Reaction Branching Ratios Research Articles

Radical scavenging activity of bromophenol analogs: analysis of kinetics and mechanisms.

This theoretical study explores the antioxidant activity of five bromophenol analogs, with a particular focus on their interaction with different solvent environments of varying polarities. Key findings include the correlation between increased solvent polarity and enhanced antioxidant activity of these analogs, comparable in some instances to ascorbic acid. Notably, compound 5, developed by our research team, demonstrates superior antioxidant activity in both lipid and aqueous solutions, surpassing that of ascorbic acid and other tested analogs. This research contributes to the understanding of bromophenol analogs, presenting the first known kinetic and chemical stability data such as rate constants, pKa values, and branching ratios for reactions with the methylperoxyl radical (CH3OO•). The computational analyses were conducted using the Gaussian 09 software suite at the M05-2X/6-31 + G(d) computational level. These analyses employed conventional transition state theory to account for various potential mechanisms and effects of solvent polarity on the antioxidant activities of bromophenol analogs. The study meticulously calculated enthalpy under standard conditions (298.15K and 1atm) with necessary thermodynamic corrections. Additionally, the Quantum Mechanics-based Test for Overall Radical Scavenging Activity (QMORSA) protocol guided the evaluation of radical scavenging activity, ensuring a comprehensive assessment of the antioxidant potential of the compounds.

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.

Population transfer between degenerate continuum states via impulsive stimulated Raman scattering: application to the control of HOD photofragmentation.

This work proposes a new scheme for the coherent control of the branching ratio of photodissociation reactions. HOD's photodissociation in the first electronic-excited state illustrates the idea. The scheme involves the induction of quantum interference between the continuum eigenstates of the excited state through interaction with a non-resonant NIR ultrashort laser pulse, subsequent to electronic excitation. A high-level, frequency-dependent excited state polarizability surface of HOD is determined, in order to model the non-resonant coupling between the laser pulse and molecule. The results of this scheme on the control of the branching ratio between OD + H and OH + D are presented, as well as an analysis of the interaction between the ultrashort pulses and the excited-state eigenstates. The understanding of the degenerate nature of these continuum states is shown to be crucial for a correct description of the processes that lead to a change in the reaction's outcome, and is further discussed through an exploration of a model system.

Theoretical investigation on isomerization and decomposition reactions of pentanol radicals-part II: linear pentanol isomers.

High-level ab initio calculations are conducted for studying the kinetics of three linear pentanol radicals generated through H-atom abstraction reactions. The species involved are optimized using the M06-2X/6-311++G(d,p) level of theory, while a relaxed scan at the M06-2X/6-31g level of theory with 10° increments is used for the hindrance potential for low-frequency torsional modes. Single-point energies for all stationary points are obtained through the QCISD(T) and MP2 methods in combination with cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets, which can be extrapolated to the complete basis set (CBS) limit. The rate constants and branching ratios for isomerization and decomposition reactions are computed over a temperature range of 250-2000 K and a pressure range of 0.01-100 atm. Isomerization reactions are dominant at low temperatures, while decomposition reactions are more dominant at high temperatures. The branching ratio of the isomerization reaction exhibits a slight decrease with increasing pressure, while the trend for decomposition reactions depends on the type of the breaking bond. Based on the calculations for five branched pentanol radicals in part I, kinetics of linear and branched pentanol radicals are compared in this work and the results reveal that, for the same kind of β-scission reaction at similar positions of linear and branched pentanol radicals, the rate constants of branched ones are faster than those of linear ones at low temperatures. The hydroxyl group adjacent to the breaking bond can increase the β-scission reaction rate constants, while the effect can be ignored when the hydroxyl group is not adjacent to the breaking bond. Moreover, compared to when the hydroxyl group is located in the middle of the carbon chain, its positioning at the chain's end yields a more noticeable impact on the products and rate constants of C-O bond and O-H bond β-scission reactions. Besides, when incorporating calculated rate constants into the CRECK model, the updated mechanism shows a better performance for ignition delay times of 1-pentanol in the NTC range but exhibits lower reactivity at higher temperatures. The simulation of speciation profiles also shows better agreement with the experimental data obtained using a flow reactor.

