OH Radicals Research Articles

Radical Scavenging Capacity and In Vitro Cytoprotective Effects of Great Salt Lake-Derived Processed Mineral Water.

The Great Salt Lake, located in Utah, USA, is a saltwater lake with no outlet and is surrounded by vast mountains and salt deserts. We aimed to use Great Salt Lake-derived processed mineral water (hereafter termed as GSL-MW) for maintaining oral health. Therefore, we examined its radical scavenging activity as an antioxidant and its cytoprotective effect on human gingival fibroblasts (hGFs). The scavenging activity against O2•- radicals was determined by an electron spin resonance (ESR)-spin trapping technique using two kinds of O2•- generation systems; however, we could not reach any concrete conclusion because of the interference caused by GSL-MW in both systems. Detection of ·OH radicals using the ESR-spin trapping technique and kinetic analyses using double-reciprocal plots (corresponding to Lineweaver-Burk plots that are used to represent enzyme kinetics) revealed that GSL-MW has the ability to scavenge ·OH radicals. GSL-MW also showed a weak 2,2-diphenyl-1-picrylhydrazyl (DPPH; a stable radical)-scavenging activity. Regarding the cytoprotective effects, subconfluent hGFs pretreated with 10× and 100× dilutions of GSL-MW for 3 min and then exposed to harsh environmental conditions, such as pure water or 100 μM H2O2 for 3 min, showed enhanced cell viability rate. Moreover, 10× and 100× dilutions of GSL-MW reduced oxidative damage in confluent hGFs exposed to 12.5 and 25 mM H2O2. Our findings show that GSL-MW has antioxidant potential and cytoprotective effects on hGFs, suggesting that GSL-MW can be used to maintain oral health.

Distance-based analytical device integrated with carbon nanomaterials for sarcosine quantification in human samples.

Astraightforward distance-based paper analytical device (dPAD) was developedfor monitoring sarcosine levels in human samples for the rapid diagnosis and prognosis of prostate cancer and related symptoms. This assay eliminates the need for the expensive horseradish peroxidase (HRP) enzyme by utilizing carbon nanodots (CDs) as a peroxidase-like nanozyme. The proposed dPAD sensor consists of a sample zone pre-deposited with sarcosine oxidase (SOx) and CDs, and a detection zone containing 3,3',5,5'-tetramethylbenzidine (TMB). When a solution containing sarcosine is added to the sample zone, hydroxyl radicals (•OH) are produced through SOx oxidation and subsequent peroxidase catalysis by the CDs. The formed •OH radicals immediately flow to the detection zone via capillary force, where they oxidize TMB, resulting in a visible colour change from colourless to blue. Sarcosine quantification is effortlessly accomplished by measuring the distance of the blue colour in the detection zone. The developed dPAD offers a linear working range between 12.5 and 35.0nmol L-1 (R2 = 0.9959) and a detection limit (LOD) of 10.0nmol L-1. This covers the clinical range for urinary sarcosine determination, thereby suggesting no additional sample preparation or dilution is needed. The sensor shows high precision with the highest relative standard deviation (RSD) of 4.58% and demonstrates excellent selectivity with no observed interferences. Furthermore, recovery studies in human control urine samples ranged from 98.67 to 101.50%, with the highest RSD of 2.03%. Correspondingly, our dPAD method showed a great match with the performance of a commercial ELISA method for detecting sarcosine in human control serum. The sensor is more cost-effective, user-friendly, and accessible than previous methods. Overall, the proposed method represents a promising analytical tool for sarcosine quantification. The concept is also applicable for broader analytical applications in detecting other biomolecules.

Chemical Composition and Biological Activity of Hypericum Species-H. hirsutum, H. barbatum, H. rochelii.

