Role of the Filters in the Formation and Stabilization of Semiquinone Radicals Collected from Cigarette Smoke

The fractional pyrolysis of Bright tobacco was performed in a nitrogen atmosphere over the temperature range 240–510 °C in a specially constructed, high temperature flow reactor system. Electron paramagnetic resonance (EPR) spectroscopy was used to analyze the free radicals in the initially produced total particular matter (TPM) and in TPM after exposure to ambient air (aging). Different filters have been used to collect TPM from tobacco smoke: cellulosic, cellulose nitrate, cellulose acetate, nylon, Teflon, and Cambridge. The collection of the primary radicals (measured immediately after collection of TPM on filters) and the formation and stabilization of the secondary radicals (defined as radicals formed during aging of TPM samples on the filters) depend significantly on the material of the filter. A mechanistic explanation about different binding capabilities of the filters decreasing in the order cellulosic > cellulose nitrate > cellulose acetate > nylon ∼ Teflon is presented. Different properties were observed for the Cambridge filter. Specific care must be taken using the filters for identification of radicals from tobacco smoke to avoid artifacts in each case

Hydroxyl Radical Generation from Environmentally Persistent Free Radicals (EPFRs) in PM_2.5

Hydroxyl radicals were generated from an aqueous suspension of ambient PM_2.5 and detected utilizing 5,5-dimethyl-1-pyrroline-<i>N</i>-oxide (DMPO) as a spin trap coupled with electron paramagnetic resonance (EPR) spectroscopy. Results from this study suggested the importance of environmentally persistent free radicals (EPFRs) in PM_2.5 to generate significant levels of ·OH without the addition of H₂O₂. Particles for which the EPFRs were allowed to decay over time induced less hydroxyl radical. Additionally, higher particle concentrations produced more hydroxyl radical. Some samples did not alter hydroxyl radical generation when the solution was purged by air. This is ascribed to internal, rather than external surface associated EPFRs

Molecular Products from the Thermal Degradation of Glutamic Acid

The thermal behavior of glutamic acid was investigated in N₂ and 4% O₂ in N₂ under flow reactor conditions at a constant residence time of 0.2 s, within a total pyrolysis time of 3 min at 1 atm. The identification of the main pyrolysis products has been reported. Accordingly, the principal products for pyrolysis in order of decreasing abundance were succinimide, pyrrole, acetonitrile, and 2-pyrrolidone. For oxidative pyrolysis, the main products were succinimide, propiolactone, ethanol, and hydrogen cyanide. Whereas benzene, toluene, and a few low molecular weight hydrocarbons (propene, propane, 1-butene, and 2-butene) were detected during pyrolysis, no polycyclic aromatic hydrocarbons (PAHs) were detected. Oxidative pyrolysis yielded low molecular weight hydrocarbon products in trace amounts. The mechanistic channels describing the formation of the major product succinimide have been explored. The detection of succinimide (major product) and maleimide (minor product) from the thermal decomposition of glutamic acid has been reported for the first time in this study. Toxicological implications of some reaction products (HCN, acetonitrile, and acyrolnitrile), which are believed to form during heat treatment of food, tobacco burning, and drug processing, have been discussed in relation to the thermal degradation of glutamic acid

Kinetic Modeling of Cellulose Fractional Pyrolysis

The kinetics of cellulose fractional pyrolysis was studied for the first time in the temperature range of 200–900 °C, with 25 °C increment under nitrogen atmosphere. A detailed analysis of the major and minor pyrolysis products was performed using a System for Thermal Diagnostic Studies (STDS) and FTIR techniques. A semiglobal kinetic model was proposed, with products grouped into kinetic lumps, based on their formation profile similarity. Kinetic parameters (pre-exponential factor <i>A</i> and activation energy <i>E</i>_a) for formation of major products grouped into heavy volatiles 1 lump (levoglucosan and anhydrosugars) and light volatiles 2 lump (furans and carbonyls) were obtained based on the performed experimental studies. The final model accurately predicts not only the weight loss, the temperature-distribution of major lumped products, and the total yields of tar and gases from the fractional pyrolysis of cellulose but also shows a good performance toward literature data for experimental studies of others

Peculiarities of Pyrolysis of Hydrolytic Lignin in Dispersed Gas Phase and in Solid State

The unique decomposition pathways of hydrolytic lignin (HL) dissolved in an acetone/water mixture (9:1) and dispersed by a droplet evaporation technique under nitrogen gas flow has been investigated in a conventional reactor at atmospheric condition, a temperature region of 400–550 °C, and a residence time of 0.12 s. The results validate the fact that dispersion of the lignin into the gas phase by decreasing the sample size (as well as “minimizing the char area to avoid catalytic contact” of molecular products/radicals with the surface) may open new perspectives in understanding the chemistry of the depolymerization of lignin. Using Laser Desorption Ionization-Time of Flight-Mass Spectrometry (LDI-TOF-MS) the intrinsic ion <i>m</i>/<i>z</i> = 550, as the major MS peak from fresh HL dissolved in an acetone/water mixture before pyrolysis, was detected. Surprisingly, the expected phenolic compounds after pyrolysis were in trace amounts at less than 15% conversion of lignin. Instead, oligomeric intermediate substances with low (<550 Da) and high molecular weight (>550 Da) containing lignin-substructures (trapped on quartz wool located at the end of the reactor at ∼300 °C) were detected as major products using LDI-TOF-MS. The hypothesis about a largely disputed key question on lignin pyrolysis as to whether the phenolic compounds or oligomers (dimers, trimers, etc.) are the primary products is discussed. Additionally, a focus on the free-radical mechanism of depolymerization of solid lignin by formation of free intermediate radicals from initial lignin macromolecules as well as from inherent, low molecular weight oligomer molecules is developed based on the Low Temperature Matrix Isolation (LTMI) EPR technique

