Photoswitchable Azo- and Diazocine-Functionalized Derivatives of the VEGFR-2 Inhibitor Axitinib.

In this study, we aimed at the application of the concept of photopharmacology to the approved vascular endothelial growth factor receptor (VEGFR)-2 kinase inhibitor axitinib. In a previous study, we found out that the photoisomerization of axitinib's stilbene-like double bond is unidirectional in aqueous solution due to a competing irreversible [2+2]-cycloaddition. Therefore, we next set out to azologize axitinib by means of incorporating azobenzenes as well as diazocine moieties as photoresponsive elements. Conceptually, diazocines (bridged azobenzenes) show favorable photoswitching properties compared to standard azobenzenes because the thermodynamically stable Z-isomer usually is bioinactive, and back isomerization from the bioactive E-isomer occurs thermally. Here, we report on the development of different sulfur-diazocines and carbon-diazocines attached to the axitinib pharmacophore that allow switching the VEGFR-2 activity reversibly. For the best sulfur-diazocine, we could verify in a VEGFR-2 kinase assay that the Z-isomer is biologically inactive (IC50 >> 10,000 nM), while significant VEGFR-2 inhibition can be observed after irradiation with blue light (405 nm), resulting in an IC50 value of 214 nM. In summary, we could successfully develop reversibly photoswitchable kinase inhibitors that exhibit more than 40-fold differences in biological activities upon irradiation. Moreover, we demonstrate the potential advantage of diazocine photoswitches over standard azobenzenes.

Effects of salt concentration, pH, and their interaction on plant growth, nutrient uptake, and photochemistry of alfalfa (Medicago sativa) leaves.

In order to explore the main limiting factors affecting the growth and physiological function of alfalfa under salt and alkali stress, the effect of the salt and alkali stress on the growth and physiological function of alfalfa was studied. The results showed that effects of the excessive salt concentration (100 and 200 mM) on the growth and physiological characteristics were significantly greater than that of pH (7.0 and 9.0). Under 100 mM salt stress, there was no significant difference in the growth and photosynthetic function between pH 9.0 and pH 7.0. Under the 200 mM salt concentration the absorption of Na+ by alfalfa treated at the pH 9.0 did not increase significantly compared with absorption at the pH 7.0. However, the higher pH directly reduced the root activity, leaf's water content, and N-P-K content also decreased significantly. The PSII and PSI activities decreased with increasing the salt concentration, especially the damage degree of PSI. Although the photoinhibition of PSII was not significant, PSII donor and electron transfer from the QA to QB of the PSII receptor sides was inhibited. In a word, alfalfa showed relatively strong salt tolerance capacity, at the 100 mM salt concentration, even when the pH reached 9.0. Thus, the effect on the growth and photosynthetic function was not significant. However, at 200 mM salt concentration, pH 9.0 treatment caused damage to root system and the photosynthetic function in leaves of alfalfa was seriously injured.

Cr2S3-Co3O4 on polyethylene glycol-chitosan nanocomposites with enhanced ultraviolet light photocatalysis activity, antibacterial and antioxidant studies.

A novel chromium sulfide-cobalt oxide nanostructures and decorated on Polyethylene Glycol (PEG)-chitosan (CS) nanocomposites as catalyst was synthesized by a facile method, and characterized by XRD, SEM, UV-Vis and XPS spectrum. The as-prepared Cr2S3-Co3O4/PEGCS composites represented the photo-decompose efficiency against the decomposition of basic dye (Rhodamine B (RhB)). The band gap of nano-catalyst was determined to be in the range of 2.61 to 3.32 eV. The introduction of Cr2S3 into Co3O4 increased the photocatalytic performance slightly, and decoration of Cr2S3-Co3O4 on PEGCS, which indicated the highest photo-degradation performance. Under the light irradiation, the active species OH and O2- radicals were important active agents in the photocatalysis process. The Cr2S3-Co3O4/PEGCS nanocomposites can maintain a stable photocatalysis performance after five cycles. Finally, the reaction mechanism of photo-degradation of RhB was put forward. The antibacterial test demonstrated the remarkable properties of Cr2S3-Co3O4/PEGCS nanocomposites in this research.