St. John's wort (Hypericum perforatum, Hypericaceae) is the most well-known species in the genus Hypericum, which comprises several hundred species. This study investigates the biological and phytochemical potential of the under-researched Hypericum species, H. hirsutum, H. barbatum, and H. rochelii. A high level of similarity between the chemical profiles of H. hirsutum and H. barbatum and the official source of the herbal drug (H. perforatum) was shown, but a higher content of quercetin and rutin was also found in all three evaluated species (116-230 µg/g dry herb). The highest amount of phenolics (195 mg GAE/g) was recorded in H. hirsutum extract, while the highest amount of flavonoids (47 mg QE/g) was recorded in H. barbatum extract. The evaluated species were excellent scavengers of DPPH, OH, and NO radicals, as well as strong ferric ion reducers in the FRAP test. Prominent monoamine oxidase A and α-glucosidase inhibition was observed, compared to modest inhibition of monoamine oxidase B, α-amylase, and acetylcholinesterase. High activity against Gram-positive MRSA S. aureus was demonstrated for the tested species, with MIC/MBC values recorded at 12.5 µg/mL. Antifungal activity against Candida strains was not observed. The obtained results emphasize the need for further investigation of species of the genus Hypericum to discover potentially new sources of biologically active compounds.

Chemical profiling and bioactivity analysis of shoots and roots essential oil of Indian Blumea mollis D. Don (Merr.)

Aromatic plants contain essential oils, potent extracts renowned for therapeutic benefits. Essential oils are commonly utilized due to their diverse range of phytochemicals that possess therapeutic properties. The present study analyses the chemical composition of the essential oil obtained from shoots and roots of Blumea mollis (Family: Asteraceae), using GC-FID and GC-MS techniques. A total of 49 and 46 compounds were identified from shoots and roots accounting for 95.6 % and 88.4 % respectively. β-caryophyllene is reported as major compound 36.2 ± 0.50 % in essential oil of the shoots and 33.8 ± 0.55 % in essential oil of the roots. Both essential oils of shoots and roots were dominated by sesquiterpene hydrocarbons (59.2–76.4%), followed by oxygenated sesquiterpene (14.9–20.3%). The in vitro antioxidant activity was determined using DPPH radical scavenging activity, H2O2 radical scavenging activity, and Iron(II) complexing activity. The highest antioxidant activity was observed in root essential oil of B. mollis. The oils also inhibited the activity of α-amylase with IC50 of 3.53 ± 0.04 μg/ml (shoot), 3.45 ± 0.04 μg/ml (root). Root oil also showed good activity for protein denaturation with IC50 of 3.02 ± 0.03 g/ml as compared to shoot essential oil. This is first time that essential oil constituent and biological activity of B. mollis roots and shoots have been characterized from India.

Stage-wise kinetic analysis of ammonia addition effects on two-stage ignition in dimethyl ether

Abstract Ammonia (NH3) has gained considerable attention as a promising carbon-free hydrogen carrier fuel for internal combustion engines, but its direct use in compression-ignition engines presents challenges, often requiring high-reactivity fuels to ignite the premixed NH3/air mixture and initiate combustion. This study focuses on the ignition process of binary NH3 and dimethyl ether (DME) mixtures, as DME is a carbon-neutral, high-reactivity fuel. A key novelty of this paper is the comparison of the ignition processes of DME and NH3/DME mixtures from a temporal, process-oriented perspective, analyzing chemical kinetics across distinct ignition phases rather than focusing solely on instantaneous reactions at discrete time points. The stage-wise analysis reveals that NH3 has minimal impact on the control mechanism governing the two-stage ignition process of DME. Specifically, DME still largely depends on OH radical proliferation during low-temperature oxidation (LTO), which releases heat as the reaction progresses. As the temperature increases, LTO branching pathways gradually shift to chain-propagation pathways, reducing overall reaction activity. The reactivity and temperature rise rate of the system are then governed by the H2O2 loop mechanism before thermal ignition. However, ammonia significantly extends the ignition delay of DME by competing with OH radicals, which are critical for DME oxidation, thus inhibiting ignition. As the ignition reaction proceeds, ammonia kinetics become more involved. For example, nitrogen-containing species from NH3 oxidation, such as NO, NO2, and NH2, react with CH3OCH2 to form CH3OCHO, reducing the flux through the LTO pathway of DME. While ammonia reaction pathways also produce OH radicals, this occurs at the expense of HO2 and H radicals, leading to H2O2 formation. Overall, these findings demonstrate the substantial impact of ammonia addition on DME ignition, highlighting the need for further research to better understand NH3/DME binary fuel ignition and to optimize the design and operation of NH3/DME dual-fuel engines for improved efficiency and reliability.