Theoretical study on the potential environmental and ecological risk of 4-ethylphenol induced by hydroxyl radical

This study closely examines the environmental fate of 4-ethylphenol (4-EP), a significant byproduct of biomass combustion. We employed quantum chemical calculations to investigate the reaction mechanism, kinetics, and ecotoxicity of 4-EP initiated by OH radicals in various environments (aqueous, atmospheric liquid, atmospheric and inhomogeneous phases). Our findings highlight that solvent effects contribute to a higher OH-addition reaction branching ratio (Γadd) of 0.68 for 4-EP in an aqueous solution, compared to 0.26 in the gas-phase environment and 0.22 in the inhomogeneous environment at 298 K. We determined the rate constants for the liquid-phase, gas-phase, and nonhomogeneous phase to be 1.14 × 109 s−1 M−1, 3.09 × 109 s−1 M−1, and 6.19 × 1014 s−1 M−1, respectively. Notably, the adsorption of mineral particles considerably enhances the reaction rate of 4-EP with OH radicals. 4-ethylbenzene-1,2-diol, 4-hydroxycyclohexa-3,5-diene-1,2-dione, 1-ethyl-6-methyl-6H-benzo(c)chromene-4,9-diol, 5-ethyl-6'-(1-hydroxyethyl)-(1,1′-biphenyl)-2,3,3′-triol and 2-ethyl-4,6,9-trimethyl-6H-benzo(c) chromene are major products in both gas-phase and liquid-phase reactions, and (2Z, 4Z)-4-ethyl-6-oxohexa-2,4-dienoic acid is also one of the major products in gas-phase reactions. Toxicological predictions indicate that the ecotoxicity of 4-ethyl-6-methyl-6H-benzo(c)chromene-1,9-diol, 2-ethyl-6-methyl-6H-benzo(c)chromene-3,9-diol, and 2-ethyl-4,6,9-trimethyl-6H-benzo(c) chromene surpassed that of 4-EP. However, the toxicity of the reaction products is reduced in the presence of NOx. This investigation provides an exhaustive theoretical foundation for comprehending the degradation behavior of 4-EP and underscores the need to consider various environmental factors in assessing the potential risk of biomass combustion by products.

Understanding the Molecular Kinetics and Chemical Equilibrium Phase of Frozen CO during Bombardment by Cosmic Rays by Employing the PROCODA Code

Within the cold regions of space, ices that are enriched with carbon monoxide (CO) molecules are exposed to ionizing radiation, which triggers new reactions and desorption processes. Laboratory studies on astrochemical ices employing different projectiles have revealed the appearance of several new species. In this study, we employed the upgraded PROCODA code, which involves a calculation phase utilizing thermochemistry data, to map the chemical evolution of pure CO ice irradiated by cosmic-ray analogs. In the model, we have considered 18 different chemical species (six observed: CO, CO2, C3, O3, C2O, and C5O3; 12 unobserved: C, O, C2, O2, CO3, C3O, C4O, C5O, C2O2, C2O3, C3O2, and C4O2) coupled at 156 reaction routes. Our best-fit model provides effective reaction rates (effective rate constants, (ERCs)), branching ratios for reactions within reaction groups, several desorption parameters, and the characterization of molecular abundances at the chemical equilibrium (CE) phase. The most abundant species within the ice at the CE phase were atomic oxygen (68.2%) and atomic carbon (18.2%), followed by CO (11.8%) and CO2 (1.6%). The averaged modeled desorption yield and rate were 1.3e5 molecules ion−1 and 7.4e13 molecules s−1, respectively, while the average value of ERCs in the radiation-induced dissociation reactions was 2.4e-1 s−1 and for the bimolecular reactions it was 4.4e-24 cm3 molecule−1 s−1. We believe that the current kinetics study can be used in future astrochemical models to better understand the chemical evolution of embedded species within astrophysical ices under the presence of an ionizing radiation field.

