Relative Reactivity Research Articles

Integrating ambient carbonyl compounds provides insight into the constrained ozone formation chemistry in Zibo city of the North China Plain

Quantifying the impact of carbonyl compounds (carbonyls) on ozone (O3) photochemical formation is crucial to formulating targeted O3 mitigation strategies. To investigate the emission source of ambient carbonyls and their integrated observational constraint on the impact of O3 formation chemistry, a field campaign was conducted in an industrial city (Zibo) of the North China Plain from August to September 2020. The site-to-site variations of OH reactivity for carbonyls were in accordance with the sequence of Beijiao (BJ, urban, 4.4 s−1) > Xindian (XD, suburban, 4.2 s−1) > Tianzhen (TZ, suburban, 1.6 s−1). A 0-D box model (MCMv3.3.1) was applied to assess the O3-precursor relationship influenced by measured carbonyls. It was found that without carbonyls constraint, the O3 photochemical production of the three sites was underestimated to varying degrees, and the biases of overestimating the VOC-limited degree were also identified through a sensitivity test to NOx emission changes, which may be associated with the reactivity of carbonyls. In addition, the results of the positive matrix factorization (PMF) model indicated that the main source of aldehydes and ketones was secondary formation and background (81.6% for aldehydes, 76.8% for ketones), followed by traffic emission (11.0% for aldehydes, 14.0% for ketones). Incorporated with the box model, we found that biogenic emission contributed the most to the O3 production at the three sites, followed by traffic emission as well as industry and solvent usage. Meanwhile, the relative incremental reactivity (RIR) values of O3 precursor groups from diverse VOC emission sources featured consistencies and differences at the three sites, which further highlights the importance of the synergetic mitigation of target O3 precursors at regional and local scales. This study will help to provide targeted policy-guiding O3 control strategies for other regions.

Nucleophilicities of Cyclic α‐Diazo Carbonyl Compounds

AbstractThe one‐bond nucleophilic reactivities of seven cyclic α‐diazo carbonyl compounds in dichloromethane were determined by analyzing the kinetics of their reactions with benzhydrylium ions (one‐bond reference electrophiles) at 20 °C according to the Mayr‐Patz equation. Though not calibrated for pericyclic reactions, the identified nucleophilicities also reflect relative reactivities of the α‐diazo carbonyl compounds in 1,3‐dipolar cycloadditions with dimethyl acetylenedicarboxylate. These (3+2)‐cycloadditions primarily gave spirocyclic 3H‐pyrazoles, which underwent thermal [1,5]‐sigmatropic (van Alphen‐Hüttel) rearrangements to furnish 1H‐pyrazole‐fused tricyclic products.

Do-It-Yourself 5-Color 3D Printing of Molecular Orbitals and Electron Density Surfaces

This report outlines an approach for preparing 5-color 3D printed plastic models of molecular orbitals and electron density surfaces using a hobby-grade 3D printer. Instructions are provided for preparing 3D orbital and electron density surface (EDS) models using solid or mesh representations in ground state and transition state structures. We show that the information content of 3D orbital and surface models can be enhanced with text annotation, bisection, strut and dashed bond placement, and composite orbital-EDS model constructions. Example prints illustrate orbital concepts in organic and inorganic chemistry, such as the ethyl cation (σ–p hyperconjugation), methane (hybridization and C–H bonding), ethane (σ–σ* hyperconjugation in the staggered and eclipsed conformations), 2-hydroxytetrahydropyran (the anomeric effect/n−σ* hyperconjugation), the water dimer (hydrogen bonding/n−σ* overlap), ethylene, 1,3-butadiene, and benzene (π molecular orbitals), Re2Cl82–, and U2(COT)2 (metal–metal quadruple bonds). Transition state models illustrate orbital interactions in the SN2 reaction of cyanide with methyl, ethyl, and isopropyl chloride and in a hydroboration reaction of BH3 with propene. Composite EDS models of methyl and isopropyl chloride (for exploring their relative reactivities as SN2 electrophiles) and methylcyclohexane (visualizing 1,3-diaxial interactions) are described. Student perceptions of a multicolor 3D orbital print used in an introductory organic chemistry laboratory course are reported.

