Gas Phase Research Articles

Nucleoside Cation Radicals: Generation, Radical-Induced Hydrogen Atom Migrations, and Ribose Ring Cleavage in the Gas Phase.

Nucleoside ions that were furnished on ribose with a 2'-O-acetyl radical group were generated in the gas phase by multistep collision-induced dissociation of precursor ions tagged with radical initiator groups, and their chemistry was investigated in the gas phase. 2'-O-Acetyladenosine cation radicals were found to undergo hydrogen transfer to the acetoxyl radical from the ribose ring positions that were elucidated using specific deuterium labeling of 1'-H, 2'-H, and 4'-H and in the N-H and O-H exchangeable positions, favoring 4'-H transfer. Ion structures and transition-state energies were calculated by a combination of Born-Oppenheimer molecular dynamics and density functional theory and used to obtain unimolecular rate constants for competitive hydrogen transfer and loss of the acetoxyl radical. Migrations to the acetoxyl radical of ribose hydrogens 1'-H, 2'-H, 3'-H, and 4'-H were all exothermic, but product formation was kinetically controlled. Both Rice-Ramsperger-Kassel-Marcus (RRKM) and transition-state theory (TST) calculations indicated preferential migration of 4'-H in a qualitative agreement with the deuterium labeling results. The hydrogen migrations displayed substantial isotope effects that along with quantum tunneling affected the relative rate constants and reaction branching ratios. UV-vis action spectroscopy indicated that the cation radicals from 2'-O-acetyladenosine consisted of a mixture of isomers. Radical-driven dissociations were also observed for protonated guanosine, cytosine, and thymidine conjugates. However, for those nucleoside ions and cation radicals, the dissociations were dominated by the loss of the nucleobase or formation of protonated nucleobase ions.

Spectroscopic Evidence for Doubly Hydrogen-Bonded Cationic Dimers in the Solid, Liquid, and Gaseous Phases of Carboxyl-Functionalized Ionic Liquids.

Intermolecular interactions determine whether matter sticks together, gases condense into liquids, or liquids freeze into solids. The most prominent example is hydrogen bonding in water, responsible for the anomalous properties in the liquid phase and polymorphism in ice. The physical properties are also exceptional for ionic liquids (ILs), wherein a delicate balance of Coulomb interactions, hydrogen bonds, and dispersion interactions results in a broad liquid range and the vaporization of ILs as ion pairs. In this study, we show that strong, local, and directional hydrogen bonds govern the structures and arrangements in the solid, liquid, and gaseous phases of carboxyl-functionalized ILs. For that purpose, we explored the H-bonded motifs by X-ray diffraction and attenuated total reflection (ATR) infrared (IR) spectroscopy in the solid state, by ATR and transmission IR spectroscopy in the liquid phase, and by cryogenic ion vibrational predissociation spectroscopy (CIVPS) in the gaseous phase at low temperature. The analysis of the CO stretching bands reveals doubly hydrogen-bonded cationic dimers (c═c), resembling the archetype H-bond motif known for carboxylic acids. The like-charge doubly hydrogen-bonded ion pairs are present in the crystal structure of the IL, survive phase transition into the liquid state, and are still present in the gaseous phase even in (2,1) complexes wherein one counterion is removed and repulsive Coulomb interaction increased. The interpretation of the vibrational spectra is supported by quantum chemical methods. These observations have implications for the fundamental nature of the hydrogen bond between ions of like charge.

Ozone treatment of meat and meat products: a review

Ozone treatment is a non-thermal method for disinfection; ozone is a powerful oxidizing agent that has been shown to be effective in reducing microbial load, extending the shelf life of meat products. This mini-review covers the analysis of the antimicrobial ozone activity in different meats (beef, poultry, pork, seafood, etc.), emphasizing the ozone application methods (liquid or gaseous phase), the applied concentrations and contact times and the effects of ozone treatment on meat quality, safety, and sensory properties. It has been demonstrated that ozone is effective against a broad range of microorganisms, including both Gram-positive and Gram-negative bacteria, spores, and vegetative cells. The efficacy of ozone depends on various factors, such as concentration, type of treatment, temperature, and presence of organic material. Ozone treatment, known for its rapid decomposition and lack of residue, provides an environmentally friendly alternative to traditional chemical sanitizers. Ozone treatments exhibit promising results in enhancing the safety and extending the shelf life of meat products. According to the findings, the application of ozone is an effective technology for prolonging the shelf life of different types of meats and meat products, requiring careful establishment of conditions on a case-by-case basis.