Photo-degradation dynamics of five neonicotinoids: Bamboo vinegar as a synergistic agent for improved functional duration.

The effects of photo-degradation on the utilization of pesticides in agricultural production has been investigated. Various influencing factors were compared, with results showing that the initial pesticide concentration, light source, water quality and pH possessed different effects on neonicotinoids photo-degradation. The initial concentration and pH were found to be most critical effects. The photo-degradation rate decreased by a factor of 2-4 when the initial concentration increased from 5 mg L-1 to 20 mg L-1, particularly for acetamiprid and imidacloprid. The photo-degradation pathways and products of the five neonicotinoids were also investigated, with similar pathways found for each pesticide, except for acetamiprid. Degradation pathways mainly involved photo-oxidation processes, with products identified using liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) found to be consistent with literature reported results. Bamboo vinegar exerted a photo-quenching effect on the neonicotinoids, with an improved efficiency at higher vinegar concentrations. The photo-quenching rates of thiamethoxam and dinotefuran were 381.58% and 310.62%, respectively, when a 30-fold dilution of vinegar was employed. The photo-degradation products in bamboo vinegar were identical to those observed in methanol, with acetic acid being the main factor influencing the observed quenching effects.

Optical control of neuronal ion channels and receptors.

Light-controllable tools provide powerful means to manipulate and interrogate brain function with relatively low invasiveness and high spatiotemporal precision. Although optogenetic approaches permit neuronal excitation or inhibition at the network level, other technologies, such as optopharmacology (also known as photopharmacology) have emerged that provide molecular-level control by endowing light sensitivity to endogenous biomolecules. In this Review, we discuss the challenges and opportunities of photocontrolling native neuronal signalling pathways, focusing on ion channels and neurotransmitter receptors. We describe existing strategies for rendering receptors and channels light sensitive and provide an overview of the neuroscientific insights gained from such approaches. At the crossroads of chemistry, protein engineering and neuroscience, optopharmacology offers great potential for understanding the molecular basis of brain function and behaviour, with promises for future therapeutics.

Simultaneous photoreduction and Raman spectroscopy of red blood cells to investigate the effects of organophosphate exposure.

Simultaneous photoreduction and Raman spectroscopy with 532 nm laser has been used to study the effects of organophosphate (chlorpyrifos [CPF]) exposure on human red blood cells (RBCs). Since in RBCs, auto-oxidation causes oxidative stress, which, in turn, is balanced by the cellular detoxicants, any possible negative effect of CPF on this balance should results in an increased level of damaged (permanently oxygenated) hemoglobin. Therefore, when 532 nm laser, at a suitable power, was applied to photoreduce the cells, only common oxygenated form of hemoglobin got photoreduced leaving the permanently oxygenated hemoglobin detectable in the Raman spectra simultaneously excited by the same laser. Using the technique effects of CPF to build up oxidative stress on RBCs could be detected at concentrations as low as 10 ppb from a comparison of relative strengths of different Raman bands. Experiments performed using simultaneously exposing the cells, along with CPF, to H2 O2 (oxidative agent) and/or 3-Aminotriazole (inhibitor of anti-oxidant catalase), suggested role of CPF to suppress the cellular anti-oxidant mechanism. Since the high level of damaged hemoglobin produced by the action of CPF (at concentrations >100 ppm) is expected to cause membrane damage, atomic force microscopy (AFM) was used to identify such damages.Upper panel: Raman spectra of normal, photoreduced CPF exposed and unexposed RBCs. Lower panel: The weak Fe-O2 Raman band for CPF exposed cells shown on the left. The AFM images of unexposed and exposed cells are shown on the right. Scale bar, 2.5 µm.

Photochemical and Structural Studies on Cyclic Peptide Models.

