Acrolein Molecule Research Articles

Study on the thermal oxidation of oleic, linoleic and linolenic acids by synchrotron radiation photoionization mass spectrometry.

Cooking oil fumes contain numerous hazardous and carcinogenic chemicals, posing potential threats to human health. However, the sources of these species remain ambiguous, impeding health risk assessment, pollution control and mechanism research. To address this issue, the thermal oxidation of three common unsaturated fatty acids (UFAs), namely oleic, linoleic and linolenic acids, present in vegetable oils was investigated. The volatile and semi-volatile products were comprehensively characterized by online synchrotron radiation photoionization mass spectrometry (SR-PIMS) with two modes, which were validated and complemented using offline gas chromatography (GC)/MS methods. Tunable SR-PIMS combined with photoionization efficiency curve simulation enabled the recognition of isomers/isobars in gaseous fumes. SR-PIMS revealed over 100 products, including aldehydes, alkenes, furans, aromatic hydrocarbons, etc., such as small molecules of formaldehyde, acetaldehyde, acrolein, ethylene and furan, which are not readily detected by conventional GC/MS; and some unreported fractions, e.g. ketene, 4-ethylcyclohexene and cycloundecene(E), were also observed. Furthermore, real-time monitoring of product emissions during the thermal oxidation of the three UFAs via SR-PIMS revealed that linolenic acid may be the major source of acrolein. SR-PIMS has been demonstrated as a powerful technique for online investigation of cooking oil fumes. This study achieved comprehensive characterization of volatile and semi-volatile products from the thermal oxidation of oleic, linoleic and linolenic acids, facilitating the traceability of species in cooking fumes and aiding in exploring the thermal reactions of different vegetable oils.

Novel orthorhombic silicane nanosheet as a sensing material for acrolein and propanol—a first-principles investigation

Currently, the elemental monolayer materials attracted great interest among the research communities due to their stability, selectivity, and sensitivity towards hazardous vapour or gas molecules. In this research work, we deployed an orthorhombic silicane nanosheet (Ortho-SiNS) as a sensing element to detect acrolein and propanol at ambient conditions. Initially, the structural firmness of Ortho-SiNS is verified with the support of formation energy. Subsequently, the electronic features of the base substrate are discussed using band structure along with projected density of states maps. The estimated energy gap of Ortho-SiNS is found to be 4.179 eV. The interaction behaviour of target air pollutants on Ortho-SiNS is investigated by ascertaining Bader charge transfer, relative band gap changes, and adsorption energy. In the present work, the adsorption energy is calculated in the scope of −0.305 eV to −1.039 eV, which validates the physisorption of acrolein and propanol on Ortho-SiNS. The outcomes recommended that the Ortho-SiNS can be employed as a promising chemical sensor to sense acrolein and propanol molecules from cigarette smoke.

DFT investigation for the adsorption of acrolein onto the surface of pristine and doped C70: NBO and QTAIM analyses

Density functional theory was used in the present study to compare the sensitivity and reactivity of pristine and doped fullerene C70 variants (including Al and Si) to the acrolein (AC) molecule. It was determined that the O-head of AC is responsible for its physisorption onto the C70. The adsorption's energy was close to −3.11 kcal/mol. During adsorption, the associated cluster's electrical conductivity remained nearly unaltered. Al and Si atoms that replace C atoms in fullerene increase their activity. Si had an estimated adsorption energy of −28.23 kcal/mol, whereas Al was expected to have a value of −48.95 kcal/mol. The LUMO-HOMO energy gap appears to impact the AC molecule significantly. The stability of LUMOs in Si-doped fullerene was dramatically reduced by AC adsorption, whereas its electrical conductivity was increased. Simultaneously, electrical signals linked to the existence of AC in the environment were created. The outcomes demonstrated the high reliability of Si-doped fullerene as a AC electronic sensor. Al-doped fullerene is an Ф-type candidate to be utilized as a AC sensor due to the significant effects of the AC on its Fermi level and functions. The stable site of the AC/Al-fullerene complex showed a maximum peak at 784 nm, following the results of the time-dependent density functional theory (TD-DFT).

Cytotoxicity of a Novel Compound Produced in Foods via the Reaction of Amino Acids with Acrolein along with Formaldehyde.

