Neutral Species Research Articles

Molecular analysis of nitrogen-containing compounds in vacuum gas oils hydrodenitrogenation by (ESI+/-)-FTICR-MS

This paper is a part of a study on reactivity descriptors in vacuum gas oil hydrotreatment (VGO HDT). It aims to understand the differences in feeds of various process origins and the corresponding hydrotreated effluents on a molecular level. Four different vacuum gas oils were hydrotreated over a sulfided NiMo/Al2O3 catalyst at a wide range of temperatures and residence times in order to collect HDT effluents at a broad range of hydrodenitrogenation (HDN) conversions. Vacuum gas oils and HDT effluents have been analyzed by Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) in positive ESI(+) and negative ESI(-) electrospray ionization modes to characterize the basic and neutral nitrogen-containing species and the subtleties of HDT transformations depending on the feedstock type.

Recovery of palladium(II) from strong nitric acid solutions relevant to high-level liquid waste of PUREX process by solvent extraction with pyrazole-pyridine-based amide ligands

The extraction of Pd2+ with N,N-dialkyl-2-(3-(pyridine-2-yl)-1H-pyrazole-1-yl) acetamide (A-C-PzPy) and N,N-dialkyl-3-(pyridine-2-yl)-1H-pyrazole-1-carboxamide (A-PzPy) from HNO3 medium, as well as the complexation of Pd2+ with A-C-PzPy were investigated. The use of tert-butyl benzene (TBB) as a diluent for A-C-PzPy offered significantly better extractability toward Pd2+, compared to that of A-PzPy. This study demonstrated strong extractability, high selectivity, high loading capacity, and fast extraction kinetics for DOct-C-PzPy toward Pd2+ from highly acidic HNO3 solution (up to 5.0 mol/L). Slope analysis showed the formation of 1:1 type of extracted species of Pd2+ with DOct-C-PzPy ligand. The extraction was a spontaneous and endothermic process with increased entropy. The analyses of electrospray ionization mass spectrometry (ESI-MS), Fourier transform infrared (FT-IR) and UV–vis spectrophotometric titration revealed that the composition of the extracted neutral complex species was Pd(NO3)2(DOct-C-PzPy). Combining the results of solvent extraction and complexation study, a neutral complexation extraction model is proposed. Furthermore, the stability constants (log β) for the complexation of Pd2+ with A-C-PzPy are also presented.

The distribution of F-containing species in atmospheric nanosecond He/CF4 plasma with downstream dielectric material

A two-dimensional self-consistent model has been established in order to investigate the distribution of F-containing species in He/CF4 atmospheric pressure plasma jet and the effect of CF4 concentration on the reactive F-containing species. A portion of electron energy is consumed whenever an F is ionized from the CF4, resulting that the average densities of , and CF+ decrease sequentially. The density of is greater than density due to Penning ionization of He* with CF4 and He+ + CF4 → + F + He. In the case of He + 0.5% CF4 at 200 ns, the electron impact reactions mainly concentrate on the streamer head on the dielectric surface. The Penning ionization of He* with CF4 dominates in the region of 0 < r < 2.2 mm benefits from long-lived He* of high density and the high concentration CF4 in this region. As gas flow gradually mixes with ambient air (r > 2.2 mm), the Penning ionization of metastable He with N2 and O2 dominates in this area. As the CF4 concentration increases from 0.1% to 1%, the densities of F-containing positive ions all increase significantly. CF3, F and F2 also show the upward trend while there is little change in the spatial densities of CF2 and CF. The F-containing neutral species flux benefits from two factors: the diffusion and the conversion of positive ions. In the case of 0.1% CF4, due to the low density of , CF+ and F+ and the diffusion of F, the F flux for is consistent with CF2 and is greater than CF. However, when CF4 concentration exceeds 0.5%, the concentration of , and CF+ are much higher than F+. The quenching of positive ions dominates on the dielectric surface in the case of 0.5% and 1% CF4, resulting that the flux of F is lower than that of CF2 and CF.

