Search Results (824)

Abiotic processes have ramifications in wastewater treatment, in situ degradation of organic matter, and cycling of nutrients in wetland ecosystems. Experiments were conducted to investigate abiotic oxidation of organic compounds (lactate) as a function of electron acceptors (ferric citrate and hydrous ferric oxide (HFO), media composition, and pH under anaerobic conditions, using sodium bicarbonate as the buffering agent. Dissolved inorganic carbon (DIC) was used as a proxy for the oxidation of substrates. HFO media generated more DIC compared to ferric citrate containing media. Light and pH had major roles in the oxidation of lactate in the presence of ferric iron. Under dark conditions in the presence or absence of Fe(III), the DIC produced was low in all pH conditions. Inhibition of DIC production was also observed upon photo exposure when Fe (III) was absent. Isotopically, the system showed initial mixing between the bicarbonate and the carbon dioxide produced from oxidation later being dominated by carbon isotope value of lactate used. These redox conditions align with previous studies suggesting cleavage of organic compounds by hydroxyl radicals. The slower redox processes observed here, compared to previous studies, could be due to the scavenging effect of chloride ion on the hydroxyl radical. Full article

Vanillin photoinduced deprotonation was evaluated and analyzed. Vibronic states and transitions were computationally investigated. Optimizations and vertical electron transitions in the gas phase and with the continuum solvation model were computed using the time-dependent density functional theory. Static absorption and emission (photostatic optical) spectra were statistically averaged over the excited instantaneous molecular conformers fluctuating on quantum–classical molecular dynamic trajectories. Photostatic optical spectra were generated using the hybrid quantum–classical molecular dynamics for explicit solvent models. Conical intersection searching and nonadiabatic molecular dynamics simulations defined potential energy surface propagations, intersections, dissipations, and dissociations. The procedure included mixed-reference spin–flip excitations for both procedures and trajectory surface hopping for photodynamics. Insignificant structural deformations vs. hydroxyl bond cleavage followed by deprotonation were demonstrated starting from different initial structural conditions, which included optimized, transition state, and several other important fluctuating configurations in various environments. Vanillin electronic structure changes were illustrated and analyzed at the key points on conical intersection and nonadiabatic molecular dynamics trajectories by investigating molecular orbital symmetry and electron density difference. The hydroxyl group decomposed on transition to a σ-molecular orbital localized on the elongated O–H bond. Full article

Microgreens, having short growth cycles and efficient nutrient uptake, are ideal candidates for biofortification. This study investigated the effects of selenium (Se) and zinc (Zn) on photosynthetic performance in four hydroponically grown Brassica microgreens (broccoli, pak choi, kohlrabi, and kale), using direct and modulated chlorophyll a fluorescence and chlorophyll-to-carotenoid ratios (Chl/Car). The plants were treated with Na₂SeO₄ at 0 (control), 2, 5, and 10 mg/L or ZnSO₄ × 7H₂O at 0 (control), 5, 10, and 20 mg/L. The results showed species-specific responses with Se or Zn uptake. Selenium enhanced photosynthetic efficiency in a dose-dependent manner for most species (8–26% on average compared to controls). It increased the plant performance index (PI_tot), particularly in pak choi (+62%), by improving both primary photochemistry and inter-photosystem energy transfer. Kale and kohlrabi exhibited high PSII-PSI connectivity for efficient energy distribution, with increased cyclic electron flow around PSI and reduced Chl/Car up to 8.5%, while broccoli was the least responsive. Zinc induced variable responses, reducing PI_tot at lower doses (19–23% average decline), with partial recovery at 20 mg/L (9% average reduction). Broccoli exhibited higher susceptibility, with inhibited Q_A re-oxidation, low electron turnover due to donor-side restrictions, and increased pigment ratio (+3.6%). Kohlrabi and pak choi tolerated moderate Zn levels by redirecting electron flow, but higher Zn levels impaired PSII and PSI function. Kale showed the highest tolerance, maintaining stable photochemical parameters and total electron flow, with increased pigment ratio (+4.5%) indicating better acclimation. These results highlight the beneficial stimulant role of Se and the dual essential/toxic nature of Zn, thus emphasizing genotype and dose-specific optimizations for effective biofortification. Full article

