-step laser desorption ionization (LDI). Online analysis of secondary organic aerosol (SOA) from α-pinene ozonolysis was performed by laser desorption–electron ionization (LD–EI). Matrix-assisted laser desorption ionization (MALDI) was also performed, and the molecular ion signal was enhanced with a dynamic RF trapping method. [Copyright &y& Elsevier]

The detailed structural characterization of complex polymer architectures, like copolymers and polymer mixtures, by mass spectrometry presents a challenge. Even though soft ionization analyses revolutionized the characterization of large molecules and provided a means for determining the polymer’s molecular weight distribution, polydispersity, and end groups, full microstructure elucidation and monomer sequencing by soft ionization alone is not possible. The combination of high-resolution Fourier transform mass spectrometry (FTMS) and tandem mass spectrometry (MSn) provides a powerful analytical tool for addressing these challenges. This tool was used in our work to separate and identify the products of polymerization between 12-hydroxystearic acid (HSA) and stearic acid (SA), to provide precise information about the exact location of caprolactones on the Tris(2-hydroxyethyl)isocyanurate (THEIC) molecule, and to sequence a glycidyl methacrylate/methyl methacrylate (GMA/MMA) copolymer. The results highlight the value of ultrahigh resolution and tandem mass spectrometry for fine structural characterization and sequencing of polymers. [ABSTRACT FROM AUTHOR]

Abstract: Matrix-assisted laser desorption/ionization (MALDI) was performed using two-pulsed lasers with wavelengths in the infrared and ultraviolet regions. A 2.94μm pulsed optical parametric oscillator laser system and a 337nm pulsed nitrogen laser irradiated the same spot on the sample target. Sinapinic acid (SA), 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CCA), and 4-nitroaniline (NA) were used as matrices, and bovine insulin and cytochrome C were used as analytes. The laser energy was adjusted so that one-laser MALDI and LDI was at a minimum and the matrix and analyte ion signal was enhanced when the two lasers were fired together. Two-laser LDI was observed with SA, DHB, and NA matrices and two-laser MALDI was observed with SA and DHB. Plots of ion signal as a function of delay between the IR and UV lasers show two-laser signal from 0ns up to a delay of 500ns when the IR laser is fired before the UV laser. The results are interpreted in terms of IR laser heating of the target that leads to an enhancement in UV LDI and MALDI. [Copyright &y& Elsevier]

Abstract: Laser desorption ionization (LDI) mass spectra have been obtained for the photolysis products of tri-9-anthrylborane (TAB) in the solvents toluene, cyclohexene, and tetrahydrofuran; and for the solid triarylboranes: TAB, trimesitylborane (TMB), and tri-(2,6-dimethylphenyl)borane (TXyB). The major single solution photolysis product of TAB is 9,9′-dianthryl. Other products are rationalized in terms of an anthrylborylene intermediate (AnthB:). LDI mass spectrometry of the triarylboranes yields molecular ions in good abundance, providing a simple and selective method of characterization. Fragmentation patterns in some cases are interpreted in terms of photochemical reactions prior to ionization. [Copyright &y& Elsevier]

The molecular weights of plasma proteins from healthy subjects and from patients with well-or badly-controlled diabetes mellitus have been determined by use of a matrix-assisted laser desorption ionization method, representing a highly accurate technique for the determination of the molecular weight of large biomolecules. Using this approach, different molecular weights of human serum albumin have been found for healthy (66,572-66,694 dalton) and diabetic (66,785-68,959 dalton) subjects. Such differences can be rationalized as being due to the different number of glucose molecules condensed on the protein and/or their further oxidation products; in the case of our diabetic patients this number is in the range of 1.4-14.8. The data show the high validity and specificity of the technique, which allows us to evaluate, without any protein degradation procedure, the number of glucose molecules condensed on a specific protein and ascertain the relationship of this number to the physiopathogenetic conditions of the subjects studied. [ABSTRACT FROM AUTHOR]

Marine microorganisms adapt to their habitat by structural modification of their membrane lipids. This concept is the basis of numerous molecular proxies used for paleoenvironmental reconstruction. Archaeal tetraether lipids from ubiquitous marine planktonic archaea are particularly abundant, well preserved in the sedimentary record and used in several molecular proxies. We here introduce the direct, extraction-free analysis of these compounds in intact sediment core sections using laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). LDI FTICR-MS can detect the target lipids in single submillimeter-sized spots on sediment sections, equivalent to a sample mass in the nanogram range, and could thus pave the way for biomarker-based reconstruction of past environments and ecosystems at subannual to decadal resolution. We demonstrate that ratios of selected archaeal tetraethers acquired by LDI FTICR-MS are highly correlated with values obtained by conventional liquid chromatography/MS protocols. The ratio of the major archaeal lipids, caldarchaeol and crenarchaeol, analyzed in a 6.2-cm intact section of Mediterranean sapropel S1 at 250-µm resolution (∼ 4-y temporal resolution), provides an unprecedented view of the fine-scale patchiness of sedimentary biomarker distributions and the processes involved in proxy signal formation. Temporal variations of this lipid ratio indicate a strong influence of the ∼ 200-y de Vries solar cycle on reconstructed sea surface temperatures with possible amplitudes of several degrees, and suggest signal amplification by a complex interplay of ecological and environmental factors. Laser-based biomarker analysis of geological samples has the potential to revolutionize molecular stratigraphic studies of paleoenvironments.