Free radical scavenging activity of gallic acid toward various reactive oxygen, nitrogen, and sulfur species: a DFT approach

Gallic acid is a well-recognized naturally occurring compound possessing antioxidant activities. The free radical scavenging ability of gallic acid for fifty reactive species, such as oxygen, nitrogen, and sulfur-containing species, has been studied using the formal hydrogen atom transfer mechanism. The theoretical studies have been conducted in the gas phase and aqueous solution at M05-2X/6-311++G** level using the density functional theory (DFT) calculations. The relative damaging potential of all the reactive species has been compared by investigating their hydrogen atom and electron affinity. Furthermore, a comparison of their relative reactivity was made by evaluating several global chemical reactivity descriptors. Additionally, the feasibility of scavenging the species by gallic acid has been studied by computing the redox potentials and equilibrium constants for the overall process in the aqueous solution.

Insight on efficiently oriented oxidation of petroleum hydrocarbons by redistribution of oxidant through inactivation of soil organic matter coupled with passivation of manganese minerals.

While extensive works focused on the enhancement of the activity of heterogeneous Fenton catalysts, little was paid attention to the inhibition of soil organic matter (SOM) and Mn minerals in soil remediation. Here, the oxidation of petroleum hydrocarbons in soils (S1: 4.28% SOM, S2: 6.04% SOM, S3: 10.33% SOM) with inactivated SOM and passivated Mn oxides regulating by calcium superphosphate (Ca(H2PO4)2) was carried out. Oily sludge pyrolysis residue was used as precursors to prepare an oleophilic iron-supported solid catalyst (Fe-N@PR). For regulated systems, under the optimal conditions of 1.8mmol/g H2O2 and 0.05g/g Fe-N@PR, 72 ∼ 91% of total petroleum hydrocarbons (TPHs: 15,616.58mg/kg) were oxidized, which was 38 ∼ 45% higher than that of control systems. The mechanism of efficient oxidation was proposed that the passivated Mn minerals stabilized H2O2 redistributing more H2O2 to sustainably produce •OH, and the inactivated SOM improved the relative reactivity of •OH to TPHs. Additionally, the passivation of Mn oxides was mainly related to the binding of H2PO4-, and the inactivation of SOM was realized by Ca2+ combing with -OH and C-O-C to form stable complexes. This study brought us a new perspective on soil remediation through passivating Mn minerals and inactivating SOM.

Lactone Ring-opening Equilibria in Methanol by 1H NMR Analysis: An Assessment of the Ring-opening Polymerizability of Lactone Monomers.

The purpose of this study was to learn if a convenient 1H NMR method could be developed to serve as a tool for estimating the propensity of a given lactone to participate in ring-opening transesterification polymerization (ROTEP). The methanolysis of each of 18 lactones was initially examined in CD3OD solution in the presence of sulfuric acid as a Brønsted catalyst at ambient temperature. Once equilibrium was established, the ratio of remaining lactone to the ring-opened methyl ester/alcohol could be readily measured by NMR spectroscopy. The observed thermodynamic driving force observed for the methanol ring-openings are roughly in line with the extent of ROTEP for the various classes of lactones. This is the case even though the reaction conditions for these methanolyses vs. ROTEP reactions are substantially different. Qualitative evaluations of the rates of the ring-opening methanolyses were also made, and several non-obvious relative reactivities were observed. Finally, employing this simple NMR methanolysis using low concentrations of methanol in CDCl3 is recommended as the preferred protocol for initial evaluation of the polymerizability of any new lactone monomer that researchers may prepare in the future.

Spectroscopic, crystal structure and DFT-assisted studies of some nickel(II) chelates of a heterocyclic-based NNO donor aroylhydrazone: in vitro DNA binding and docking studies.