Direct and Indirect Effects for Radiosensitization of Gold Nanoparticles in Proton Therapy.

The radiosensitization characteristics of gold nanoparticles (GNPs) have been investigated in a single cell irradiated with monoenergetic beams of protons of various energies using TOPAS-nBio, an advanced toolkit of TOPAS. Both direct and indirect effects against single-strand breaks (SSBs) are investigated and their double-strand breaks (DSBs) have been calculated. A single spherical cell interaction with a detailed DNA structure has been modeled and simulated under different conditions such as particle sizes and concentrations of GNPs, their biodistributions and associated proton energies. The physical interaction among protons, suspension water and GNPs has been simulated using a dual physics approach, while the interaction between water radiolysis and OH radicals was considered in the chemical process to save computational time. The present simulations involve irradiating the cell geometry with a dose of 1 Gy. The range of DSBs (Gy-1 Gbp-1) obtained was 2.1 ± 0.09 to 21.74 ± 0.4 for all GNPs of sizes 6-50 nm the proton energies in the range of 5-50 MeV. Regardless of proton energy and GNP size, the calculations showed that the contribution of indirect and hybrid DSBs remains higher in all simulation types than that of direct DSBs. New simulation outcomes of the indirect DSBs illustrate a percentage increase, while we cannot get an increase in the direct and hybrid DSBs in most cases when compared with no GNPs cases. The indirect DSBs provide the highest enhancement factor of 1.89 at 30 nm GNPs in size for 30 MeV protons energy, and the direct and hybrid DSBs indicate a slight increase in enhancement. The work indicates that the use of GNPs increased indirect DNA DSBs, while hybrid DSBs show only a slight increase in enhancement, and no enhancement is shown in direct DNA DSBs. It is significant to consider other mechanisms such as DNA damage repair when investigating DNA damage.

Experimental and reaction mechanism study on laminar burning velocity and characteristics of OH/NH generation in ammonia co-combustion

Developing fuels without carbon, such as ammonia (NH3), is crucial for achieving carbon reduction. Laminar burning velocity (LBV) is investigated, and distribution characteristics of OH and NH radicals are identified through planar laser-induced fluorescence. Rate of production of main free radicals and sensitivity analysis are also studied. The addition of NH3 to CH4-air mixtures results in a decrease in the LBV, a rise in preheating zone height, a reduction in OH radical fluorescence intensity, and an enhancement in NH radical fluorescence intensity. Simulation reveals that the high NH3 ratio enhance the negative impact of nitrogen-containing elementary reactions on LBV. The addition of NH3 enhances the initial consumption of more OH via reaction R248:NH2+OH=NH+H2O, leading to increased NH production, and indicating a negative effect on LBV. The decrease in OH concentration is the main factor leading to a decrease in LBV. The reactions affecting the OH generation and consumption are R39:H+O2=O+OH and R85:OH+H2=H+H2O, respectively. The addition of NH3 leads to a more significant reduction in R39.