Halogenation of heterobimetallic triple-decker complexes containing an E5 middle deck (E = P, As)

The halogenation of the heterobimetallic triple-decker complexes [(Cp*Fe)(Cp‴Co)(µ,η5:η4-E5)] (E = P (1), As (6), Cp* = η5-C5Me5, Cp‴ = 1,2,4-tri(tert-butyl)cyclopentadienyl) was investigated. Compound 1 has been oxidised to the isostructural ionic compounds [(Cp*Fe)(Cp‴Co)(µ-PX)(µ,η2:η1:η1-P4X4)][Y] (X = I, Y = [I3] (2), X = Br, Y = [FeBr4] (3)) and to the neutral species [(Cp*Fe)(Cp‴Co)(µ-PCl2)(µ,η2:η1:η1-P4Cl4)] (4) and [(Cp*Fe)(Cp‴Co)(µ-PCl2)2(µ,η1:η1-P2Cl3)] (5). Compounds 2, 3 and 4 possess a heterobimetallic nortricyclane-like FeCoP5 core. The oxidation of the heavier homologue 6 with bromine and iodine afforded the homometallic complexes [(Cp‴Co)2(µ,η4:η4-As4X)][FeX4] (X = I (7) and X = Br (9)). With iodine as halogenating agent, the trinuclear monocation bearing an As6 prism as ligand [(Cp*Fe)(Cp‴Co)2(µ3,η4:η4:η4-As6)][FeI4] (8) was additionally isolated. When PCl5 was used as oxidizing agent, the initially folded As5 ligand planarised resulting in the dicationic species [(Cp*Fe)(Cp‴Co)(µ,η5:η5-As5)][FeCl4]2 (10).

Infrared Spectra of 1-Quinolinium (C9H7NH+) Cation and Quinolinyl Radicals (C9H7NH and 3-, 4-, 7-, and 8-HC9H7N) Isolated in Solid para-Hydrogen.

Large protonated polycyclic aromatic hydrocarbons (H+PAH) and the corresponding nitrogen heterocycles (H+PANH) have been proposed as possible carriers of unidentified infrared (UIR) emission bands from galactic objects. The nitrogen atom in H+PANH is expected to induce a blue shift of the band associated with the CC-stretching mode of H+PAH near 6.3 μm so that their emission bands might agree better with the UIR band near 6.2 μm. We report the IR spectrum of protonated quinoline (1-quinolinium cation, C9H7NH+) and its neutral species (1-quinolinyl radical, C9H7NH) measured upon electron bombardment during the deposition of a mixture of quinoline (C9H7N) and para-hydrogen (p-H2) at 3.2 K, indicating that the protonation and hydrogenation occur mainly at the N atom site. Additional experiments on the irradiation of C9H7N/Cl2/p-H2 matrices at 365 nm to generate Cl atoms, followed by irradiation with IR light to generate H atoms via Cl + H2 (v = 1), were performed to induce the reaction H + C9H7N. This method proved to be efficient for hydrogenation reactions in solid p-H2; we identified, in addition to C9H7NH observed in electron-bombardment experiments, four radicals with hydrogenation at the C-atom site─3-, 4-, 7-, and 8-HC9H7N. Spectral assignments were achieved according to the behavior upon secondary photolysis and a comparison of experimental results with vibrational wavenumbers and IR intensities predicted with the B3LYP/6-311++G(d,p) method. The observed lines at 1641.4, 1598.4, and 1562.0 cm-1 associated with the CC-stretching mode of C9H7NH+ are blue-shifted from those at 1618.7, 1580.8, 1556.7, and 1510.0 cm-1 of the corresponding protonated naphthalene (C10H9+).

DFT-based study on the molecular interaction of hydrochloric acid with different extractants

As an important chemical raw material, hydrochloric acid widely exists in various chemical production processes. After being used in industrial production, an acidic waste solution will be produced, creating a need to recover hydrochloric acid from the waste solution. Solvent extraction is considered to be an efficient and easy-to-operate method. This paper uses DFT theory to study the binding characteristics of different kinds of extractants and hydrochloric acid molecules. The comprehensive analysis of RDG, AIM, and ELF found that hydrogen proton transfer occurs during hydrochloric acid extraction by amine extractants, and HCl is extracted by ionic association. At the same time, alcohols, ketones, esters, and neutral phosphorus-containing species are all bonded with HCl in the form of a hydrogen bond. In addition, by studying the changes of Gibbs free energy before and after the extraction process, it was found that amines had the most potent binding force to HCl. Moreover, the binding force of TEHA to HCl is much smaller than that of other amines, which not only retains the ability to extract HCl but also makes it have excellent stripping performance. Finally, the results of the DFT calculation are verified by experiments.