Comparison of isoprene chemical mechanisms under atmospheric night-time conditions in chamber experiments: evidence of hydroperoxy aldehydes and epoxy products from NO3 oxidation

Abstract. The gas-phase reaction of isoprene with the nitrate radical (NO3) was investigated in experiments in the outdoor SAPHIR chamber under atmospherically relevant conditions specifically with respect to the chemical lifetime and fate of nitrato-organic peroxy radicals (RO2). Observations of organic products were compared to concentrations expected from different chemical mechanisms: (1) the Master Chemical Mechanism, which simplifies the NO3 isoprene chemistry by only considering one RO2 isomer; (2) the chemical mechanism derived from experiments in the Caltech chamber, which considers different RO2 isomers; and (3) the FZJ-NO3 isoprene mechanism derived from quantum chemical calculations, which in addition to the Caltech mechanism includes equilibrium reactions of RO2 isomers, unimolecular reactions of nitrate RO2 radicals and epoxidation reactions of nitrate alkoxy radicals. Measurements using mass spectrometer instruments give evidence that the new reactions pathways predicted by quantum chemical calculations play a role in the NO3 oxidation of isoprene. Hydroperoxy aldehyde (HPALD) species, which are specific to unimolecular reactions of nitrate RO2, were detected even in the presence of an OH scavenger, excluding the possibility that concurrent oxidation by hydroxyl radicals (OH) is responsible for their formation. In addition, ion signals at masses that can be attributed to epoxy compounds, which are specific to the epoxidation reaction of nitrate alkoxy radicals, were detected. Measurements of methyl vinyl ketone (MVK) and methacrolein (MACR) concentrations confirm that the decomposition of nitrate alkoxy radicals implemented in the Caltech mechanism cannot compete with the ring-closure reactions predicted by quantum chemical calculations. The validity of the FZJ-NO3 isoprene mechanism is further supported by a good agreement between measured and simulated hydroxyl radical (OH) reactivity. Nevertheless, the FZJ-NO3 isoprene mechanism needs further investigations with respect to the absolute importance of unimolecular reactions of nitrate RO2 and epoxidation reactions of nitrate alkoxy radicals. Absolute concentrations of specific organic nitrates such as nitrate hydroperoxides would be required to experimentally determine product yields and branching ratios of reactions but could not be measured in the chamber experiments due to the lack of calibration standards for these compounds. The temporal evolution of mass traces attributed to product species such as nitrate hydroperoxides, nitrate carbonyl and nitrate alcohols as well as hydroperoxy aldehydes observed by the mass spectrometer instruments demonstrates that further oxidation by the nitrate radical and ozone at atmospheric concentrations is small on the timescale of one night (12 h) for typical oxidant concentrations. However, oxidation by hydroxyl radicals present at night and potentially also produced from the decomposition of nitrate alkoxy radicals can contribute to their nocturnal chemical loss.

Study of Low- and Intermediate-Temperature Oxidation Kinetics of Diethyl Ether in a Supercritical Pressure Jet-Stirred Reactor.

Growing demand for low-emission and high-efficiency propulsion systems spurs interest in understanding low-temperature and ultra-high-pressure combustion of alternative biofuels like diethyl ether (DEE). In this study, DEE oxidation experiments are performed at 10 and 100 atm, over a temperature range of 400-900 K, at fuel-lean, stoichiometric, and fuel-rich conditions by using a supercritical pressure jet-stirred reactor (SP-JSR). The experimental data show that DEE is very reactive and exhibits an uncommon low-temperature oxidation behavior with two negative temperature coefficient (NTC) zones. The first NTC zone is mainly governed by the competition reactions of QOOH + O2 = O2QOOH and QOOH = 2CH3CHO + OH, while the second one is mainly governed by the competition reactions of R + O2 = RO2 and the β-scission reaction of fuel radical R. It is shown that the increase of pressure stabilizes RO2 and promotes HO2 chemistry. Moreover, the branching ratios of β-scission reactions of R and QOOH decrease. As a result, it is shown that, with the increase of pressure, both NTC zones become weaker at 100 atm. In addition, the intermediate-temperature oxidation is shifted considerably to lower temperature at 100 atm. The existing DEE model in the literature well predicts the experimental data at low temperature; however, it underpredicts the fuel consumptions at intermediate temperature. The H2/O2 subset in the existing DEE model is updated in this study based on the Princeton updated HP-Mech, including the singlet/triplet competing channels of HO2 related reactions. The updated model improves the overall predictability of key species, especially at intermediate temperature.

