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Municipal wastewater treatment plants are required to monitor persistent organic pollutants (POPs) in their wastewater treatment related discharges and to assess the impact of the discharges on the environment and public health. One tool for monitoring chlorinated organic pollutants particularly is a gas chromatographic (GC) system coupled to a pair of halogen-specific electron capture detectors (ECDs) with helium (He) as the mobile phase. He supplies, however, has become inconsistent and unreliable lately. In its place, N 2 gas is evaluated in this study as a potential substitute for He in quantifying organochlorine pesticides, polychlorinated biphenyls, chlordane congeners and toxaphene in wastewater treatment related matrices (influent, effluent, benthic sediment, mussel tissue, and biosolids/sludge). N 2 is inert, inexpensive and requires no additional hardware to incorporate into the basic functions of a GC-ECD. Our results show that, with the usual data quality controls (blank, laboratory control, matrix spike/duplicate and proficiency testing samples, and the fact that certified reference materials data met requirements), N 2 can replace He for regulatory purposes. And when necessary, the N 2 -based retention times (t N ) can be predicted reliably from He-based retention times (t He ), irrespective of column chemistry or POPs (here: t N = 1.90t He + 0.04, R 2 = 0.996)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (Copyright © 2024 Elsevier B.V. All rights reserved.)

The anticrossing spectra of the helium line λ1s4l D3,F-1s2p P3=447.2 nm emitted after electron capture by He+ ions in He+-He collisions were measured for projectile energies of 10-29 keV. Furthermore, considering the excited states' time evolution, the theoretical intensity functions were calculated. The electric field and density distributions of the target He atoms in the collision volume were taken into account, and by fitting the theoretical intensities to the measured ones, the post-collisional states of the charge-transferred He atoms were determined. The results indicate that for the intermediate projectile energy range, the electronic charge distributions were asymmetric, but the electric dipole moments did not change, as in the case of the target atoms excited directly in the collisions. This result shows that the Paul trap mechanism may play an important role in the charge transfer excitation in this energy range.

On-line coupled high performance liquid chromatography-gas chromatography-flame ionisation detection (HPLC-GC-FID) was used to compare the effect of hydrogen, helium and nitrogen as carrier gases on the chromatographic characteristics for the quantification of mineral oil hydrocarbon (MOH) traces in food related matrices. After optimisation of chromatographic parameters nitrogen carrier gas exhibited characteristics equivalent to hydrogen and helium regarding requirements set by current guidelines and standardisation such as linear range, quantification limit and carry over. Though nitrogen expectedly led to greater peak widths, all required separations of standard compounds were sufficient and humps of saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) were appropriate to enable quantitation similar to situations where hydrogen or helium had been used. Slightly increased peak widths of individual hump components did not affect shapes and widths of the MOSH and MOAH humps were not significantly affected by the use of nitrogen as carrier gas. Notably, nitrogen carrier gas led to less solvent peak tailing and smaller baseline offset. Overall, nitrogen may be regarded as viable alternative to hydrogen or helium and may even extend the range of quantifiable compounds to highly volatile hydrocarbon eluting directly after the solvent peak., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Hydrodynamics, efficiency, and loading capacity of two semi-packed columns with different cross sections (NANO 315 µm x 18 µm; CAP 1000 µm x 28 µm) and similar pillar diameter and pillar-pillar distance (respectively 5 µm and 2.5 µm) have been compared in high-pressure gas chromatography. A flow prediction tool has been first designed to determine pressure variations and hold-up time across the chromatographic system taking into account the rectangular geometry of the ducts into the semi-packed columns. Intrinsic values of Height Equivalent to Theoretical Plate were determined for NANO and CAP columns using helium as carrier gas and similar values have been obtained (30 µm) for the two columns. Loading capacity of semi-packed columns were determined for decane at 70 °C using helium, and the highest value was obtained from CAP column (larger cross section and stationary phase content). Finally, significant HETP improvement (down to 15 µm) and peak shape were observed when carbon dioxide was used as carrier gas, suggesting mobile phase adsorption on stationary phase in high pressure conditions., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Ambroisine Michel, Eric COLINET and Régis BARATTIN have financial interest/personal relationships with APIX ANALYTICS. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Background: In recent years, due to the global shortage of helium gas, the development of gas chromatography (GC) analytical methods using alternatives to helium carrier gases is necessary., Objective: The objective of this study was to examine the applicability of hydrogen and nitrogen as alternative carrier gases using the test method for azo compounds in the Act on Control of Household Products Containing Harmful Substances of Japan., Method: The gas chromatograph mass spectrometer (GC-MS) analytical method using hydrogen and nitrogen as alternative carrier gases was compared with a method using helium for 26 primary aromatic amines (PAAs) originated from azo dyes., Results: When hydrogen and nitrogen were used as carrier gases under the same conditions used during analysis using helium (same column, gas flow rate, oven temperature conditions, etc.), sufficient peak separation of 26 PAAs was obtained. The sensitivities of the methods using helium and hydrogen were comparable, whereas the sensitivity was lower when nitrogen was used, with the detection limits ranging from 1/220 to 1/25. However, all carrier gases achieved quantification at concentrations below the standard value (30 μg/g) of the Act on Control of Household Products Containing Harmful Substances, and the results were in agreement with the standard value for the target product., Conclusions: Our results indicated that hydrogen or nitrogen can be used as alternative carrier gases to helium for GC-MS analysis of azo compounds producing specific aromatic amines., Highlights: Using hydrogen or nitrogen as an alternative carrier gas to helium, azo compounds could be quantified with excellent accuracy., (© The Author(s) 2023. Published by Oxford University Press on behalf of AOAC INTERNATIONAL. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

HeHHe + is the only potential molecule comprised of atoms present in the early universe that is also easily observable in the infrared. This molecule has been known to exist in mass spectrometry experiments for nearly half-a-century and is likely present, but as-of-yet unconfirmed, in cold plasmas. There can exist only a handful of plausible primordial molecules in the epochs before metals (elements with nuclei heavier than 4 He as astronomers call them) were synthesized in the universe, and most of these are both rotationally and vibrationally dark. The current work brings HeHHe + into the discussion as a possible (and potentially only) molecular candle for probing high-z and any metal-deprived regions due to its exceptionally bright infrared feature previously predicted to lie at 7.43 μ m. Furthermore, the present study provides new insights into its possible formation mechanisms as well as marked stability, along with the decisive role of anharmonic zero-point energies. A new entrance pathway is proposed through the triplet state ( 3 B 1 ) of the He 2 H + molecule complexed with a hydrogen atom and a subsequent 10.90 eV charge transfer/photon emission into the linear and vibrationally-bright 1 Σ g + HeHHe + form.