Fine-scale abundance of rocky shore macroalgae species with distribution limits in NW Iberia in 2020/2021.

BackgroundClimate change has been increasing at an unprecedented rate in the last decades. Global warming has been causing a variety of impacts in marine ecosystems, including shifts in the geographical ranges of species. The north-western Iberian Peninsula coast is particularly interesting to study distribution shifts as it features a strong latitude thermal gradient, establishing a biogeographical transitional region where several cold- and warm-adapted species have their equatorward or poleward distributions. In the early 2000s, it appeared that, while warm-water species were already responding to warming, cold-water species did not display a coherent response. It is now necessary to gather up-to-date data on the distribution of the same group of species to understand if current patterns of change confirm or deny those observed back then, which may give us important clues about the mechanisms setting species limits in the area.New informationThis study provides a fine-scale description of the occurrence of intertidal macroalgae species in the rocky shores of the north-western Iberian coast. Specifically, the spatial distribution and semi-quantitative abundance of 34 native and invasive species were assessed at 70 wave-exposed locations. This included 19 species of cold-water affinity, 10 species of warm-water affinity and five neutral species. When contrasted with historical observations, these new data can be used to quantify and map biodiversity change in the region, as well as help understanding the mechanisms constraining species distributions.

A DFT study of the tautomerism of 1H-benzo[de]cinnolines and their protonated forms

1H-Benzo[de]cinnolines and 1H-indeno[6,7,1-def]cinnolines have been studied theoretically at the B3LYP/6-311++G(d,p) level in the gas-phase and in water solution (PCM model); gas-phase geometries were used to calculate absolute shieldings (GIAO) that were transformed into chemical shifts using empirical equations. The annular tautomerism of neutral species and of protonated cations have been determined, and the most stable cations coincide with those determined experimentally.

Qualification of uniform large area multidipolar ECR hydrogen plasma

The design and characterization of a multi-dipolar microwave electron cyclotron resonance (ECR) hydrogen plasma reactor are presented. In this configuration, 16 ECR sources are disposed uniformly along the azimuthal direction at a constant distance from the center of a cylindrical reactor. Several plasma diagnostics have been used to determine key parameters such as neutral species temperature; electron density and temperature; and H+, H2+, and H3+ ion energy distributions. The experimental characterization is supported by electromagnetic and magnetostatic field simulations as well as Particle In-Cell Monte Carlo Collisions simulations to analyze the observed ion energy distribution functions. Especially, we show that both electron density and temperature are spatially uniform, i.e., 1011 cm−3 and 3 eV, respectively. This plasma enables generating ion flux and energy in the ranges 1019–1022 ions m−2 s−1 and few keVs, respectively. The H2+ ion distribution function shows two populations which were attributed to surface effects. These features make this reactor particularly suitable for studying hydrogen plasma surface interaction under controlled conditions.

Excess-electron attachment and ionization of aqueous uridine monophosphate anion

We applied quantum mechanics/classical mechanics simulations to study excess-electron attachment and ionization of uridine monophosphate anion (dUMP−) in explicit aqueous solutions. We calculated vertical electron affinities (VEAs), adiabatic electron affinities (AEAs), vertical detachment energies (VDEs), vertical ionization energies (VIEs), and adiabatic ionization energies (AIEs) of the 40 structures obtained from molecular dynamic trajectory. The excess-electron and hole distributions were analyzed in electron attachment and ionization of aqueous dUMP−. The converged mean VEA (−0.31 eV) and AEA (2.13 eV) suggest that excess-electron can easily attach to dUMP−. The mean vertical (−0.50 e) and adiabatic (−0.62 e) excess-electron on uracil reveal that main excess-electrons are localized on nucleobases at the most snapshots. The distributions at several special snapshots demonstrate the excess-electron delocalization over nucleobases/ribose or ribose/phosphate group after the structural relaxations of dUMP2− dianion. The VDE value (2.78 eV) indicates that dUMP2− dianion could be very stable. Moreover, the mean VIE is 8.13 eV which is in agreement with the previous calculation using solvation model. The hole distributions on uracil suggest that the nucleobases are easily ionized after the irradiation of high-energy rays. In vertical ionizations, the holes would be delocalized over uracil and ribose at several snapshots. Observing the adiabatic hole distributions, it can be found that electrons on phosphate group and holes on nucleobases can be transferred to ribose at the special snapshots in the structural relaxation of neutral species.

