Search Results (84)

High temperature has an adverse effect on apple production worldwide. Photosynthesis is a process especially vulnerable to heat stress, which can reduce photosynthetic efficiency, plant growth, development, and ultimately yield. Although the effects of heat stress on apples have been partially examined, the photochemical reactions and heat tolerance of specific rootstocks have still not been sufficiently investigated. Identification of rootstocks with better photosynthetic performance and adaptation to heat stress enables the selection of rootstocks, which could contribute to stable yields and good fruit quality even at elevated temperatures. In this study, chlorophyll a fluorescence (ChlF) induction kinetics was used to investigate the heat tolerance between two apple rootstocks (M.9 and G.210). In addition, we employed lipid peroxidation measurements, hydrogen peroxide quantification, proline content, and total phenolic and flavonoid assessments. Analysis of chlorophyll fluorescence parameters and OJIP curves (different steps of the polyphasic fluorescence transient; O–J–I–P phases) revealed significant differences in their responses, with higher values of the PI_ABS parameter indicating better PS II stability and overall photosynthetic efficiency in M.9 rootstock. The higher contents of chlorophyll, carotenoids, proline, and significant increase in the accumulation of phenolics, and flavonoids in this rootstock also contributed to its better adaptation to heat stress. Oxidative stress was more pronounced in G.210 through higher H₂O₂ and MDA levels, which could point to its lower capacity to adjust to heat stress conditions. This research can provide a scientific basis for further breeding programs and growing plans due to climate change and the occurrence of extremely high temperatures. Full article

Atmospheric pollution results from toxic gases in low concentrations, originating from natural processes and human activities. These gases interact with each other in the presence of solar radiation, forming much more complex compounds that contribute to the formation of photochemical smog. This study presents a mathematical model to estimate the daily concentrations of primary and secondary pollutants, assuming that spatial variation is not considered within a control volume. The model includes nitrogen oxides, ozone, hydrocarbons, aldehydes, alcohols, and other gases, which are related through 52 chemical and photochemical reactions with rate constants that depend on factors such as the time of day and temperature. The model formulation results in 31 ordinary differential equations that are solved using a variable-step algorithm in MATLAB R2019a. Two scenarios are simulated: the “closed-box” model (CBM), where there are no inflows or outflows of gaseous flux, and the “open-box” model (OBM), which includes inflows and outflows within the control volume. The OBM is particularly useful for predicting concentrations during thermal inversion episodes. The results show that several pollutants reach their maximum concentrations at midday, suggesting an increase in the formation of secondary pollutants under high solar radiation, especially in the closed-box model. In the open-box model, concentration peaks shift toward the afternoon. To compare both models, the closed-box system conditions are considered, incorporating airflow into the open-box model without accounting for pollutants transported by this flow. The complex nonlinear dynamics observed in the pollutants highlight the combined influence of solar radiation, temperature, and emission rates on air quality. This study underscores the usefulness of mathematical models in developing effective mitigation strategies and assessing environmental and public health impacts. Full article

Mercury (Hg) poses significant risks to human health, the environment, and plant physiology, with its effects influenced by chemical form, concentration, exposure route, and organism vulnerability. This study evaluates the physiological impacts of Hg on Handroanthus impetiginosus (Ipê Roxo) seedlings through SPAD index measurements, chlorophyll fluorescence analysis, and Hg quantification in plant tissues. Four-month-old seedlings were exposed for eight days to distilled water containing Hg at 0, 1, 3, 5, and 7 mg L⁻¹. The SPAD index decreased by 28.17% at 3, 5, and 7 mg L⁻¹, indicating reduced photosynthetic capacity. Chlorophyll a fluorescence analysis revealed a 50.58% decline in maximum efficiency (Fv/Fm) and a 58.33% reduction in quantum yield (ΦPSII) at 7 mg L⁻¹, along with an 83.04% increase in non-photochemical quenching (qn), suggesting oxidative stress and PSII damage. Transpiration decreased by 26.7% at 1 mg L⁻¹ and by 55% at 3, 5, and 7 mg L⁻¹, correlating with Hg levels and leaf senescence. Absorption, translocation, bioconcentration, and bioaccumulation factors varied among treatments. Hg accumulated mainly in stems (40.23 μg g⁻¹), followed by roots (0.77 μg g⁻¹) and leaves (2.69 μg g⁻¹), with limited translocation to leaves. These findings highlight Hg’s harmful effects on H. impetiginosus, an ecologically and commercially valuable species, addressing a gap in research on its Hg tolerance and phytoremediation potential. Full article