Evaluation of soot emission and wall heat loss for the fuels with high aromatic contents using the coupled analysis of chemical luminescence images with heat flux

The stricter regulations on the sulfur content of marine fuel oil in the general sea area that came into effect in January 2020 have led to a prediction of the increase of light cycle oil with high aromatic contents. The higher aromatic content is expected to result in higher soot in the exhaust gas. During combustion, soot emits radiant heat because of blackbody radiation, some of which passes through the walls of the combustion chamber and is released outside. Therefore, the exhaust emission characteristics and wall heat loss are affected if soot formation during combustion differs depending on the aromatic content of the fuel oil. This study developed an analytical method that combines the temporal and spatial distributions of C2 and OH radicals (these species contribute to soot formation and oxidation) to evaluate the emission and wall heat loss characteristics of different aromatics in fuel oils via combustion and heat flux analysis. The method was applied to test fuels containing different aromatic contents. Two test fuels containing 60 vol% each of toluene (monocyclic) and 1-methylnaphthalene (bicyclic) were evaluated in a rapid compression machine with a 100 mm wall-to-wall distance combustion chamber. The results suggested that the differences in soot emissions were observed because of differences in aromatics, and no differences in the wall heat flux were observed. The distributions of C2 and OH radical luminescence intensities between the walls were examined, and the differences in soot production were attributed to differences in the C2 radical production upstream of the flame in the region of low air entrainment. The lack of difference in the heat flux between the test fuels can be attributed to the the differences in the C2 and OH luminescence intensities, which are related to the heat release rate and heat flux, being almost nonexistent near the walls.

Rate coefficients for the reactions of OH radicals with C3–C11 alkanes determined by the relative-rate technique

Rate coefficients for the reactions of OH radicals with C₃–C₁₁ alkanes determined by the relative-rate technique

Spontaneous Production of H2O2 at the Liquid-Ice Interface: A Potential Source of Atmospheric Oxidants.

We present experimental evidence for the spontaneous production of hydrogen peroxide (H2O2) at the liquid-ice interface during the freezing of dilute salt solutions. Specifically, sample solutions containing NaCl, NaBr, NH4Cl, and NaI at concentrations between 10-6 and 10-1 M were subjected to freezing-melting cycles and then analyzed for H2O2 content. The relationship between the production rate of H2O2 and the salt concentration follows that of the Workman-Reynolds freezing potential (WRFP) values as a function of the salt concentration. Our results suggest that H2O2 is formed at the liquid-ice interface from the self-recombination of hydroxyl radicals (OH·), produced from the oxidation of hydroxide anions due to the high electric field generated at the aqueous-ice interface under the WRFP effect. Furthermore, the involvement of O2 likely acting as an electron capturer could promote to produce more OH radicals and hydroperoxyl radicals (HO2·), thus enhancing the production of H2O2 at the liquid-ice interface. Overall, this study suggests a novel mechanism of H2O2 formation in ice via its spontaneous production at the liquid-ice interface, induced by the Workman-Reynolds effect.

Investigating combustion efficiency and NOx emission reduction in fluidized bed ammonia-coal co-firing

Ammonia, a carbon-free fuel, can significantly reduce CO2 emissions when co-fired with coal in power plants. Fluidized bed combustion, known for its excellent gas-solid mixing and low NOx emissions, is a promising method for ammonia-coal co-firing. However, challenges remain in optimizing ammonia injection and controlling nitrogen oxide emissions. This study investigates these aspects using a lab-scale fluidized bed reactor with flexible ammonia injection points. Key variables, such as ammonia co-firing ratios, injection location, temperature, and outlet oxygen concentration, are examined. The results show that with ammonia injection ratios up to 70 %, NO and N2O emissions slightly increase, while ammonia escape is maintained below 5 ppm. Air staging effectively controls NOx emissions, and higher temperatures promote N2O decomposition, but increase NOx levels. Ammonia injection does not raise unburned carbon content. Rate of production and sensitivity analyses highlight the role of OH radicals in ammonia conversion and identify the critical reactions affecting NO generation. This study highlights the feasibility of fluidized bed ammonia-coal co-firing technology.