Redox-Active Hydrocarbons: Isolation and Structural Determination of Cationic States toward Advanced Response Systems.

Organic chemistry has developed rapidly as a carbon-based science. Particularly, hydrocarbons with aromatic rings have attracted much attention as molecular materials for use in organic electronics. In principle, aromatic species can be constructed if carbon and hydrogen atoms are available. Therefore, revealing the nature of pure hydrocarbons with an (anti)aromatic nature should pave the way for the development of as yet unexplored organic materials. In this Review, we focus on pure hydrocarbons composed of only carbon and hydrogen atoms, and present recent studies on their intrinsic electrochemical and spectroscopic properties and structural characterization of their cationic states. We also address more sophisticated hydrocarbon-based response systems that are capable of modulating their properties in response to external stimuli such as light, heat, and electric potential.

On the Curcumin and β‐Cyclodextrin Interaction in Aqueous Media. Spectrophotometric and Electrochemical Study

AbstractIt is shown from UV/Vis spectrophotometry measurements, that up to two inclusion complexes between curcumin and β‐cyclodextrin, namely H3Cur(β‐CD) and H3Cur(β‐CD)2, can be formed in aqueous solution at pH=3.6, where the fully protonated and neutral species of curcumin, H3Cur, predominate depending on the β‐CD concentration. The thermodynamic formation constants of these supramolecular complexes were determined and the molar absorptivity coefficients of H3Cur, H3Cur(β‐CD) and H3Cur(β‐CD)2 species were assessed. In the absence of β‐CD, curcumin degradation increases linearly with time at a rate of 3.25 % min−1. However, in its presence, the rate drastically diminishes to 0.11 % min−1. These results were corroborated from independent electrochemical measurements using a bare carbon paste electrode. At 0.01 M β‐CD the first voltammogram cycle displayed single anodic and cathodic peaks while the second cycle is formed by two anodic peaks and one cathodic, all of them being due to single‐electron adsorption‐controlled processes. The current of these peaks can be used to quantify curcumin concentration in real samples.

PENGGUNAAN PEMODELAN SUMBER PLASMA HELIUM PADA KEADAAN SETIMBANG UNTUK APLIKASI PLAK GIGI

Helium plasma source modelling was performed in order to obtain species density at balanced conditions under pressure of 1 atm. The software used in this modelling is matrix laboratory software (MATLAB). The equation used is a continuity equation that depends on the position and parameters of Arrhenius. Plasma temperatures used were 0.1 eV, 0.2 eV, 0.3 eV, and 0.5 eV. Species involved in a plasma consist of electrons, He, He + , He 2 + , He *, and He 2 * . The modelling results showed that the density value of He species increases as temperature increases. It is noted that the obtained the density of He (n He ) when reaching a balanced condition at the temperature of T = 0.1, 0.2, 0.3, and 0.5 are 3.0137 × 10 25 , 7.9506 × 10 26 , n He = 1.6489 × 10 28 , and 7.1384 × 10 29 , respectively. This is because He is a noble gas that is monatomic and chemically inert. Thus resulting in stable plasma production and gaining an increase in density value. Plasma-charged species are the main media that cause the disinfection of microorganisms because they can break the hydrogen bond of the organic molecules that make up the dental plaque. So the influence of charged species when applied to dental plaque has more effective than that of neutral reactive species.

Memantine-Derived Schiff Bases as Transdermal Prodrug Candidates.

Condensation reactions of salicylaldehyde, 2-pyridinecarboxaldehyde, and pyridoxaldehyde with memantine (Me) produced novel memantine-derived Schiff bases (1–3). Speciation predictions and calculations of Log P, Log D, and of the percentage (%) of neutral species for (1–3) were carried out. In comparison with Me, the Schiff bases presented increased log P and log D in all cases and pH values, suggesting higher hydrophobicity. The determined solubilities in n-octanol were 34.7 mg/mL for memantine hydrochloride and 67.3 mg/mL for (3). According to the molecular weights and calculated logP, compounds (1–3) are suitable for transdermal administration, especially compound (3). In addition, hydrolysis of 3 with the release of pyridoxal, a daily cofactor in human metabolism, was observed. The results suggested that 3 is the most promising compound and that formation of the pyridoxal Schiff base with Me might be an effective strategy to obtain a prodrug candidate with increased lipophilicity, which would be able to passively cross biological barriers during transdermal delivery and might have applications in the treatment of Alzheimer’s disease and other neurological disorders.