The photofragmentation of halothane (CF₃CHBrCl) was studied with synchrotron radiation by photoionization efficiency (PIE) measurements and photoelectron–photoion coincidence (PEPICO) experiments, as well as by a theoretical exploration of potential energy surfaces. Among the other fragments, the formation of the CHClF⁺ and CHBrF⁺ ions, which involves the transfer of a F atom between the two moieties of the parent molecule, was observed. To understand the mechanisms leading to the halogen migration, a detailed theoretical study of the production of CHClF⁺, m/z 67⁺, based on DFT calculations and natural bond orbital (NBO) analysis was conducted. The results contribute to the understanding of the photochemistry of halothane, its polluting behavior in the high atmosphere, and the formation of highly reactive species. Full article

Background: The Index of Orthodontic Treatment Need (IOTN) is widely used to assess the need for orthodontic treatment. IOTN consists of the Dental Health Component (DHC) and the Aesthetic Component (AC), evaluating malocclusion morphologically and aesthetically, respectively. However, the discriminatory power of individual DHC items and their relationship with AC grades remain unclear. Objective: This study aimed to evaluate the effectiveness of individual DHC items in school dental examinations and investigate their contribution to AC grades among junior high and high school students. Methods: A total of 726 students (443 males, 283 females; aged 12–18 years) from Tsurumi University Junior and Senior High School, excluding 168 students undergoing or having completed orthodontic treatment, were included. Nine calibrated orthodontists assessed DHC and AC using IOTN during standardized school examinations. The discriminatory power and information precision of DHC items were evaluated by Item Response Theory (IRT) analysis using three-, two-, or one-parameter logistic models depending on convergence. Correspondence analysis visualized the correlation between DHC and AC grades. Simple linear regression analyzed the contribution of each DHC item to AC grades. Results: Orthodontic treatment need was identified in 21.1% of students. Females showed a higher rate of treatment need than males. Correspondence analysis suggested that aesthetic evaluations were more lenient than morphological evaluations. IRT and regression analysis revealed that crowding (4.d), increased overjet (2.a), and increased overbite (2.f) demonstrated high discriminatory power and significant contributions to AC grades. Conclusions: Among the DHC items, crowding, increased overjet, and increased overbite had higher discriminatory power for malocclusion and contributed more significantly to AC evaluations compared to other items. Full article

Pinus radiata D. Don is planted in South Central Chile on a wide range of sites using genetically improved genotypes for timber production. As drought events are expected to increase with ongoing climatic change, the variability in gas exchange, which could impact growth and water use, needs to be evaluated. In this study, we assessed the genotypic variability of leaf-level light-saturated photosynthesis (A_sat), stomatal conductance (g_s), transpiration (E), intrinsic water use efficiency (iWUE), and Chlorophyll a fluorescence (OJIP-test parameters) among 30 P. radiata genotypes (i.e., full-sib families) from third-cycle parents at age 6 years on three sites in Central Chile. We also evaluated tree height (HT), diameter at breast height (DBH), and stem index volume (VOL). Families were ranked for HT as top-15 and bottom-15. In the OJIP-test parameters we observed differences at the family level for the maximum quantum yield of primary PSII photochemistry (Fv/Fm), the probability that a photon trapped by the PSII reaction center enters the electron transport chain (ψ_Eo), and the potential for energy conservation from photons captured by PSII to the reduction in intersystem electron acceptors (PI_ABS). Fv/Fm, PI_ABS, and ψ_Eo ranged from 0.82 to 0.87, 45 to 95, and 0.57 to 0.64, respectively. Differences among families for growth and not for leaf-level physiology were detected. DBT, H, and VOL were higher in the top-15 families (12.6 cm, 8.4 m, and 0.10 m³, respectively) whereas A_sat, g_s, E, and iWUE were similar in both the top-15 and bottom-15 families (4.0 μmol m⁻² s⁻¹, 0.023 mol m⁻² s⁻¹, 0.36 mmol m⁻² s⁻¹, and 185 μmol mol m⁻² s⁻¹, respectively). However, no family by site interaction was detected for growth and leaf-level physiology. The results of this study suggest that highly improved genotypes of P. radiata have uniformity in leaf-level physiological rates, which could imply uniform water use at the stand-level. The family variation found in PI_ABS suggests that this parameter could be incorporated to select genotypes tolerant to environmentally stressful conditions. Full article