Probing the pyrolysis of ethyl formate in the dilute gas phase by synchrotron radiation and theory.

The thermal decomposition of the atmospheric constituent ethyl formate was studied by coupling flash pyrolysis with imaging photoelectron photoion coincidence (iPEPICO) spectroscopy using synchrotron vacuum ultraviolet (VUV) radiation at the Swiss Light Source (SLS). iPEPICO allows photoion mass-selected threshold photoelectron spectra (ms-TPES) to be obtained for pyrolysis products. By threshold photoionization and ion imaging, parent ions of neutral pyrolysis products and dissociative photoionization products could be distinguished, and multiple spectral carriers could be identified in several ms-TPES. The TPES and mass-selected TPES for ethyl formate are reported for the first time and appear to correspond to ionization of the lowest energy conformer having a cis (eclipsed) configuration of the O=C(H)-O-C(H2 )-CH3 and trans (staggered) configuration of the O=C(H)-O-C(H2 )-CH3 dihedral angles. We observed the following ethyl formate pyrolysis products: CH3 CH2 OH, CH3 CHO, C2 H6 , C2 H4 , HC(O)OH, CH2 O, CO2 , and CO, with HC(O)OH and C2 H4 pyrolyzing further, forming CO + H2 O and C2 H2 + H2 . The reaction paths and energetics leading to these products, together with the products of two homolytic bond cleavage reactions, CH3 CH2 O + CHO and CH3 CH2 + HC(O)O, were studied computationally at the M06-2X-GD3/aug-cc-pVTZ and SVECV-f12 levels of theory, complemented by further theoretical methods for comparison. The calculated reaction pathways were used to derive Arrhenius parameters for each reaction. The reaction rate constants and branching ratios are discussed in terms of the residence time and newly suggest carbon monoxide as a competitive primary fragmentation product at high temperatures.

The KOSMA-τ PDR model

Numerical models of photodissociation regions (PDRs) are an essential tool to quantitatively understand observations of massive star forming regions through simulations. Few mature PDR models are available and the Cologne KOSMA-τ PDR model is the only sophisticated model that uses a spherical cloud geometry, thereby allowing us to simulate clumpy PDRs. We present the current status of the code as a reference for modelers and for observers that plan to apply KOSMA-τ to interpret their data. For the numerical solution of the chemical problem, we present a superior Newton-Raphson stepping algorithm and discuss strategies to numerically stabilize the problem and speed up the iterations. The chemistry in KOSMA-τ is upgraded to include the full surface chemistry in an up-to-date formulation and we discuss a novel computation of branching ratios in chemical desorption reactions. The high dust temperature in PDRs leads to a selective freeze-out of oxygen-bearing ice species due to their higher condensation temperatures and we study changes in the ice mantle structures depending on the PDR parameters, in particular the impinging ultraviolet field. Selective freeze-out can produce enhanced C abundances and higher gas temperatures, resulting in a fine-structure line emission of atomic carbon [C i] enhanced by up to 50% if surface reactions are considered. We show how recent Atacama Large Millimeter Array (ALMA) observations of HCO+ emission in the Orion Bar with high spatial resolution on the scale of individual clumps can be interpreted in the context of nonstationary, clumpy PDR ensembles. Additionally, we introduce WL-PDR, a simple plane-parallel PDR model written in Mathematica to act as a numerical testing environment of PDR modeling aspects.

