Search Results (14)

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

Excited state intramolecular proton transfer (ESIPT) within molecules in solvents plays important roles in photo-chemistry and photo-biology. Herein, the influence of 1-ethyl-3-methyl-imidazolium bis (trifluoromethylsulfonyl) imide ([EMIm][NTf₂]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF₆]) on the ESIPT of 4′-N,N-diethylamino-3-hydroxyflavone (DEAHF) was explored. The density functional theory and time-dependent density functional theory methodologies were used. The calculated fluorescence spectrum reveals that the fluorescence peaks of DEAHF in [EMIm][NTf₂] and [BMIm][PF₆] originate from the emission of N* and T* forms. The structure’s optimization, infrared spectra, non-covalent interactions and the scanning of potential energy curves collectively demonstrate that the ESIPT of DEAHF likely happen more in [EMIm][NTf₂] than in [BMIm][PF₆]. The solvation effects in [BMIm][PF₆] exhibit greater prominence compared to those in [EMIm][NTf₂], as evidenced by the free energy curve. The alterations in dipole moment indicate a substantial solvation relaxation during the ESIPT processes. Our aforementioned research offers backing for the advancement of novel fluorescent probes. Full article

Salt stress could be a significant factor limiting the growth and development of vegetables. In this study, Fulvic Acid (FA) (0.05%, 0.1%, 0.15%, 0.2%, and 0.25%) was applied under nitrate stress (150 mM), with normal Hoagland nutrient solution as a control to investigate the influence of foliar spray FA on spinach growth, photosynthesis, and oxidative stress under nitrate stress. The results showed that nitrate stress significantly inhibited spinach growth, while ROS (reactive oxygen species) accumulation caused photosystem damage, which reduced photosynthetic capacity. Different concentrations of FA alleviated the damage caused by nitrate stress in spinach to varying degrees in a concentration-dependent manner. The F3 treatment (0.15% FA + 150 mM NO₃⁻) exhibited the most significant mitigating effect. FA application promoted the accumulation of biomass in spinach under nitrate stress and increased chlorophyll content, the net photosynthetic rate, the maximum photochemical quantum yield of PSII (Photosystem II) (Fv/Fm), the quantum efficiency of PSII photochemistry [Y(II)], the electron transport rate, and the overall functional activity index of the electron transport chain between the PSII and PSI systems (PItotal); moreover, FA decreased PSII excitation pressure (1 − qP), quantum yields of regulated energy dissipation of PSII [Y(NPQ)], and the relative variable initial slope of fluorescence. FA application increased superoxide dismutase, peroxidase, and catalase activities and decreased malondialdehyde, H₂O₂, and O₂⁻ levels in spinach under nitrate stress. FA can enhance plant resistance to nitrate by accelerating the utilization of light energy in spinach to mitigate excess light energy and ROS-induced photosystem damage and increase photosynthetic efficiency. Full article

The dependence of photochemistry on excitation wavelength is not a recently observed phenomenon; nonetheless, it has, surprisingly enough, been largely ignored in the field. The reasons for this situation are not fully understood but might be related to a provisional extension of Kasha’s rule to photochemistry, or perhaps to a difficulty to justify the kind of short time-scales implied in such photochemistry, that challenges the usually held view giving predominance to fast internal conversion and vibrational relaxation. Regardless of the reasons, it is still a matter of fact that a complete and satisfactory interpretation for experimentally proven wavelength-dependent photochemistry is not yet available and the community endeavor to build a holistic understanding and a comprehensive view of the phenomenon. The present review is a non-exhaustive overview of the published data in the field, reporting on some of the most prominent features, issues, and interpretations. Full article