Trajectory-Based Time-Resolved Mechanism for Benzene Reductive Elimination from Cyclopentadienyl Mo/W Phenyl Hydride Complexes.

Calculated potential energy structures and landscapes are very often used to define the sequence of reaction steps in an organometallic reaction mechanism and interpret kinetic isotope effect (KIE) measurements. Underlying most of this structure-to-mechanism translation is the use of statistical rate theories without consideration of atomic/molecular motion. Here we report direct dynamics simulations for an organometallic benzene reductive elimination reaction, where nonstatistical intermediates and dynamic-controlled pathways were identified. Specifically, we report single spin state as well as mixed spin state quasiclassical direct dynamics trajectories in the gas phase and explicit solvent for benzene reductive elimination from Mo and W bridged cyclopentadienyl phenyl hydride complexes ([Me2Si(C5Me4)2]M(H)(Ph), M = Mo and W). Different from the energy landscape mechanistic sequence, the dynamics trajectories revealed that after the benzene C-H bond forming transition state (often called reductive coupling), σ-coordination and π-coordination intermediates are either skipped or circumvented and that there is a direct pathway to forming a spin flipped solvent caged intermediate, which occurs in just a few hundred femtoseconds. Classical molecular dynamics simulations were then used to estimate the lifetime of the caged intermediate, which is between 200 and 400 picoseconds. This indicates that when the η2-π-coordination intermediate is formed, it occurs only after the first formation of the solvent-caged intermediate. This dynamic mechanism intriguingly suggests the possibility that the solvent-caged intermediate rather than a coordination intermediate is responsible (or partially responsible) for the inverse KIE value experimentally measured for W. Additionally, this dynamic mechanism prompted us to calculate the kH/kD KIE value for the C-H bonding forming transition states of Mo and W. Surprisingly, Mo gave a normal value, while W gave an inverse value, albeit small, due to a much later transition state position.

Reactive transport modelling of iron bentonite interaction in the FEBEX in situ experiment

The evolution of steel/bentonite interfaces in engineered barrier systems of radioactive waste disposal is governed by the corrosion of the steel and the interaction of corrosion products with the bentonite. In the early post-closure phase of the repository, the transition from aerobic to anaerobic corrosion in combination with evolving temperature conditions and chemical gradients due to the hydration of the bentonite take place. In situ tests in underground laboratories provide a high degree of representativeness for the early transient evolution of the interfaces. Complex Fe-bentonite interaction patterns have been observed, which include a concave Fe accumulation front and distinct coloured halos around the corroding steel. A reactive transport model for the FEBEX in situ test is presented, which describes the transition from aerobic to anaerobic corrosion, the transport of O2 in the gas and liquid phase and the chemical evolution of the steel/bentonite interface during the 18 years of the experiment. The model successfully reproduces the major steps of the interface evolution: an aerobic corrosion phase characterized by accumulation of goethite in the corrosion layer, and an anaerobic corrosion phase, where Fe(II) and Fe(II)/Fe(III) corrosion products form, including a gradual re-dissolution of the aerobic corrosion products. In the anaerobic corrosion phase, some of the Fe(II) diffuses into the bentonite, where it partly reacts with remaining O2 to form Fe(III) precipitates or interacts with the clay minerals via surface complexation or cation exchange. Two different approaches for the implementation of a potential electron transfer from sorbed Fe(II) to structural Fe(III) are presented, but the lack of experimental data does not allow evaluation of their representativeness for the FEBEX in situ experiment. The model calculations qualitatively reproduce the concave shape of the Fe accumulation front in the bentonite and a distinct zonation with an iron-oxide precipitation dominated zone adjacent to the steel and a Fe(II) sorption dominated zone further into the bentonite. Sensitivity cases with respect to the hydration of the bentonite and the transport parameters point to the importance of the fast O2 diffusion in the gas phase for the formation of these characteristic interface features. The calculated thickness of the Fe-bentonite interaction zone varies from 1 to 4 cm, which is smaller than observed in some areas of the experiment, where locally this zone extended >10 cm into the bentonite. It is possible that this difference is due to a more complex flow pattern in the in situ experiment that is not captured by the model or due to an additional decoupled electron transport across oxide rich layers.