Kinetic isotope effects for dissociative recombination of tritiated ketenyl ion (3HCCO+): A surface-hopping ab initio molecular dynamics study

Dissociative recombination (DR) reactions are important when modeling charged species in the presence of free electrons. While experimental measurements of DR reaction rates are challenging, surface hopping ab initio molecular dynamics (SH-AIMD) simulations provide an attractive alternative. SH-AIMD is especially well-suited for estimating branching ratios, i.e., the relative rates of competing production channels, for DR reactions. Although the radiolysis of diatomic tritium has been studied experimentally, previous attempts to model these systems have failed to account for isotope effects in DR reactions. Previous SH-AIMD studies have also not investigated tritium isotope effects for the branching ratios of DR reactions. In this study, we compute the DR branching ratios of the protiated and tritiated ketenyl ion. Comparison with literature values for the protiated branching ratios provides confidence in the reliability of our SH-AIMD results. Our simulations predict a significant increase of the HC + CO branching ratio for the tritiated system.

Toward Accurate Formation Routes of Complex Organic Molecules in the Interstellar Medium: The Paradigmatic Cases of Acrylonitrile and Cyanomethanimine

The investigation of reaction mechanisms in the interstellar medium requires the evaluation of reaction rates and branching ratios, which can be effectively obtained in the framework of the ab-initio transition state/master equation formalism. However, the reliability of this approach relies on the computation of accurate reaction enthalpies and activation energies for all the paths characterizing the potential energy surface under investigation. Two effective yet reliable parameter-free model chemistries are introduced to obtain accurate energies of all stationary points, with structural determination performed using double-hybrid density functionals. After their validation, these model chemistries have been employed to analyze the competition between hydrogen abstraction and addition/elimination in the reaction between the CN radical and ethylene or methanimine. The energetics has then been complemented by a kinetic study. The results provide new information about important reactive channels operative in different regions of the interstellar medium and in the atmospheres of exoplanets. These further extend the recent general addition/elimination mechanism for the formation of “complex imines” from the reaction of methanimine with a small radical species.

Study of a single line of sight gamma ray diagnostics for measurements of the absolute gamma ray emission from JET

The fusion power produced in a DT thermonuclear reactor is currently determined by measuring the absolute 14 MeV neutron yield of the D(T, α)n fusion reaction. Measurements of 17 MeV gamma rays born from the much less probable D(T, 5He)γ reaction (branching ratio of ∼10−5) have been proposed as an alternative independent method to validate the neutron counting method and also to fulfill the requests of the nuclear regulator for licensing ITER DT operations. However, the development of absolute 17 MeV gamma ray emission measurements entails a number of requirements, such as: (i) knowledge of the 17 MeV gamma ray to 14 MeV neutron emission branching ratio; (ii) the simulation of the gamma ray transport from the extended plasma source to the gamma ray detectors; (iii) a careful determination of the absolute efficiency of previously calibrated gamma ray spectrometers. In this work, we have studied the possibility to infer the global gamma ray emission rate from measurements made with a 3″ × 6″ LaBr3 spectrometer installed at the end of a collimated tangential line of sight at the JET tokamak and using the neutron emission from deuterium plasmas of the most recent experimental campaigns. Results show that 17 MeV gamma ray fluxes at the end of this tangential line of sight have a weak dependence (less than 5%) on the plasma profile and can therefore be used to infer the total emission from the plasma.

Formation of Phosphorus Monoxide (PO) in the Interstellar Medium: Insights from Quantum-chemical and Kinetic Calculations