Five new nickel(II) complexes have been synthesised with an NNO donor tridentate aroylhydrazone (HFPB) employing the chloride, nitrate, acetate and perchlorate salts, and all the complexes are physiochemically characterized. Elemental analyses suggested stoichiometries as Ni(FPB)(NO3)]·2H2O (1), [Ni(HFPB)(FPB)]Cl (2), [Ni(FPB)(OAc)(DMF)] (3), [Ni(FPB)(ClO4)]·DMF (4), [Ni(FPB)2] (5). Aroylhydrazone is found coordinating in deprotonated iminolate form in four of the complexes (1, 3, 4, 5) however in one case (complex 2), two aroylhydrazone moieties are binding to the metal centre in the neutral and anionic forms. The structure of the bisligated complex 5, found using single crystal X ray diffraction studies confirmed that the metal has a distorted octahedral N4O2 coordination environment, with each of the two deprotonated ligands coordinating through the pyridine nitrogen, imino-hydrazone nitrogen and the enolate oxygen of the hydrazone moiety. To compare and study, the electronic interactions and stabilities of the metal complexes, various quantum chemical parameters were calculated. Moreover, Hirshfeld surface analysis was carried out for complex 5 to determine the intermolecular interactions. The biophysical attributes of the ligand and complex5 have been investigated with CT-DNA and experimental outcomes show that the Ni(II) complex exhibited higher binding propensity towards DNA as compared to ligand. Furthermore, to specifically understand the type of interactions of the metal complexes with DNA, molecular docking studies were effectuated. In addition, the electronic and related reactivity behaviors of the ligand and five Ni(II) complexes were studied using B3LYP/6-31 + + G**/LANL2DZ level. As expected, the obtained results from Natural Bond Orbital (NBO) computations displayed that the resonance interactions (n → π* and π → π*) play a determinant role in evaluating the chemical attributes of the reported compounds.

Oxidative N-Dealkylation of N,N-Dimethylanilines by Non-Heme Manganese Catalysts

Non-heme manganese(II) complexes [(IndH)MnIICl2] (1) and [(N4Py*)MnII(CH3CN)](ClO4)2 (2) with tridentate isoindoline and pentadentate polypyridyl ligands (IndH = 1,3-bis(2′-pyridylimino)isoindoline; N4Py* = N,N-bis(2-pyridylmethyl)-1,2- di(2-pyridyl)ethylamine) proved to be suitable to catalyze the oxidative demethylation of N,N-dimethylaniline (DMA) with various oxidants such as tert-butyl hydroperoxide (TBHP), peracetic acid (PAA), and meta-chloroperoxybenzoic acid (mCPBA), resulting N-methylaniline (MA) as a main product with N-methylformanilide (MFA) as a result of a free-radical chain process under air. The effect of electron-donating and electron-withdrawing substituents on the aromatic ring on the relative reactivity of the substrates and on the product composition (MA/MFA) was also studied and showed a significant impact on the catalytic N-demethylation reaction. Based on the Hammett correlation with ρ = −0.38 (PAA), −0.45 (mCPBA), and −0.63 (TBHP) for 1 and ρ = −0.38 (PAA) and −0.37 (mCPBA) for 2, an electrophilic intermediate is suggested as the key oxidant. Furthermore, the spectral investigation (UV-Vis) resulted in direct evidence for the formation of a high-valent oxomanganese(IV) and a transient radical cation intermediate, p-Me-DMA•+, suggesting that the initial step in the manganese-catalyzed oxidations is a fast electron-transfer between the amine and the high valent oxometal species. The mechanisms of the subsequent steps are discussed.