Unveiling the potential of TPA-based molecules to tune the optoelectronic properties and enhance the efficiency of dye-sensitized solar cells.

The world's energy and environmental requirements are changing due to rapid population growth and industrial growth, and solar cells can be used to meet these demands. Dye-sensitized solar cells (DSSCs) are solar cells in which energy conversion occurs via a process similar to photosynthesis in plants. DSSC development is still in its infancy. DSSCs can operate under cloudy conditions and indirect sunlight and have attracted considerable attention due to their low cost and high efficiency. We designed two metal-free TPA-based dyes (Dye2 and Dye3) based on the reference dye Mg207 (Dye1) by increasing the donor strength of the molecule, as such dyes have shown enhanced efficiency in DSSCs. Moreover, the triphenylamine (TPA) moiety has been demonstrated to be a good donor that prevents charge recombination. Intramolecular charge transfer (ICT) from the donor to acceptor moiety was found in the sensitizers, and electrons were promoted to the conduction band (CB) of the TiO2 semiconductor. The negative binding energy of the dye@TiO2 clusters indicated that dye adsorption on the semiconductor surface was stable. The double donor increased the electron injection and electronic coupling constants in Dye2 and Dye3, indicating that these newly designed dyes have superior charge injection capacity. Accordingly, the efficiencies of DSSCs with Dye2 and Dye3 were 9.77% and 9.62%, respectively, and substitution with the TPA unit at the -R1 and -R2 positions in Dye1 resulted in better power conversion compared to the parent compound (9.09%). Increased donor strength improved photovoltaic performance by increasing current density and light-harvesting efficiency. This is a good molecular design approach for preparing targeted donor- -acceptor (D- -A) organic dyes with high DSSC efficiency. To predict the charge transport and optoelectronic characteristics of the TPA dyes, quantum chemical calculations were carried out using Gaussian16. The ground-state (S0) optimized geometries of the sensitizers were computed by utilizing DFT at the B3LYP/6-31G** level. The absorption spectra ( max) were computed by employing TD-DFT with various functionals (B3LYP, PBE1PBE, CAM-B3LYP, and BHandHLYP) in the gas and solvent (DCM) phases. Among the studied functionals, BHandHLYP was found to be best at successfully reproducing the experimental data. Thus, the absorption spectra of the newly designed dyes and dye@TiO2 were calculated at the BHandHLYP/6-31G** level. The dye@TiO2 cluster optimizations were carried out at the B3LYP/6-31G**(LANL2DZ) level.

Boosting the Electrochemical Performance of Primary and Secondary Lithium Batteries with Mn-Doped All-Fluoride Cathodes.

Transition metal fluorides are potentially high specific energy cathode materials of next-generation lithium batteries, and strategies to address their low conductivity typically involve a large amount of carbon coating, which reduces the specific energy of the electrode. In this study, MnyFe1-yF3@CFx was generated by the all-fluoride strategy, converting most of the carbon in MnyFe1-yF3@C into electrochemical active CFx through a controllable NF3 gas phase fluorination method, while still retaining a tightly bound graphite layer to provide initial conductivity, which greatly improved the energy density of the composite. This synergistic effect of nonfluorinated residual carbon (∼11%) and Mn doping ensures the electrochemical kinetics of the composite. The loading mass of the active substance had been increased to 86%. The theoretical and actual discharge capacity of MnyFe1-yF3@CFx composite was up to 765 mAh g-1 (pure FeF3 is 712 mAh g-1) and 728 mAh g-1, respectively. The discharge capacity at the high-voltage (3.0 V) platform was more than three times higher than that of the non-Mn-doped composite (FeF3@CFx).