Abstract In recent years, phosphorus monoxide (PO), an important molecule for prebiotic chemistry, has been detected in star-forming regions and in the comet 67P/Churyumov-Gerasimenko. These studies have revealed that, in the interstellar medium (ISM), PO is systematically the most abundant P-bearing species, with abundances that are about one to three times greater than those derived for phosphorus nitride (PN), the second-most abundant P-containing molecule. The reason why PO is more abundant than PN remains still unclear. Experimental studies with phosphorus in the gas phase are not available, probably because of the difficulties in dealing with its compounds. Therefore, the reactivity of atomic phosphorus needs to be investigated using reliable computational tools. To this end, state-of-the-art quantum-chemical computations have been employed to evaluate accurate reaction rates and branching ratios for the P + OH → PO + H and P + H2O → PO + H2 reactions in the framework of a master equation approach based on ab initio transition state theory. The hypothesis that OH and H2O can be potential oxidizing agents of atomic phosphorus is based on the ubiquitous presence of H2O in the ISM. Its destruction then produces OH, which is another very abundant species. While the reaction of atomic phosphorus in its ground state with water is not a relevant source of PO because of emerged energy barriers, the P + OH reaction represents an important formation route of PO in the ISM. Our kinetic results show that this reaction follows an Arrhenius–Kooij behavior, and thus its rate coefficients (α = 2.28 × 10−10 cm3 molecule−1 s−1, β = 0.16 and γ = 0.37 K) increase by increasing the temperature.

Energy Dependence of Ensemble-Averaged Energy Transfer Moments and Its Effect on Competing Decomposition Reactions.

We carried out a direct dynamics study on the internal-energy dependence of the ensemble-averaged energy transfer moments of the isobutyl radical in collisions with N2 bath gas. We find a linear dependence of the downward moment ⟨ΔEd⟩ and the root-mean-square moment on the initial internal energy, but the upward moment ⟨ΔEu⟩ is found to be independent of the molecule's internal energy. We improved the exponential-down relaxation model by including a linear dependence of ⟨ΔEd⟩ on the initial energy, and we used the improved treatment in the 1D master equation for isobutyl radical decomposition reactions and for a model of competitive reactions with a larger difference in barrier heights. We calculated phenomenological rate constants and branching ratios from chemically significant eigenmodes of the master equation and showed that the energy dependence of ⟨ΔEd⟩ has a greater influence on channels with higher barriers in competitive reactions. Rate constants and branching ratios from master equation calculations indicate that for a given temperature and pressure, there is a constant ⟨ΔEd⟩ that can reproduce results obtained with an E-dependent ⟨ΔEd⟩. But a constant ⟨ΔEd⟩ cannot do this for all temperatures and pressures, with larger differences when the barriers for the competing channels differ more. We conclude that when the branching ratio of competitive reactions is sensitive to pressure, including the energy dependence of ⟨ΔEd⟩ in master equation simulations can make a significant difference in the results.

