Ionization Potential Research Articles

Computer-aided drug design supporting sunscreen research: a showcase study using previously synthesized hybrid UV filter-antioxidant compounds.

Although quantum mechanical calculations have proven effective in accurately predicting UV absorption and assessing the antioxidant potential of compounds, the utilization of computer-aided drug design (CADD) to support sustainable synthesis research of new sunscreen active ingredients remains an area with limited exploration. Furthermore, there are ongoing concerns about the safety and effectiveness of existing sunscreens. Therefore, it remains crucial to investigate photoprotection mechanisms and develop enhanced strategies for mitigating the harmful effects of UVR exposure, improving both the safety and efficacy of sunscreen products. A previous study conducted synthesis research on eight novel hybrid compounds (I-VIII) for use in sunscreen products by molecular hybridization of trans-resveratrol (RESV), avobenzone (AVO), and octinoxate (OMC). Herein, time-dependent density functional theory (TD-DFT) calculations performed in the gas phase on the isolated hybrid compounds (I-VIII) proved to reproduce the experimental UV absorption. Resveratrol-avobenzone structure-based hybrids (I-IV) present absorption maxima in the UVB range with slight differences between them, while resveratrol-OMC structure-based hybrids (V-VIII) showed main absorption in the UVA range. Among RESV-OMC hybrids, compounds V and VI exhibited higher UV absorption intensity, and compound VIII stood out for its broad-spectrum coverage in our simulations. Furthermore, both in silico and in vitro analyses revealed that compounds VII and VIII exhibited the highest antioxidant activity, with compound I emerging as the most reactive antioxidant within RESV-AVO hybrids. The study suggests a preference for the hydrogen atom transfer (HAT) mechanism over single-electron transfer followed by proton transfer (SET-PT) in the gas phase. With a strong focus on sustainability, this approach reduces costs and minimizes effluent production in synthesis research, promoting the eco-friendly development of new sunscreen active ingredients. The SPARTAN'20 program was utilized for the geometry optimization and energy calculations of all compounds. Conformer distribution analysis was performed using the Merck molecular force field 94 (MMFF94), and geometry optimization was carried out using the parametric method 6 (PM6) followed by density functional theory (DFT/B3LYP/6-31G(d)). The antioxidant behavior of the hybrid compounds (I-VIII) was determined using the highest occupied molecular orbital (εHOMO) and the lowest unoccupied molecular orbital (εLUMO) energies, as well as the bond dissociation enthalpy (BDE), ionization potential (IP), and proton dissociation enthalpy (PDE) values, all calculated at the same level of structural optimization. TD-DFT study is carried out to calculate the excitation energy using the B3LYP functional with the 6-31G(d) basis set. The calculated transitions were convoluted with a Gaussian profile using the Gabedit program.

Photolysis of tolfenamic acid in aqueous and organic solvents: a kinetic study.

Tolfenamic acid (TA) is a non-steroidal anti-inflammatory drug that was studied for its photodegradation in aqueous (pH 2.0-12.0) and organic solvents (acetonitrile, methanol, ethanol, 1-propanol, 1-butanol). TA follows first-order kinetics for its photodegradation, and the apparent first-order rate constants (k obs) are in the range of 0.65 (pH 12.0) to 6.94 × 10-2 (pH 3.0) min-1 in aqueous solution and 3.28 (1-butanol) to 7.69 × 10-4 (acetonitrile) min-1 in organic solvents. The rate-pH profile for TA photodegradation is an inverted V (∧) or V-top shape, indicating that the cationic form is more susceptible to acid hydrolysis than the anionic form of TA, which is less susceptible to alkaline hydrolysis. The fluorescence behavior of TA also exhibits a V-top-shaped curve, indicating maximum fluorescence intensity at pH 3.0. TA is highly stable at a pH range of 5.0-7.0, making it suitable for formulation development. In organic solvents, the photodegradation rate of TA increases with the solvent's dielectric constant and solvent acceptor number, indicating solute-solvent interactions. The values of k obs decreased with increased viscosity of the solvents due to diffusion-controlled processes. The correlation between k obs versus ionization potential and solvent density has also been established. A total of 17 photoproducts have been identified through LC-MS, of which nine have been reported for the first time. It has been confirmed through electron spin resonance (ESR) spectrometry that the excited singlet state of TA is converted into an excited triplet state through intersystem crossing, which results in an increased rate of photodegradation in acetonitrile.