Competitive Intramolecular Hydrogen Bonding: Offering Molecules a Choice.

The conformational preferences of N-((6-methylpyridin-2-yl)carbamothioyl)benzamide were studied in solution, the gas phase and the solid state via a combination of NMR, density functional theory (DFT) and single crystal X-ray techniques. This acyl thiourea derivative can adopt two classes of low energy conformation, each stabilized by a different 6-membered intramolecular hydrogen bond (IHB) pseudoring. Analysis in different solvents revealed that the conformational preference of this molecule is polarity dependent, with increasingly polar environments yielding a higher proportion of the minor conformer containing an NH⋅⋅⋅N IHB. The calculated barrier to interconversion is consistent with dynamic behaviour at room temperature, despite the propensity of 6-membered IHB pseudorings to be static. This work demonstrates that introducing competitive IHB pathways can render static IHBs more dynamic and that such systems could have potential as chameleons in drug design.

Proton Transfer Processes in 2-Butenenitrile Dimer Cation Studied by Mass-Selective Infrared Spectroscopy.

2-Butenenitrile (2-Bu) is a recently discovered crucial interstellar molecule. Herein, an abnormal NH band was observed in the infrared spectrum of the 2-Bu dimer cation, suggestive of a proton transfer reaction within the cluster. Through a comprehensive theoretical analysis of the IR spectrum of (2-Bu)2+, we discovered not only the formation of a new C-N bond through the attachment of one 2-Bu to another but also the occurrence of a proton transfer reaction in the cluster. This proton was identified as originating from the methyl group of the attaching 2-Bu in the cluster based on the analysis of IR spectra of (2-Bu)+ and [2-Bu-acrylonitrile (AN)]+. Furthermore, the detailed reaction process of this ion-molecule reaction is examined with theoretical calculation. This finding contributes significantly to our deeper understanding of ion-molecule reactions in the gas phase and the formation of nitrogen-containing prebiotic molecules in the interstellar medium.

A Zero-Gap Gas Phase Photoelectrolyzer for CO2 Reduction with Porous Carbon Supported Photocathodes.

A modified Metal-Organic Framework UiO-66-NH2-based photocathode in a zero-gap gas phase photoelectrolyzer was applied for CO2 reduction. Four types of porous carbon fiber layers with different wettability were employed to tailor the local environment of the cathodic surface reactions, optimizing activity and selectivity towards formate, methanol, and ethanol. Results are explained by mass transport through the different type and arrangement of carbon fiber support layers in the photocathodes and the resulting local environment at the UiO-66-NH2 catalyst. The highest energy-to-fuel conversion efficiency of 1.06 % towards hydrocarbons was achieved with the most hydrophobic carbon fiber (H23C2). The results are a step further in understanding how the design and composition of the photoelectrodes in photoelectrochemical electrolyzers can impact the CO2 reduction efficiency and selectivity.

Possibilities of an Electronic Nose on Piezoelectric Sensors with Polycomposite Coatings to Investigate the Microbiological Indicators of Milk.

Milk and dairy products are included in the list of the Food Security Doctrine and are of paramount importance in the diet of the human population. At the same time, the presence of many macro- and microcomponents in milk, as available sources of carbon and energy, as well as the high activity of water, cause the rapid development of native and pathogen microorganisms in it. The goal of the work was to assess the possibility of using an array of gas chemical sensors based on piezoquartz microbalances with polycomposite coatings to assess the microbiological indicators of milk quality and to compare the microflora of milk samples. Piezosensors with polycomposite coatings with high sensitivity to volatile compounds were obtained. The gas phase of raw milk was analyzed using the sensors; in parallel, the physicochemical and microbiological parameters were determined for these samples, and species identification of the microorganisms was carried out for the isolated microorganisms in milk. The most informative output data of the sensor array for the assessment of microbiological indicators were established. Regression models were constructed to predict the quantity of microorganisms in milk samples based on the informative sensors' data with an error of no more than 17%. The limit of determination of QMAFAnM in milk was 243 ± 174 CFU/cm3. Ways to improve the accuracy and specificity of the determination of microorganisms in milk samples were proposed.