Ultra-violet (UV) irradiation has a significant impact on the structure and function of proteins that is supposed to be in relationship with the tryptophan-mediated photolysis of disulfide bonds. To investigate the correlation between the photoexcitation of Trp residues in polypeptides and the associated reduction of disulfide bridges, a series of small, cyclic oligopeptide models were analyzed in this work. Average distances between the aromatic side chains and the disulfide bridge were determined following molecular mechanics (MM) geometry optimizations. In this way, the possibility of cation⁻π interactions was also investigated. Molecular mechanics calculations revealed that the shortest distance between the side chain of the Trp residues and the disulfide bridge is approximately 5 Å in the cyclic pentapeptide models. Based on this, three tryptophan-containing cyclopeptide models were synthesized and analyzed by nuclear magnetic resonance (NMR) spectroscopy. Experimental data and detailed molecular dynamics (MD) simulations were in good agreement with MM geometry calculations. Selected model peptides were subjected to photolytic degradation to study the correlation of structural features and the photolytic cleavage of disulfide bonds in solution. Formation of free sulfhydryl groups upon illumination with near UV light was monitored by fluorescence spectroscopy after chemical derivatization with 7-diethylamino-3-(4-maleimidophenyl)-4-methylcoumarin (CPM) and mass spectrometry. Liquid cromatography-mass spectrometry (LC-MS) measurements indicated the presence of multiple photooxidation products (e.g., dimers, multimers and other oxidated products), suggesting that besides the photolysis of disulfide bonds secondary photolytic processes take place.

Cu nanoparticles synthesis using biological molecule of P. granatum seeds extract as reducing and capping agent: Growth mechanism and photo-catalytic activity.

In view of extended applications of nanoparticles, the nanoparticles synthesis is an extensive research field and green synthesis is one of the co-friendly methodologies. Plant extract mediated synthesis of nanoparticles has gained much attention in current decade. In current investigation, copper nanoparticles (CuNPs) were prepared using P. granatum seeds extract (biological molecules) from copper(II) chloride salt. The synthesized CuNPs were characterized by UV-vis spectroscopy, X-ray diffraction measurements (XRD), scanning electron microscopy (SEM), Energy Dispersive X- Ray Spectroscopy (EDX), Fourier transform infra-red spectroscopy (FTIR) and atomic force microscopy techniques. The CuNPs formation occurred through reduction of metal ions followed by nucleation. The size of the CuNPs was in the range of 40-80nm (average particle size was 43.9nm) with semi spherical shape and uniformly distribution. Photocatalytic activity was evaluated by degrading methylene blue dye (150mg/L) at various CuNPs doses (10mg/L-100mg/L). The synthesized CuNPs showed excellent PCA for the degradation of methylene blue (MB) under solar light irradiation and up to 87.11% degradation was achieved. The oxidative degradation mechanism for MB was proposed. In view of efficient PCA, the use of biological molecules of P. granatum seeds extracts for the synthesis of CuNPs.

[Optically dissecting brain nicotinic receptor function with photo-controllable designer receptors]. / Dissection optique du rôle des récepteurs nicotiniques neuronaux à l'aide de récepteurs photo-contrôlables.

Nicotinic acetylcholine receptors (nAChRs) are pentameric ligand-gated ion channels widely expressed in the central nervous system and the periphery. They play an important modulatory role in learning, memory and attention, and have been implicated in various diseases such as Alzheimer's disease, Parkinson's disease, epilepsy, schizophrenia and addiction. These receptors are activated by the endogenous neurotransmitter acetylcholine, or by nicotine, the alkaloid found in tobacco leaves. Both molecules open the ion channel and cause the movement of cations across the membrane, which directly affects neuronal excitability and synaptic plasticity. nAChRs are very heterogeneous in their subunit composition (α2-10 et ß2-4), in their brain distribution (cortex, midbrain, striatum…) and in their sub-cellular localization (pre- vs post-synaptic, axonal, dendritic…). This heterogeneity highly contributes to the very diverse roles these receptors have in health and disease. The ability to activate or block a specific nAChR subtype, at a defined time and space within the brain, would greatly help obtaining a clearer picture of these various functions. To this aim, we are developing novel optogenetic pharmacology strategies for optically controlling endogenous nAChR isoforms within the mouse brain. The idea is to tether a chemical photoswitch on the surface of a cysteine-modified nAChR, and use light for rapidly and reversibly turning that receptor mutant on and off. Here we will discuss the history of optogenetic pharmacology, and the recent advances for the optical control of brain nicotinic receptors in vivo.