Light quality is a fundamental factor in greenhouses, since different light wavelengths affect plant photosynthesis and photomorphogenesis differently, they thus affect crop growth and productivity. The aim of this study was to evaluate the effect of an experimental greenhouse cover film with UV-to-Red spectral shifting properties on photosynthesis, plant growth, fruit yield, and the quality of two crops spanning over a year-long cultural cycle: aubergines (Solanum melongena L.), as a spring–summer crop, followed by strawberries (Fragaria × ananassa Duch.), as an autumn–spring crop. Trials were carried out in a multispan greenhouse where two sectors were covered, each one with a different light diffusing polyethylene film: one sector was covered with a UV-to-Red photoluminescent film, doped with a blend of rare-earth elements partially converting the UV solar radiation into Red wavelengths, while a light diffusing polyethylene film was used as the control. At the physiological level, spectral shifting affected the chlorophyll fluorescence parameters related to the photochemistry of photosynthesis, which were found to be positively related to crop yield. Moreover, differential analysis of the fast Chlorophyll a fluorescence transients (or OJIP kinetics) showed that spectral shifting affected different steps of the plant photochemical metabolism. Full article

Photothermal reactions, involving both photochemical and thermal reaction steps, are the most abundant sequences in photochemistry. The derivation of their rate laws is standardized, but the integration of these rate laws has not yet been achieved. Indeed, the field still lacks integrated rate laws for the description of these reactions’ behavior and/or identification of their reaction order. This made difficult a comprehensive account of the photokinetics of photothermal reactions, which created a gap in knowledge. This gap is addressed in the present paper by introducing an unprecedented general model equation capable of mapping out the kinetic traces of such reactions when exposed to light or in the dark. The integrated rate law model equation also applies when the reactive medium is exposed to either monochromatic or polychromatic light irradiation. The validity of the model equation was established against simulated data obtained by a fourth-order Runge–Kutta method. It was then used to describe and quantify several situations of photothermal reactions, such as the effects of initial concentration, spectator molecules, and incident radiation intensity, and the impact of the latter on the photonic yield. The model equation facilitated a general elucidation method to determine the intrinsic reaction parameters (quantum yields and absorptivities of the reactive species) for any photothermal mechanism whose number of species is known. This paper contributes to rationalizing photokinetics along the same general guidelines adopted in chemical kinetics. Full article

Bulk 2D electronic–vibrational (2D-EV) and 2D vibrational–electronic spectroscopies (2D-VE) were previously developed to correlate the electronic and vibrational degrees of freedom simultaneously, which allow for the study of couplings between electronic and vibrational transitions in photo-chemical systems. Such bulk-dominated methods have been used to extensively study molecular systems, providing unique information such as coherence sensitivity, molecular configurations, enhanced resolution, and correlated states and their dynamics. However, the analogy of interfacial 2D spectroscopy has fallen behind. Our recent work presented interface-specific 2D-EV spectroscopy (i2D-EV). In this work, we develop interface-specific two-dimensional vibrational–electronic spectroscopy (i2D-VE). The fourth-order spectroscopy is based on a Mach–Zehnder IR interferometer that accurately controls the time delay of an IR pump pulse pair for vibrational transitions, followed by broadband interface second-harmonic generation to probe electronic transitions. We demonstrate step-by-step how a fourth-order i2D-VE spectrum of AP3 molecules at the air/water interface was collected and analyzed. The line shape and signatures of i2D-VE peaks reveal solvent correlations and the spectral nature of vibronic couplings. Together, i2D-VE and i2D-EV spectroscopy provide coupling of different behaviors of the vibrational ground state or excited states with electronic states of molecules at interfaces and surfaces. The methodology presented here could also probe dynamic couplings of electronic and vibrational motions at interfaces and surfaces, extending the usefulness of the rich data that are obtained. Full article

Benzylic C–H oxidation to form carbonyl compounds, such as ketones, is a fundamental transformation in organic synthesis as it allows for the preparation of versatile intermediates. In this review, we highlight the synthesis of aromatic ketones via catalytic, electrochemical, and photochemical oxidation of alkylarenes using different catalysts and oxidants in the past 5 years. Additionally, we also discuss the synthesis of heterocyclic molecules using benzylic C–H oxidation as a key step. These methods can potentially be used in medicinal, synthetic, and inorganic chemistry. Full article