Previous biological tests have shown that some resveratrol analogs exhibited significant antioxidative and cholinesterase inhibitory potential, as evidenced by lower IC₅₀ values compared to the established standards, resveratrol and galantamine, respectively. Photochemical transformations were made in parallel on these compounds in the presence of porphyrin photocatalysts in batch and microreactor, showing the significant advantage of flow photochemistry concerning productivity, selectivity, and yields. In this research, the products of photocatalysis and direct irradiation (photolysis) of resveratrol analogs were compared to elucidate how the types and ratios of the products depend on the excitation energy, to reveal the effects of the substituent on the photoinduced reactions and to rationalize experimentally and computationally the nature and ratio of the obtained products. Thus, two main paths were computed in agreement with the experimental results: isomerization with the participation of triplet state intermediates to yield the experimentally detected cis-isomers and subsequent cyclization following a pathway not available for the trans-isomers. The investigation of five model compounds confirmed the advantages of the flow photoreactor in the photochemical reactions of heterocyclic resveratrol analogs. Full article

Since drought stress is one of the key risks for the future of agriculture, exploring the molecular mechanisms of photosynthetic responses to water deficit stress is, therefore, fundamental. By using chlorophyll fluorescence imaging analysis, we evaluated the responses of photosystem II (PSII) photochemistry in young and mature leaves of Arabidopsis thaliana Col-0 (cv Columbia-0) at the onset of water deficit stress (OnWDS) and under mild water deficit stress (MiWDS) and moderate water deficit stress (MoWDS). Moreover, we tried to illuminate the underlying mechanisms in the differential response of PSII in young and mature leaves to water deficit stress in the model plant A. thaliana. Water deficit stress induced a hormetic dose response of PSII function in both leaf types. A U-shaped biphasic response curve of the effective quantum yield of PSII photochemistry (Φ_PSII) in A. thaliana young and mature leaves was observed, with an inhibition at MiWDS that was followed by an increase in Φ_PSII at MoWDS. Young leaves exhibited lower oxidative stress, evaluated by malondialdehyde (MDA), and higher levels of anthocyanin content compared to mature leaves under both MiWDS (+16%) and MoWDS (+20%). The higher Φ_PSII of young leaves resulted in a decreased quantum yield of non-regulated energy loss in PSII (Φ_NO), under both MiWDS (−13%) and MoWDS (−19%), compared to mature leaves. Since Φ_NO represents singlet-excited oxygen (¹O₂) generation, this decrease resulted in lower excess excitation energy at PSII, in young leaves under both MiWDS (−10%) and MoWDS (−23%), compared to mature leaves. The hormetic response of PSII function in both young and mature leaves is suggested to be triggered, under MiWDS, by the intensified reactive oxygen species (ROS) generation, which is considered to be beneficial for activating stress defense responses. This stress defense response that was induced at MiWDS triggered an acclimation response in A. thaliana young leaves and provided tolerance to PSII when water deficit stress became more severe (MoWDS). We concluded that the hormesis responses of PSII in A. thaliana under water deficit stress are regulated by the leaf developmental stage that modulates anthocyanin accumulation in a stress-dependent dose. Full article

Chromophoric dissolved organic matter (CDOM) is the main sunlight absorber in surface waters and a very important photosensitiser towards the generation of photochemically produced reactive intermediates (PPRIs), which take part in pollutant degradation. The absorption spectrum of CDOM (A_CDOM(λ), unitless) can be described by an exponential function that decays with increasing wavelength: A_CDOM(λ) = 100 d DOC A_o e^− Sλ, where d [m] is water depth, DOC [mg_C L⁻¹] is dissolved organic carbon, A_o [L mg_C⁻¹ cm⁻¹] is a pre-exponential factor, and S [nm⁻¹] is the spectral slope. Sunlight absorption by CDOM is higher when A_o and DOC are higher and S is lower, and vice versa. By the use of models, here we investigate the impact of changes in CDOM spectral parameters (A_o and S) on the steady-state concentrations of three PPRIs: the hydroxyl radical (^•OH), the carbonate radical (CO₃^•−), and CDOM excited triplet states (³CDOM*). A first finding is that variations in both A_o and S have impacts comparable to DOC variations on the photochemistry of CDOM, when reasonable parameter values are considered. Therefore, natural variability of the spectral parameters or their modifications cannot be neglected. In the natural environment, spectral parameters could, for instance, change because of photobleaching (prolonged exposure of CDOM to sunlight, which decreases A_o and increases S) or of the complex and still poorly predictable effects of climate change. A second finding is that, while the steady-state [³CDOM*] would increase with increasing A_CDOM (increasing A_o, decreasing S), the effect of spectral parameters on [^•OH] and [CO₃^•−] depends on the relative roles of CDOM vs. NO₃⁻ and NO₂⁻ as photochemical ^•OH sources. Full article