Effects of acetylacetone on the photoconversion of pharmaceuticals in natural and pure waters.

Acetylacetone (AcAc) has proven to be a potent photo-activator in the degradation of color compounds. The effects of AcAc on the photochemical conversion of five colorless pharmaceuticals were for the first time investigated in both pure and natural waters with the UV/H2O2 process as a reference. In most cases, AcAc played a similar role to H2O2. For example, AcAc accelerated the photodecomposition of carbamazepine, oxytetracycline, and tetracycline in pure water. Meanwhile, the toxicity of tetracyclines and carbamazepine were reduced to a similar extent to that in the UV/H2O2 process. However, AcAc worked in a way different from that of H2O2. Based on the degradation kinetics, solvent kinetic isotope effect, and the inhibiting effect of O2, the underlying mechanisms for the degradation of pharmaceuticals in the UV/AcAc process were believed mainly to be direct energy transfer from excited AcAc to pharmaceuticals rather than reactive oxygen species-mediated reactions. In natural waters, dissolved organic matter (DOM) played a crucial role in the photoconversion of pharmaceuticals. The role of H2O2 became negligible due to the scavenging effects of DOM and inorganic ions. Interestingly, in natural waters, AcAc first accelerated the photodecomposition of pharmaceuticals and then led to a dramatic reduction with the depletion of dissolved oxygen. Considering the natural occurrence of diketones, the results here point out a possible pathway in the fate and transport of pharmaceuticals in aquatic ecosystems.

Diversity of strategies for escaping reactive oxygen species production within photosystem I among land plants: P700 oxidation system is prerequisite for alleviating photoinhibition in photosystem I.

In land plants, photosystem I (PSI) photoinhibition limits carbon fixation and causes growth defects. In addition, recovery from PSI photoinhibition takes much longer than PSII photoinhibition when the PSI core-complex is degraded by oxidative damage. Accordingly, PSI photoinhibition should be avoided in land plants, and land plants should have evolved mechanisms to prevent PSI photoinhibition. However, such protection mechanisms have not yet been identified, and it remains unclear whether all land plants suffer from PSI photoinhibition in the same way. In the present study, we focused on the susceptibility of PSI to photoinhibition and investigated whether mechanisms of preventing PSI photoinhibition varied among land plant species. To assess the susceptibility of PSI to photoinhibition, we used repetitive short-pulse (rSP) illumination, which specifically induces PSI photoinhibition. Subsequently, we found that land plants possess a wide variety of tolerance mechanisms against PSI photoinhibition. In particular, gymnosperms, ferns and mosses/liverworts exhibited higher tolerance to rSP illumination-induced PSI photoinhibition than angiosperms, and detailed analyses indicated that the tolerance of these groups could be partly attributed to flavodiiron proteins, which protected PSI from photoinhibition by oxidizing the PSI reaction center chlorophyll (P700) as an electron acceptor. Furthermore, we demonstrate, for the first time, that gymnosperms, ferns and mosses/liverworts possess a protection mechanism against photoinhibition of PSI that differs from that of angiosperms.

Optical control of GIRK channels using visible light.

G-protein coupled inwardly rectifying potassium (GIRK) channels are an integral part of inhibitory signal transduction pathways, reducing the activity of excitable cells via hyperpolarization. They play crucial roles in processes such as cardiac output, cognition and the coordination of movement. Therefore, the precision control of GIRK channels is of critical importance. Here, we describe the development of the azobenzene containing molecule VLOGO (Visible Light Operated GIRK channel Opener), which activates GIRK channels in the dark and is promptly deactivated when illuminated with green light. VLOGO is a valuable addition to the existing tools for the optical control of GIRK channels as it circumvents the need to use potentially harmful UV irradiation. We therefore believe that VLOGO will be a useful research tool for studying GIRK channels in biological systems.