The C1s core levels of polycyclic aromatic hydrocarbons and styrenic polymers: A first-principles study.

Understanding core level shifts in aromatic compounds is crucial for the correct interpretation of x-ray photoelectron spectroscopy (XPS) of polycyclic aromatic hydrocarbons (PAHs), including acenes, as well as of styrenic polymers, which are increasingly relevant for the microelectronic industry, among other applications. The effect of delocalization through π aromatic systems on the stabilization of valence molecular orbitals has been widely investigated in the past. However, little has been reported on the impact on the deeper C1s core energy levels. In this work, we use first-principles calculations at the level of many body perturbation theory to compute the C1s binding energies of several aromatic systems. We report a C1s red shift in PAHs and acenes of increasing size, both in the gas phase and in the molecular crystal. C1s red shifts are also calculated for stacked benzene and naphthalene pairs at decreasing intermolecular distances. A C1s red shift is in addition found between oligomers of poly(p-hydroxystyrene) and polystyrene of increasing length, which we attribute to ring-ring interactions between the side-chains. The predicted shifts are larger than common instrumental errors and could, therefore, be detected in XPS experiments.

A sub-solar Fe/O, log (T/K) ∼ 7.5 gas component permeating the milky way’s CGM

Abstract Our study focuses on characterizing the highly ionized gas within the Milky Way’s (MW) Circumgalactic Medium (CGM) that gives rise to ionic transitions in the X-ray band 2 - 25 Å. Utilizing stacked Chandra/ACIS-S MEG and LETG spectra toward QSO sightlines, we employ the self-consistent hybrid ionization code PHASE to model our data. The stacked spectra are optimally described by three distinct gas phase components: a warm (log (T/K) ∼ 5.5), warm-hot (log (T/K) ∼6), and hot (log (T/K) ∼ 7.5) components. These findings confirm the presence of the hot component in the MW’s CGM indicating its coexistence with a warm and a warm-hot gas phases. We find this hot component to be homogeneous in temperature but inhomogeneous in column density. The gas in the hot component requires over-abundances relative to solar to be consistent with the Dispersion Measure (DM) from the Galactic halo reported in the literature. For the hot phase we estimated a DM = $55.1^{+29.9}_{-23.7}$ pc cm−3. We conclude that this phase is either enriched in Oxygen, Silicon, and Sulfur, or has metallicity over 6 times solar value, or a combination of both. We do not detect Fe L-shell absorption lines, implying O/Fe ≥ 4. The non-solar abundance ratios found in the super-virial gas component in the Galactic halo suggest that this phase arises from Galactic feedback.

Migration behavior of iron and phosphorus during gas-based reduction for high-phosphorus iron ore

With the depletion of high-grade iron ore, it is necessary to develop low-quality high-phosphorus iron ore through economical and sustainable solutions. In this study, we presented simultaneous enrichment of iron (Fe) and phosphorus (P) to recover P from high-phosphorus iron ore and clarified the migration of P from the original apatite to reduced iron during the direct reduction process. To capture the migration route, gas-based reduction at a relatively slow rate was conducted on two typical iron ores samples (low-grade and high-grade) at different temperatures and times. Results indicate that there are concentration gradients for P and Fe of reaction products in the low-grade iron ore at 1400 °C. The P content continuously increased in the sequence from metallic iron (Fe), wustite (FeO), and fayalite (Fe2SiO4), to apatite (Ca3(PO4)3F). Conversely, the content of Fe gradually decreased. During this process, P dissolved from apatite entered and formed P-bearing fayalite. For the high-grade iron ore, P-bearing fayalite with a metastable structure disappeared as the reduction progressed, and P was released and then reduced to a gaseous state, finally absorbed by metallic iron. Furthermore, when metallic iron was not formed in the initial 60 min at 1300 °C, the P migrated from the apatite to the fayalite and gas phase. As the reduction time increased from 60 min to 240 min, the formed metallic iron provided a site for gasified P, which inhibited the volatilization of P and contributed to Fe and P enrichment.

Pseudo-Wet Plasma Mechanism Enabling High-Throughput Dry Etching of SiO2 by Cryogenic-Assisted Surface Reactions.