Objectives: Nanosized polymeric micelles (PMs) with an average size of about 80 nm and moderately positive ζ potential, based on an amphiphilic poly(4-methyl-piperazin-1-yl)-propenone)-b-polylactide (PMPP-PLA) block copolymer, were prepared. They were used as platforms for the delivery of bioactive sesquiterpene lactones from Inula helenium L. root extract. Methods: The PMs were characterized with good encapsulation efficiency as a maximum value of 72% was reached at a polymer-to-extract mass ratio of 10:1. The loaded micelles exhibited good colloidal stability. An in vitro release was performed showing a burst release profile. The biocompatibility of the resulting PMs was confirmed by assessing their cytotoxic effect on human keratinocytes in vitro by colorimetric assay and flow cytometry. Results: The systems demonstrated the capability to reduce the biomass of pre-formed Gram-positive and Gram-negative bacterial biofilms. Conclusions: The obtained data clearly determine a trend for a strong combined effect between the PMs and the root extract, distinguishing them with an excellent anti-biofilm potential and prospects for future applications in medical practice. Full article

In this study, the functions of the photosynthetic machinery were evaluated using chlorophyll a fluorescence technique (PAM and JIP test) in pea plants (Pisum sativum L. cv Borec) and its LHC II oligomerization variants (mutants Costata 2/133 and Coeruleovireus 2/16). The oligomeric forms of LHCII increased in the following order: Costata 2/133 < Borec wt < Coeruleovireus 2/16. Data revealed that the mutant with higher LHCII oligomerization (Coeruleovireus 2/16) at low light intensity (LL, 150 µmol photons/m²·s) exhibited the following: (i) decreased energy dissipation and increased electron transport efficiency; (ii) higher reaction center density; (iii) increased amounts of the open reaction centers (qp) and their excitation efficiency (Φexc); and (iv) influenced the reoxidation of Q_A⁻, alleviating its interaction with plastoquinone. These effects enhanced photosynthetic performance related to PSII photochemistry (PI_ABS) and overall photosynthetic efficiency (PItotal). High light intensity (HL, 500 µmol photons/m²·s) caused a reduction in open reaction centers (qp), excitation efficiency (Φexc), photochemical energy conversion of PSII (Φ_PSII), maximum efficiency of PSII photochemistry in light (Fv′/Fm′), and linear electron transport via PSII, with more pronounced effects observed in membranes with a lower degree of LHCII oligomerization (Costata 2/133). This study provides novel experimental evidence for the pivotal role of the LHCII structural organization in determining the efficiency of light-dependent reactions of photosynthesis. Full article