Facile synthesis of BiOI in hierarchical nanostructure preparation and its photocatalytic application to organic dye removal and biocidal effect of bacteria.

Novel BiOI hierarchical nanostructures with porous architecture was prepared at room temperature by an economical, facile and rapid route. The coupling adsorption and degradation efficiency of rhodamine B (RhB), methylene blue (MB), and methyl orange (MO) could achieve 98.7%, 43.2%, 76.9% within 180min in the presence of BiOI, respectively. BiOI hierarchical nanostructures also exhibit excellent effective biocidal performances, and the disinfection rate of the typical biofouling bacteria Bacillus sp. and Pseudoalteromonas sp. could reach 99.9% and 99.8% in 60min, respectively. The circulate photocatalytic degradation of RhB experiment verified the good stability and reusability of BiOI hierarchical nanostructures. Based on active specie trapping experiments, the superoxide radicals (O2(-)) and holes (h(+)) were proved to be the main reactive species in the BiOI-based system. The obviously enhanced coupling adsorption and photocatalytic degradation performance of BiOI hierarchical nanostructures could be mainly attributed to the large surface area (64.5m(2)/g), negatively charged surface and the intrinsic electron structure. This study provides a new strategy to develop novel photocatalysts for water treatment and marine antifouling.

Photocatalytic and antibacterial activity of cadmium sulphide/zinc oxide nanocomposite with varied morphology.

Nanocomposites with multifunctional application prospects have already dragged accelerating interests of materials scientists. Here we present CdS/ZnO nanocomposites with different morphology engineering the precursor molar ratio in a facile wet chemical synthesis route. The materials were structurally and morphologically characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX) and high-resolution transmission electron microscopy (HRTEM). The growth mechanism of the composite structure with varying molar ratio is delineated with oriented attachment self assemble techniques. Photocatalytic activity of CdS/ZnO nanocomposites with varying morphology were explored for the degradation of rhodamine B (RhB) dye in presence of visible light irradiation and the results reveal that the best catalytic performance arises in CdS/ZnO composite with 1: 1 ratio. The antibacterial efficiency of all nanocomposites were investigated on Escherichia coli, Staphylococcus aureus and Klebsiella pneumonia without light irradiation. Antibacterial activity of CdS/ZnO nanocomposites were studied using the bacteriological test-well diffusion agar method and results showed significant antibacterial activity in CdS/ZnO composite with 1:3 ratio. Overall, CdS/ZnO nanocomposites excel in different potential applications, such as visible light photocatalysis and antimicrobial activity with their tuneable structure.

Emerging Targets in Photopharmacology.

The field of photopharmacology uses molecular photoswitches to establish control over the action of bioactive molecules. It aims to reduce systemic drug toxicity and the emergence of resistance, while achieving unprecedented precision in treatment. By using small molecules, photopharmacology provides a viable alternative to optogenetics. We present here a critical overview of the different pharmacological targets in various organs and a survey of organ systems in the human body that can be addressed in a non-invasive manner. We discuss the prospects for the selective delivery of light to these organs and the specific requirements for light-activatable drugs. We also aim to illustrate the druggability of medicinal targets with recent findings and emphasize where conceptually new approaches have to be explored to provide photopharmacology with future opportunities to bring "smart" molecular design ultimately to the realm of clinical use.

Production of biomass and lipids by the oleaginous microalgae Monoraphidium sp. QLY-1 through heterotrophic cultivation and photo-chemical modulator induction.

A two-step strategy comprising heterotrophic cultivation and photo-chemical modulator induction was developed to enhance biomass and lipid accumulation in the oleaginous Monoraphidium sp. QLY-1, which was isolated from Qilu Lake in Yunnan Plateau. The algae were first cultivated heterotrophically to achieve high biomass concentration (5.54gL(-1)) with a lipid content of 22.47%. The cultivated algae were diluted, transferred to light environment, and treated with different chemical elicitors. Results showed that the lipid content increased to 36.68% after 3-day of photoinduction. The lipid content was further enhanced by 1.21, 1.32, and 1.29 folds in algal cells treated with nitrogen deficiency, 20gL(-1) NaCl, and 5mM glycine betaine, respectively. The maximum lipid content (48.54%) and lipid productivity (121.27mgL(-1)d(-1)) were obtained in treatments with 20gL(-1) NaCl and 5mM GB, respectively. This study proposes a strategy to efficiently produce lipids by using microalgae.