Deciphering the interactions between altertoxins and glutenin based on molecular dynamic simulation: inspiration from detection.

Mycotoxin contamination of food has been gaining increasing attention. Hidden mycotoxins that interact with biological macromolecules in food could make the detection of mycotoxins less accurate, potentially leading to the underestimation of the total exposure risk. Interactions of the mycotoxins alternariol (AOH) and alternariol monomethyl ether (AME) with high-molecular glutenin were explored in this study. The recovery rates of AOH and AME (1, 2, and 10 μg kg-1) in three types of grains (rice, corn, and wheat) were relatively low. Molecular dynamics (MD) simulations indicated that AOH and AME bound to glutenin spontaneously. Hydrogen bonds and π-π stacking were the primary interaction forces at the binding sites. Alternariol with one additional hydroxyl group exhibited stronger binding affinity to glutenin than AME when analyzing average local ionization energy. The average interaction energy between AOH and glutenin was -80.68 KJ mol-1, whereas that of AME was -67.11 KJ mol-1. This study revealed the mechanisms of the interactions between AOH (or AME) and high-molecular glutenin using MD and molecular docking. This could be useful in the development of effective methods to detect pollution levels. These results could also play an important role in the evaluation of the toxicological properties of bound altertoxins. © 2024 Society of Chemical Industry.

Exploring the nonlinear optical characteristics of supersalt-decorated graphyne via DFT analysis: unveiling quantum insights into light-matter interaction

In this comprehensive study, we explore into the nonlinear optical (NLO) properties of graphyne (GRY) and its compounds decorated with a super salt (OLi3BeF3), namely GRY@SS1, and GRY@SS2) using the rB3LYP/6−31G(d,p) DFT method. Our findings reveal a substantial enhancement in the electron transfer properties of decorated compounds compared to the pristine GRY surface. This enhancement is evidence by the reduction in the bandgap energies (Eg) from 3.52 eV to 1.68 eV and remarkable boost in maximum absorption ( λmax) from 372.66 to 807.73 nm. Noteably, GRY@SS2 exhibits a significant increase in linear polarizability ( α0 ) (538.18 au), first hyperpolarizability ( β0 ) (3872.76 au), and second hyperpolarizability ( γ0 ) (1.00 × 106) due to reduced excitations energies compared to the GRY ( α0 = 448.61, β0 = 0.14 and γ0 = 5.97 × 105 au). NBO charges show that electrons are transferring from the dopant (supersalt) to the GRY sheet. Furthermore, Non-covalent interactions (NCl), iso-surface, infrared (IR), 1H NMR, and 13C NMR studies have been conducted to provide insights into the nature of interactions, vibrational frequencies, and structural-functional aspects of GRY and GRY@SS1, and GRY@SS2. According to TD-DFT calculations, all compounds demonstrate superior vertical ionization potential, UV–vis absorbance, HOMO–LUMO characteristics, as well as interaction energies. Our results underscore the potential of these compounds as valuable NLO materials, particularly highlighting the promising prospects of GRY@SS2.

Hydrogen storage on MgO supported TiMgn (n = 2–6) clusters: A first principle investigation

The current study explores the potential of MgO-supported finite-sized TiMgn (n = 2–6) nanoclusters as hydrogen storage materials, employing density functional theory with a spin-polarized generalized gradient approximation (GGA). These systems' structural stability and electronic characteristics reveal that supported clusters offer superior hydrogen storage capabilities compared to their unassisted counterparts. Various parameters, including cluster-adsorption energy (Eads), hydrogen-adsorption energy in supported clusters (Eads-H), HOMO-LUMO gap, vertical ionization potential (VIP), vertical electron affinity (VEA), chemical potential (μ), and chemical hardness (ɳ) are computed. Substrate support notably enhances the thermodynamic stability and chemical reactivity of the TiMg5 cluster when contrasted with the bare TiMg5 cluster. Furthermore, a remarkable increase in the gravimetric hydrogen storage density, from 1.63 wt% for bare Mg5 clusters to 3.45 wt% for bare TiMg5 clusters, reaching 5.62 wt% in the supported TiMg5 cluster system is observed. These findings indicate the substrate-supported TiMg5 cluster as a promising candidate for hydrogen storage applications.