Potato, Solanum tuberosum L., one of the most commonly cultivated horticultural crops throughout the world, is susceptible to a variety of herbivory insects. In the present study, we evaluated the consequence of feeding by the sap-sucking insect Halyomorpha halys on potato leaf photosynthetic efficiency. By using chlorophyll fluorescence imaging methodology, we examined photosystem II (PSII) photochemistry in terms of feeding and at the whole leaf area. The role of reactive oxygen species (ROS) in potato’s defence response mechanism immediately after feeding was also assessed. Even 3 min after feeding, increased ROS generation was observed to diffuse through the leaf central vein, probably to act as a long-distance signalling molecule. The proportion of absorbed energy being used in photochemistry (Φ_PSII) at the whole leaf level, after 20 min of feeding, was reduced by 8% compared to before feeding due to the decreased number of open PSII reaction centres (qp). After 90 min of feeding, Φ_PSII decreased by 46% at the whole leaf level. Meanwhile, at the feeding zones, which were located mainly in the proximity of the leaf midrib, Φ_PSII was lower than 85%, with a concurrent increase in singlet-excited oxygen (¹O₂) generation, which is considered to be harmful. However, the photoprotective mechanism (Φ_NPQ), which was highly induced 90 min after feeding, was efficient to compensate for the decrease in the quantum yield of PSII photochemistry (Φ_PSII). Therefore, the quantum yield of non-regulated energy loss in PSII (Φ_NO), which represents ¹O₂ generation, remained unaffected at the whole leaf level. We suggest that the potato PSII response to sap-sucking insect feeding underlies the ROS-dependent signalling that occurs immediately and initiates a photoprotective PSII defence response to reduce herbivory damage. A controlled ROS burst can be considered the primary plant defence response mechanism to herbivores. Full article

A fundamental goal of photochemistry is to understand how structural features of a chromophore can make specific bonds within a molecule prone to cleavage by light, or photolabile. The meta effect is an example of a regiochemical explanation for photolability, in which electron donating groups on an aromatic ring cause photolability selectively at the meta position. Here, we show, using a chromophore containing one ring with a meta-methoxy group and one ring with a para-methoxy group, that two stereoisomers of the same compounds can react with light differently, based simply on the three-dimensional positioning of a meta anisyl ring. The result is that the stereoisomers of the compound with the same configuration at both stereogenic centers are photolabile while the stereoisomers with opposite configuration do not react with light. Furthermore, time-dependent density functional theory (TD-DFT) calculations show distinct excitation pathways for each stereoisomer. Full article

Excited state intramolecular proton transfer (ESIPT) in 3-hydroxyflavone (3HF) has been known for its dependence on excitation wavelength. Such a behavior violates Kasha’s rule, which states that the emission and photochemistry of a compound would only take place from its lowest excited state. The photochemistry of 3HF was studied using femtosecond transient absorption spectroscopy at a shorter wavelength excitation (266 nm), and these new experimental findings were interpreted with the aid of computational studies. These new results were compared with those from previous studies that were obtained with a longer wavelength excitation and show that there exists a pathway of proton transfer that bypasses the normal first excited state from the higher excited state to the tautomer from first excited state. The experimental data correlate with the electron density difference calculations such that the proton transfer process is faster on the longer excitation wavelength than compared to the shorter excitation wavelength. Full article

