Assessing Heavy Metals in the Sele River Estuary: An Overview of Pollution Indices in Southern Italy.

Rapid industrialization, coupled with a historical lack of understanding in toxicology, has led in an increase in estuary pollution, frequently resulting in unexpected environmental situations. Therefore, the occurrence of heavy metals (HMs) constitutes a major environmental issue, posing a serious risk both to aquatic ecosystems and public health. This study aimed to evaluate the levels of eight HMs (As, Hg, Cd, Cr, Cu, Ni, Pb, and Zn) in water, suspended particles, and sediment near the Sele River estuary (Italy) in order to assess their environmental impacts on the sea and health risks for humans. The results revealed an increasing order of HM concentration according to the scheme suspended particulate matter (SPM) > sediment (SED) > dissolved phase (DP) and a moderate contamination status in sediment. The health risk assessment indicated that the non-carcinogenic risk was negligible. Carcinogenic risk, expressed as the incremental lifetime cancer risk (ILCR), was negligible for Cd and Ni and within tolerable limits for As, Pb, and Cr. The findings suggested that, even if there are currently no specific limits for chemical parameters in the transitional waters of Italy, monitoring systems should be implemented to determine pollution levels and implement effective steps to improve river water quality and reduce human health risks.

Understanding Hearing Health: A Cross-Sectional Study of Determinants in a Metropolitan Area.

Hearing health prevention has emerged as a significant public health concern worldwide. With nearly two and a half billion people experiencing some degree of hearing loss, and around seven hundred million requiring medical intervention, the impact on global health is substantial. The economic burden is equally substantial, with estimated health costs reaching 980 billion dollars in the United States alone. To shed light on this issue, we conducted a survey-based cross-sectional study involving 1150 individuals. Utilizing multiple linear regression across three models, we aimed to explore the association between demographic variables and knowledge, attitude, and behaviors related to hearing health. In Model I, we observed a correlation between knowledge and several factors, including age, smoking habits, marital status, and education. In Model II, attitudes were found to associate with non-smoking habits, education, and knowledge. Model III revealed a statistically significant correlation between behaviors and age, gender, parenthood, knowledge, and attitudes. These findings emphasize the importance of targeted public health programs aimed at improving behaviors among the general population. Such interventions can be both effective and relatively inexpensive. By addressing these determinants, we can enhance overall hearing health in the community. Our study contributes valuable information about the knowledge, attitudes, and behaviors related to hearing health in the general population. Understanding these factors is crucial in developing evidence-based strategies to promote hearing health and prevent hearing loss effectively. As we continue to work towards better hearing health, the findings from this study can serve as a cornerstone for informed decision-making and successful intervention implementation.

Sulphur- and Selenium-for-Oxygen Replacement as a Strategy to Obtain Dual Type I/Type II Photosensitizers for Photodynamic Therapy.

The effect on the photophysical properties of sulfur- and selenium-for-oxygen replacement in the skeleton of the oxo-4-dimethylaminonaphthalimide molecule (DMNP) has been explored at the density functional (DFT) level of theory. Structural parameters, excitation energies, singlet-triplet energy gaps (ΔES-T), and spin-orbit coupling constants (SOC) have been computed. The determined SOCs indicate an enhanced probability of intersystem crossing (ISC) in both the thio- and seleno-derivatives (SDMNP and SeDMNP, respectively) and, consequently, an enhancement of the singlet oxygen quantum yields. Inspection of Type I reactions reveals that the electron transfer mechanisms leading to the generation of superoxide is feasible for all the compounds, suggesting a dual Type I/Type II activity.

On the origin of photodynamic activity of hypericin and its iodine-containing derivatives.

The main photophysical properties, useful for establishing whether hypericin in anionic form and some of its derivatives containing heavy atoms such as iodine, can be proposed for their use in photodynamic therapy, were determined using density functional based computations. The results showed that in the anionic form and in the iodinated derivatives, the absorption wavelength undergoes a bathochromic shift, the singlet-triplet energy gap assumes values ​that allow to excite the oxygen molecule from its ground to the excited singlet state, and that the spin-orbit couplings between singlet and triplet states significantly increase.

Occurrence, Distribution, and Risk Assessment of Organophosphorus Pesticides in the Aquatic Environment of the Sele River Estuary, Southern Italy.