Energetic and Electronic Properties of UO0/± and UF0/±.

High-level electronic structure calculations were conducted to examine the bonding and spectroscopic properties of the UO0/± and UF0/± diatomic molecules. The low-lying Ω states were described by using multireference SO-CASPT2 calculations. The adiabatic electronic affinity (AEA), adiabatic ionization energy (IE), and bond dissociation energy (BDE) were calculated at the Feller-Peterson-Dixon (FPD) level. The ground state of UO is predicted to be 5I4, and that of UF is 4I9/2. The calculated AEAs of UO and UF are 1.123 and 0.453 eV, respectively, and the corresponding IEs are 5.976 and 6.278 eV. The BDE of UO (749.5 kJ/mol) is predicted to be considerably higher than that of UF (627.2 kJ/mol), and both are higher than those predicted for UB, UC, and UN. NBO calculations show strong ionic character for the ground states of UO and UF and bond orders that range from 2 to 3 and from 1 to 2, respectively. Comparisons of the calculated properties to those of the series comprising UB, UC, and UN diatomic molecules are given.

Compositional Metrics of Fast and Slow Alfvénic Solar Wind Emerging from Coronal Holes and Their Boundaries

We seek to understand the composition and variability of fast solar wind (FSW) and slow Alfvénic solar wind emerging from coronal holes (CHs). We leverage an opportune conjunction between Solar Orbiter and Parker Solar Probe (PSP) during PSP Encounter 11 to include compositional diagnostics from the Solar Orbiter Heavy Ion Sensor as these variations provide crucial insights into the origin and nature of the solar wind. We use potential field source surface and magnetohydrodynamic models to connect the observed plasma at PSP and Solar Orbiter to its origin footpoint in the photosphere and compare these results with the in situ measurements. A very clear signature of a heliospheric current sheet crossing as evidenced by enhancements in low first ionization potential (FIP) elements, ion charge state ratios, proton density, low Alfvénicity, and polarity estimates validates the combination of modeling, data, and mapping. We identify two FSW streams emerging from small equatorial CHs with low ion charge state ratios, low FIP bias, high Alfvénicity, and low footpoint brightness, yet anomalously low alpha particle abundance for both streams. We identify high-Alfvénicity slow solar wind emerging from the overexpanded boundary of a CH having intermediate alpha abundance, high Alfvénicity, and dips in ion charge state ratios corresponding to CH boundaries. Through this comprehensive analysis, we highlight the power of multi-instrument conjunction studies in assessing the sources of the solar wind.

A theoretical study on the electronic and optical properties of M-TiO2/ZnO (M=Li, Na, K, Fe) toward application in photocatalysis

This study employs the tight-binding density functional method GFN1-xTB to investigate the structural and electronic properties of TiO2-ZnO and TiO2-ZnO composite materials modified by Li, Na, K, and Fe metals. Computational analyses reveal the formation of weak covalent bonds between the TiO2 and ZnO components within the composite system. Doping TiO2-ZnO with metals induces significant alterations in the electronic structure, particularly in terms of ionization energy and global electrophilic index. The UV-VIS spectra are calculated using real-time time-dependent density functional theory with xTB Hamiltonians. The obtained results demonstrate minimal impact of metal presence on the absorption spectrum of TiO2-ZnO, but significant influence on the recombination potential of photogenerated charge carriers. It is suggested that Fe/TiO2-ZnO and Li/TiO2-ZnO will demonstrate higher photocatalytic activity than the pristine TiO2-ZnO material.