MO143UTILITY OF SIFT-MS TO EVALUATE VOLATILE ORGANIC COMPOUNDS IN NEPHROPATHIC PATIENTS' BREATH

Abstract Background and Aims Breath analysis techniques allow detection and quantification of multiple analytes present in breath to the low parts per billion volume (ppbv) level. One such technique is selected ion flow tube–mass spectrometry (SIFT-MS), which can measure numerous volatile organic compounds (VOCs) in breath on-line and in real-time. This technique has already been used in an innovative manner to monitor infectious, inflammatory status and metabolic conditions. However, there is no evidence on its use in ambulatory patients with chronic kidney disease (CKD). End-stage-renal-disease patients are characterized by "uremic halitosis" caused by the accumulation of uremic toxins that are detectable in breath such as ammonia and amines. The aims of this study are identifying a possible correlation between the detected VOCs and the presence of CKD, moreover, exploring the range of VOCs levels in patients with different CKD stage. Method In the present study, a mobile Voice200ultra® SIFT-MS instrument was made available by the Agilent SRA Division. The SIFT-MS allowed to quantify the VOCs in CKD patients. The SIFT-MS uses a precise and controlled application of “soft” chemical ionization. We enrolled 50 CKD patients, divided into two subgroups according to the estimated glomerular filtration rate (eGFR): eGFR ≥30 mL/min/1.73m2 (A) and eGFR <30 mL/min/1.73m2 (B) compared to 18 healthy subjects (C). The anamnestic data and information about any comorbidities such as arterial hypertension, cardiovascular and metabolic diseases, were collected for each patient. In order to reduce the possible interferences in the exhaled composition induced by different lifestyles, all participants were instructed to perform hygienic procedures before the test execution. The exhaled was sampled through the use of a standard spirometry mouthpiece for single use, directly connected with the input probe to the MS detector of the instrument that was able to detect more than 30 VOCs. The processing of the sample was made through the direct use of an internal comparison library (Syft library). The SIFT-MS software instantly calculates the absolute concentration of the target compounds by interpolating mass-to-charge ratios, reaction rate coefficients and branching ratios. Results Among all the VOCs analyzed, the most significant results are observed for ammonia and isoprene. In particular, the ROC curve of ammonia highlighted statistically significant differences between the three subgroups respectively A vs C AUC=0,756 p=0,001; B vs C AUC=0,942 p<0,001; A vs B AUC=0,797 p<0,001 (Figure 1). Youden index J between subgroups B and C defines the best cut-off =0,8704 associated with the criterion ammonia concentration ≤4700 ppbv with sensitivity =94,44% and specificity = 92,59%. The ROC curve of isoprene showed statistically significant differences between the three subgroups respectively B vs C AUC=0,669 p=0,050; A vs B AUC=0,691 p=0,014 (Figure 2). These data allow us to define this a highly accurate test. The same significant results were observed also with Anova one-way test that highlighted an inversely correlation between the ammonia breath concentration and eGFR, and a direct correlation between isoprene and eGFR. Conclusion This preliminary data confirms the potential utility of SIFT-MS for the CKD diagnosis and the possible relation between the VOCs concentration and CKD stage. This exam could be a new, non-invasive, fast-performing diagnostic technique with real-time results useful for clinical management of CKD. The study was inserted in the projects: “MioMenù: nuova filiera dell’agro-industria e una cucina tracciata natura/benessere- Lazio Region” and “BioSynOL- Oil and Legumes: biodynamic and synergistic crops for naturally fortified foods and innovative products for health and sport – G.O.Tuscany Region”.

An experimental and modeling study on the low-temperature oxidation of methylcyclopentane in a jet-stirred reactor

Cycloalkanes are important compounds of conventional petroleum-based fuel. Methylcyclopentane (MCP) is a representative five-membered ring cycloalkane, but studies on its oxidation behavior are still limited. Therefore, a comprehensive experimental and kinetic study on MCP low-temperature oxidation was conducted. The experiments were carried out in a jet-stirred reactor (JSR) at the equivalence ratios of 0.5, 1.0 and 2.0, in the temperature range T = 500–1100 K and at atmospheric pressure. Mole fractions of MCP, oxygen, CO, CO2 and other intermediates during fuel oxidation were measured using a gas chromatograph, at the residence time of 2 s and initial fuel mole fraction of 0.5%. Further, a detailed MCP oxidation kinetic model including both high- and low-temperature reaction pathways was developed based on the models reported in the literature, and the updated model was validated against the mole fraction profiles of the oxidation species measured in this study, and the ignition delay times in the literature. To improve the model performance, the rate constants of beta-scission reactions of methylcyclopentyl radicals were calculated at CCSD(T)/CBS//M06-2X/6–311++G(d,p) level of theory by solving the Rice-Ramsperger-Kassel-Marcus/Master Equation. The results show that our updated model has a satisfactory agreement with the oxidation species mole fraction profiles in current study and the ignition delay times in the literature. Reaction pathway analysis indicates that the reactivity difference at different equivalence ratios is attributed to the branching ratios of beta-scission reactions of methylcyclopentyl radicals.