Dynamics of Hydrogen in Silicon at Finite Temperatures from First Principles

Hydrogen defects in silicon still hold unsolved problems, whose disclosure is fundamental for future advances in Si technologies. Among the open issues is the mechanism for the condensation of atomic hydrogen into molecules in Si quenched from above to room temperature. Based on first‐principles calculations, the thermodynamics of hydrogen monomers and dimers is investigated at finite temperatures within the harmonic approximation. Free energies of formation indicate that the population of cannot be neglected when compared to that of at high temperatures. The results allow us to propose that molecular formation occurs during cooling processes, in the temperature window , above which the molecules collide with Si—Si bonds and dissociate, and below which the fraction of becomes negligible. The formation of and most notably of a fast‐diffusing neutral species can also provide an explanation for the apparent accelerated diffusivity of atomic hydrogen at elevated temperatures in comparison to the figures extrapolated from measurements carried out at cryogenic temperatures. Finally, it is shown that the observed diffusivity of molecules is better described upon the assumption that they are nearly free rotors, all along the migration path, including at the transition state.

Rotational excitation of CO2 induced by He: New potential energy surface and scattering calculations.

The CO2 molecule is of great interest for astrophysical studies since it can be found in a large variety of astrophysical media where it interacts with the dominant neutral species, such as He, H2, or H2O. The CO2-He collisional system was intensively studied over the last two decades. However, collisional data appear to be very sensitive to the potential energy surface (PES) quality. Thus, we provide, in this study, a new PES of the CO2-He van der Waals complex calculated with the coupled-cluster method and a complete basis set extrapolation in order to provide rotational rate coefficients that are as accurate as possible. The PES accuracy was tested through the calculations of bound state transition frequencies and pressure broadening coefficients that were compared to experimental data. An excellent agreement was globally found. Then, revised collisional data were provided for the 10-300K temperature range. Rate coefficients were compared to previously computed ones and are found to be up to 50% greater than previously provided ones. These differences can induce non-negligible consequences for the modeling of CO2 abundance in astrophysical media.

Lords of the biosphere: Plant winners and losers in the Anthropocene

Societal Impact StatementThe impact of humans on Earth's biodiversity varies across the Tree of Life. The extirpation and extinction of species is often determined by compatibility with human activities. Here we classify, where data are available, a significant portion (~30%) of vascular plant species as winners or losers with respect to this compatibility and show that currently losers greatly outnumber winners and that these losers will continue to exceed winners in the future even if species now deemed tentative winners succeed. In a rapidly changing world, species may tolerate shifting conditions, adapt, or migrate to new habitats. Species that benefit humankind may have an additional advantage of survival. Those that cannot tolerate, adapt, migrate, or prove useful will be the ultimate losers in the Anthropocene and may become extinct.Summary The impact of humans on the Earth continues to accelerate, affecting climate, land use, resource exploitation, species migrations, and habitat pollution. All of these changes have the potential to result in a massive extinction of populations and species of plants, fungi, and animals. However, the impact will vary across the diversity of life: some species, the “losers,” will decline and become extinct while others, the “winners,” will thrive as a result of human activities. We surveyed a variety of sources of information on economic uses, environmental tolerances, and conservation status and were able to classify 86,592 species of vascular plant into seven categories of winners and losers as follows: winners useful to humans and winners not useful to humans, losers useful to humans and losers not useful to humans, and currently neutral species. We also recognized tentative winners and potential losers, which we could not confidently categorize into the above five classes. We then mapped, both taxonomically and phylogenetically, the clear winners and losers across the major groups of vascular plants. The results suggest that currently many more species are losers than winners and that if the tentative winners and potential losers realize their projected trajectories, losers in the future will continue to greatly outnumber future winners. Furthermore, although winners and losers are today distributed across nearly all orders of vascular plants, all but two of the nine major phylogenetic lineages favor losers over winners. A significant phylogenetic signal was detected for percentages of both winners and losers and some of the smaller ancestral orders with a high percentage of losers may be at risk of extinction. In a rapidly changing world, plant species that tolerate human pressures, adapt, or shift distributions will continue to be the winners and survive the extinction bottleneck while the many more species that cannot do so will become the ultimate losers in the Anthropocene.