This study investigates the temporal dynamics, sources, and photochemical behaviour of key volatile organic compounds (VOCs) along Marylebone Road, London (1 January 2015–1 January 2023), a heavily trafficked urban area. Hourly measurements of benzene, toluene, ethylbenzene, ethene, propene, isoprene, propane, and ethyne, alongside ozone (O₃) and meteorological data, were analysed using correlation matrices, regression, cross-correlation, diurnal/seasonal analysis, wind-sector analysis, PCA (Principal Component Analysis), and clustering. Strong inter-VOC correlations (e.g., benzene–ethylbenzene: r = 0.86, R² = 0.75; ethene–propene: r = 0.68, R² = 0.53) highlighted dominant vehicular sources. Diurnal peaks of benzene, toluene, and ethylbenzene aligned with rush hours, while O₃ minima occurred in early mornings due to NO titration. VOCs peaked in winter under low mixing heights, whereas O₃ was highest in summer. Wind-sector analysis revealed dominant VOC emissions from SSW (south-southwest)–WSW (west-southwest) directions; ethyne peaked from the E (east)/ENE (east-northeast). O₃ concentrations were highest under SE (southeast)–SSE (south-southeast) flows. PCA showed 39.8% of variance linked to traffic-related VOCs (PC1) and 14.8% to biogenic/temperature-driven sources (PC2). K-means clustering (k = 3) identified three regimes: high VOCs/low O₃ in stagnant, cool air; mixed conditions; and low VOCs/high O₃ in warmer, aged air masses. Findings highlight complex VOC–O₃ interactions and stress the need for source-specific mitigation strategies in urban air quality management. Full article

The microalgal defense strategies for different white light intensities (70–700 μmol m⁻² s⁻¹) were investigated in isolates from unexplored habitats, focusing on photosynthetic performance. Chlorella sorokiniana strain F4 from a Mediterranean inland swamp and two strains related to Pectinodesmus pectinatus (PEC) and Ettlia pseudoalveolaris (ETI) from an Ecuadorian highland lake were exposed to light over 18 h. The results showed that PSII photochemical efficiency was affected with increasing light due to photoinhibition or photodamage. F4 showed a low threshold of saturation light intensity, after which NPQ was compromised and total antioxidant levels were increased, leading to a reduction in its PSII photochemistry performance. F4 exhibited limited capacity for antennae reorganization in response to light stress. ETI and PEC differed in their photophysiological responses, although they came from the same habitat. ETI maintained high Chlb to Chla (i.e., large antennae), exhibited sustained energy dissipation, and preserved a high antioxidant pool (i.e., mycosporine-like amino acids) in all lights. Differently, in PEC, NPQ, antennae rearrangement, and reactive oxygen species scavenger pool were induced in a light-dependent manner. This study revealed the complex relationship between light parameters and microalgal physiology affected by environmental constraint adaptation and phylogenetic diversity. Full article

Background/Objectives: Candidiasis, an opportunistic fungal infection caused by Candida species, is a major health problem, particularly in immunocompromised individuals. Increasing resistance of yeasts such as Candida spp. to pharmacological antifungal agents makes it necessary to explore alternative treatments. The aim of this study was to evaluate the antifungal potential of Gomortega keule essential oil (GKEO) against Candida spp. by assessing growth and development at 24 and 48 h. Encapsulation and characterization of a stable nanoemulsion were carried out to enhance efficacy. Methods: The anti-yeast activity of both free GKEO and the nanoemulsion against Candida albicans, C. glabrata, and C. guilliermondii was evaluated using a microdilution method to determine the minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) at 24 and 48 h. Results: GC-MS/MS analysis identified forty-one components in GKEO, the main ones being eucalyptol (21.41%), 4-terpineol (19.62%), and α-terpinyl acetate (13.89%). Antifungal assays revealed that both free and nanoemulsion-formulated GKEO inhibited the growth of all tested Candida strains. At 48 h, the nanoformulated GKEO achieved a MIC value of 32 µg/mL and an MFC of 64 µg/mL for C. albicans and C. glabrata and showed higher antifungal activity compared to the free oil, in particular against C. albicans, exhibiting a four-fold lower MFC value. The activity of the nanoformulation was comparable to or better than fluconazole against C. glabrata and C. guilliermondii. Conclusions: The GKEO nanoemulsion potentiated anti-yeast activity against Candida spp. The formulation improved the efficacy of GKEO, suggesting its potential as an alternative or adjunctive treatment for candidiasis. Full article