New insight into formation mechanism, source and control strategy of severe O3 pollution: The case from photochemical simulation in the Wuhan Metropolitan Area, Central China

The Wuhan Metropolitan Area, located in Central China, has experienced severe O3 pollution in recent years; thus urging to diagnose formation regime and propose reasonable control strategies. Multi-source data of air pollutants and meteorological factors in 4 cities during August 2019 when severe regional O3 pollution occurred were obtained; then, in-situ O3 formation mechanism, the O3-precursors sensitivity, the sources and control strategies of O3 were evaluated based on the combination of the 0-D photochemical observation-based model and the positive matrix factorization model through the analysis of local ozone budget, the relative incremental reactivity, an empirical kinetic model approach and source apportionment. The results indicated the P(O3) (net O3 production rate) was 25 ppbv h−1 in Ezhou and 11–13 ppbv h−1 in other 3 cities. The dominated photochemical production of O3 was NO + HO2 reaction (62–71%), whereas the main pathway to destroy O3 during daytime was NO2 + OH (>70%) and nocturnal loss of O3 with alkenes even reached up to 39–46%. Generally, O3 formation was sensitive to AVOC (Anthropogenic Volatile Organic Compounds), in which reactive aromatics, OVOCs (Oxygenated VOCs), and alkenes (xylenes, ethylene, isoprene, methyl vinyl ketone, hexanal, toluene and methacrolein, specifically) as well as abundant i-pentane should be targeted to alleviate O3 pollution. The highly reactive VOCs sources for O3 formation in this region were vehicular exhaust (28–41%), industrial emissions (20–29% except Ezhou), and solvent use (17–29% except Huangshi). Co-reduction of O3 precursors in aforementioned reactive emissions according to optimal ratios of AVOC to NO2, i.e., 5:1 (Wuhan and Huanggang), 4:1 (Ezhou), and 6:1 (Huangshi), could achieve local O3 effective mitigation. Surprisingly, P(O3) could reduce by 38% and 48% under 40% AVOC cut accompanied by NO2 in more contaminated cities (Wuhan and Ezhou). Overall, our study provides new insight to future collaborative O3 alleviation strategies formulation in Central China, which quantified O3 formation at different precursors levels in different cities suffering from regional O3 pollution, concluded best precursors control ratios and confirmed validity of O3 mitigation through precursors-oriented emission reduction in vital sources.

S-15-5: GAPS AND ADVANCES FOR THE PREVENTION OF HYPERTENSION IN AFRICA: INSIGHTS FROM THE EXAMIN YOUTH SA STUDY

Paediatric hypertension is becoming a global health problem which is paralleled by overweight and obesity in children and adolescents, and tracks into adulthood. Therefore, promoting primary prevention of hypertension at early ages will reduce the increasing trends of hypertension in Africa. The prevalence of hypertension in South African children ranges between 7.5% and 22.3%, while care and treatment of hypertension remains a major challenge and health crisis. From the Exercise, Arterial Modulation and Nutrition in Youth South Africa (ExAMIN Youth SA) study using the latest 2017 American Academy of Pediatrics Clinical Practice Guidelines, we reported unique sex and ethnic differences of blood pressure (BP) in 5–9 year old children (n = 1062) and identified 14.1% children with elevated BP and almost 23% within the range of stage 1 or 2 hypertension. We also reported that 15.2% of the children were overweight and 4.4% obese according to the age and sex standardized body mass index (BMI) z-scores. Overweight and obesity were more prevalent in white children, while diastolic BP and total vascular resistance were higher in black children. The odds of having elevated BP were 60% higher with every standard deviation increase of BMI z-score. We analysed cortisol reactivity in relation to physical fitness to underpin the role of environmental stressors and physiological responses after inducing physical stress. We showed that white children had lower cardiorespiratory fitness (CRF) compared to children of African ancestry. However, African children had lower cortisol reactivity and unfavourable lower morning cortisol levels compared to white children. We demonstrated that lower CRF and higher BP are associated with lower cortisol responses in young children. In the same children and in comparison with a Swiss cohort, we investigated the role of high BP, obesity and ethnicity on retinal microvascular phenotype. We reported that obesity, hypertension and African ancestry are the main factors contributing to arteriolar narrowing. Since the microvasculature is also well represented by the kidneys, and the kidneys regulate BP, we also analysed a marker of proximal tubular function, alpha-1 microglobulin (A1 M), to identify early pathways of hypertension development in children. A1 M levels increased with higher BP, especially in children of African ancestry. With childhood lifestyle and behavioural risk factors being the most important for the prediction of cardiovascular events in adulthood, we argue that targeting health behaviour and optimising health education in early life are the most promising prospects to prevent early cardiovascular disease development in Africa.