Acrolein (ACR) and formaldehyde (FA) are toxic aldehydes co-produced in foods. This work found that amino acids, the nucleophiles ubiquitously existing in foods, can react simultaneously with them. Six amino acids, including γ-aminobutyric acid (GABA), glycine, alanine, serine, threonine, and glutamine, can scavenge ACR and FA at 37, 85, and 160 °C. GABA had the highest scavenging capacity for ACR and FA, by 79 and 13% at 37 °C for 2 h, and 99 and 48% at 160 °C for 30 min, respectively. Moreover, a new type of compound with a basic structure of 5-formyl-3-methylene-3,6-dihydropyridin was identified in all reactions and formed by 1 molecule of FA and amino acid and 2 molecules of ACR. The content of this compound was higher than that of free ACR in typical thermally processed foods. Moreover, the compounds produced from different amino acids showed different cytotoxicity values. In gastric epithelial and human intestinal epithelial cell lines, the cytotoxicity values of serine-sourced and threonine-sourced products were lower than that of ACR but higher than that of FA, whereas others had less toxicity compared with the two aldehydes. Considering that the content of serine-sourced products was the highest in almost all tested foods, their safety needs to be evaluated.

Low-Dose Acrolein, an Endogenous and Exogenous Toxic Molecule, Inhibits Glucose Transport via an Inhibition of Akt-Regulated GLUT4 Signaling in Skeletal Muscle Cells.

Urinary acrolein adduct levels have been reported to be increased in both habitual smokers and type-2 diabetic patients. The impairment of glucose transport in skeletal muscles is a major factor responsible for glucose uptake reduction in type-2 diabetic patients. The effect of acrolein on glucose metabolism in skeletal muscle remains unclear. Here, we investigated whether acrolein affects muscular glucose metabolism in vitro and glucose tolerance in vivo. Exposure of mice to acrolein (2.5 and 5 mg/kg/day) for 4 weeks substantially increased fasting blood glucose and impaired glucose tolerance. The glucose transporter-4 (GLUT4) protein expression was significantly decreased in soleus muscles of acrolein-treated mice. The glucose uptake was significantly decreased in differentiated C2C12 myotubes treated with a non-cytotoxic dose of acrolein (1 μM) for 24 and 72 h. Acrolein (0.5–2 μM) also significantly decreased the GLUT4 expression in myotubes. Acrolein suppressed the phosphorylation of glucose metabolic signals IRS1, Akt, mTOR, p70S6K, and GSK3α/β. Over-expression of constitutive activation of Akt reversed the inhibitory effects of acrolein on GLUT4 protein expression and glucose uptake in myotubes. These results suggest that acrolein at doses relevant to human exposure dysregulates glucose metabolism in skeletal muscle cells and impairs glucose tolerance in mice.

Distinction of photoelectron spectroscopy of cis- and trans-acrolein explored by theoretical computation

• The photoelectron spectra for the two lowest cationic states of cis - and trans -acrolein have been simulated. • Trans -acrolein is identified as the primary isomer responsible for the experimental photoelectron spectra. • The cis -acrolein anion is calculated to be more stable than the trans form, contrary to acrolein molecules. • The barrier for trans - cis isomerization of acrolein anion is high, and which isomer of acrolein anion will be produced is unknown We calculated the equilibrium structures and harmonic vibrational frequencies of acrolein (including molecule, cation and anion) using the B3LYP, PBE0, and M06-2X approaches. We also computed the Franck–Condon factors and simulated the photoelectron spectra of acrolein molecules and anions. The adiabatic ionization energy (AIE) and electron affinity were computed using the CCSD(T) approach via extrapolation to the complete basis set limit. Trans -acrolein is identified as the primary isomer responsible for the photoelectron spectra of acrolein being observed. The calculated AIEs were consistent with the experiment. The cis -acrolein anion is predicted to be more stable than its trans- counterpart. However, the potential barrier might prohibit the isomerization of the acrolein anion. Accordingly, the type of isomer of acrolein anion that will be produced from electron-attaching to the more stable trans -acrolein molecule remains unknown. The simulated photoelectron spectra of the acrolein anion can be used to identify the isomer being produced.

Structural, electronic, and energetic investigations of acrolein adsorption on B36 borophene nanosheet: a dispersion-corrected DFT insight.