Gas chromatography mass spectrometry (GC-MS) is a commonly used method for organic geochemistry for both academic research and applications such as petroleum analysis. Gas chromatography requires a carrier gas, which needs to be both volatile and stable and in most organic geochemical applications helium or hydrogen have been used, with helium predominating for gas chromatography mass spectrometry. Helium, however, is becoming an increasingly scarce resource and is not sustainable. Hydrogen is the most commonly considered alternative carrier gas to helium but has characteristics that in certain respects make its use less practical, foremost is that hydrogen is flammable and explosive. But as hydrogen is increasingly used as a fuel, higher demand may also make its use less desirable. Here we show that nitrogen can be used for the GC-MS analysis of fossil lipid biomarkers. Using nitrogen, chromatographic separation of isomers and homologues can be achieved, but sensitivity is orders of magnitude less than for helium. It is reasonable to use nitrogen as a carrier gas in applications where low levels of detection are not needed, such as the characterization of samples of crude oil or foodstuffs, or potentially as part of a gas-mixture seeking to reduce helium-demand but maintain a level of chromatographic separation sufficient to support proxy-based characterizations of petroleum., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

Purpose: To evaluate the applicability of microdosimetric kinetic model (MKM) to helium-ion therapy by forming a spread-out Bragg peak (SOBP) of a helium-ion beam using the MKM developed for carbon-ion radiotherapy and confirming the predictions in biological experiments., Methods: Using a ridge filter, a 90-mm wide SOBP for a 210 MeV/u helium-ion beam was created in a broad beam delivery system. The ridge filter was designed such that a uniform biological response was achieved with a cell survival rate of 7% over the SOBP region. Biological experiments were then performed using the SOBP beam in a human salivary gland (HSG) cell line to measure the cell survival rates., Results: The biological responses were uniform in the SOBP region, as expected by the MKM; however, the mean of the measured cell survival rates was (11.2 ± 0.6) % in the SOBP region, which was 60% higher than the designed rate. When investigating the biological parameters of the HSG cell line used in the experiments, we found that they were altered slightly from the MKM parameters used for carbon-ion radiotherapy. The new β parameter reproduced the measured survival rates within 6.5% in the SOBP region., Conclusion: We produced biologically uniform SOBP using MKM for carbon-ion radiotherapy. The measured survival rates in the SOBP region were higher than expected, and the survival rates were reproduced by modifying the MKM parameter. This study was limited to one SOBP, and further investigations are required to prove that MKM is generally applicable to helium-ion radiotherapy., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Associazione Italiana di Fisica Medica e Sanitaria. Published by Elsevier Ltd. All rights reserved.)

It is now known that the heavier noble gases (Ng=Ar-Rn) show some varying degrees of reactivity with a gradual increase in reactivity along Ar-Rn. However, because of their very small size and very high ionization potential, helium and neon are the hardest targets to crack. Although few neon complexes are isolated at very low temperatures, helium needs very extreme situations like very high pressure. Here, we find that protonated BeO, BeOH + can bind helium and neon spontaneously at room temperature. Therefore, extreme conditions like very low temperature and/or high pressure will not be required for their experimental isolation. The Ng-Be bond strength is very high for their heavier homologs and the bond strength shows a gradual increase from He to Rn. Moreover, the Ng-Be attractive energy is almost exclusively originated from the orbital interaction which is composed of one Ng(s/p σ )→BeOH + σ-donation and two weaker Ng(p π )→BeOH + π-donations, except for helium. Helium uses its low-lying vacant 2p orbitals to accept π-electron density from BeOH + . Previously, such electron-accepting ability of helium was used to explain a somewhat stronger helium bond than neon for neutral complexes. However, the present results indicate that such π-back donations are too weak in nature to decide any energetic trend between helium and neon., (© 2022 Wiley-VCH GmbH.)

We propose a combined helium-chemical modifier method for a faster and more convenient separation and detection of xylene isomers. The method employs high-field asymmetric waveform ion mobility spectrometry (FAIMS) to investigate the separation and identification of three xylene isomers. A homemade hollow needle-ring ion source was used, and five chemical modifiers, represented by methanol, ethanol, acetone, ethyl acetate, and acetic acid, were doped into the xylene target analytes to observe the separation and identification of the three isomers. This was based on the fact that the addition of helium and the increase of the RF voltage could no longer improve the resolution of the field asymmetric waveform ion mobility spectrometry system. The experimental results at an RF field voltage of 15 kV cm -1 showed that the spectral peak shifts of o -, m -, and p -xylene in a normal nitrogen environment were -0.21, -0.21, and -0.24 V, respectively. o -Xylene showed a spectral peak of -1.33 V after the addition of helium; however, the separation was not evident. The FAIMS spectrum of xylene showed multiple cluster ion peaks upon addition of the chemical modifiers on top of helium. The alcohol chemical modifiers caused three spectral peaks, with the best effect for methanol, and the characteristic ion peak positions of -7.16, -6.90, and -6.01 V for o -, m -, and p -xylene, respectively. The separation using proton-based chemical modifiers was confirmed to be stronger than that using non-proton-based chemical modifiers, and appropriate volume fractions of chemical modifiers provided a better separation of the target analytes. This study introduces a novel concept and method for the separation and identification of xylene isomers.

The ion chemistry of helium currently embraces a large variety of species, mostly cationic, which range from simple small-size molecular fragments or complexes to large-size cluster ions and encapsulation products. These species are usually observed under the isolated conditions of the gas phase or theoretically investigated by high-level of theory calculations. In the current years, the highest interest is focused on classical topics such as the interaction between helium atoms and monoatomic, diatomic, and simple polyatomic ions as well as on research themes which have more recently emerged, such as the study of ionized helium clusters and the fullerene-helium chemistry. The aim of the present article is to give an account of selected recent advances in these fields and to put them in the perspective of the previous most relevant acquisitions concerning the ion chemistry of helium. In particular, the literature covered here concerns the ionised helium clusters Hen+ and Hen- (n ≥ 2), the hydrogen-containing helium clusters HenH+ and HenH- (n ≥ 1), the adducts of one or more helium atoms with a variety of singly- and multiply-charged monoatomic, diatomic, and polyatomic ions, and cage compounds such as He @ C60+ and other related cationic and anionic species. [Copyright &y& Elsevier]

The combination of helium charge transfer dissociation mass spectrometry (He-CTD-MS) with ultrahigh performance liquid chromatography (UHPLC) is presented for the analysis of a complex mixture of acidic and neutral human milk oligosaccharides (HMOs). The research focuses on the identification of the monosaccharide sequence, the branching patterns, the sialylation/fucosylation arrangements, and the differentiation of isomeric oligosaccharides in the mixture. Initial studies first optimized the conditions for the UHPLC separation and the He-CTD-MS conditions. Results demonstrate that He-CTD is compatible with UHPLC timescales and provides unambiguous glycosidic and cross-ring cleavages from both the reducing and the nonreducing ends, which is not typically possible using collision-induced dissociation. He-CTD produces informative fragments, including 0,3An and 0,4An ions, which have been observed with electron transfer dissociation, electron detachment dissociation, and ultraviolet photodissociation (UVPD) and are crucial for differentiating the α-2,3- versus α-2,6-linked sialic acid (Neu5Ac) residues present among sialyllacto-N-tetraose HMOs. In addition to the linkage positions, He-CTD is able to differentiate structural isomers for both sialyllacto-N-tetraoses and lacto-N-fucopentaoses structures by providing unique, unambiguous cross-ring cleavages of types 0,2An, 0,2Xn, and 1,5An while preserving most of the labile Neu5Ac and fucose groups., (© The Author(s) 2022. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

SARS-CoV-2 virions enter the host cells by docking their spike glycoproteins to the membrane-bound Angiotensin Converting Enzyme 2. After intracellular assembly, the newly formed virions are released from the infected cells to propagate the infection, using the extra-cytoplasmic ACE2 docking mechanism. However, the molecular events underpinning SARS-CoV-2 transmission between host cells are not fully understood. Here, we report the findings of a scanning Helium-ion microscopy study performed on Vero E6 cells infected with mNeonGreen-expressing SARS-CoV-2. Our data reveal, with unprecedented resolution, the presence of: (1) long tunneling nanotubes that connect two or more host cells over submillimeter distances; (2) large scale multiple cell fusion events (syncytia); and (3) abundant extracellular vesicles of various sizes. Taken together, these ultrastructural features describe a novel intra-cytoplasmic connection among SARS-CoV-2 infected cells that may act as an alternative route of viral transmission, disengaged from the well-known extra-cytoplasmic ACE2 docking mechanism. Such route may explain the elusiveness of SARS-CoV-2 to survive from the immune surveillance of the infected host., (© 2022. The Author(s).)