The intensive use of organophosphorus pesticides (OPPs) causes concern among authorities in different countries, as many of them, remaining unchanged for a long time, pose a threat to environmental sustainability. This study assessed the spatio-temporal trends of nine OPPs in the water dissolved phase (WDP), suspended particulate matter (SPM), and sediment samples from the Sele River estuary, Southern Italy. Samples were collected in 10 sampling sites during four seasons. The highest levels were found at the mouth (mean value 28.25 ng L-1 as WDP + SPM) and then decreased moving southwards to the Mediterranean Sea. Moreover, highest concentrations were detected in the warm season (July) with a mean value of 27.52 ng L-1. The load contribution to the Mediterranean Sea was evaluated in about 61.5 kg year-1, showing that the river was an important source of OPPs through discharge into the sea. The risk assessment revealed that no high-risk indices for the general-case scenario were observed, but for the worst-case scenario, potential risks were associated with chlorpyrifos, pyrimifos-methyl, and parathion, suggesting that OPP contamination should not be neglected. This study makes up the first record of OPPs in the surface waters of the Sele River and provides helpful data as a starting point for future studies.

Polycyclic Aromatic Hydrocarbons (PAHs) in the Dissolved Phase, Particulate Matter, and Sediment of the Sele River, Southern Italy: A Focus on Distribution, Risk Assessment, and Sources.

The Sele River, located in the Campania Region (southern Italy), is one of the most important rivers and the second in the region by average water volume, behind the Volturno River. To understand the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in the Sele River, water sediment samples were collected from areas around the Sele plain at 10 sites in four seasons. In addition, the ecosystem health risk and the seasonal and spatial distribution of PAHs in samples of water and sediment were assessed. Contaminant discharges of PAHs into the sea were calculated at about 1807.9 kg/year. The concentration ranges of 16 PAHs in surface water (DP), suspended particulate matter (SPM), and sediment were 10.1-567.23 ng/L, 121.23-654.36 ng/L, and 331.75-871.96 ng/g, respectively. Isomeric ratio and principal component analyses indicated that the PAH concentrations in the water and sediment near the Sele River were influenced by industrial wastewater and vehicle emissions. The fugacity fraction approach was applied to determine the trends for the water-sediment exchange of 16 priority PAHs; the results indicated that fluxes, for the most part, were from the water into the sediment. The toxic equivalent concentration (TEQ) of carcinogenic PAHs ranged from 137.3 to 292.6 ngTEQ g-1, suggesting that the Sele River basin presents a definite carcinogenic risk.

Chalcogen Effects in the Photophysical Properties of Dimethylamino-1,8-naphthalimide Dyes Revealed by DFT Investigation.

Thionation of carbonyl groups of known dyes is a rapidly emerging strategy to propose an advance toward heavy-atom-free photosensitizers to be used in photodynamic therapy (PDT). The sulfur-for-oxygen replacement has recently proved to enhance the singlet oxygen quantum yield of some existing fluorophores and to shift the absorption band at longer wavelengths. Drawing inspiration from this challenging evidence, the effect of both sulfur- and selenium-for-oxygen replacement in the skeleton of the oxo-4-dimethylamino-1,8-naphthalimide molecule (DMN) has been analyzed by means of a DFT study. The thio- and seleno-derivatives (SDMN and SeDMN, respectively) have been shown to offer the possibility to access a multitude of ISC (intersystem crossing) pathways involved in the triplet deactivation mechanisms with a consequent enhancement of the singlet oxygen production, also arising from the change of orbital type involved in the radiationless 1nπ* → 3ππ* transitions. Moreover, the change in nature from a 1ππ* to a 1nπ* observed in the SeDMN has been revealed to be crucial to reach more clinically useful regions of the spectrum suggesting that the selenium-for-oxygen replacement can be proposed as a strategy to achieve more suitable PDT agents while proposing an advance toward heavy-atom-free PSs.

The Contribution of Density Functional Theory to the Atomistic Knowledge of Electrochromic Processes.

In this review, we provide a brief overview of the contribution that computational studies can offer to the elucidation of the electronic mechanisms responsible for the electrochromism phenomenon, through the use of the density functional theory (DFT) and its time-dependent formulation (TDDFT). Although computational studies on electrochromic systems are not as numerous as those for other physico-chemical processes, we will show their reliability and ability to predict structures, excitation energies, and redox potentials. The results confirm that these methods not only help in the interpretation of experimental data but can also be used for the rational design of molecules with interesting electrochromic properties to be initiated for synthesis and experimental characterization.

Photophysical properties of heavy atom containing tetrasulfonyl phthalocyanines as possible photosensitizers in photodynamic therapy.