Structural and morphological studies of g-C3N4-functionalized MWCNTs nanocomposite for sunlight-responsive photocatalytic activity

Photocatalytic degradation of organic contaminants has been proven to be one of the greatest economical and efficient techniques to address environmental pollution problems. Multi-walled carbon nanotubes (MWCNTs)/g-C3N4 (GCN) nanocomposites (NCs) were synthesized by a hydrothermal process aided by ultrasound to produce active photocatalysts. The effective synthesis of GCN, MWCNTs, and MWCNTs/GCN NCs was confirmed by X-ray diffraction (XRD) patterns. The fabrication of GCN nanosheets (NSs), the nanotubular structure of MWCNTs, and a network of neuron-like structures for MWCNTs/GCN NCs were all revealed by structural and morphological characterization. The elemental mapping of NCs containing the suitable quantity of MWCNTs revealed a uniform distribution of the sample's component elements. When the optical properties of the fabricated nanomaterials were examined by employing UV–visible spectroscopy, the results revealed a blue shift (a shift of maximum absorption to the UV region), which suggests that the addition of MWCNTs increased the band-gap energy. The behaviour of e––h+ pair recombination was revealed by measuring the charge carrier movement and trapping efficiency using photoluminescence (PL) spectroscopy. Crystal violet (CV) dye was photocatalytically degraded using prepared NCs in the presence of sunlight, and the synergistic effects of GCN and MWCNTs were examined. With a degradation efficiency of 99.32 %, MWCNTs/GCN NCs demonstrated the best sunlight-irradiated photocatalytic activity for CV degradation. The degradation of CV was discovered to follow pseudo-first-order kinetics. Throughout five consecutive studies, the NCs demonstrated the highest levels of catalytic efficiency and recyclability, with 5 % reduced degrading activities. The trapping tests showed that the primary reactive species involved in the breakdown of CV were the •O2– and •OH radicals.

Reactive Oxygen Species Generated in Situ During Carbamazepine Photodegradation at 222 nm Far-UVC: Unexpected Role of H2O Molecules.

When 222 nm far-UVC is used to drive AOPs, photolysis emerges as a critical pathway for the degradation of numerous organic micropollutants (OMPs). However, the photodegradation mechanisms of the asymmetrically polarized OMPs at 222 nm remain unclear, potentially posing a knowledge barrier to the applications of far-UVC. This study selected carbamazepine (CBZ), a prevalent aquatic antiepileptic drug that degrades negligibly at 254 nm, to investigate its photodegradation mechanisms at 222 nm. Accelerated CBZ treatment by 222 nm far-UVC was mainly attributed to in situ ROS generation via self-sensitized photodegradation of CBZ. By quenching experiments and EPR tests, •OH radicals were identified as the major contributor to the CBZ photodegradation, whereas O2•- played a minor role. By deoxygenation and solvent exchange experiments, the H2O molecules were demonstrated to play a crucial role in deactivating the excited singlet state of CBZ (1CBZ*) at 222 nm: generating •OH radicals via electron transfer interactions with 1CBZ*. In addition, 1CBZ* could also undergo a photoionization process. The transformation products and pathways of CBZ at 222 nm were proposed, and the toxicities of CBZ's products were predicted. These findings provide valuable insights into OMPs' photolysis with 222 nm far-UVC, revealing more mechanistic details for far-UVC-driven systems.

Synergistic Palladium Single Sites and Nanoparticles Implanted Into a Novel Zr‐Based Metal–Organic Framework via Solvent‐Free Processing for Upgrading Oxidative Desulfurization Performance