Manufacturing semiconductor devices requires advanced patterning technologies, including reactive ion etching (RIE) based on the synergistic interactions between ions and etch gas. However, these interactions weaken as devices continuously scale down to sub-nanoscale, primarily attributed to the diminished transport of radicals and ions into the small features. This leads to a significant decrease in etch rate (ER). Here, a novel synergistic interaction involving ions, surface-adsorbed chemistries, and materials at cryogenic temperatures is found to exhibit a significant increase in the ER of SiO2 using CF4/H2 plasmas. The ER increases twofold when plasma with H2/(CF4 + H2) = 33% is used and the substrate temperature is lowered from 20 to -60°C. The adsorption of HF and H2O on the SiO2 surface at cryogenic temperatures is confirmed using in situ Fourier transform infrared spectroscopy. The synergistic interactions of the surface-adsorbed HF/H2O as etching catalysts and plasma species result in the ER enhancement. Therefore, a mechanism called "pseudo-wet plasma etching" is proposed to explain the cryogenic etching process. This synergy demonstrates that the enhanced etch process is determined by the surface interactions between ions, surface-adsorbed chemistry, and the material being etched, rather than interactions between ion and gas phase, as observed in the conventional RIE.

Measurements of Nuclear Magnetic Shielding in Molecules.

The origin of nuclear magnetic shielding in diamagnetic molecules is discussed, pointing out various contributions to the shielding from electrons and the effects of intra- and intermolecular interactions. In NMR practice, chemical shifts are determined first as the measure of shielding in observed samples. The descriptions of shielding and chemical shifts are not fully consistent. Gas phase studies permit the withdrawal of intermolecular contributions from shielding and obtaining the magnetic shielding data in isolated molecules. The shielding determination in molecules is possible using at least three methods delivering the reference shielding standards for selected nuclei. The known shielding of one magnetic nucleus can be transferred to other nuclei if the appropriate nuclear magnetic moments are available with satisfactory accuracy. It is possible to determine the nuclear magnetic dipole moments using the most advanced ab initio shielding calculations jointly with the NMR frequencies measurements for small-sized isolated molecules. Helium-3 gas is postulated as all the molecules' primary and universal reference standard of shielding. It can be easily applied using common deuterium lock solvents as the secondary reference standards. The measurements of absolute shielding are available for everyone with the use of standard NMR spectrometers.

Investigation on flow structure and pressure fluctuation of gas-liquid two-phase flow in a mixed flow pump

Abstract Mixed flow pump is characterized by high-efficiency operation and wide range of flow rate conditions, while research on transporting gas-liquid two-phase flow is quite limited. The present work investigates the energy performance, two-phase flow pattern and pressure fluctuations of a mixed flow pump, on basis of the numerical method of inhomogeneous Eulerian-Eulerian multiphase flow model. Results show that the pump head and efficiency decline with the increase of gas volume fraction. In impeller, gas phase is mainly distributed at the tip clearance, the blade pressure side and suction side, and the hub outlet. The low pressure of tip leakage vortex core leads to the gas phase concentration and the formation of gas strip. Moreover, X-shaped gas strip appears at high gas volume fraction (GVF). In guide vane, gas phase is mainly distributed at the leading edge of blade pressure side, the blade suction side, and the middle of passage. As the inlet GVF increases, the spatial-temporal evolution of the gas phase shows obvious differences. The strong gas-liquid interaction causes broad low-frequency fluctuations, and the rotor-stator interference causes significant blade passing frequencies in the mixed flow pump.