The excitation energies, singlet-triplet energy gap and spin-orbit coupling constants for Zn-, GaCl-, Pd-, and Pt- tetrasulfonyl phthalocyanines complexes (ZnPc, GaClPc, PdPc, and PtPc) have been computed by using the density functional theory and employing the M06 exchange-correlation functional. Results show that these systems possess interesting photophysical properties, which make them possible photosensitizers to be proposed in photodynamic therapy (PDT). Absorption energies of all the complexes examined have been found falling inside the so-called therapeutic window (550-800 nm). Singlet-triplet energy gap values are higher than those required for the production of cytotoxic molecular oxygen and the spin-orbit coupling constants are such as to ensure an efficient spin orbit intersystem crossing. The obtained data are consistent with the experimental oxygen singlet quantum yields. The platinum complex appears to be the most effective candidate to propose for PDT.

Quantum Mechanical Predictions of the Antioxidant Capability of Moracin C Isomers.

The antioxidant capability of moracin C and iso-moracin C isomers against the OOH free radical was studied by applying density functional theory (DFT) and choosing the M05-2X exchange-correlation functional coupled with the all electron basis set, 6-311++G(d,p), for computations. Different reaction mechanisms [hydrogen atom transfer (HAT), single electron transfer (SET), and radical adduct formation (RAF)] were taken into account when considering water- and lipid-like environments. Rate constants were obtained by applying the conventional transition state theory (TST). The results show that, in water, scavenging activity mainly occurs through a radical addition mechanism for both isomers, while, in the lipid-like environment, the radical addition process is favored for iso-moracin C, while, redox- and non-redox-type reactions can equally occur for moracin C. The values of pKa relative to the deprotonation paths at physiological pH were predicted in aqueous solution.

Theoretical investigation on bisarylselanylbenzo-2,1,3-selenadiazoles as potential photosensitizers in photodynamic therapy.

Density functional theory and time-dependent (TDDFT) calculations were carried out for recently reported bisarylselanylbenzo-2,1,3-selenadiazoles derivatives capable of producing singlet oxygen (1O2) under UV-Vis irradiation. Conformational behaviors, excitation energies, singlet-triplet energy gaps, and spin-orbit coupling constants were evaluated. The conformational analysis evidences that two different conformers have to be taken into consideration to completely describe the photophysical properties of this class of molecules. TDDFT results show that these compounds, though possessing absorption wavelengths that fall in the violet region, are characterized by singlet-triplet energy gaps greater than the energy required to excite the molecular oxygen, thus being able to produce the cytotoxic species, spin-orbit coupling constants large enough to ensure efficient singlet-triplet intersystem spin crossing, and even the highly reactive superoxide anion O2 •(-) by autoionization and subsequent electron transfer to molecular oxygen in its ground state.

Iodine substituted phosphorus corrole complexes as possible photosensitizers in photodynamic therapy: Insights from theory.

The search for new dyes to be used as photosensitizers in photodynamic therapy (PDT) is a field of great interest from both experimental and theoretical viewpoints. In this study, the main photophysical properties (excitation energies, singlet-triplet energy gap, and spin orbit coupling matrix elements) of some unsubstituted and iodine substituted phosphorus corrole complexes have been determined by using density functional theory and its time-dependent formulation. Results show that these compounds can be proposed as photosensitizers in PDT. The heavy atom effects have been rationalized on the basis of El-Sayed rules.

Photophysical Exploration of Dual-Approach PtII-BODIPY Conjugates: Theoretical Insights.

Two-component PtII-BODIPY dyes were recently proposed as potential multitarget agents able to conjugate the photobased photodynamic therapy (PDT) treatment with the classical chemotherapy approach based on PtII complexes. A careful first-principle investigation is herein presented on the above-mentioned conjugates (Pt-1 and Pt-2) and on the two metal-free precursors (1 and 2), aimed at revealing the influence of the platinum moiety on the physicochemical behavior of the photosensitizer (PS) and to inspect, in turn, the possible modulation of the hydrolysis rate of the PtII ligand induced by the PS. The investigated photophysical properties for singlet and triplet states and the amplitude of the computed spin-orbit matrix elements reveal that the Pt-containing systems are able to enhance the cytotoxic 1O2 production. The PtII moiety, instead, follows an activation mechanism similar to that previously found for cisplatin and its analogues already used in cancer therapy.

Rational Design of Modified Oxobacteriochlorins as Potential Photodynamic Therapy Photosensitizers.

The modulation of the photophysical properties of a series of recently synthetized oxobacteriochlorins with the introduction of heavy atoms in the macrocycles, was investigated at density functional level of theory and by means of the time-dependent TDDFT formulation. Absorption frequencies, singlet-triplet energy gaps and spin-orbit coupling (SOC) constants values were computed for all the investigated compounds. Results show how the sulfur- selenium- and iodine-substituted compounds possess improved properties that make them suitable for application in photodynamic therapy (PDT).