The parasitic protozoan Giardia intestinalis, the causative agent of giardiasis, presents a stable and elaborated cytoskeleton, which shapes and supports several intracellular structures, including the ventral disc, the median body, the funis, and four pairs of flagella. Giardia trophozoite is the motile form that inhabits the host small intestine and attaches to epithelial cells, leading to infection. The ventral disc is considered one important element of adhesion to the intestinal cells. It is adjacent to the plasma membrane in the ventral region of the cell and consists of a spiral layer of microtubules and microribbons. In this work, we studied the organization of the cytoskeleton in the ventral disc of G. intestinalis trophozoites using high-resolution scanning electron microscopy or helium ion microscopy in plasma membrane-extracted cells. Here, we show novel morphological details about the arrangement of cross-bridges in different regions of the ventral disc. Results showed that the disc is a non-uniformly organized structure that presents specific domains, such as the margin and the ventral groove region. High-resolution scanning electron microscopy allowed observation of the labeling pattern for several anti-tubulin antibodies using secondary gold particle-labeled antibodies. Labeling in the region of the emergence of the microtubules and supernumerary microtubules using an anti-acetylated tubulin antibody was observed. Ultrastructural analysis and immunogold labeling for gamma-tubulin suggest that disc microtubules originate from a region bounded by the bands of the banded collar and merge with microtubules formed at the perinuclear region. Actin-like filaments and microtubules of the disc are associated, showing an interconnection between elements of the cytoskeleton of the trophozoite., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The low sensitivity of NMR spectroscopy is of historical concern in the field, and various approaches have been developed to mitigate this limitation. On the shoulder of giants, today one can routinely implement, for example, the pulse/Fourier transform NMR with the cross polarization together with the ultra-low temperature MAS DNP under high-field conditions. We show in this work this current opportunity should further be augmented by combining them with the cryogenic signal amplification. Our presented MAS DNP probe operates with the closed-cycle helium MAS system, and cools the internal preamplifier-duplexer module with the "return" helium gas on its way back to the compressor in the loop. The signal-to-noise (S/N) gain relative to the room-temperature measurements of a factor of 4.6 and 2.4 was found for the measurement using the cold- and room-temperature preamplifier, respectively, at the sample temperature of T = 20 K at B 0  = 16.4 T. The ratio of these factors reveals ∼ two-fold sensitivity improvement that results purely from the introduction of the cold signal amplification, i.e., noise reduction. Together with the increase of the thermal Boltzmann polarization at low temperatures, the combined S/N gain of max. ∼70-fold is possible without DNP. The DNP enhancement factor of ∼40 as we found in this work for a microcrystalline MLF sample may be multiplied to this gain. We also demonstrated the sensitivity improvement with a 13 C-detected 2D NCaCx spectrum, illustrating the generality of the S/N gain from combining DNP with the cold signal amplification., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Author(s). Published by Elsevier Inc. All rights reserved.)

The early mechanisms by which ionizing rays damage biological structures by so-called direct effects are largely elusive. In a recent picosecond pulse radiolysis study of concentrated uridine monophosphate solutions [J. Ma, S. A. Denisov, J.-L. Marignier, P. Pernot, A. Adhikary, S. Seki and M. Mostafavi, J. Phys. Chem. Lett. , 2018, 9 , 5105], unexpected results were found regarding the oxidation of the nucleobase. The signature of the oxidized nucleobase could not be detected 5 ps after the electron pulse, but only the oxidized phosphate, raising intriguing questions about the identity of charge-transfer mechanisms that could explain the absence of U + . We address here this question by means of advanced first-principles atomistic simulations of solvated uridine monophosphate, combining Density Functional Theory (DFT) with polarizable embedding schemes. We contrast three very distinct mechanisms of charge transfer covering the atto-, femto- and pico-second timescales. We first investigate the ionization mechanism and subsequent hole/charge migrations on a timescale of attoseconds to a few femtoseconds under the frozen nuclei approximation. We then consider a nuclear-driven phosphate-to-oxidized-nucleobase electron transfer, showing that it is an uncompetitive reaction channel on the sub-picosecond timescale, despite its high exothermicity and significant electronic coupling. Finally, we show that non-adiabatic charge transfer is enabled by femtosecond nuclear relaxation after ionization. We show that electronic decoherence and the electronic coupling strength are the key parameters that determine the hopping probabilities. Our results provide important insight into the interplay between electronics and nuclear motions in the early stages of the multiscale responses of biological matter subjected to ionizing radiation.

HeHHe + is the only potential molecule comprised of atoms present in the early universe that is also easily observable in the infrared. This molecule has been known to exist in mass spectrometry experiments for nearly half-a-century and is likely present, but as-of-yet unconfirmed, in cold plasmas. There can exist only a handful of plausible primordial molecules in the epochs before metals (elements with nuclei heavier than 4 He as astronomers call them) were synthesized in the universe, and most of these are both rotationally and vibrationally dark. The current work brings HeHHe + into the discussion as a possible (and potentially only) molecular candle for probing high-z and any metal-deprived regions due to its exceptionally bright infrared feature previously predicted to lie at 7.43 μ m. Furthermore, the present study provides new insights into its possible formation mechanisms as well as marked stability, along with the decisive role of anharmonic zero-point energies. A new entrance pathway is proposed through the triplet state ( 3 B 1 ) of the He 2 H + molecule complexed with a hydrogen atom and a subsequent 10.90 eV charge transfer/photon emission into the linear and vibrationally-bright 1 Σ g + HeHHe + form. [ABSTRACT FROM AUTHOR]

44 Sc has favorable properties for cancer diagnosis using Positron Emission Tomography (PET) making it a promising candidate for application in nuclear medicine. The implementation of its production with existing compact medical cyclotrons would mean the next essential milestone in the development of this radionuclide. While the production and application of 44 Sc has been comprehensively investigated, the development of specific targetry and irradiation methods is of paramount importance. As a result, the target was optimized for the 44 Ca(p,n) 44 Sc nuclear reaction using CaO instead of CaCO 3 , ensuring decrease in target radioactive degassing during irradiation and increased radionuclidic yield. Irradiations were performed at the research cyclotron at the Paul Scherrer Institute (~11 MeV, 50 µA, 90 min) and the medical cyclotron at the University of Bern (~13 MeV, 10 µA, 240 min), with yields varying from 200 MBq to 16 GBq. The development of targetry, chemical separation as well as the practical issues and implications of irradiations, are analyzed and discussed. As a proof-of-concept study, the 44 Sc produced at the medical cyclotron was used for a preclinical study using a previously developed albumin-binding prostate-specific membrane antigen (PSMA) ligand. This work demonstrates the feasibility to produce 44 Sc with high yields and radionuclidic purity using a medical cyclotron, equipped with a commercial solid target station.