The adsorption of acrolein (AC) onto the surface of B36 borophene nanosheet was studied using dispersion-corrected density functional theory (DFT). The structural and electronic properties were scrutinized by several quantum chemical parameters such as HOMO-LUMO gap, condensed Fukui function, molecular electrostatic potential (ESP), and the density of states (DOS). The non-covalent interactions (NCI) were explored by combined reduced density gradient (RDG-NCI) and energy decomposition analysis (EDA) techniques. It was found that the adsorption of acrolein on both convex and concave surfaces of borophene is mainly governed by van der Waals interactions. Our calculations showed that the adsorption energy is strengthened and favored when multiple acrolein molecules adsorb on the edge sides of borophene through their terminal carbonyl oxygen atom. Furthermore, the calculated HOMO-LUMO energy gaps were significantly reduced upon adsorption affecting, therefore, the electrical conductance of borophene. These results should be useful in designing acrolein sensors.

Mass transfer intensification by microinterface: Efficient dehydration of glycerol into acrolein in a water/oil pickering emulsion system

Abstract Chemical reactions with products of high reactivity generally suffer from low yields due to the severe side reactions. This is the case for the synthesis of acrolein from glycerol dehydration. To improve the yield of acrolein, fast removal of high reactive acrolein molecules from the reaction system is desirable but remains a major challenge, due to the high viscosity of glycerol. To tackle this problem, the Pickering emulsion was chosen as the reaction system in this work to accelerate the removal of acrolein. A water-in-oil Pickering emulsion was fabricated for the liquid phase dehydration of glycerol to acrolein, which exhibits twice yield of acrolein compared with the homogeneous system. The combination of the transfer experiments and IR analysis confirmed the drastic restrain of the side reactions between acrolein and glycerol, due to the intensified mass transfer of acrolein from the liquid phase by the larger microinterface of emulsion. Furthermore, the transfer rate of acrolein through the water-oil interface can be tuned via a shift in the interfacial properties of the silica emulsifier by silylation treatment. The highest acrolein yield of nearly 50% was obtained with the highest transfer rate of acrolein on the silica silylated by (MeO)3Si(CH2)11CH3.

Nitrogen-containing secondary organic aerosol formation by acrolein reaction with ammonia/ammonium

Abstract. Ammonia-driven carbonyl-to-imine conversion is an important formation pathway to the nitrogen-containing organic compounds (NOCs) in secondary organic aerosols (SOAs). Previous studies have mainly focused on the dicarbonyl compounds as the precursors of light-absorbing NOCs. In this work, we investigated whether acrolein could also act as an NOC precursor. Acrolein is the simplest α, β-unsaturated mono-carbonyl compound, and it is ubiquitous in the atmosphere. Experiments probing multiphase reactions of acrolein as well as bulk aqueous-phase experiments were carried out to study the reactivity of acrolein towards ammonia and ammonium ions. Molecular characterization of the products based on gas chromatography mass spectrometry, high-resolution mass spectrometry, surface-enhanced Raman spectrometry and ultraviolet/visible spectrophotometry was used to propose possible reaction mechanisms. We observed 3-methylpyridine (commonly known as 3-picoline) in the gas phase in Tedlar bags filled with gaseous acrolein and ammonia or ammonium aerosols. In the ammonium-containing aqueous phase, oligomeric compounds with formulas (C3H4O)m(C3H5N)n and pyridinium compounds like (C3H4O)2C6H8N+ were observed as the products. The pathway to 3-methylpyridine was proposed to be the intramolecular carbon–carbon addition of the hemiaminal, which resulted from sequential carbonyl-to-imine conversions of acrolein molecules. The 3-methylpyridine was formed in the aqueous phase, but some of the 3-methylpyridine could revolatilize to the gas phase, explaining the observation of gaseous 3-methylpyridine in the bags. The (C3H4O)2C6H8N+ was a carbonyl-to-hemiaminal product from acrolein dimer and 3-methylpyridine, while the oligomeric products of (C3H4O)m(C3H5N)n were polymers of acroleins and propylene imines formed via carbonyl-to-imine conversion and condensation reactions. The pH value effect on the liquid products was also studied in the bulk aqueous-phase experiments. While the oligomeric compounds were forming in both acidic and alkaline conditions, the pyridinium products favored moderately acidic conditions. Both the oligomeric products and the pyridinium salts are light-absorbing materials. This work suggests that acrolein may serve as a precursor of light-absorbing heterocyclic NOCs in SOA. Therefore, secondary reactions of α, β-unsaturated aldehydes with reduced nitrogen should be taken into account as a source of light-absorbing NOCs in SOA.