Thermodynamic properties over two phase region of U-Al system: Knudsen Effusion Mass Spectrometric study

High temperature vaporisation thermodynamic studies over <UAl2(cr)+U(cr)> two-phase region of U-Al system were carried out by employing Knudsen Effusion Mass Spectrometry (also known as High Temperature Mass Spectrometry) in the temperature range of 1146-1327 K. The vaporisation reaction occurs incongruently and Al(g) was the neutral vapour species observed in the equilibrium vapour. Partial pressure-temperature relation of Al(g) was derived as log(pAl/Pa) = (−19809 ± 209)/T + (12.58 ± 0.17). Using the p˗T relation, ΔrH298.15∘ of the following reaction: UAl2(cr) = 2Al(g) + U(cr) was evaluated by second and third law methods. Subsequently, enthalpy and Gibbs energy of formation of UAl2(cr) were deduced as ΔfH298.15∘ = −89.9 ± 24.1 kJ mol−1 and ΔfG298.15∘= −89.9 + 24.1 kJ mol−1, respectively. The vaporisation studies on this two phase region are being reported for the first time.

Lipidomic Analysis of TRPC1 Ca2+-Permeable Channel-Knock Out Mouse Demonstrates a Vital Role in Placental Tissue Sphingolipid and Triacylglycerol Homeostasis Under Maternal High-Fat Diet.

The transient receptor potential canonical channel 1 (TRPC1) is a ubiquitous Ca2+-permeable integral membrane protein present in most tissues, including adipose and placenta, and functionally regulates energetic homeostasis. We demonstrated that elimination of TRPC1 in a mouse model increased body adiposity and limited adipose accumulation under a high fat diet (HFD) even under conditions of exercise. Additionally, intracellular Ca2+ regulates membrane lipid content via the activation of the protein kinase C pathway, which may impact placental membrane lipid content and structure. Based upon this we investigated the effect of HFD and TRPC1 elimination on neutral lipids (triacylglycerol and cholesteryl ester), membrane lipids (phosphatidylcholine and phosphatidylethanolamine), and other multifunctional lipid species (unesterified cholesterol, sphingomyelins, ceramides). The concentration of unesterified cholesterol and sphingomyelin increased with gestational age (E12.5 to E 18.5.) indicating possible increases in plasma membrane fluidity. Diet-dependent increases ceramide concentration at E12.5 suggest a pro-inflammatory role for HFD in early gestation. TRPC1-dependent decreases in cholesterol ester concentration with concomitant increases in long-chain polyunsaturated fatty acid -containing triacylglycerols indicate a disruption of neutral lipid homeostasis that may be tied to Ca2+ regulation. These results align with changes in lipid content observed in studies of preeclamptic human placenta.

A Computational and Experimental View of Hydrogen Bonding in Glycerol Water Clusters.

Polyol-water clusters provide a template to probe ionization and solvation processes of paramount interest in atmospheric and interstellar chemistry. We generate glycerol water clusters in a continuous supersonic jet expansion and interrogate the neutral species with synchrotron-based tunable vacuum ultraviolet photoionization mass spectrometry. A series of glycerol fragments (m/z 44, 61, 62, and 74) clustered with water are observed. A judicious combination of backing pressure, nozzle temperature, and water vapor pressure allows for tuning the mol % of glycerol. The recorded appearance energies of the water cluster series m/z 62 and 74 are similar to that observed in pure glycerol, while the m/z 61 series shows a dependence on cluster composition. Furthermore, this series also tracks the water concentration of the beam. Theoretical calculations on neutral and ionized clusters visualize the hydrogen bond network in these water clusters and provide an assessment of the number of glycerol-glycerol, glycerol-water, and water-water hydrogen bonds in the cluster, as well as their interaction energies. This method of bond counting and interaction energy assessment explains the changes in the mass spectrum as a function of mol % and offers a glimpse of the disruption of the hydrogen bond network in glycerol-water clusters. The calculations also reveal interesting barrierless chemical processes in photoionized glycerol water clusters that are either activated or do not occur without the presence of water. Examples include spontaneous intramolecular proton transfer within glycerol to form a distonic ion, nonactivated breaking of a C-C bond, and spontaneous proton transfer from glycerol to water. These results appear relevant to radiation-induced chemical processing of alcohol-water ices in the interstellar medium.