Kinetic modeling of the behavior of complex chemical and biochemical systems is an effective approach to study of the mechanisms of the process. A kinetic model of coronaviral infection development with a description of the dynamic behavior of the main variables, including the concentration of viral particles, affected cells, and pathogenic microflora, is proposed. Changes in the concentration of hydrogen ions in the lungs and the pH -dependence of carbonic anhydrase activity (a key breathing enzyme) are critical. A significant result is the demonstration of an acute bifurcation transition that determines life or system collapse. This transition is connected with exponential growth of concentrations of the process participants and with functioning of the key enzyme carbonic anhydrase in development of toxic effects. Physical and chemical interpretations of the therapeutic effects of the body temperature rise and the potential therapeutic effect of "thermoheliox" (respiration with a thermolized mixture of helium and oxygen) are given. The phenomenon of "thermovaccination" is predicted, which involves stimulation of the immune response by "thermoheliox"., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Isolation of biomolecules in vacuum facilitates characterization of the intramolecular interactions that determine three-dimensional structure, but experimental quantification of conformer thermochemistry remains challenging. Infrared spectroscopy of molecules trapped in helium nanodroplets is a promising methodology for the measurement of thermochemical parameters. When molecules are captured in a helium nanodroplet, the rate of cooling to an equilibrium temperature of ca. 0.4 K is generally faster than the rate of isomerization, resulting in "shock-freezing" that kinetically traps molecules in local conformational minima. This unique property enables the study of temperature-dependent conformational equilibria via infrared spectroscopy at 0.4 K, thereby avoiding the deleterious effects of spectral broadening at higher temperatures. Herein, we demonstrate the first application of this approach to ionic species by coupling electrospray ionization mass spectrometry (ESI-MS) with helium nanodroplet infrared action spectroscopy to probe the structure and thermochemistry of deprotonated DNA dinucleotides. Dinucleotide anions were generated by ESI, confined in an ion trap at temperatures between 90 and 350 K, and entrained in traversing helium nanodroplets. The infrared action spectra of the entrained ions show a strong dependence on pre-pickup ion temperature, consistent with the preservation of conformer population upon cooling to 0.4 K. Non-negative matrix factorization was utilized to identify component conformer infrared spectra and determine temperature-dependent conformer populations. Relative enthalpies and entropies of conformers were subsequently obtained from a van't Hoff analysis. IR spectra and conformer thermochemistry are compared to results from ion mobility spectrometry (IMS) and electronic structure methods. The implementation of ESI-MS as a source of dopant molecules expands the diversity of molecules accessible for thermochemical measurements, enabling the study of larger, non-volatile species.

Water radical cations, (H 2 O) n +• , are of great research interest in both fundamental and applied sciences. Fundamental studies of water radical reactions are important to better understand the mechanisms of natural processes, such as proton transfer in aqueous solutions, the formation of hydrogen bonds and DNA damage, as well as for the discovery of new gas-phase reactions and products. In applied science, the interest in water radicals is prompted by their potential in radiobiology and as a source of primary ions for selective and sensitive chemical ionization. However, in contrast to protonated water clusters, (H 2 O) n H + , which are relatively easy to generate and isolate in experiments, the generation and isolation of radical water clusters, (H 2 O) n +• , is tremendously difficult due to their ultra-high reactivity. This review focuses on the current knowledge and unknowns regarding (H 2 O) n +• species, including the methods and mechanisms of their formation, structure and chemical properties.

Single protein imaging and understanding their interactions are of paramount importance to understand the life phenomena. Recently reported multiplex protein SIMS imaging methodology using metal-oxide nanoparticle conjugated antibodies can be extended to a single protein imaging methodology using He ion microscopy (HIM). It is proposed here that single protein can be imaged in the microscale and the nanoscale by the complementary use of SIMS and HIM.

The connection between monosaccharides influences the structure, solubility, and biological function of carbohydrates. Although tandem mass spectrometry (MS/MS) often enables the compositional identification of carbohydrates, traditional MS/MS fragmentation methods fail to generate abundant cross-ring fragments of intrachain monosaccharides that could reveal carbohydrate connectivity. We examined the potential of helium-charge transfer dissociation (He-CTD) as a method of MS/MS to decipher the connectivity of β-1,4- and β-1,3-linked oligosaccharides. In contrast to collision-induced dissociation (CID), He-CTD of isolated oligosaccharide precursors produced both glycosidic and cross-ring cleavages of each monosaccharide. The radical-driven dissociation in He-CTD induced single cleavage events, without consecutive fragmentations, which facilitated structural interpretation. He-CTD of various standards up to a degree of polymerization of 7 showed that β-1,4- and β-1,3-linked carbohydrates can be distinguished based on diagnostic 3,5 A fragment ions that are characteristic for β-1,4-linkages. Overall, fragment ion spectra from He-CTD contained sufficient information to infer the connectivity specifically for each glycosidic bond. When testing He-CTD to resolve the order of β-1,4- and β-1,3-linkages in mixed-linked oligosaccharide standards, He-CTD spectra sometimes provided less confident assignment of connectivity. Ion mobility spectrometry-mass spectrometry (IMS-MS) of the standards indicated that ambiguity in the He-CTD spectra was caused by isobaric impurities in the mixed-linked oligosaccharides. Radical-driven dissociation induced by He-CTD can thus expand MS/MS to carbohydrate linkage analysis, as demonstrated by the comprehensive fragment ion spectra on native oligosaccharides. The determination of connectivity in true unknowns would benefit from the separation of isobaric precursors, through UPLC or IMS, before linkage determination via He-CTD.

This article describes a new simultaneous method for the analysis of sulfur-type poisons, hydrocarbons and permanent gases affecting the productivity of the Ziegler Natta catalyst during the synthesis of polypropylene on an industrial scale in a fluidized-bed reactor. The identification was achieved employing a configuration of the seven-valve chromatographic system, with events at different times, allowing distribution of the sample through multiple columns, and finally reaching the helium ionization detectors of pulsed discharge, flame ionization and mass spectrometry. The results obtained show a good precision of the method used because the variability was less than 1.02% in area and 0.49% in retention time for short term precisión and longer term precision . The quantification of these species was successful after performing the calibration curve with the dynamic mixer showing an r 2 higher than 0.9945 and excellent linearity. The lowest LOD value was 0.01 mg kg -1 for carbonyl sulphide, hydrogen sulfide, ethylmercaptan and propylmercaptan and the lowest LOQ was 0.03 mg kg -1 for hydrogen sulfide. The highest LOD and LOQ values were for oxygen and carbon dioxide with 0.40 and 0.93 mg kg -1 respectively. With this configuration, the correlation of data between the three detectors was simplified, having almost identical retention times for the analytes studied. The poisons detected and quantified in the samples were: hydrogen sulfide (0.1-0.5 mg kg -1 ), carbonyl sulphide (0.012-0.06 mg kg -1 ), carbon disulphide (0.04-0.22 mg kg -1 ), methylmercaptan (0.12-12.51 mg kg -1 ), ethylmercaptan (0.9-5.5 mg kg -1 ), carbon dioxide (0.10-3.0 mg kg -1 ), oxygen (0.55-6.1 mg kg -1 ), acetylene (0.15-3.5 mg kg -1 ) and methylacetylene (0.04-0.2 mg kg -1 ). The productivity losses were between 5 and 22%., Competing Interests: Declaration of Competing Interest None., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Radiolysis of biomolecules by fast ions has interest in medical applications and astrobiology. The radiolysis of solid D-valine (0.2-2 μm thick) was performed at room temperature by 1.5 MeV H + , He + , N + , and 230 MeV S 15+ ion beams. The samples were prepared by spraying/dropping valine-water-ethanol solution on ZnSe substrate. Radiolysis was monitored by infrared spectroscopy (FTIR) through the evolution of the intensity of the valine infrared 2900, 1329, 1271, 948, and 716 cm -1 bands as a function of projectile fluence. At the end of sample irradiation, residues (tholins) presenting a brownish color are observed. The dependence of the apparent (sputtering + radiolysis) destruction cross section, σ d , on the beam stopping power in valine is found to follow the power law σ d = aS e n , with n close to 1. Thus, σ d is approximately proportional to the absorbed dose. Destruction rates due to the main galactic cosmic ray species are calculated, yielding a million year half-life for solid valine in space. Data obtained in this work aim a better understanding on the radioresistance of complex organic molecules and formation of radioproducts.