The aromatic Claisen rearrangement of a 1,2-azaborine.

The first aromatic Claisen rearrangement of a 1,2-azaborine is described along with a quantitative kinetic comparison of the reaction of the azaborine with its direct all-carbon analogue. The azaborine A rearranged in a clean, regioselective fashion and reacted faster than the all-carbon substrate B at all temperatures from 140-180 °C. Activation free energies were extracted from observed first-order rate constants (A: ΔG‡298K = 32.7 kcal mol-1; B: ΔG‡298K = 34.8 kcal mol-1) corresponding to a twenty fold faster rate for A at observed reaction temperatures. DFT calculations show that the rearrangement proceeds via a concerted six-membered transition state and that the electronic structure of the BN and CC rings is mostly responsible for the observed regioselectivity and relative reactivity.

Исследование относительной реакционной способности паров алкилацетатов по отношению к компонентам плазмы импульсного разряда в воздухе

A study was made of the relative reactivity of vapors of a number of acetic acid esters (alkyl acetates) with respect to plasma components of a pulsed corona discharge with a voltage of 100 kV and a duration of 40 ns. On model mixtures based on methyl-, ethyl-, propyl-, isopropyl, isobutyl-, butyl-, and vinyl acetate with a content of 250–500 ppm in air and nitrogen, the relative reactivity parameters were obtained. The reactivity of acetic acid esters increases with an increase in the hydrocarbon substituent. The high reactivity of vinyl acetate is due to the double bond reaction with ozone.

Comparative evaluation of gold nanoparticles and Alum as immune enhancers against rabies vaccine and related immune reactivity, physiological, and histopathological alterations: in vivo study.

The present study aimed to compare the immune-enhancing potential of gold nanoparticles (AuNPs) to Alum against rabies vaccine and the related immunological, physiological, and histopathological effects. Alum and AuNPs sole and in combination with rabies vaccine were used at 0.35 mg/mL and 40 nM/mL, respectively. Rats used were categorized into six groups (20/each): control rats, rabies vaccine, aluminum phosphate gel, rabies vaccine adsorbed to Alum, AuNPs, and rabies vaccine adjuvant AuNPs. Liver and kidney functions were in the normal range after AuNPs and Alum adjuvanted vaccine compared to control. Interleukin-6 and interferon-γ levels were significantly increased in groups immunized with Alum and AuNPs adjuvanted vaccine, the peak level was in the case of AuNP adjuvanted vaccine on the 14th day. Ninety days post-vaccination, total immunoglobulin G (IgG) against adjuvanted rabies vaccine showed a significantly elevated anti-rabies IgG with AuNPs and Alum adsorbed vaccine compared with unadjuvanted one. The total antioxidant capacity, malondialdehyde (MDA) levels, superoxide dismutase, and glutathione peroxidase activities were significantly increased post-adjuvanted AuNPs adjuvanted vaccine vaccination than in Alum adsorbed vaccine, while MDA was significantly decreased. The histopathological examination revealed detectable alterations post-AuNPs and Alum adjuvanted vaccine immunization compared with liver and kidney profiles post-administration of unadjuvanted and non-immunized groups, meanwhile, splenic tissue revealed hyperplasia of lymphoid follicles indicating increased immune reactivity. The AuNPs are promising enhancers of the immune response as Alum, and the undesirable effects of AuNPs could be managed by using suitable sizes, shapes, and concentrations.

Adsorption dynamics of O2 on Cu(111): a supersonic molecular beam study.