Reaction Pathways in Acrolein Oxidation over a Mixed‐Oxide Catalyst

AbstractA reaction network detailing the mechanistic origins of 17 C1−C7 byproducts in acrolein oxidation over a vanadium molybdate mixed oxide catalyst doped with antimony and copper is proposed based on measurements of acrolein oxidation rates with co‐feeds of C1−C7 organics formed as byproducts, acrylic acid 13C isotopic tracer experiments, and probe molecule reactions. C1 and C2 products form via C−C bond scission of either the single or double C−C bond in acrolein and acrylic acid. C4−C7 products form by addition of one or two acrolein or acrylic acid molecules to a C2 surface species coupled with decarbonylation or decarboxylation events. Two‐carbon ethyl and vinyl surface species and three‐carbon acrolein‐derived surface species are involved in all pathways that lead to byproduct formation; controlling the relative abundance and reactivity of such intermediates is integral to prescribing process conditions and material compositions for selective oxidation of acrolein.

Molecular Binding Contributes to Concentration Dependent Acrolein Deposition in Rat Upper Airways: CFD and Molecular Dynamics Analyses.

Existing in vivo experiments show significantly decreased acrolein uptake in rats with increasing inhaled acrolein concentrations. Considering that high-polarity chemicals are prone to bond with each other, it is hypothesized that molecular binding between acrolein and water will contribute to the experimentally observed deposition decrease by decreasing the effective diffusivity. The objective of this study is to quantify the probability of molecular binding for acrolein, as well as its effects on acrolein deposition, using multiscale simulations. An image-based rat airway geometry was used to predict the transport and deposition of acrolein using the chemical species model. The low Reynolds number turbulence model was used to simulate the airflows. Molecular dynamic (MD) simulations were used to study the molecular binding of acrolein in different media and at different acrolein concentrations. MD results show that significant molecular binding can happen between acrolein and water molecules in human and rat airways. With 72 acrolein embedded in 800 water molecules, about 48% of acrolein compounds contain one hydrogen bond and 10% contain two hydrogen bonds, which agreed favorably with previous MD results. The percentage of hydrogen-bonded acrolein compounds is higher at higher acrolein concentrations or in a medium with higher polarity. Computational dosimetry results show that the size increase caused by the molecular binding reduces the effective diffusivity of acrolein and lowers the chemical deposition onto the airway surfaces. This result is consistent with the experimentally observed deposition decrease at higher concentrations. However, this size increase can only explain part of the concentration-dependent variation of the acrolein uptake and acts as a concurrent mechanism with the uptake-limiting tissue ration rate. Intermolecular interactions and associated variation in diffusivity should be considered in future dosimetry modeling of high-polarity chemicals such as acrolein.

Keggin-type molybdovanadophosphoric acids loaded on ZSM-5 zeolite as a bifunctional catalyst for oxidehydration of glycerol

Glycerol is a promising renewable feedstock for the manufacture of C3 derivatives. We investigated the one-pass oxidehydrarion of glycerol through the dehydration of glycerol into acrolein, followed by the oxidation of acrolein. A novel bifunctional catalyst for this reaction was prepared by loading the Keggin-type molybdovanadophosphoric acid H3+xPVxMo12-xO40 (x = 0–3) on ZSM-5 (MFI) zeolite (Si/Al = 45) exhibiting both dehydration and oxidation activity. H5PV2Mo10O40 and H6PV3Mo9O40 were stable and dispersed on ZSM-5 zeolite, and the acidic property of the ZSM-5 zeolite was retained. The oxidehydration of glycerol was catalyzed by H5PV2Mo10O40 loaded on the ZSM-5 zeolite with high selectivity of acrylic acid. In-situ IR analysis suggests that acrolein molecules adsorbed on H5PV2Mo10O40/ZSM-5 were converted into acrylic acid due to the inhibition of side-reactions such as polymerization and auto-condensation, which induced coke formation, compared with the other Mo and V-based oxides loaded on ZSM-5 zeolite.