Studying the Thermodynamic Phase Stability of Organic–Inorganic Hybrid Perovskites Using Machine Learning

As an important photovoltaic material, organic–inorganic hybrid perovskites have attracted much attention in the field of solar cells, but their instability is one of the main challenges limiting their commercial application. However, the search for stable perovskites among the thousands of perovskite materials still faces great challenges. In this work, the energy above the convex hull values of organic–inorganic hybrid perovskites was predicted based on four different machine learning algorithms, namely random forest regression (RFR), support vector machine regression (SVR), XGBoost regression, and LightGBM regression, to study the thermodynamic phase stability of organic–inorganic hybrid perovskites. The results show that the LightGBM algorithm has a low prediction error and can effectively capture the key features related to the thermodynamic phase stability of organic–inorganic hybrid perovskites. Meanwhile, the Shapley Additive Explanation (SHAP) method was used to analyze the prediction results based on the LightGBM algorithm. The third ionization energy of the B element is the most critical feature related to the thermodynamic phase stability, and the second key feature is the electron affinity of ions at the X site, which are significantly negatively correlated with the predicted values of energy above the convex hull (Ehull). In the screening of organic–inorganic perovskites with high stability, the third ionization energy of the B element and the electron affinity of ions at the X site is a worthy priority. The results of this study can help us to understand the correlation between the thermodynamic phase stability of organic–inorganic hybrid perovskites and the key features, which can assist with the rapid discovery of highly stable perovskite materials.

The elusive phenylethynyl radical and its cation: synthesis, electronic structure, and reactivity.

Alkynyl radicals and cations are crucial reactive intermediates in chemistry, but often evade direct detection. Herein, we report the direct observation of the phenylethynyl radical (C6H5CC˙) and its cation (C6H5CC+), which are two of the most reactive intermediates in organic chemistry. The radical is generated via pyrolysis of (bromoethynyl)benzene at temperatures above 1500 K and is characterized by photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). Photoionization of the phenylethynyl radical yields the phenylethynyl cation, which has never been synthesized due to its extreme electrophilicity. Vibrationally-resolved ms-TPES assisted by ab initio calculations unveiled the complex electronic structure of the phenylethynyl cation, which appears at an adiabatic ionization energy (AIE) of 8.90 ± 0.05 eV and exhibits an uncommon triplet (3B1) ground state, while the closed-shell singlet (1A1) state lies just 2.8 kcal mol-1 (0.12 eV) higher in energy. The reactive phenylethynyl radical abstracts hydrogen to form ethynylbenzene (C6H5CCH) but also isomerizes via H-shift to the o-, m-, and p-ethynylphenyl isomers (C6H4CCH). These radicals are very reactive and undergo ring-opening followed by H-loss to form a mixture of C8H4 triynes, along with low yields of cyclic 3- and 4-ethynylbenzynes (C6H3CCH). At higher temperatures, dehydrogenation from the unbranched C8H4 triynes forms the linear tetraacetylene (C8H2), an astrochemically relevant polyyne.

Cobalt(VI)-oxo species-mediated selective oxidation of electron-rich organic contaminants by Co-loaded hydroxylated g-C3N4 with high resistance to an inhibitory effect of background constituents

Understanding of the selectivity of high-valent cobalt-oxo species (Co(IV)O) toward diverse organic pollutants with different characteristics in the presence of background constituents remains limited. Here, we prepared Co-loaded hydroxyl group-grafted graphitic carbon nitride (Co-OHCN) using a facile method for the effective formation of Co(IV)O. The role of the hydroxyl group in anchoring Co ions was investigated using several characterization methods (TEM, XRD, FT-IR, and XPS). Co-OHCN exhibited superior efficiency in degrading 4-chlorophenol (4-CP) (98.0 % ± 0.3 %) within 15 min of peroxymonosulfate (PMS) activation reaction. In the Co-OHCN/PMS system, Co(IV)O had the highest steady-state concentration ([Co(IV)O] = 1.40 × 10−10 M), significantly exceeding that of other reactive oxygen species (ROS) ([SO4−] = 9.22 × 10−13 M, [OH] = 1.82 × 10−13 M). The dominant role of Co(IV)O in 4-CP degradation was further revealed through scavenger tests, probe methods, and electrochemical analysis. Additionally, the anti-interference of Co(IV)O in the degradation of electron-rich organic substrates to background constituents (NOM and halide ions) was systemically validated using three organic pollutants with different ionization potential values (diclofenac, 4-CP, and benzoic acid). This study provides insight into an efficient strategy for Co(IV)O -mediated pollutant elimination and organic substrate-dependent selectivity of Co(IV)O during water decontamination.