Theoretical insight into joint photodynamic action of a gold(i) complex and a BODIPY chromophore for singlet oxygen generation.

Density functional theory is herein employed to provide theoretical insight into the mechanism involved in 1O2 photosensitization by a gold-BODIPY combined complex proposed as a promising photodynamic therapy agent. The protocol is thus used to compute the non-radiative rate constants for the S1 → Tj intersystem crossing transitions. Calculations show that while the incorporation of an iodine atom into the core skeleton of BODIPY enhances the singlet-triplet intersystem crossing (ISC) efficiency due to the occurrence of the singlet-triplet transition between states with different orbital characters (ππ* → πn*), the presence of a gold atom, even if not directly anchored to the chromophore core but through a triplet bond, equally entails an increase of the spin-orbit coupling constant due to the heavy atom effect. In this way, the system is able to generate singlet molecular oxygen, the key cytotoxic agent in PDT. Our results fit well with the experimental singlet oxygen quantum yield and cytotoxicity determination.

Photophysical Properties of Nitrated and Halogenated Phosphorus Tritolylcorrole Complexes: Insights from Theory.

The photophysical properties of a series of nitrated and halogenated phosphorus tritolylcorrole complexes were studied in dichloromethane solvent by using the density functional theory. Particular emphasis was given to the absorption spectra, the energy gap between the excited singlet and triplet states, and the magnitude of the spin-orbit couplings for a series of possible intersystem crossing channels between those excited states. The proposed study provides a better description of the photophysical properties of these systems while giving insights into their possible use as photosensitizers in photodynamic therapy.

Computational Investigation of the Influence of Halogen Atoms on the Photophysical Properties of Tetraphenylporphyrin and Its Zinc(II) Complexes.

How the tetraphenylporphyrin (TPP) and its zinc(II) complexes (ZnTPP) photophysical properties (absorption energies, singlet-triplet energy gap and spin-orbit coupling contributions) can change due to the presence of an increasing number of heavy atoms in their molecular structures has been investigated by means of density functional theory and its time-dependent formulation. Results show that the increase of the atomic mass of the substituted halogen strongly enhances the spin-orbit coupling values, allowing a more efficient singlet-triplet intersystem crossing. Different deactivation channels have been considered and rationalized on the basis of El-Sayed and Kasha rules. Most of the studied compounds possess the appropriate properties to generate cytotoxic singlet molecular oxygen (1Δg) and, consequently, they can be proposed as photosensitizers in photodynamic therapy.

Excitation energies, singlet-triplet energy gaps, spin-orbit matrix elements and heavy atom effects in BOIMPYs as possible photosensitizers for photodynamic therapy: a computational investigation.

Bis(borondifluoride)-8-imidazodipyrromethene (BOIMPY) based molecules show interesting photophysical properties. We have undertaken a computational study at DFT and TDDFT levels of theory with the aim of verifying if the non-fluorescent BOIMPYs meet those properties necessary to be proposed as potential photosensitizers for photodynamic therapy (PDT). In particular, we have computed the absorption wavelengths, the singlet-triplet energy gaps and the spin-orbit matrix elements. The effect of halogen atom substitution (Br, I), in different amounts and positions in the BOIMPY skeleton, on the photophysical properties, has been elucidated. Some possible pathways for the population of the lowest triplet state have been examined and rationalized on the basis of Kasha rules. The results indicate that many of the studied systems can be indicated as potential photosensitizers for photodynamic therapy.

On the Electrochromic Properties of Borepins: A Computational Prediction.

The spectroelectrochemical features of some recently synthesized borepins have been predicted herein using the methods based on density functional theory. The computed electronic spectra of neutral, radical anion, and dianion species clearly suggest that these molecules can be used as new electrochromic materials. The excellent agreement with the available structural and absorption experimental data for the neutral systems made us confident for the results obtained for charged species and suggests their potential use as electrochromic materials.

Time-Dependent Density Functional Computations of the Spectrochemical Properties of Dithiolodithiole and Thiophene Electrochromic Systems.

The importance of organic electrochromic materials has grown considerably in recent decades due to their application in smart window, automotive, and aircraft technologies. Theoretical prediction of the optical properties should contribute to their better characterization and help the explanation of the experimental data. By using various exchange-correlation functionals, we show how density functional theory (DFT) and the related time-dependent formulation (TDDFT) are able to correctly reproduce the spectrochemical properties of dithiolodithiole and thiophene organic electrochromic systems.