Description of the structure-chemoselectivity relationship in the transfer hydrogenation of α,β-unsaturated aldehydes and ketones with alcohols in the presence of magnesium oxide

The vapour-phase catalytic transfer hydrogenation (CTH) of fifteen acyclic α,β-unsaturated carbonyl compounds, i.e. ten aldehydes and five ketones, with ethanol or 2-propanol as hydrogen donors has been studied over pure MgO as the catalyst. The obtained values of the yields of unsaturated alcohols (UOLs) have been used to calculate a normalized value called the relative directional reactivity (RDR). Among substituted α,β-unsaturated aldehydes transfer hydrogenated with ethanol only two of them have shown a lower reactivity (RDRE < 1) than that noted for acrolein (for which RDRE = 1), namely 3,3-dimethyl- and 2-phenylacrolein. It has been found that the introduction of an alkyl substituent into position 2 in an acrolein molecule as well as a phenyl group into position 3 leads to a distinct increase of an RDRE value for such aldehydes. In contrast, very pronounced differences in relative directional reactivity values (RDRP) for both α,β-unsaturated aldehydes and ketones have been observed when 2-propanol was used as the hydrogen donor. The ranges of the RDRP values are: 0.45–2.52 and 0.04–1.71 for aldehydes and ketones, respectively. The proposed normalization procedure allowed us to obtain values which could be used to make meaningful conclusions as to the influence of the structure of α,β-unsaturated carbonyl compounds on their reactivity. Moreover, it was used to determine which of these compounds react in accordance with the thermodynamic description, and whose reactivity is kinetically controlled.

Metabolism of Foodborne Heterocyclic Aromatic Amines by Lactobacillus reuteri DSM 20016.

The heterocyclic aromatic amine (HAA) 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) is converted into 7-hydroxy-5-methyl-3-phenyl-6,7,8,9-tetrahydropyrido[3',2':4,5]imidazo[1,2-a]pyrimidin-5-ium chloride (PhIP-M1) via a chemical reaction with 3-hydroxypropionaldehyde or acrolein derived from glycerol by reuterin producing gut bacteria. Because it is unknown whether this reaction also applies to other HAAs, seven foodborne HAAs (2-amino-9H-pyrido[2,3-b]indole (AαC), 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), 2-amino-3-methyl-3H-imidazo[4,5-f]quinoline (IQ), 2-amino-3,4-dimethyl-3H-imidazo[4,5-f]quinoline (MeIQ), 2-amino-3,8-dimethyl-3H-imidazo[4,5-f]quinoxaline (MeIQx), 9H-pyrido[3,4-b]indole (norharman), and 1-methyl-9H-pyrido[3,4-b]indole (harman)) were anaerobically incubated with Lactobacillus reuteri DSM 20016 in the presence of glycerol. The extent of conversion, as analyzed by HPLC-DAD/FLD, was dependent on both the studied HAAs and the glucose/glycerol ratio, indicating reuterin to be involved in HAA metabolism. Based on HRMS analyses, PhIP-M1-type metabolites were detected for AαC, Trp-P-1, IQ, MeIQ, MeIQx, harman, and norharman. In the case of AαC, this was confirmed by metabolite isolation (AαC-M8, 2,3,4,10-tetrahydro-1H-indolo[2,3-b][1,8]naphthyridin-2-ol) and one- (1H) and two-dimensional (HSQC, HMBC, COSY, DOSY) NMR spectroscopy. In addition, based on HRMS and/or NMR spectroscopy, a new type of HAA metabolite, resulting from the reaction with two molecules of 3-hydroxypropionaldehyde or acrolein, is hypothesized for AαC, Trp-P-1, IQ, MeIQ, and MeIQx.

The Interaction of Acrolein with Pristine and N-doped TiO2 Anatase Nanoparticles: A DFT Study.

Density functional theory calculations were carried out in order to study the effects of the adsorption of acrolein molecule on the structural and electronic properties of TiO2 anatase nanoparticles. The ability of pristine and N-doped TiO2 anatase nanoparticles to recognize toxic acrolein (C3H4O) molecule was surveyed in detail. It was concluded that acrolein molecule chemisorbs on the N-doped anatase nanoparticles with large adsorption energy and small distance with respect to the nanoparticle. The results indicate that the adsorption of acrolein on the N-doped TiO2 is energetically more favorable than the adsorption on the pristine one, suggesting that the N doping can energetically facilitate the adsorption of acrolein on the N-doped nanoparticle. It means that the N-doped TiO2 nanoparticle can react with acrolein molecule more efficiently. The interaction between acrolein molecule and N-doped TiO2 can induce substantial variations in the HOMO/LUMO molecular orbitals of the nanoparticle, changing its electrical conductivity which is helpful for developing novel sensor devices for the removal of harmful acrolein molecule. The large overlaps in the projected density of states spectra reveal the formation of chemical bond between two interacting atoms. Charge analysis based on Mulliken charges indicates that charge is transferred from the acrolein molecule to the TiO2 nanoparticle.