Newly Designed Quasi-intrinsic Photosensitizers for Fluorescence Image-Guided Two-Photon Photodynamic Therapy with Type I/II Photoreactions.

In this work, a set of quasi-intrinsic photosensitizers are theoretically proposed based on the 2-amino-8-(1'-β-d-2'-deoxyribofuranosyl)-imidazo[1,2-α]-1,3,5-triazin-4(8H)-one (P), which could pair with the 6-amino-5-nitro-3-(1'-β-d-2'-deoxyribofuranosyl)-2(1H)-pyridone (Z) and keep the essential structural characters of nucleic acid. It is revealed that the ring expansion and electron-donating/electron-withdrawing substitution bring enhanced two-photon absorption and bright photoluminescence of these monomers, thereby facilitating the selective excitation and tumor localization through fluorescence imaging. However, instead of undergoing radiative transition (S1 → S0), the base pairing induced fluorescence quenching and rapid intersystem crossing (S1 → Tn) are observed and characterized by the reduced singlet-triplet energy gaps and large spin-orbit coupling values. To ensure the phototherapeutic properties of the considered base pairs in long-lived T1 state, we examined the vertical electron affinity as well as vertical ionization potential for production of superoxide anions via Type I photoreaction, and their required T1 energy (0.98 eV) to generate singlet oxygen 1O2 via Type II mechanism.

Laser polarization control of ionization-injected electron beams and x-ray radiation in laser wakefield accelerators

In this paper, we have studied the influence of laser polarization on the dynamics of the ionization-injected electron beams, and subsequently, the properties of the emitted betatron radiation in laser wakefield accelerators (LWFAs). While ionizing by strong field laser radiation, the generated photo-electrons carry a residual transverse momentum in excess of the ionization potential via the above threshold ionization (ATI) process. This ATI momentum explicitly depends on the polarization state of the ionizing laser and eventually governs the dynamics of the electron beam trapped inside the wake potential. In order to systematically investigate the effect of the laser polarization, here, we have employed complete three-dimensional particle-in-cell simulations in the nonlinear bubble regime of the LWFAs. We focus, in particular, on the effects the laser polarization has on the ionization injection mechanism, and how these features affect the final beam properties, such as beam charge, energy, energy spread, and transverse emittance. We have also found that as the laser polarization gradually changes from linear to circular, the helicity of the electron trajectory, and hence the angular momentum carried by the beam, increases significantly. Studies have been further extended to reveal the effect of laser polarization on the radiation emitted by the accelerated electrons. The far-field radiation spectra have been calculated for the linear and circular polarization states of the laser. It has been shown that the spatial distributions and the polarization properties (Stokes parameters) of the emitted radiation in the above two cases are substantially different. Therefore, our study provides a facile and efficient alternative to regulate the properties of the accelerated electron beams and x-ray radiation in LWFAs, utilizing ionization injection mechanism.

Interpretable Data‐Driven Descriptors for Establishing the Structure‐Activity Relationship of Metal‐Organic Frameworks Toward Oxygen Evolution Reaction

The development of readily accessible and interpretable descriptors is pivotal yet challenging in the rational design of metal‐organic framework (MOF) catalysts. This study presents a straightforward and physically interpretable activity descriptor for the oxygen evolution reaction (OER), derived from a dataset of bimetallic Ni‐based MOFs. Through an artificial‐intelligence (AI) data‐mining subgroup discovery (SGD) approach, a combination of the d‐band center and number of missing electrons in eg states of Ni, as well as the first ionization energy and number of electrons in eg states of the substituents, is revealed as a gene of a superior OER catalyst. The found descriptor, obtained from the AI analysis of a dataset of MOFs containing 3‐5d transition metals and 13 organic linkers, has been demonstrated to facilitate in‐depth understanding of structure–activity relationship at the molecular orbital level. The descriptor is validated experimentally for 11 Ni‐based MOFs. Combining SGD with physical insights and experimental verification, our work offers a highly efficient approach for screening MOF‐based OER catalysts, simultaneously providing comprehensive understanding of the catalytic mechanism.