AbstractDesulfurization is a significant approach to producing clean fuel. The design of novel host–guest catalysts with multiple active sites at atomic‐ and nano‐scales, opens a new door to gain an ultrahigh synergistic performance for targeted applications. Herein, an in situ solvent‐free approach is conducted for synchronously implanting Pd single sites (PdSS) and nanoparticles (PdNP) into a novel Zr‐based metal–organic framework (Zr‐MOF). The optimal catalyst exhibits ultrahigh oxidative desulfurization (ODS) performance that can oxidize 1 000 ppm sulfur with diluted oxidant at 40 °C within 5 min. The turnover frequency of the catalyst at 40 °C reaches 774.7 h−1 which is 47.4 times higher than host Zr‐MOF and surpasses the most reported ODS catalysts. A substantial synergistic effect between PdSS and PdNP is responsible for the upgradation of ODS performance. Experimental and theoretical results indicate that PdSS in Zr‐MOF can readily absorb H2O2, and synergistically decompose H2O2 with the assistance of PdNP for accelerated generation of •OH radicals that dominates the ODS performance. This work provides a new solvent‐free way for in situ implanting synergistic catalytic sites into MOFs to upgrade their catalytic performance in targeted reactions.

Catalyst for the Generation of OH Radicals in Advanced Electrochemical Oxidation Processes: Present and Future Perspectives

Heterogeneous Advanced Oxidation Processes (H-AOPs) are considered a new process for removing emerging pollutants. In this case, the high reactivity of hydroxyl radicals is used to degrade persistent organic pollutants. This review explores the state-of-the-art catalyst for hydroxyl radical generation in AOPs. As a parasite reaction, chloride ions appear in alkaline conditions and compete with the active sites. The theoretical foundation of catalyst performance is explored, focusing on the fundamental principles that govern the efficiency and mechanism of hydroxyl or chloride radical production. The synthesis and electronic modification sections explore the modifications of catalysts. It discusses key methodologies for catalyst preparation, with a particular emphasis on electronic modification that enhances both activity and stability. Finally, laboratory and pilot applications highlight the effectiveness of novel or modified catalysts in different scenarios. These last findings provide insights into the future directions for research and application, aiming to draw attention to the gap between laboratory studies and real-world implementations.

Three-dimensional radiation dosimetry of carbon ion beams using surfactant hydrogels: Fundamental investigation.

In carbon ion radiotherapy, accurate measurement of the three-dimensional (3D) absorbed dose distribution is critical for effectively targeting tumors. Although micellar gel dosimeters exhibit considerable potential for measuring 3D absorbed dose distributions, few studies have focused on radiotherapy using carbon ion beams. This study investigated the applicability of the surfactant hydrogel dosimeter (SHD), a micellar gel dosimeter, to measuring a 3D dose absorbed through carbon ion beam irradiation. A cubic target region of 34mm per side was established at a depth of 46mm below the upper surface of an SHD specimen. Scanning irradiation was performed using a pencil beam of carbon ions at the Ion-beam Radiation Oncology Center in Kanagawa ("i-ROCK"), Japan, under irradiation conditions set by the treatment planning system ("Monaco for Carbon", Ver. 5.20, Elekta AB, Sweden) to create a spread-out Bragg peak within the target. The physical dose was set to 10Gy at the isocenter, situated at the center of the target. The SHD responsiveness was measured twice using optical computed tomography (CT) ("Vista 15", Modus Medical Devices, Canada) for three irradiated specimens, and six types of measured optical attenuation coefficient (OAC) were obtained. To assess whether the OAC represented the absorbed dose expected in the treatment plan, we compared the relative distribution of the OAC and that of the absorbed dose. Relative fraction (RF) was used to measure the difference between the relative value of the OAC and that of the absorbed dose. Moreover, the distribution of OH radical (•OH) concentration obtained by Monte Carlo simulation ("PHITS" ver. 3.24 JAEA, Japan) and that of the OAC were compared. In the direction of beam travel, the relative distribution of the OAC was lower than that of the absorbed dose. This discrepancy could be attributed to a decrease in the concentration of •OH produced by irradiation owing to the recombination reaction, which does not accurately reflect the absorbed dose. By contrast, the distributions in the plane perpendicular to the beam travel were consistent. The RF increased from±3% to±13% along the beam travel direction. The small RF in the plane perpendicular to the beam travel could be attributed to the constant distribution of linear energy transfer, regardless of the irradiation position, and the generation of radicals proportionally to the absorbed dose. The increase in RF along the beam travel direction was ascribed to ring artifacts in the irradiated region. The measurement of the absorbed dose distribution in the beam travel direction should be improved. The observed discrepancy is attributed to the reduced reactivity of the SHD due to a high liner energy transfer near the Bragg peak. However, the absorbed dose distribution can be effectively evaluated in the plane perpendicular to the direction of beam travel.