Protonated rare gas clusters have previously been shown to display markably different structures than their pure, cationic counterparts. Here we have performed high resolution mass spectrometry measurements of protonated and pristine clusters of He containing up to 50 atoms. We identify notable differences between the magic numbers present in the two types of clusters, but in contrast to heavier rare gas clusters, neither the protonated nor pure clusters exhibit signs of icosahedral symmetries. These findings are discussed in light of results from heavier rare gases and previous theoretical work on protonated helium.

Using methods of pulsed laser ablation from a silicon target in helium (He)-nitrogen (N 2 ) gas mixtures maintained at reduced pressures (0.5-5 Torr), we fabricated substrate-supported silicon (Si) nanocrystal-based films exhibiting a strong photoluminescence (PL) emission, which depended on the He/N 2 ratio. We show that, in the case of ablation in pure He gas, Si nanocrystals exhibit PL bands centered in the "red - near infrared" (maximum at 760 nm) and "green" (centered at 550 nm) spectral regions, which can be attributed to quantum-confined excitonic states in small Si nanocrystals and to local electronic states in amorphous silicon suboxide (a-SiO x ) coating, respectively, while the addition of N 2 leads to the generation of an intense "green-yellow" PL band centered at 580 nm. The origin of the latter band is attributed to a radiative recombination in amorphous oxynitride (a-SiN x O y ) coating of Si nanocrystals. PL transients of Si nanocrystals with SiO x and a-SiN x O y coatings demonstrate nonexponential decays in the micro- and submicrosecond time scales with rates depending on nitrogen content in the mixture. After milling by ultrasound and dispersing in water, Si nanocrystals can be used as efficient non-toxic markers for bioimaging, while the observed spectral tailoring effect makes possible an adjustment of the PL emission of such markers to a concrete bioimaging task., Competing Interests: The authors declare no conflict of interest.

Glycosaminoglycans (GAGs) are a physio- and pharmacologically highly relevant class of complex saccharides, possessing a linear sequence and strongly acidic character. Their repetitive linear core makes them seem structurally simple at first glance, yet differences in sulfation and epimerization lead to an enormous structural diversity with only a few GAGs having been successfully characterized to date. Recent infrared action spectroscopic experiments on sulfated mono- and disaccharide ions show great promise. Here, we assess the potential of two types of gas-phase action spectroscopy approaches in the range from 1000 to 1800 cm -1 for the structural analysis of complex GAG oligosaccharides. Synthetic tetra- and pentasaccharides were chosen as model compounds for this benchmark study. Utilizing infrared multiple photon dissociation action spectroscopy at room temperature, diagnostic bands are largely unresolved. In contrast, cryogenic infrared action spectroscopy of ions trapped in helium nanodroplets yields resolved infrared spectra with diagnostic features for monosaccharide composition and sulfation pattern. The analysis of GAGs could therefore significantly benefit from expanding the conventional MS-based toolkit with gas-phase cryogenic IR spectroscopy. Graphical abstract.

The present work focuses on unraveling the collisional processes leading to the fragmentation of the gas-phase furan molecules under the He + and He 2+ cations impact in the energy range 5-2000 eV. The presence of different mechanisms was identified by the analysis of the optical fragmentation spectra measured using the collision-induced emission spectroscopy (CIES) in conjunction with the ab initio calculations. The measurements of the fragmentation spectra of furan were performed at the different kinetic energies of both cations. In consequence, several excited products were identified by their luminescence. Among them, the emission of helium atoms excited to the 1 s 4 d 1 D 2 , 3 D 1,2,3 states was recorded. The structure of the furan molecule lacks an He atom. Therefore, observation of its emission lines is spectroscopic evidence of an impact reaction occurring via relocation of the electronic charge between interacting entities. Moreover, the recorded spectra revealed significant variations of relative band intensities of the products along with the change of the projectile charge and its velocity. In particular, at lower velocities of He + , the relative cross-sections of dissociation products have prominent resonance-like maxima. In order to elucidate the experimental results, the calculations have been performed by using a high level of quantum chemistry methods. The calculations showed that in both impact systems two collisional processes preceded fragmentation. The first one is an electron transfer from furan molecules to cations that leads to the neutralization and further excitation of the cations. The second mechanism starts from the formation of the He-C 4 H 4 O +/2+ temporary clusters before decomposition, and it is responsible for the appearance of the narrow resonances in the relative cross-section curves.

Objectives: The influence of commercial helium-oxygen saturation diving on divers' gut microbiotas was assessed to provide dietary suggestion., Methods: Faecal samples of 47 divers working offshore were collected before (T1), during (T2) and after (T3) saturation diving. Their living and excursion depths were 55-134 metres underwater with a saturation duration of 12-31 days and PaO 2 of 38-65 kPa. The faecal samples were examined through 16S ribosomal DNA amplicon sequencing based on the Illumina sequencing platform to analyse changes in the bacteria composition in the divers' guts., Results: Although the α and β diversity of the gut microbiota did not change significantly, we found that living in a hyperbaric environment of helium-oxygen saturation decreased the abundance of the genus Bifidobacterium , an obligate anaerobe, from 2.43%±3.83% at T1 to 0.79%±1.23% at T2 and 0.59%±0.79% at T3. Additionally, the abundance of some short-chain fatty acid (SCFA)-producing bacteria, such as Fusicatenibacter, Faecalibacterium , rectale group and Anaerostipes , showed a decreased trend in the order of before, during and after diving. On the contrary, the abundance of species, such as Lactococcus garvieae , Actinomyces odontolyticus , Peptoclostridium difficile , Butyricimonas virosa , Streptococcus mutans , Porphyromonas asaccharolytica and A. graevenitzii , showed an increasing trend, but most of them were pathogens., Conclusions: Occupational exposure to high pressure in a helium-oxygen saturation environment decreased the abundance of Bifidobacterium and some SCFA-producing bacteria, and increased the risk of pathogenic bacterial infection. Supplementation of the diver diet with probiotics or prebiotics during saturation diving might prevent these undesirable changes., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2019. No commercial re-use. See rights and permissions. Published by BMJ.)