Environmentally Persistent Free Radicals (EPFRs). 3. Free versus Bound Hydroxyl Radicals in EPFR Aqueous Solutions

Additional experimental evidence is presented for <i>in vitro</i> generation of hydroxyl radicals because of redox cycling of environmentally persistent free radicals (EPFRs) produced after adsorption of 2-monochlorophenol at 230 °C (2-MCP-230) on copper oxide supported by silica, 5% Cu­(II)­O/silica (3.9% Cu). A chemical spin trapping agent, 5,5-dimethyl-1-pyrroline-<i>N</i>-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed. Experiments in spiked O¹⁷ water have shown that ∼15% of hydroxyl radicals formed as a result of redox cycling. This amount of hydroxyl radicals arises from an exogenous Fenton reaction and may stay either partially trapped on the surface of particulate matter (physisorbed or chemisorbed) or transferred into solution as free OH. Computational work confirms the highly stable nature of the DMPO–OH adduct, as an intermediate produced by interaction of DMPO with physisorbed/chemisorbed OH (at the interface of solid catalyst/solution). All reaction pathways have been supported by <i>ab initio</i> calculations

Molecular Products and Fundamentally Based Reaction Pathways in the Gas-Phase Pyrolysis of the Lignin Model Compound <i>p</i>‑Coumaryl Alcohol

The fractional pyrolysis of lignin model compound para-coumaryl alcohol (<i>p</i>-CMA) containing a propanoid side chain and a phenolic OH group was studied using the System for Thermal Diagnostic Studies at temperatures from 200 to 900 °C, in order to gain mechanistic insight into the role of large substituents in high-lignin feedstocks pyrolysis. Phenol and its simple derivatives <i>p-</i>cresol, ethyl-, propenyl-, and propyl-phenols were found to be the major products predominantly formed at low pyrolysis temperatures (<500 °C). A cryogenic trapping technique was employed combined with EPR spectroscopy to identify the open-shell intermediates registered at pyrolysis temperatures above 500 °C. These were characterized as radical mixtures primarily consisting of oxygen-linked conjugated radicals. A comprehensive potential energy surface analysis of <i>p-</i>CMA and <i>p-</i>CMA + H atom systems was performed using various DFT protocols to examine the possible role of concerted molecular eliminations and free-radical mechanisms in the formation of major products. Other significant unimolecular concerted reactions along with formation and decomposition of primary radicals are also described and evaluated. The calculations suggest that a set of the chemically activated secondary radical channels is relevant to the low temperature product formation under fractional pyrolysis conditions

New Features of Laboratory-Generated EPFRs from 1,2-Dichlorobenzene (DCB) and 2‑Monochlorophenol (MCP)

The present research is primarily focused on investigating the characteristics of environmentally persistent free radicals (EPFRs) generated from commonly recognized aromatic precursors, namely, 1,2-dichlorobenzene (DCB) and 2-monochlorophenol (MCP), within controlled laboratory conditions at a temperature of 230 °C, termed as DCB230 and MCP230 EPFRs, respectively. An intriguing observation has emerged during the creation of EPFRs from MCP and DCB utilizing a catalyst 5% CuO/SiO2, which was prepared through various methods. A previously proposed mechanism, advanced by Dellinger and colleagues (a conventional model), postulated a positive correlation between the degree of hydroxylation on the catalyst’s surface (higher hydroxylated, HH and less hydroxylated, LH) and the anticipated EPFR yields. In the present study, this correlation was specifically confirmed for the DCB precursor. Particularly, it was observed that increasing the degree of hydroxylation at the catalyst’s surface resulted in a greater yield of EPFRs for DCB230. The unexpected finding was the indifferent behavior of MCP230 EPFRs to the surface morphology of the catalyst, i.e., no matter whether copper oxide nanoparticles are distributed densely, sparsely, or completely agglomerated. The yields of MCP230 EPFRs remained consistent regardless of the catalyst type or preparation protocol. Although current experimental results confirm the early model for the generation of DCB EPFRs (i.e., the higher the hydroxylation is, the higher the yield of EPFRs), it is of utmost importance to closely explore the heterogeneous alternative mechanism(s) responsible for generating MCP230 EPFRs, which may run parallel to the conventional model. In this study, detailed spectral analysis was conducted using the EPR technique to examine the nature of DCB230 EPFRs and the aging phenomenon of DCB230 EPFRs while they exist as surface-bound o-semiquinone radicals (o-SQ) on copper sites. Various aspects concerning bound radicals were explored, including the hydrogen-bonding tendencies of o-semiquinone (o-SQ) radicals, the potential reversibility of hydroxylation processes occurring on the catalyst’s surface, and the analysis of selected EPR spectra using EasySpin MATLAB. Furthermore, alternative routes for EPFR generation were thoroughly discussed and compared with the conventional model