We have studied the adsorption of O2 on Cu(111) using supersonic molecular beam techniques. For incident energies ranging between 100 and 400 meV, we have determined the sticking probability as a function of angle of incidence, surface temperature, and coverage. Initial sticking probabilities range from near 0 to 0.85 with an onset near 100 meV, making Cu(111) considerably less reactive than Cu(110) and Cu(100). Normal energy scaling applies and reactivity increases appreciably over the entire range of surface temperatures from 90 to 670 K. A strictly linearly decreasing coverage dependence on sticking precludes adsorption and dissociation via an extrinsic or long-lived mobile precursor state. We cannot exclude that sticking also occurs molecularly at the lowest surface temperatures. However, all tell tales from our experiments suggest that sticking is predominantly direct and dissociative. Comparison to earlier data shows implications for the relative reactivity of Cu(111) vs. Cu/Ru(0001) overlayers.

A kinetic study of thiol addition to N-phenylchloroacetamide.

Irreversible enzyme inhibitors bind covalently to their target and permanently limit its function. The redox-sensitive thiol group on the side chain of cysteine (Cys) residues is often the nucleophilic group that is targeted for reaction with the electrophilic warhead of irreversible inhibitors. While the acrylamide group is the warhead applied most frequently currently in the design of inhibitors with therapeutic potential, the chloroacetamide group offers a comparable reactivity profile. In that context, we have studied the details of the mechanism of thiol addition to N-phenylchloroacetamide (NPC). A kinetic assay was developed to accurately monitor the reaction progress between NPC and a small library of thiols with varying pKa values. From these data, a Brønsted-type plot was constructed, from which a βnucRS- value of 0.22 ± 0.07 was derived, indicative of a relatively early transition state with respect to attack by the thiolate. The halide leaving group was also varied, for the reaction with one thiol, providing rate constants consistent with a transition state that is early with respect to leaving group departure. The effects of temperature and ionic strength were also studied, and all data are consistent with an early transition state for a concerted SN2 mechanism of addition. Molecular modelling was also performed, and these calculations confirm the concerted transition state and relative reactivity of the haloacetamides. Finally, this study allows a detailed comparison of the reactivity and reaction mechanisms of the chloroacetamide group with the benchmark acrylamides used in many irreversible inhibitor drugs.

Comparative quantitative kinetic study of rapid iodination of thiazole and its methyl derivatives in aqueous medium

AbstractThe study provides a quantitative framework for the assessment of the relative reactivity of thiazole and its two methyl derivatives namely 2‐methylthiazole and 4‐methylthiazole towards iodination reaction. Thiazole and its derivatives have a wide range of industrial and medicinal applications attributed to the ability of thiazole to manifest substituents around the core scaffold. The kinetic study of the iodination reactions of these substrates helps in the above applications since kinetics is an important investigational tool in configuring the mechanism of the reaction. In the present work, molecular iodine (I2) and iodine monochloride (ICl) were used as reagents for the iodination of thiazole, 2‐methylthiazole, and 4‐methylthiazole in aqueous medium. The iodination reactions are rapid electrophilic substitution reactions and hence special technique known as hydrodynamic voltammetry was employed for the kinetic study. Iodine is the only electro‐reducible species in the reactions. As the solution is devoid of iodide ions, a decrease in the concentration of iodine is measured in terms of diffusion current using a rotating platinum electrode with a saturated calomel electrode (SCE) as a reference electrode. The reactivity correlation of substrates towards iodination reaction was quantitively assessed by determining the reaction rate constants and thermodynamic parameters. The study shows overall rate of iodination of 4‐methylthiazole is faster than 2‐methylthiazole which is faster than thiazole. The study helps to develop a mechanistic approach considering the effect of substituent present on the thiazole ring. The order of reactivity of the reagents was determined based on obtained rate constants and explained owing to the nature of the reagent.

Compounded Interplay of Kinetic and Thermodynamic Control over Comonomer Sequences by Lewis Pair Polymerization.