Environment-Driven Variability in Absolute Band Edge Positions and Work Functions of Reduced Ceria.

The absolute band edge positions and work function (Φ) are the key electronic properties of metal oxides that determine their performance in electronic devices and photocatalysis. However, experimental measurements of these properties often show notable variations, and the mechanisms underlying these discrepancies remain inadequately understood. In this work, we focus on ceria (CeO2), a material renowned for its outstanding oxygen storage capacity, and combine theoretical and experimental techniques to demonstrate environmental modifications of its ionization potential (IP) and Φ. Under O-deficient conditions, reduced ceria exhibits a decreased IP and Φ with significant sensitivity to defect distributions. In contrast, the IP and Φ are elevated in O-rich conditions due to the formation of surface peroxide species. Surface adsorbates and impurities can further augment these variabilities under realistic conditions. We rationalize the shifts in energy levels by separating the individual contributions from bulk and surface factors, using hybrid quantum mechanical/molecular mechanical (QM/MM) embedded-cluster and periodic density functional theory (DFT) calculations supported by interatomic-potential-based electrostatic analyses. Our results highlight the critical role of on-site electrostatic potentials in determining the absolute energy levels in metal oxides, implying a dynamic evolution of band edges under catalytic conditions.

Analytical Model for the Molecular Ionization Energy in an External Electric Field.

A model for the molecular ionization energy in an applied electric field is presented on the basis of a perturbation expansion in the electric field. The leading term arises from the Frenkel approach, which is the same for all molecules normally used in the Poole-Frenkel model for conductivity in an electric field. For a set of test molecules, the quality of the results is comparable to that of previous results using constrained density functional theory. We conclude that the Frenkel term is dominant and sufficient at relatively low fields and that the dipole and polarizability terms, the leading terms dependent on the properties of the individual molecule, make a significant contribution only at high fields and for relatively large molecules. Because the presented model is analytical, quantum chemical calculations are avoided for a variety of electric field strengths and molecular orientations, and the model can therefore be applied directly in coarse-grained models for electronic processes in dielectric condensed phases.

Ionization of Small Atmospheric Acid–Base Clusters and Its Prospective Role in Seeding the Growth of Aqueous Clusters

In the present study, we have examined the ionization of a set of small atmospheric acid–base clusters. The calculated ionization energy (IE) ranges from ∼660 kJ mol–1 to ∼1120 kJ mol–1, with clusters consisting of just the bases yielding the smallest IEs, while those of the acids yield the largest. For neutral clusters that form most readily, the IEs range from ∼790 kJ mol–1 to ∼880 kJ mol–1. These values are generally smaller than those of other chemicals with significant atmospheric presence. Thus, the radical cations of the acid–base clusters are not likely to ionize other atmospheric species. Charged atmospheric species have been hypothesized to facilitate the growth of large clusters. We have carried out a case study of the sequential hydration of an acid–base cluster and compared our results with previous studies of forming pure water clusters. The neutral acid–base cluster binds water more strongly than pure water clusters. Further strengthening of the binding can be seen for the radical cationic acid–base cluster. The resulting acid–base–water clusters may further represent a source of H3O+, which may proceed to facilitate cloud formation.