We investigated flavonoid accumulation and lipid peroxidation in young leaves (YL) and mature leaves (ML) of Arabidopsis thaliana plants, whose watering stopped 24 h before sampling, characterized as onset of drought stress (OnDS), six days before sampling, characterized as mild drought stress (MiDS), and ten days before sampling, characterized as moderate drought stress (MoDS). The response to drought stress (DS) of photosystem II (PSII) photochemistry, in both leaf types, was evaluated by estimating the allocation of absorbed light to photochemistry (Φ_PSII), to heat dissipation by regulated non-photochemical energy loss (Φ_NPQ) and to non-regulated energy dissipated in PSII (Φ_NO). Young leaves were better protected at MoDS than ML leaves, by having higher concentration of flavonoids that promote acclimation of YL PSII photochemistry to MoDS, showing lower lipid peroxidation and excitation pressure (1 − q_p). Young leaves at MoDS possessed lower 1 − q_p values and lower excess excitation energy (EXC), not only compared to MoDS ML, but even to MiDS YL. They also possessed a higher capacity to maintain low Φ_NO, suggesting a lower singlet oxygen (¹O₂) generation. Our results highlight that leaves of different developmental stage may display different responses to DS, due to differential accumulation of metabolites, and imply that PSII photochemistry in Arabidopsis thaliana may not show a dose dependent DS response. Full article

The conformational stability, infrared spectrum, and photochemistry of phenyl 1-hydroxy-2-naphthoate (PHN) were studied by matrix isolation infrared spectroscopy and theoretical computations performed at the DFT(B3LYP)/6-311++G(d,p) level of theory. The main intramolecular interactions determining the relative stability of seven conformers of the molecule were evaluated. According to the calculations, the twofold degenerated O–H···O=C intramolecularly hydrogen-bonded conformer with the phenyl ring ester group ±68.8° out of the plane of the substituted naphtyl moiety is the most stable conformer of the molecule. This conformer is considerably more stable than the second most stable form (by ~15 kJ mol⁻¹), in which a weaker O–H···O–C intramolecular hydrogen bond exists. The compound was isolated in cryogenic argon and N₂ matrices, and the conformational composition in the matrices was investigated by infrared spectroscopy. In agreement with the predicted relative energies of the conformers, the analysis of the spectra indicated that only the most stable conformer of PHN was present in the as-deposited matrices. The matrices were then irradiated at various wavelengths by narrowband tunable UV light within the 331.7–235.0 nm wavelength range. This resulted in the photodecarbonylation of PHN, yielding 2-phenoxynaphthalen-1-ol, together with CO. The extension of the decarbonylation was found to depend on the excitation wavelength. Full article

Conversion of sunlight into photochemistry depends on photoprotective processes that allow safe use of sunlight over a broad range of environmental conditions. This review focuses on the ubiquity of photoprotection associated with a group of interconvertible leaf carotenoids, the xanthophyll cycle. We survey the striking plasticity of this process observed in nature with respect to (1) xanthophyll cycle pool size, (2) degree and speed of interconversion of its components, and (3) flexibility in the association between xanthophyll cycle conversion state and photoprotective dissipation of excess excitation energy. It is concluded that the components of this system can be independently tuned with a high degree of flexibility to produce a fit for different environments with various combinations of light, temperature, and other factors. In addition, the role of genetic variation is apparent from variation in the response of different species growing side-by-side in the same environment. These findings illustrate how field studies can generate insight into the adjustable levers that allow xanthophyll cycle-associated photoprotection to support plant photosynthetic productivity and survival in environments with unique combinations of environmental factors. Full article

An excited dimer is an important complex formed in nano- or pico-second time scales in many photophysics and photochemistry applications. The spectral and temporal profile of the excimer state of a laser from a new conjugated polymer, namely, poly (9,9-dioctylfluorenyl-2,7-diyl) (PFO), under several concentrations in benzene were investigated. These solutions were optically pumped by intense pulsed third-harmonic Nd:YAG laser (355-nm) to obtain the amplified spontaneous emission (ASE) spectra of a monomer and an excimer with bandwidths of 6 and 7 nm, respectively. The monomer and excimer ASEs were dependent on the PFO concentration, pump power, and temperature. Employing a sophisticated picosecond spectrometer, the time evolution of the excimer state of this polymer, which is over 400 ps, can be monitored. Full article