The design of facile synthetic routes to well-defined block copolymers (BCPs) from direct polymerization of one-pot comonomer mixtures, rather than traditional sequential additions, is both fundamentally and technologically important. Such synthetic methodologies often leverage relative monomer reactivity toward propagating species exclusively and therefore are rather limited in monomer scope and control over copolymer structure. The recently developed compounded sequence control (CSC) by Lewis pair polymerization (LPP) utilizes synergistically both thermodynamic (Keq) and kinetic (kp) differentiation to precisely control BCP sequences and suppress tapering and misincorporation errors. Here, we present an in-depth study of CSC by LPP, focusing on the complex interplay of the fundamental Keq and kp parameters, which enable the unique ability of CSC-LPP to precisely control comonomer sequences across a variety of polar vinyl monomer classes. Individual Lewis acid equilibrium and polymerization rate parameters of a range of commercially relevant monomers were experimentally quantified, computationally validated, and rationalized. These values allowed for the judicious design of copolymerizations which probed multiple hypotheses regarding the constructive vs conflicting nature of the relationship between Keq and kp biases, which arise during CSC-LPP of comonomer mixtures. These relationships were thoroughly explored and directly correlated with resultant copolymer microstructures. Several examples of higher-order BCPs are presented, further demonstrating the potential for materials innovation offered by this methodology.

Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity

AbstractTwo oxoiron(IV) isomers (R2a and R2b) of general formula [FeIV(O)(RPyNMe3)(CH3CN)]2+ are obtained by reaction of their iron(II) precursor with NBu4IO4. The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between R2a and R2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that R2a reacts one order of magnitude faster than R2b, which is explained by a repulsive noncovalent interaction between the ligand and the substrate in R2b. Interestingly, the electronic properties of the R substituent in the ligand pyridine ring do not have a significant effect on reaction rates. Overall, the intrinsic structural aspects of each isomer define their relative HAT reactivity, overcoming changes in electronic properties of the ligand.

Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity.

Two oxoiron(IV) isomers (R 2a and R 2b) of general formula [FeIV (O)(R PyNMe3 )(CH3 CN)]2+ are obtained by reaction of their iron(II) precursor with NBu4 IO4 . The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between R 2a and R 2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that R 2a reacts one order of magnitude faster than R 2b, which is explained by a repulsive noncovalent interaction between the ligand and the substrate in R 2b. Interestingly, the electronic properties of the R substituent in the ligand pyridine ring do not have a significant effect on reaction rates. Overall, the intrinsic structural aspects of each isomer define their relative HAT reactivity, overcoming changes in electronic properties of the ligand.

Sensitivity of Ozone Formation in Summer in Jinan Using Observation-Based Model

According to online monitoring data on atmospheric ozone and the pollution characteristics of its precursors obtained in Jinan in June 2021, we analyzed different sites: urban sites (city monitoring station, Quancheng Square), an industrial park site (oil refinery), and a suburban site (Paomaling). The relative incremental reactivity of different precursors was calculated using a photochemical observation-based model to explore the sensitivity of O3 generation at each site and to draw a curve using the empirical kinetics modeling approach. The PMF model was used to analyze the origin of volatile organic compounds (VOCs) pollution in Jinan. The results showed that the concentration of O3 at the industrial park was higher than that in the urban area in Jinan, which may be related to the fact that ozone precursor concentrations in the industrial park were significantly higher than those in the urban area (the AVOCs concentration at the industrial park site was 56.9 ppbv, approximately twice that of the urban site), and there are emission peaks at night; alkanes, oxygenated compounds, and halogenated hydrocarbons were the main components of the AVOCs, and olefins, alkanes, and aromatic hydrocarbons were the main active components in Jinan. The O3 generation in urban areas generally occurred in the VOCs-sensitive zones, while the O3 generation in the other areas occurred in the VOCs-NOx transition zone; there was a clear diurnal variation in the sensitivity of the industrial park, with the site being in the obvious VOCs-sensitive zone from nighttime to morning hours and shifting to the VOCs-NOx transition zone in the afternoon hours; the relative incremental reactivity (RIR) value of AVOCs for O3 generation in Jinan was the largest, and olefins were the most sensitive component of O3. The AVOCs in Jinan mainly originated from motor vehicle exhaust, oil and gas volatilization, industrial emissions, and solvent use, and ozone prevention and control in summer should strengthen the control of these sources.