Here we validate a GC, Flame Ionization Detection (GC-FID), liquid injection method using hydrogen as a carrier gas combining analysis of toxic volatile alcohols (VA): methanol, ethanol, isopropanol, acetone, as well as glycols, ethylene glycol (EG) and propylene glycol (PG), in a single method., Methodology: 200 μL of calibrator, QC, or patient specimen were deproteinized with 400 μL of acetonitrile containing internal standards (10 mmol/L N-propyl alcohol for VA and 2.5 mmol/L 1,2-butanediol for glycols). GC-FID analysis using hydrogen carrier gas and nitrogen makeup gas utilized an Agilent 7890 system equipped with Agilent 7683 liquid autosampler on a 30 m × 530 μm RTX-200 fused silica column. Method validation included repeatability, recovery, carryover, linearity, lower limit of quantification (LLOQ), accuracy, selectivity and measurement uncertainty., Results: The 8.3 min from injection to injection reduced time of analysis by 45% over a previously reported method using Helium carrier gas with no loss in resolution. Within-run and Between-run variability were ≤1.4% and ≤6.8% respectively. Recovery was 100% within a 95% confidence interval. Carryover was negligible for all but EG. LLOQ was <1 mmol/L for all analytes. The upper range of linearity was 120 mmol/L for methanol, ethanol and isopropanol, 100 mmol/L for acetone and 50 mmol/L for EG. Analytes demonstrated acceptable accuracy and measurement uncertainty using College of American Pathologists (CAP) criteria. Toluene can cause a false positive EG, while benzene, xylene and 1,3 butanediol can cause false negative EG., Conclusions: Converting from Helium to Hydrogen carrier gas benefits patient care through a reduction in turnaround time and provides a cost savings to the laboratory., (Copyright © 2019 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.)

We apply the formally exact quantum power functional framework ( J. Chem. Phys. 2015 , 143 , 174108) to a one-dimensional Hooke's helium model atom. The physical dynamics are described on the one-body level beyond the density-based adiabatic approximation. We show that gradients of both the microscopic velocity and acceleration field are required to correctly describe the effects due to interparticle interactions. We validate the proposed analytical forms of the superadiabatic force and transport contributions by comparison to one-body data from exact numerical solution of the Schrödinger equation. Superadiabatic contributions beyond the adiabatic approximation are important in the dynamics and they include effective dissipation.

Methylation of arginine residues in proteins, an enzyme-mediated post-translational modification (PTM), is important for mRNA processing and transport and for the regulation of many protein-protein interactions. However, proteolytic peptides resulting from alternative sites of post-translational methylation have identical masses and cannot be readily separated by standard liquid chromatography-mass spectrometry. Unlike acetylation or phosphorylation, methylation of arginine does not strongly affect the charge states of peptide ions, multiple instances of methylation can occur on a single amino acid residue, and the relative mass of the modification is <1% that of the typical proteolytic peptide. High field asymmetric waveform ion mobility spectrometry (FAIMS) is an orthogonal separation method to liquid chromatography that can rapidly separate gaseous ions prior to detection by mass spectrometry. Here, we report that FAIMS can be used to separate arginine-methylated peptides that differ by the position of a single methyl group for both mono- and dimethylated variants. Although the resolution of separation for these arginine-methylated peptides improved with increasing amounts of helium in the FAIMS carrier gas as expected, we found that the site of methylation can strongly affect the dependence of the electric field used for ion transmission on the extent of helium in the carrier gas. Thus, certain isobaric peptides can be cotransmitted at high helium concentrations whereas lower concentrations can be used for successful separations of such peptide mixtures. The capability to rapidly resolve isobaric arginine-methylated peptides should be useful in the future for the detailed analysis of protein arginine methylation in biological samples.

We herein report the development of a compact and robust optical emission spectrometry (OES)-based technique for the ultrasensitive determination of Se and As utilizing hydride generation (HG) as the sampling technique and direct-current atmospheric pressure glow discharge in He (APGD) as the radiation source. The emission sensitivities of 50 ng mL -1 Se and As in the newly designed HG-APGD were enhanced more than 3-fold by constraining the spatial volume between two hollow-tube APGD electrodes, and the stability was significantly improved. The developed technique achieved Se and As detection limits of 0.13 and 0.087 ng mL -1 , respectively, with the corresponding relative standard deviations at analyte concentrations of 50 ng mL -1 being <0.5% in both cases. Moreover, the HG-APGD-OES procedure was advantageous in that it exhibited a low power consumption (<17 W) and a low gas consumption (<100 mL min -1 ). Its accuracy and practicality were also demonstrated by the determination of GBW10024 (scallop) and GBW07381 (stream sediments) certified reference materials and mice blood samples. The results showed good agreement with the certified values and values obtained using inductively coupled plasma-mass spectrometry.

Exposure to the types of radiation encountered outside the magnetic field of the earth can disrupt cognitive performance. Exploratory class missions to other planets will include both male and female astronauts. Because estrogen can function as a neuroprotectant, it is possible that female astronauts may be less affected by exposure to space radiation than male astronauts. To evaluate the effectiveness of estrogen to protect against the disruption of cognitive performance by exposure to space radiation intact and ovariectomized female rats with estradiol or vehicle implants were tested on novel object performance and operant responding on an ascending fixed-ratio reinforcement schedule following exposure to 12 C (290 MeV/n) or 4 He (300 MeV/n) particles. The results indicated that exposure to carbon or helium particles did not disrupt cognitive performance in the intact rats. Estradiol implants in the ovariectomized subjects exacerbated the disruptive effects of space radiation on operant performance. Although estrogen does not appear to function as a neuroprotectant following exposure to space radiation, the present data suggest that intact females may be less responsive to the deleterious effects of exposure to space radiation on cognitive performance, possibly due to the effects of estrogen on cognitive performance., (Copyright © 2019 The Committee on Space Research (COSPAR). All rights reserved.)

Among additive manufacturing (AM) techniques, laser or electron beam based processes have been widely investigated for metallic implants. Despite the potential in manufacturing of patient-specific biomedical implants, 3D inkjet powder printing (3DIJPP, a variant of AM) of biomaterials is still in its infancy, as little is known quantitatively about the transient process physics and dynamics. An equally important challenge has been the ink formulation to manufacture biomaterials with reliable mechanical properties and desired biocompatibility. We have developed, for the very first time, the theoretical foundation and experimental formulation of a unique process strategy involving the 'on-demand' delivery of a novel in situ polymerisable acrylic ink system to print a model biomaterial, Ti-6Al-4V. The post-ejection in-flight dynamics of ink droplets have been captured in situ by employing high speed stroboscopic shadowgraphy, to quantitatively estimate the dimensionless numbers of fluid physics for 'printability' assessment. Washburn model was adapted extensively to quantify the capillary ink infiltration time in porous powder bed of finite thickness. On the other hand, particle tracking mode in diffusing wave spectroscopy (DWS) was exploited to analyse the timescale for effective binding of powder particles during in situ polymerisation. The clinically relevant combination of 3D porous architecture with 98.4% interconnectivity among 10-40 μm pores together with modest combination of elastic modulus (4 GPa) and strength reliability (Weibull modulus ∼8.1) establish the potential of inkjet printed Ti-6Al-4V as cortical bone analogue. A better cell attachment, viability, cytoskeletal spreading with pronounced proliferation of murine fibroblasts and pre-osteoblasts on 3DIJPP Ti-6Al-4V, when benchmarked against the metallurgically processed (commercial) or selective laser melted (SLM) Ti-6Al-4V, has been demonstrated, in vitro. The enhanced cellular activities on the 3DIJPP Ti-6Al-4V was explained in terms of an interplay among the elastic stiffness, surface roughness and wettability against the same benchmarking. It is conceived that the quantitative understanding of the integrated process physics and dynamics to print Ti-6Al-4V with reliable mechanical properties together with better cytocompatibility can lead to a paradigm shift in adapting the scalable 3DIJPP for manufacturing of metallic biomaterials., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Cold Atmospheric Plasma (CAP) is a novel promising tool developed in several biomedical applications such as cutaneous wound healing or skin cancer. Nevertheless, in vitro studies are lacking regarding to CAP effects on cellular actors involved in healthy skin healing and regarding to the mechanism of action. In this study, we investigated the effect of a 3 minutes exposure to CAP-Helium on human dermal fibroblasts and Adipose-derived Stromal Cells (ASC) obtained from the same tissue sample. We observed that CAP treatment did not induce cell death but lead to proliferation arrest with an increase in p53/p21 and DNA damages. Interestingly we showed that CAP treated dermal fibroblasts and ASC developed a senescence phenotype with p16 expression, characteristic morphological changes, Senescence-Associated β-galactosidase expression and the secretion of pro-inflammatory cytokines defined as the Senescence-Associated Secretory Phenotype (SASP). Moreover this senescence phenotype is associated with a glycolytic switch and an increase in mitochondria content. Despite this senescence phenotype, cells kept in vitro functional properties like differentiation potential and immunomodulatory effects. To conclude, we demonstrated that two main skin cellular actors are resistant to cell death but develop a senescence phenotype while maintaining some functional characteristics after 3 minutes of CAP-Helium treatment in vitro.