Unimolecular reactions of the resonance-stabilized cyclopentadienyl radicals and their role in the polycyclic aromatic hydrocarbon formation

Resonance-stabilized cyclopentadienyl radicals are important intermediate species in the combustion of transportation fuels. It not only serves as precursors for polycyclic aromatic hydrocarbon (PAH) formation, but also involves in the formation of fundamental PAH precursors such as propargyl and acetylene. In this work, the unimolecular reactions of the cyclopentadienyl radicals are theoretically studied based on high-level quantum chemistry and RRKM/master equation calculations. Stationary points on the potential energy surface (PES) are calculated at the CCSD(T)/CBS//M06–2X/6–311++(d,p) level of theory. The branching ratios of unimolecular reactions of the cyclopentadienyl radicals are analyzed for a broad temperature range from 500 to 2500 K and pressures from 0.01 to 100 atm. It is found that the isomerization reaction of the cyclopentadienyl radical via 1,2-hydrogen transfer dominates at low temperatures and high pressures, while the well-skipping decomposition reaction which forms propargyl and acetylene is important at high temperatures and low pressures. Both the decomposition reaction of the cyclopentadienyl radicals and its reverse reaction show pronounced pressure dependence, and their reaction rate constants are compared against available low-pressure experimental measurements and theoretical studies. The temperature- and pressure-dependent rate coefficients for important reactions involved on the C5H5 PES are calculated and updated in a chemical kinetic model. Impacts of the unimolecular reactions of the cyclopentadienyl radicals on the PAH formation are explored by the numerical modeling of a low-pressure cyclopentene counterflow diffusion flame.

A novel Ka-band chirped-pulse spectrometer used in the determination of pressure broadening coefficients of astrochemical molecules

A novel chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer has been constructed to cover the Ka-band (26.5 GHz-40 GHz) for use in the CRESUCHIRP project, which aims to study the branching ratios of reactions at low temperatures using the chirped-pulse in uniform flow technique. The design takes advantage of recent developments in radio-frequency components, notably, high-frequency, high-power solid-state amplifiers. The spectrometer had a flatness of 5.5 dB across the spectral range, produced harmonic signals below -20 dBc, and the recorded signal scaled well to 6 × 106 averages. The new spectrometer was used to determine pressure broadening coefficients with a helium collider at room temperature for three molecules relevant to astrochemistry, applying the Voigt function to fit the magnitude of the Fourier-transformed data in the frequency domain. The pressure broadening coefficient for carbonyl sulfide was determined to be (2.45 ± 0.02) MHz mbar-1 at room temperature, which agreed well with previous measurements. Pressure broadening coefficients were also determined for multiple transitions of vinyl cyanide and benzonitrile. Additionally, the spectrometer was coupled with a cold, uniform flow from a Laval nozzle. The spectrum of vinyl cyanide was recorded in the flow, and its rotational temperature was determined to be (24 ± 11) K. This temperature agreed with a prediction of the composite temperature of the system through simulations of the experimental environment coupled with calculations of the solution to the optical Bloch equations. These results pave the way for future quantitative studies in low-temperature and high-pressure environments using CP-FTMW spectroscopy.

Breakdown curves of CH2(+), CH3(+), and CH4(+) molecules

Aims. The aim of this work is to provide semi-empirical branching ratios (BRs) for the kinetic databases used in astrochemistry, such as the KInetic Database for Astrochemistry (KIDA). Our work focuses on the CHy(+) species (y = 2–4) excited by cosmic rays (CR), electrons, and photons (UV), or the intermediate excited complexes CHy(+) resulting from chemical reactions. It also intends to test the sensitivity of benchmark calculations to those new physical inputs in cold quiescent clouds and in photo-dissociation regions (PDRs). Methods. We constructed semi-empirical breakdown curves (BDCs) based on the collision of CHy+ (y = 2–4) projectiles of constant velocity (250 keV uma−1) with He atoms as explained in a previous paper, where BRs for UV, CR, and electronic processing were also derived. The same BDCs were applied to predict BRs for chemical reactions (bi-molecular neutral and ionic reactions, charge exchange). The effect of the new BRs on the chemical composition of cold dark clouds was tested using the time-dependent Nautilus gas-grain model. The same effect on the chemical composition of PDRs was tested using the Meudon PDR code. Results. Branching ratio predictions of the model are found to be in good agreement with available BR measurements for charge exchange reactions and the reaction between C and H3+. The chemistry for both cold clouds and PDRs is found to be not strongly affected by this update of BRs.