Methane photolysis is a very important initiation reaction from the perspective of hydrogen production for alternative energy applications. In our recent work, we demonstrated using our recently developed novel method, non-adiabatic excited-state time-dependent $GW$ (TD$GW$) molecular dynamics (MD), how the decomposition reaction of methane into a methyl radical and a hydrogen atom was captured accurately via the time-tracing of all quasiparticle levels. However, this process requires a large amount of photoabsorption energy (PAE ∼$10.2$ eV). Moreover, only one hydrogen atom is produced via a single photon absorption. Transition metal atoms can be used as agents for photochemical reactions, to reduce this optical gap and facilitate an easier pathway for hydrogen production. Here, we explore the photolysis of methane in the presence of a Ni atom by employing TD$GW$-MD. We show two possibilities for hydrogen-atom ejection with respect to the location of the Ni atom, towards the Ni side or away from it. We demonstrate that only the H ejection away from the Ni side facilitates the formation of a hydrogen molecule with the quasiparticle level corresponding to it having an energy close to the negative ionization potential of an isolated H₂ molecule. This is achieved at a PAE of 8.4 eV which is lower compared to that of pristine methane. The results obtained in this work are an encouraging step towards transition metal-mediated hydrogen production via photolysis of hydrocarbons. Full article

The reactivity of nitrogen oxide, NO, as a ligand in complexes with [Fe2-S2] and [Co2-S2] non-planar rhombic cores is examined by density functional theory (DFT). The cobalt-containing nitrosyl complexes are less stable than the iron complexes because the Co-S bonds in the [Co2-S2] core are weakened upon NO coordination. Various positions of NO were examined, including its binding to sulfur centers. The release of NO molecules can be monitored photochemically. The ability of NO to form a (NO)₂ dimer provides a favorable route of electrochemical reduction, as protonation significantly stabilizes the dimeric species over the monomers. The quasilinear dimer ONNO, with trans-orientation of oxygen atoms, gains higher stability under protonation and reduction via proton–electron transfer. The first two reduction steps lead to an N₂O intermediate, whose reduction is more energy demanding: in the two latter reaction steps the highest energy barrier for Co₂S₂(CO)₆ is 109 kJ mol⁻¹, and for Fe₂S₂(CO)₆, it is 133 kJ mol⁻¹. Again, the presence of favorable light absorption bands allows for a photochemical route to overcome these energy barriers. All elementary steps are exothermic, and the final products are molecular nitrogen and water. Full article

Nanotechnology is revolutionizing fields of high social and economic impact. such as human health preservation, energy conversion and storage, environmental decontamination, and art restoration. However, the possible global-scale application of nanomaterials is raising increasing concerns, mostly related to the possible toxicity of materials at the nanoscale. The possibility of using nanomaterials in cosmetics, and hence in products aimed to be applied directly to the human body, even just externally, is strongly debated. Preoccupation arises especially from the consideration that nanomaterials are mostly of synthetic origin, and hence are often seen as “artificial” and their effects as unpredictable. Melanin, in this framework, is a unique material since in nature it plays important roles that specific cosmetics are aimed to cover, such as photoprotection and hair and skin coloration. Moreover, melanin is mostly present in nature in the form of nanoparticles, as is clearly observable in the ink of some animals, like cuttlefish. Moreover, artificial melanin nanoparticles share the same high biocompatibility of the natural ones and the same unique chemical and photochemical properties. Melanin is hence a natural nanocosmetic agent, but its actual application in cosmetics is still under development, also because of regulatory issues. Here, we critically discuss the most recent examples of the application of natural and biomimetic melanin to cosmetics and highlight the requirements and future steps that would improve melanin-based cosmetics in the view of future applications in the everyday market. Full article

Photosystem I (PSI) is one of the two main pigment–protein complexes where the primary steps of oxygenic photosynthesis take place. This review describes low-temperature frequency-domain experiments (absorption, emission, circular dichroism, resonant and non-resonant hole-burned spectra) and modeling efforts reported for PSI in recent years. In particular, we focus on the spectral hole-burning studies, which are not as common in photosynthesis research as the time-domain spectroscopies. Experimental and modeling data obtained for trimeric cyanobacterial Photosystem I (PSI₃), PSI₃ mutants, and PSI₃–IsiA₁₈ supercomplexes are analyzed to provide a more comprehensive understanding of their excitonic structure and excitation energy transfer (EET) processes. Detailed information on the excitonic structure of photosynthetic complexes is essential to determine the structure–function relationship. We will focus on the so-called “red antenna states” of cyanobacterial PSI, as these states play an important role in photochemical processes and EET pathways. The high-resolution data and modeling studies presented here provide additional information on the energetics of the lowest energy states and their chlorophyll (Chl) compositions, as well as the EET pathways and how they are altered by mutations. We present evidence that the low-energy traps observed in PSI are excitonically coupled states with significant charge-transfer (CT) character. The analysis presented for various optical spectra of PSI₃ and PSI₃-IsiA₁₈ supercomplexes allowed us to make inferences about EET from the IsiA₁₈ ring to the PSI₃ core and demonstrate that the number of entry points varies between sample preparations studied by different groups. In our most recent samples, there most likely are three entry points for EET from the IsiA₁₈ ring per the PSI core monomer, with two of these entry points likely being located next to each other. Therefore, there are nine entry points from the IsiA₁₈ ring to the PSI₃ trimer. We anticipate that the data discussed below will stimulate further research in this area, providing even more insight into the structure-based models of these important cyanobacterial photosystems. Full article