Ion computed tomography (iCT) represents a potential replacement for x-ray CT (xCT) in ion therapy treatment planning to reduce range uncertainties, inherent in the semi-empirical conversion of xCT information into relative stopping power (RSP). In this work, we aim to quantify the increase in dosimetric accuracy associated with using proton-, helium- and carbon-CT compared to conventional xCT for clinical scenarios in proton therapy. Three cases imaged with active beam-delivery using an ideal single-particle-tracking detector were investigated using FLUKA Monte-Carlo (MC) simulations. The RSP accuracy of the iCTs was evaluated against the ground truth at similar physical dose. Next, the resulting dosimetric accuracy was investigated by using the RSP images as a patient model in proton therapy treatment planning, in comparison to common uncertainties associated with xCT. Finally, changes in relative biological effectiveness (RBE) with iCT particle type/spectrum were investigated by incorporating the repair-misrepair-fixation (RMF) model into FLUKA, to enable first insights on the associated biological imaging dose. Helium-CT provided the lowest overall RSP error, whereas carbon-CT offered the highest accuracy for bone and proton-CT for soft tissue. For a single field, the average relative proton beam-range variation was  -1.00%, +0.09%, -0.08% and  -0.35% for xCT, proton-, helium- and carbon-CT, respectively. Using a 0.5%/0.5mm gamma-evaluation, all iCTs offered comparable accuracy with a better than 99% passing rate, compared to 83% for xCT. The RMF model predictions for RBE for cell death relative to a diagnostic xCT spectrum were 0.82-0.85, 0.85-0.89 and 0.97-1.03 for proton-, helium-, and carbon-CT, respectively. The corresponding RBE for DNA double-strand break induction was generally below one. iCT offers great clinical potential for proton therapy treatment planning by providing superior dose calculation accuracy as well as lower physical and potentially biological dose exposure compared to xCT. For the investigated dose level and ideal detector, proton-CT and helium-CT yielded the best performance.

Purpose: To compare in vivo lung morphometry parameters derived from theoretical gas diffusion models, the cylinder model and stretched exponential model, in a range of acinar microstructural length scales encountered in healthy and diseased lungs with 3 He and 129 Xe diffusion-weighted MRI., Methods: Three-dimensional multiple b-value 3 He and 129 Xe diffusion-weighted MRI was acquired with compressed sensing at 1.5 T from 51 and 31 subjects, respectively, including healthy volunteers, ex-smokers, idiopathic pulmonary fibrosis, and chronic obstructive pulmonary disease patients. For each subject, the stretched exponential model-derived mean diffusive length scale (Lm D ) was calculated from the diffusion signal decay, and was compared with the cylinder model-derived mean chord length (Lm) and mean alveolar diameter (L Alv ) in order to determine the relationships among the different lung morphometry parameters., Results: For both 3 He and 129 Xe diffusion-weighted MRI, the mean global Lm D value was significantly related (P < .001) to Lm in a nonlinear power relationship, whereas the L Alv demonstrated excellent linear correlation (P < .001) with Lm D . A mean bias of +1.0% and - 2.6% toward Lm D was obtained for Bland-Altman analyses of 3 He and 129 Xe Lm D and L Alv values, suggesting that the two morphometric parameters are equivalent measures of mean acinar dimensions., Conclusion: Within the experimental range of parameters considered here for both 3 He and 129 Xe, the stretched exponential model-derived Lm D is related nonlinearly to cylinder model-derived Lm, and demonstrates excellent agreement with the cylinder model-derived L Alv ., (© 2018 International Society for Magnetic Resonance in Medicine.)

The tissue-equivalent proportional counter (TEPC) is the most accurate device for measuring the microdosimetric properties of a particle beam but, since the lower operation limit of common TEPCs is ~0.3 μm, no detailed information on the track structure of the impinging particles can be obtained. The pattern of particle interactions at the nanometric level is measured directly by only three different nanodosimeters worldwide: practical instruments are not yet available. In order to partially fill the gap between microdosimetry and track-nanodosimetry, a low-pressure avalanche-confinement TEPC was designed and constructed for simulating tissue-equivalent sites down to the nanometric region. The present paper aims at describing the response of this TEPC in the range 0.3 μm-25 nm to a 62 MeV/n 4He ion beam. The experimental results, for depths near the Bragg peak, show good agreement with FLUKA simulations and suggest that, for smaller depths, the distribution is highly influenced by secondary electrons., (© The Author(s) 2018. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

The high Lewis basicity and small ionic radius of fluoride promote the formation of strong ionic hydrogen bonds in the complexation of fluoride with protic molecules. Herein, we report that carbonic acid, a thermodynamically disfavored species that is challenging to investigate experimentally, forms a complex with fluoride in the gas phase. Intriguingly, this complex is highly stable and is observed in abundance upon nanoelectrospray ionization of an aqueous sodium fluoride solution in the presence of gas-phase carbon dioxide. We characterize the structure and properties of the carbonic acid-fluoride complex, F - (H 2 CO 3 ), and its deuterated isotopologue, F - (D 2 CO 3 ), by helium nanodroplet infrared action spectroscopy in the photon energy range of 390-2800 cm -1 . The complex adopts a C 2 v symmetry structure with the carbonic acid in a planar trans-trans conformation and both OH groups forming ionic hydrogen bonds with the fluoride. Substantial vibrational anharmonic effects are observed in the infrared spectra, most notably a strong blue shift of the symmetric hydrogen stretching fundamental relative to predictions from the harmonic approximation or vibrational second-order perturbation theory. Ab initio thermostated ring-polymer molecular dynamics simulations indicate that this blue shift originates from strong coupling between the hydrogen stretching and bending vibrations, resulting in an effective weakening of the OH···F - ionic hydrogen bonds.