A complete basis set study of the lowest n–π* and π–π* electronic transitions of acrolein in explicit water environment

The solvatochromic shift of the first n–π* and π–π* transitions of s-trans acrolein molecule in water is systematically investigated. Monte Carlo simulations are made to generate solute–solvent configurations used in CIS(D)/aug-cc-pVXZ (X = 2, 3, 4, 5, 6) calculations. Analysis of the convergence of the results with the cardinal number and the number of explicit solvent molecules is made. Our results elucidate the solvatochromic shift of the n–π* transition dominated by electrostatic interaction and the π–π* transition requiring non-electrostatic interaction.

Density functional theory study of acrolein adsorption on graphyne

We have used density functional theory to study the effect of acrolein adsorption on the electronic properties of graphyne. It is found that the acrolein molecule is physisorbed on graphyne sheets with small adsorption energy and large adsorption distance. Mulliken charge analysis indicates that charge is transferred from the acrolein molecule to the graphyne sheets. In the presence of this charge donor molecule, α- and β-graphyne with semimetallic properties and γ-graphyne with semiconducting property become n-type semiconductors. The sensitivity of the electronic properties of graphyne to the presence of acrolein indicates that graphyne sheets are appropriate materials to use as a sensor for acrolein detection.

Single-Atom Alloy Pd–Ag Catalyst for Selective Hydrogenation of Acrolein

Pd–Ag alloy catalysts with very dilute amounts of Pd were synthesized. EXAFS results demonstrated that when the concentration of Pd was as low as 0.01 wt %, Pd was completely dispersed as isolated single atoms in Ag nanoparticles. The activity for the hydrogenation of acrolein was improved by the presence of these isolated Pd atoms due to the creation of sites with lower activation energy for H2 dissociation. In addition, for the same particle size, the 0.01% Pd/8% Ag alloy nanoparticles exhibited higher selectivity than their monometallic counterparts, suggesting that the Pd atom may act as a site for the favorable bonding of the acrolein molecule for facile hydrogenation of the aldehyde functionality.

Generalized trajectory surface-hopping method for internal conversion and intersystem crossing.

Trajectory-based fewest-switches surface-hopping (FSSH) dynamics simulations have become a popular and reliable theoretical tool to simulate nonadiabatic photophysical and photochemical processes. Most available FSSH methods model internal conversion. We present a generalized trajectory surface-hopping (GTSH) method for simulating both internal conversion and intersystem crossing processes on an equal footing. We consider hops between adiabatic eigenstates of the non-relativistic electronic Hamiltonian (pure spin states), which is appropriate for sufficiently small spin-orbit coupling. This choice allows us to make maximum use of existing electronic structure programs and to minimize the changes to available implementations of the traditional FSSH method. The GTSH method is formulated within the quantum mechanics (QM)/molecular mechanics framework, but can of course also be applied at the pure QM level. The algorithm implemented in the GTSH code is specified step by step. As an initial GTSH application, we report simulations of the nonadiabatic processes in the lowest four electronic states (S0, S1, T1, and T2) of acrolein both in vacuo and in acetonitrile solution, in which the acrolein molecule is treated at the ab initio complete-active-space self-consistent-field level. These dynamics simulations provide detailed mechanistic insight by identifying and characterizing two nonadiabatic routes to the lowest triplet state, namely, direct S1 → T1 hopping as major pathway and sequential S1 → T2 → T1 hopping as minor pathway, with the T2 state acting as a relay state. They illustrate the potential of the GTSH approach to explore photoinduced processes in complex systems, in which intersystem crossing plays an important role.

DFT studies of acrolein molecule adsorption on pristine and Al- doped graphenes

The ability of pristine graphene (PG) and Al-doped graphene (AlG) to detect toxic acrolein (C3H4O) was investigated by using density functional calculations. It was found that C3H4O molecule can be adsorbed on the PG and AlG with adsorption energies about -50.43 and - v30.92 kcal mol(-1) corresponding to the most stable configurations, respectively. Despite the fact that interaction of C3H4O has no obvious effects on the of electronic properties of PG, the interaction between C3H4O and AlG can induce significant changes in the HOMO/LUMO energy gap of the sheet, altering its electrical conductivity which is beneficial to sensor designing. Thus, the AlG may be sensitive in the presence of C3H4O molecule and might be used in its sensor devices. Also, applying an external electric filed in an appropriate orientation (almost stronger than 0.01 a.u.) can energetically facilitate the adsorption of C3H4O molecule on the AlG.