Photochemical reactions of salicylhydroxamic acid were induced using tunable UV laser radiation followed by FTIR spectroscopy. Four pairs of co-products were experimentally found to appear in the photolysis: C₆H₄(OH)NCO⋯H₂O (1), C₆H₄(OH)C(O)N⋯H₂O (2), C₆H₄(OH)₂⋯HNCO (3), and C₆H₄(OH)NHOH⋯CO (4). The comparison of the theoretical spectra with the experimental ones allowed us to determine the structures of the complexes formed in the matrices. The mechanisms of the reaction channels leading to the formation of the photoproducts were proposed. It was concluded that the first step in the formation of the complexes (1), (2), and (3) was the scission of the N-O bond, whereas the creation of complex (4) was due to cleavage of the C-N bond. Full article

Access to complex three-dimensional molecular architectures via dearomatization of ubiquitous aryl rings is a powerful synthetic tool, which faces, however, an inherent challenge to overcome energetic costs due to the loss of aromatic stabilization energy. Photochemical methods that allow one to populate high-energy states can thus be an ideal strategy to accomplish otherwise prohibitive reaction pathways. We present an original dearomative rearrangement of heteroaryl acryloylallenamides that leads to complex fused tricycles. The visible-light-promoted method occurs under mild conditions and tolerates a variety of functional groups. According to DFT modeling used to rationalize the outcome of the cascade, the reaction involves a sequential [2+2] allene–alkene photocycloaddition, which is followed by a selective retro- [2+2] step that paves the way for the dearomatization of the heteroaryl partner. This scenario is original with respect to the reported photochemical reactivity of similar substrates and thus holds promise for ample future developments. Full article

Graphitic carbon nitride (g-C₃N₄) is a metal-free photocatalyst used for visible-driven hydrogen production, CO₂ reduction, and organic pollutant degradation. In addition to the most attractive feature of visible photoactivity, its other benefits include thermal and photochemical stability, cost-effectiveness, and simple and easy-scale-up synthesis. However, its performance is still limited due to its low absorption at longer wavelengths in the visible range, and high charge recombination. In addition, the exfoliated nanosheets easily aggregate, causing the reduction in specific surface area, and thus its photoactivity. Herein, we propose the use of ultra-thin porous g-C₃N₄ nanosheets to overcome these limitations and improve its photocatalytic performance. Through the optimization of a novel multi-step synthetic protocol, based on an initial thermal treatment, the use of nitric acid (HNO₃), and an ultrasonication step, we were able to obtain very thin and well-tuned material that yielded exceptional photodegradation performance of methyl orange (MO) under visible light irradiation, without the need for any co-catalyst. About 96% of MO was degraded in as short as 30 min, achieving a normalized apparent reaction rate constant (k) of 1.1 × 10⁻² min⁻¹mg⁻¹. This represents the highest k value ever reported using C₃N₄-based photocatalysts for MO degradation, based on our thorough literature search. Ultrasonication in acid not only prevents agglomeration of g-C₃N₄ nanosheets but also tunes pore size distribution and plays a key role in this achievement. We also studied their performance in a photocatalytic hydrogen evolution reaction (HER), achieving a production of 1842 µmol h⁻¹ g⁻¹. Through a profound analysis of all the samples’ structure, morphology, and optical properties, we provide physical insight into the improved performance of our optimized porous g-C₃N₄ sample for both photocatalytic reactions. This research may serve as a guide for improving the photocatalytic activity of porous two-dimensional (2D) semiconductors under visible light irradiation. Full article

In this communication, we report a novel acceptor structural unit, TVDPP, that can be distinguished from classical materials based on TDPP structures. By designing a synthetic route via retrosynthetic analysis, we successfully prepared this monomer and further prepared polymer P2TVDPP with high yield using a Stille-coupling polymerization reaction. The polymer showed several expected properties, such as high molecular weight, thermal stability, full planarity, small π−π stacking distance, smooth interface, and so on. The absorption spectra and energy levels of the polymer were characterized via photochemical and electrochemical analysis. The organic field-effect transistor (OFET), which is based on P2TVDPP, exhibited excellent carrier mobility and an on/off current ratio of 0.41 cm² V⁻¹ s⁻¹ and ~10⁷, respectively, which is an important step in expanding the significance of DPP-based materials in the field of optoelectronic devices and organic electronics. Full article