Temperature dependence of the rain-gas and snow-gas partition coefficients for nearly a thousand chemicals

Compared to the particle-gas partition coefficients (KPG), the rain-gas (KRG) and snow-gas (KSG) partition coefficients are also essential in studying the environmental behavior and fate of chemicals in the atmosphere. While the temperature dependence for the KPG have been extensively studied, the study for KRG and KSG are still lacking. Adsorption coefficients between water surface-air (KIA) and snow surface-air (KJA), as well as partition coefficients between water-air (KWA) and octanol-air (KOA) are vital in calculating KRG and KSG. These four basic adsorption and partition coefficients are also temperature-dependent, given by the well-known two-parameters Antoine equation logKXY = AXY + BXY/T, where KXY is the adsorption or partition coefficients, AXY and BXY are Antoine parameters (XY stand for IA, JA, WA, and OA), and T is the temperature in Kelvin. In this study, the parameters AXY and BXY are calculated for 943 chemicals, and logKXY can be estimated at any ambient temperature for these chemicals using these Antoine parameters. The results are evaluated by comparing these data with published experimental and modeled data, and the results show reasonable accuracy. Based on these coefficients, temperature-dependence of logKRG and logKSG is studied. It is found that both logKRG and logKSG are linearly related to 1/T, and Antoine parameters for logKRG and logKSG are also estimated. Distributions of the 943 chemicals in the atmospheric phases (gas, particle, and rain/snow), are illustrated in a Chemical Space Map. The findings reveal that, at environmental temperatures and precipitation days, the dominant state for the majority of chemicals is the gaseous phase. All the AXY and BXY values for logKSG, logKRG, and basic adsorption and partition coefficients, both modeled by this study and collected from published work, are systematically organized into an accessible dataset for public utilization.

Occurrence and distribution of pesticides and transformation products in ambient air in two European agricultural areas

Pesticides present a significant risk for both humans and the environment. However, quantitative data for a broad range of airborne pesticides in agricultural areas are missing. During or after the application, pesticides can reach the atmosphere and partition between the particulate and gaseous phase. As part of the EU project SPRINT, weekly ambient air samples were collected from two agricultural areas in Portugal (vineyard) and the Netherlands (potatoes, onions, and sugarbeet) between April 2021 and June 2022 using high-volume air samplers. The samples were analysed for 329 pesticides, of which 99 were detected. The most frequently detected compounds included the fungicides folpet, fenpropidin and mandipropamid, the insecticide chlorpyrifos-methyl, the herbicide terbuthylazine, and the metabolite prothioconazole-desthio, which were found with detection frequencies between 40 and 57 %. Pesticide concentrations ranged between 0.003 ng/m3 and 10 ng/m3. Remarkably, 97 % of the samples contained at least one pesticide and in 95 % of the samples, pesticide mixtures were present. The calculated particle phase fractions correlated with the octanol-air partitioning coefficient for most of the investigated compounds. Furthermore, calculated daily inhalation rates for individual pesticides and pesticide mixtures were far below the Acceptable Daily Intake (ADI) with a margin of exposure (MOE) of >1000 for the highest calculated daily inhalation rate for a child. However, as this value only includes pesticide intake from food and drinking water and considering that 91 % of the detected pesticides are associated with potential adverse human health effects. These findings highlight the broad range of airborne pesticides in agricultural areas and the need for quantitative data to include the intake of mixtures of highly hazardous pesticides by inhalation in human risk assessment.

Distinct antithrombin activation modes for fondaparinux and natural heparins detected using millisecond hydrogen deuterium exchange and collision induced unfolding

Low molecular weight heparin and synthetic mimetics such as fondaparinux show different binding kinetics, protease specificity, and clinical effects. A combination of allosteric and template-mediated bridging mechanisms have been proposed to explain the differences in rate acceleration and specificity. The difficulty in working with heterogeneous heparin species has rendered a crystallographic interpretation of the differences in antithrombin activation between mimetics and natural heparin inaccessible. In this study, we examine the allosteric changes in antithrombin caused by binding fondaparinux, enoxaparin and depolymerized natural heparins using millisecond hydrogen deuterium exchange mass spectrometry (TRESI-HDX MS) and relate these conformational changes to complex stability in the gas phase using collision induced unfolding (CIU). This exploration reveals that in addition to the dynamic changes caused by fondaparinux, long chain heparins reduce structural flexibility proximal to Arg393, the cleavable residue in the reactive centre loop of the protein. These local changes in protein dynamics are associated with an increase in overall complex stability that increases with heparin chain length. Ultimately, these results shed light on the molecular mechanisms underlying differences in activity and specificity between heparin mimetics and natural heparins.