Silver nanoparticles (AgNPs) have attracted tremendous attention in recent years due to their unique physicochemical properties, including pronounced surface plasmon resonance, tunable size, and amenability to functionalization. These attributes underpin the growing interest in AgNPs as SMART nanocarriers for targeted drug delivery and as active components in biosensing platforms. In this work, we discuss various synthesis strategies for AgNPs—ranging from conventional chemical methods to green approaches—and highlight their subsequent functionalization with anticancer drugs, notably doxorubicin (DOX). We also examine the potential of AgNPs in biosensor applications, emphasizing electrochemical and optical detection modalities capable of monitoring drug release, oxidative stress, and relevant biomarkers. Our experimental data support the conclusion that AgNPs can effectively improve therapeutic efficacy by exploiting tumor-specific conditions (e.g., lower pH) while also enhancing biosensor sensitivity via surface plasmon resonance and electrochemical signal amplification. We provide a thorough discussion of the results, including mechanistic aspects of reactive oxygen species (ROS) generation, drug release kinetics, and sensor performance metrics. Overall, AgNP-based nanocarriers emerge as a powerful platform to address current challenges in precision oncology and medical diagnostics. Full article

Nitro-functionalized heterocycles, such as nitroimidazoles, are significant environmental contaminants and have been identified as components of secondary organic aerosols (SOA) and biomass-burning organic aerosols (BBOA). Their strong absorption in the near-UV (300–400 nm) makes photochemistry a critical aspect of their atmospheric processing. This study investigates both the direct near-UV photochemistry and hydroxyl radical (OH) oxidation of 4-nitroimidazole (4-NI). The atmospheric photolysis rate of 4-NI in the near-UV (300–400 nm) was found to be J_4-NI = 4.3 × 10⁻⁵ (±0.8) s⁻¹, corresponding to an atmospheric lifetime of 391 (±77) min under bulk aqueous conditions simulating aqueous aerosols and cloud water. Electrospray ionization mass spectrometry (ESI-MS) analysis following irradiation indicated loss of the nitro group, while NO elimination was observed as a more minor channel in direct photolysis. In addition, the rate constant for the reaction of 4-NI with OH radicals, k_NI+OH, was determined to be 2.9 × 10⁹ (±0.6) M⁻¹s⁻¹. Following OH oxidation, ESI-MS results show the emergence of a dominant peak at m/z = 130 amu, consistent with hydroxylation of 4-NI. Computational results indicate that OH radical addition occurs with the lowest barrier at the C2 and C5 positions of 4-NI. The combined results from direct photolysis and OH oxidation experiments suggest that OH-mediated degradation is likely to dominate under aerosol-phase conditions, where OH radical concentrations are elevated, while direct photolysis is expected to be the primary loss mechanism in high-humidity environments and bulk cloud water. Full article

The generation of solvated electrons (SEs) from solid-state sources represents a transformative approach to driving challenging reduction reactions under ambient conditions. Diamond, with its almost unique negative electron affinity (NEA) and tunable electronic properties, is emerging as a promising candidate for SE generation in aqueous media. This perspective article reviews the current state of diamond-based SE generators and discusses their potential to catalyze sustainable nitrogen reduction (NRR) to ammonia, carbon dioxide reduction (CO₂RR), and the degradation of persistent environmental pollutants. Emphasis is placed on the fundamental processes enabling SE photoinjection from diamond to water, recent experimental breakthroughs, and the prospects for scalable, green applications. Full article

This review focuses on photocyclization reactions involving alkenes and arenes. Photochemistry opens up synthetic opportunities difficult for thermal methods, using light as a versatile tool to convert stable ground-state molecules into their reactive excited counterparts. This difference can be particularly striking for aromatic molecules, which, according to Baird’s rule, transform from highly stable entities into their antiaromatic “evil twins”. We highlight classical reactions, such as the photocyclization of stilbenes, to show how alkenes and aromatic rings can undergo intramolecular cyclizations to form complex structures. When possible, we explain how antiaromaticity develops in excited states and how this can expand synthetic possibilities. The review also examines how factors such as oxidants, substituents, and reaction conditions influence product selectivity, providing useful insights for improving reaction outcomes and demonstrating how photochemical methods can drive the development of new synthetic strategies. Full article