Hints to lightning breakdown enhancement for synthetic ester insulating oil: Unraveling the impact of molecular chain length on electron structural parameters under electric field stress

The high flash point and biodegradability of synthetic ester insulating oil offer transformers both operational stability and environmental protection. However, its poor lightning breakdown characteristics under long oil gaps and inhomogeneous electric field often lead to rapid streamer discharges, posing challenges and limits to the use of synthetic ester insulating oil and hinders the development of low-carbon, eco-friendly high voltage power transformers. To address this issue, we propose improving the lightning breakdown characteristics through molecular chain length design. Using density functional theory, time-dependent density functional theory, and wave function analysis, we investigate how microscopic factors like molecular polarity, discharge active sites, frontier orbitals, traps, ionization and electron affinity, and excitation processes influence macroscopic discharge characteristics. Our findings show that under an electric field, chain length is positively correlated with electron transfer, enhancing charge polarization. Chain length also correlates positively with dipole moment, facilitating the formation of space charge centers. While chain length minimally affects discharge active sites, the electric field can intensify their formation. Additionally, a longer chain length decreases the energy gap, increasing electron trap levels more than hole trap levels, thus capturing charges longer. Chain length is negatively correlated with ionization energy, promoting electron impact ionization, and has little effect on the excitation energy of S(0) → S(1), making excitation under high electric fields unlikely.

Critical roles of soil composition and pollutant properties on the degradation of PPCPs during ferrous/persulfate processes

Pharmaceuticals and personal care products (PPCPs) are widely used worldwide and cause potential soil pollution. Fe2+-activated persulfate (PS) processes (Fe-PAPs) are promising techniques for soil remediation. However, a knowledge gap exists in the mechanistic insights into the dominant factors affecting the degradation of different PPCPs in varied soil types. This study systematically investigated the roles of soil components and pollutant properties in the degradation of three PPCPs (triclosan (TCS), triclocarban (TCC), and naproxen (NPS)) in the nine soils in the Fe2+/PS system. The degradation efficiencies of TCS and NPS ranged from 10.92 % to 91.62 % and 46.59 % to 99.81 %, respectively, whereas nearly no degradation was observed for TCC. PPCPs with high water- solubility, high energies of the highest occupied molecular orbital (EHOMO), low pKa values, low energy gap (ΔE), or low vertical ionization potential (VIP) were more favorable for degradation. XPS analysis suggested that aliphatic carbon (Ali–C–C(H)), ether or alcohol carbon (C–O), and aldehyde or ketonic carbon (CO) on SOM significantly inhibited TCS degradation. The results of ROS quenching experiments showed that SO4•− and 1O2 played major roles in TCS and NPS degradation in the six soils, with the relative contributions ranged from 24.82 % to 99.14 % and 0.15 % to 73.40 %, respectively. The interaction between soil components, active species, and pollutants resulted in the distinct intermediates of TCS and NPS in different soils. Our findings provide in-depth insights into the role of soil composition and pollutant properties on the remediation of PPCP-contaminated soils in Fe-PAPs.

Exploring the mechanism of nerve agent (Tabun and Sarin) adsorption on carbon nanocones: Computational insights

Carbon NanoCones (CNCs), distinguished by their conical shape and large surface area, are evaluated for their potential application in nerve gas [tabun (GA) and sarin (GB)] adsorption. Density Functional Theory (DFT) calculations, Molecular Dynamics (MD), and Monte Carlo (MC) simulations are employed to investigate this phenomenon comprehensively. The study findings indicate that tabun (GA) and sarin (GB) undergo spontaneous adsorption, characterized by significant negative energy values. Density Functional Theory (DFT) calculations indicate electron donation tendencies of nerve agents to CNC surfaces. Computational analysis shows higher adsorption efficiency in the inner portion (P1) of CNCs. Molecular Dynamics (MD) and Monte Carlo (MC) simulations confirm planar adsorption configurations parallel to CNC surfaces. The DFT calculations show that GA has a far greater adsorption energy on a Carbon Nanocone compared to GB (−44.96 kcal/mol for GA, whereas GB has an adsorption energy of −35.95 kcal/mol). Furthermore, the analysis reveals significant differences between Sarin and Tabun nerve agents. Sarin exhibits higher global hardness, indicating increased stability, while Tabun shows higher overall softness, suggesting greater reactivity. Despite similar electronegativities, Sarin’s greater ionization energy and electron affinity imply enhanced stability and reactivity. Differences in HOMO and LUMO energies highlight unique reactivity profiles, with Sarin being more susceptible to nucleophilic attacks and Tabun to electrophilic attack. Sarin’s larger energy gap between HOMO and LUMO orbitals signifies its superior stability under electronic disturbances.