Synthesis, spectroscopic characterization, DFT analysis, antibacterial, antifungal, antioxidant, molecular docking, and ADME study of 3,4-dihydro-2H-napthalen-1-one tagged chalcone derivatives

Chalcone derivatives were synthesized from 3,4-dihydro-2H-naphthalen-1-one using a base-catalyzed Claisen-Schmidt reaction and characterized by FT-IR, ¹H NMR, and ¹³C NMR spectroscopy. Density functional theory (DFT) with the B3LYP/6-311G(d,p) basis set was employed to explore the structural, electronic, and quantum properties of the compounds. Simulated electronic absorption spectra for compounds 3c and 3e in gas phase, DMSO, and DCM were generated using time-dependent DFT (TD-DFT). Compound 3c's first singlet excited state shifted from 376.10 nm in the gas phase to 390.08 nm in DMSO, while compound 3e shifted from 381.58 nm to 383.54 nm in DMSO. Experimental absorption values matched the theoretical predictions, with higher oscillator strengths in DMSO and DCM indicating solvent-enhanced transition probabilities. The antimicrobial activity of the chalcones was evaluated against four bacterial strains (E. coli, B. subtilis, S. aureus, and Streptococcus spp.) and four fungal strains (R. oryzae, P. chrysogenum, A. niger, and C. albicans). Compounds 3d and 3f showed strong antibacterial activity with MIC values of 3.9 µg/mL and moderate antifungal activity. Antioxidant properties were assessed using DPPH and hydroxyl radical assays, with compound 3d demonstrating 75.8 % and 76.4 % scavenging activity for OH and DPPH radicals, respectively. ADME studies were conducted to evaluate pharmacokinetics, and molecular docking studies revealed strong binding affinities. Compounds 3a and 3e had docking scores of -8.7 kcal/mol with the E. coli protein (PDB ID: 1KZN), while 3d and 3f performed best against B. subtilis (PDB ID: 1BAG) and S. aureus gyrase (PDB ID: 2XCT), with scores of -9.1 and -8.3 kcal/mol, respectively. Molecular dynamics simulation of compound 3d with 1BAG over 100 ns confirmed stable binding. These findings suggest chalcone derivatives have strong potential for pharmaceutical development.

Atmospheric Chemistry of Chloroprene Initiated by OH Radicals: Combined Ab Initio/DFT Calculations and Kinetics Analysis.

Chloroprene (CP; CH2═C(Cl)-CH═CH2) is a significant toxic airborne pollutant, often originating from anthropogenic activities. However, the environmental fate of CP is incompletely understood. High level CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ calculations combined with kinetic modeling were employed here to glean new insight into the reaction mechanism, energies, and kinetics of the reaction of CP with OH radical (•OH). We report the energies of four different addition pathways and six different abstraction pathways. The •OH attack on the terminal C1 atom of the =CH2 group (which is directly attached to the =CCl moiety), leading to the formation of HOCH2-•C(Cl)-CH═CH2, was found to be a major path. The barrier height for the formation of the corresponding transition state was found to be -1.9 kcal mol-1 below that of the starting CP + •OH reactants. Rate coefficients were calculated for addition and abstraction pathways involving the CP + •OH reaction under pre-equilibrium approximation conditions, employing a combination of canonical variational transition state theory and small curvature tunneling. The overall rate coefficient for the reaction of CP + •OH at 298 K was found to be 1.4 × 10-10 cm3 molecule-1 s-1. The thermochemistry of the possible channels and atmospheric implications are provided. In addition, the fate of HOCH2-•C(Cl)-CH═CH2 in the presence of 3O2 was investigated. We found the reaction of the CP-derived peroxy radical adduct with HO2 and NO to make contributions to the formation of products such as formaldehyde, HO2 radical, Cl atom, HOCH2C(OOH)(Cl)CH═CH2, HOCH2C(O)Cl, ClC(O)CH═CH2, HOCH2C(O)CH═CH2, and HC(O) radical.