Central nervous system injuries are a leading cause of death and disability worldwide. Although the exact pathophysiological mechanisms of various brain injuries vary, central nervous system injuries often result in an inflammatory response, and subsequently lead to brain damage. This suggests that neuroprotection may be necessany in the treatment of multiple disease models. The use of medical gases as neuroprotective agents has gained great attention in the medical field. Medical gases include common gases, such as oxygen, hydrogen and carbon dioxide; hydrogen sulphide and nitric oxide that have been considered toxic; volatile anesthetic gases, such as isoflurane and sevoflurane; and inert gases like helium, argon, and xenon. The neuroprotection from these medical gases has been investigated in experimental animal models of various types of brain injuries, such as traumatic brain injury, stroke, subarachnoid hemorrhage, cerebral ischemic/reperfusion injury, and neurodegenerative diseases. Nevertheless, the transition into the clinical practice is still lagging. This delay could be attributed to the contradictory paradigms and the conflicting results that have been obtained from experimental models, as well as the presence of inconsistent reports regarding their safety. In this review, we summarize the potential mechanisms underlying the neuroprotective effects of medical gases and discuss possible candidates that could improve the outcomes of brain injury., Competing Interests: None

The field of taxonomy is critically important for the identification, conservation, and ecology of biological species. Modern taxonomists increasingly need to employ advanced imaging techniques to classify organisms according to their observed morphological features. Moreover, the generation of three-dimensional datasets is of growing interest; moving beyond qualitative analysis to true quantitative classification. Unfortunately, biological samples are highly vulnerable to degradation under the energetic probes often used to generate these datasets. Neutral atom beam microscopes avoid such damage due to the gentle nature of their low energy probe, but to date have not been capable of producing three-dimensional data. Here we demonstrate a means to recover the height information for samples imaged in the scanning helium microscope (SHeM) via the process of stereophotogrammetry. The extended capabilities, namely sparse three-dimensional reconstructions of features, were showcased via taxonomic studies of both flora (Arabidopsis thaliana) and fauna (Heterodontus portusjacksoni). In concert with the delicate nature of neutral helium atom beam microscopy, the stereophotogrammetry technique provides the means to derive comprehensive taxonomical data without the risk of sample degradation due to the imaging process.

Sulfasalazine (SSZ) is a well-known anti-inflammatory drug and also an inhibitor of the cystine-glutamate antiporter that is known to reduce intracellular glutathione (GSH) level and increase cellular oxidative stress, indicating its anti-tumor potential. However, the combination of SSZ with other physical modalities remains unexplored. Here, the effects of SSZ on cold atmospheric helium plasma (He-CAP), which produces approximately 24 x higher concentration of hydroxyl radicals (. OH) compared to X-irradiation (IR) in aqueous solution, and on IR-induced apoptosis in human leukemia Molt-4 cells were studied to elucidate the mechanism of apoptosis enhancement. Both the Annexin V-FITC/PI and DNA fragmentation assay revealed that pre-treatment of cells with SSZ significantly enhanced He-CAP and IR-induced apoptosis. Similar enhancement was observed during the loss of mitochondrial membrane potential, intracellular Ca 2+ ions, and mitochondria- and endoplasmic reticulum-related proteins. The concentration of intracellular reactive oxygen species (ROS) was much higher in He-CAP treated cells than in X-irradiated cells. On the other hand, strong enhancement of Fas expression and caspase-8 and -3 activities were only observed in X-irradiated cells. It might be possible that the higher concentration of intracellular and extracellular ROS suppressed caspase activities and Fas expression in He-CAP-treated cells. Notably, pretreating the cells with an antioxidant N-acetyl-L-cysteine (NAC) dramatically decreased apoptosis in cells treated by He-CAP, but not by IR. These results suggest that IR-induced apoptosis is due to specific and effective ROS distribution since intracellular ROS formation is marginal and the high production of ROS inside and outside of cells plays unique roles in He-CAP induced apoptosis. We conclude that our data provides efficacy and mechanistic insights for SSZ, which might be helpful for establishing SSZ as a future sensitizer in He-CAP or IR therapy for cancer., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Helium, a minor component of natural gas and radioactive minerals, is most commonly used as a carrier in gas chromatography-mass spectrometry (GC-MS). Its scarcity leads to limited availability and higher costs. In this experiment, hydrogen from a safe source of a hydrogen generator was tested as a substitutive carrier gas for the detection of adulterant in traditional Chinese medicine (TCM) and food supplements by GC-MS analysis. We found that the limits of detection (LODs) of using hydrogen were from 10 to 1000 μg/g. The levels of LODs tested among 170 drugs remain the same whether hydrogen or helium was used as a carrier gas with the exception of 7 drugs-benzbromarone, estradiol benzoate, bezafibrate, mefenamic acid, oxymetholone, piperidenafil and cetilistat. The real sample analysis results using hydrogen were as satisfactory as those using helium. In addition, the retention time was shortened after the chromatographic performance was optimized. In summary, it is worth considering hydrogen as a carrier gas due to its affordable costs, energy efficiency, carbon reduction and chromatographic advantages to detect adulterated drugs in TCM and dietary supplement using GC-MS., Competing Interests: The authors have declared that no competing interests exist.

Hyperpolarized 3 He gas allows the air spaces of the lungs to be imaged via MRI. Imaging of restricted diffusion is addressed here, which allows the microstructure of the lung to be characterized through the physical restrictions to gas diffusion presented by airway and alveolar walls in the lung. Measurements of the apparent diffusion coefficient (ADC) of 3 He at time scales of milliseconds and seconds are compared; measurement of acinar airway sizes by determination of the microscopic anisotropy of diffusion is discussed. This is where Dr. JJH Ackerman's influence was greatest in aiding the formation of the Washington University 3 He group, involving early a combination of physicists, radiologists, and surgeons, as the first applications of 3 He ADC were to COPD and its destruction/modification of lung microstructure via emphysema. The sensitivity of the method to early COPD is demonstrated, as is its validation by direct comparison to histology. More recently the method has been used broadly in adult and pediatric obstructive lung diseases, from severe asthma to cystic fibrosis to bronchopulmonary dysplasia, a result of premature birth. These applications of the technique are discussed briefly., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Helium ion microscopy (HIM) scans samples with a fine ion beam exploiting the very short de Broglie wavelength of helium ions. Because the radiation induces only a small sample region to emit secondary electrons (SEs), very high resolution is expected. In order to explore the applications of SE-HIM in biology, COS7 kidney fibroblast cells and C2C12 myoblast cells cultured on a silicon (Si) nitride (SiN)/Si bilayer were dried and directly observed in high vacuum, without coating or staining. High contrast, high depth-of-field images were obtained revealing the nucleus, endoplasmic reticulum, cytoskeleton and putative mitochondria above a bright background from the support. Gold-tagged antibodies were employed to aid organelle identification. Signals from the gold tags were most clearly distinguishable by secondary electron (SE)-HIM when cells were grown on thin SiN film, and the minimum gap measured between gold particles showed the resolution to be 2 nm. Wheat germ agglutinin-gold labeling revealed clusters of gold particles ~50-200 nm in diameter on COS7 cells, which might represent assemblies of glycosylated proteins, suggesting the formation of membrane raft structures that include membrane proteins. SE-HIM also delivered high contrast images of unstained, uncoated, thin sections of Epon‑embedded mouse kidney tissues mounted on a SiN/Si bilayer, revealing the details of sub-tissues and cell organelles. A charge-coupled mechanism explaining the observed SE-HIM contrast is proposed. Ionoluminescence-HIM was also performed targeting zinc oxide particles on cells. In conclusion, the high depth-of-field, high-resolution imaging achieved using HIM may have applications in various fields, including soft materials.