Optimization of the full-load combustion schemes of n-butanol/biodiesel reactivity-controlled compression ignition (RCCI) toward high-efficiency and low-emission engines

Biodiesel and n-butanol, as popular alternative fuels, can be used in advanced reactivity-controlled compression ignition (RCCI) engines for efficient and clean combustion. However, the complex interactions between n-butanol and biodiesel, as well as the best combustion schemes at different loads, remain poorly understood. Given this, the objective of this paper is to identify optimal fuel organizations for n-butanol/biodiesel RCCI engines across different load scenarios by combining engine simulation with a global optimization algorithm, explore the potential synergies of control parameters, and analyze microscopic dual-fuel interactions based on the integrated average reaction path analysis. Results show that the optimal scheme at low load employs almost homogeneous fuel-air mixtures at elevated temperature atmosphere above 390 K, with n-butanol energy share exceeding 96% and optimal biodiesel injection timing between −70 and −50 °CA. Higher n-butanol ratio coupled with increased intake temperature improves engine performance. For mid load, biodiesel injection timing is retarded to −55 to −30 °CA, and biodiesel proportion is increased to introduce reactivity stratification, while maintaining its energy share below 20% to mitigate NOx emissions. Notably, biodiesel density is identified as the primary physical property influencing NOx formation. At high load, a split combustion scheme involving premixing and subsequent diffusion combustion is optimal. The physical effects of n-butanol addition minimally impact the low-temperature ignition of biodiesel, while its chemical effects significantly defer the low-temperature reactivity. The reaction path analysis reveals that n-butanol competes with biodiesel for OH radical consumption, with a large proportion of OH and HO2 consumed in the cyclic reactions of nC4H9OH and nC4H8OH. Adjusting the reactivity stratification affects the reaction state of n-butanol entrained by the biodiesel jets. Higher reactivity gradient intensifies biodiesel reactions to induce the pyrolysis of the involved n-butanol through nC4H8OH => 2C2H4 + OH, therefore resulting in more staged heat release.

Quantification of the Contribution of Heterogeneous Surface Processes to Pollutant Abatement during Heterogeneous Catalytic Ozonation.

Heterogeneous surface processes such as adsorption and oxidation with surface-adsorbed reactive oxygen species (ROSad, e.g., adsorbed oxygen atom (*Oad) and hydroxyl radicals (•OHad)) have been suggested to play an important role in pollutant abatement during heterogeneous catalytic ozonation (HCO). However, to date, there is no reliable method to quantitatively evaluate the contribution of heterogeneous surface processes to pollutant abatement (fS) during HCO. In this study, we developed a method by combining probe compound-based experiments with kinetic modeling to distinguish heterogeneous surface processes from homogeneous bulk reactions with aqueous O3 and ROS (•OH and superoxide radicals (O2•-) in the abatement of various pollutants (e.g., atrazine, ibuprofen, tetrachloroethylene, and perfluorooctanoic acid) during HCO with reduced graphene oxide. The results show that the pollutants that have a low affinity for the rGO surface (e.g., ibuprofen and tetrachloroethylene) were essentially abated by homogeneous bulk reactions, while the contribution of heterogeneous surface processes was negligible (fS < 5%). In contrast, heterogeneous surface processes played an important or even dominant role in the abatement of pollutants that have a high surface affinity (e.g., fS = 32-82% for atrazine and perfluorooctanoic acid). This study is a critical first step in quantitatively evaluating the role of heterogeneous surface processes for pollutant abatement during HCO, which is crucial to understanding the mechanism of HCO and designing catalysts for effective pollutant abatement.