Self-decontaminating photocatalytic zinc oxide nanorod coatings for prevention of marine microfouling: a mesocosm study.

The antifouling (AF) properties of zinc oxide (ZnO) nanorod coated glass substrata were investigated in an out-door mesocosm experiment under natural sunlight (14:10 light: dark photoperiod) over a period of five days. The total bacterial density (a six-fold reduction) and viability (a three-fold reduction) was significantly reduced by nanocoatings in the presence of sunlight. In the absence of sunlight, coated and control substrata were colonized equally by bacteria. MiSeq Illumina sequencing of 16S rRNA genes revealed distinct bacterial communities on the nanocoated and control substrata in the presence and absence of light. Diatom communities also varied on nanocoated substrata in the presence and the absence of light. The observed AF activity of the ZnO nanocoatings is attributed to the formation of reactive oxygen species (ROS) through photocatalysis in the presence of sunlight. These nanocoatings are a significant step towards the production of an environmentally friendly AF coating that utilizes a sustainable supply of sunlight.

Mitochondrial Alternative Pathway-Associated Photoprotection of Photosystem II is Related to the Photorespiratory Pathway.

Respiratory electron transport has two ubiquinol-oxidizing pathways, the cytochrome pathway (CP) and the alternative pathway (AP). The AP, which is catalyzed by the alternative oxidase (AOX), is energetically wasteful but may alleviate PSII photoinhibition under light conditions excessive for photosynthesis. However, its mechanism remains unknown. We used Arabidopsis aox1a mutants lacking AOX activity and studied the mutation's effects on photoinhibition by measuring the decrease in the maximum quantum yield of PSII (Fv/Fm) after high light exposure. Since the CP compensates for the lack of AOX, we monitored the extent of photoinhibition under conditions where CP activity is partially inhibited by antimycin A. When leaves were exposed to high light at 350 µmol m-2 s-1, the decline in Fv/Fm was significantly faster in the aox1a mutants than in the wild type. However, under conditions where photorespiration was suppressed by high CO2 or low O2 levels, the decline in Fv/Fm was suppressed in the aox1a mutants, but not in the wild type, making the difference between the wild type and mutants small. Our results demonstrate that the lack of the AP causes an acceleration of PSII photoinhibition in relation to the photorespiratory pathway, suggesting that the AP can support the activity of the photorespiratory pathway under high light conditions.

The Type II NADPH Dehydrogenase Facilitates Cyclic Electron Flow, Energy-Dependent Quenching, and Chlororespiratory Metabolism during Acclimation of Chlamydomonas reinhardtii to Nitrogen Deprivation.

When photosynthetic organisms are deprived of nitrogen (N), the capacity to grow and assimilate carbon becomes limited, causing a decrease in the productive use of absorbed light energy and likely a rise in the cellular reduction state. Although there is a scarcity of N in many terrestrial and aquatic environments, a mechanistic understanding of how photosynthesis adjusts to low-N conditions and the enzymes/activities integral to these adjustments have not been described. In this work, we use biochemical and biophysical analyses of photoautotrophically grown wild-type and mutant strains of Chlamydomonas reinhardtii to determine the integration of electron transport pathways critical for maintaining active photosynthetic complexes even after exposure of cells to N deprivation for 3 d. Key to acclimation is the type II NADPH dehydrogenase, NDA2, which drives cyclic electron flow (CEF), chlororespiration, and the generation of an H(+) gradient across the thylakoid membranes. N deprivation elicited a doubling of the rate of NDA2-dependent CEF, with little contribution from PGR5/PGRL1-dependent CEF The H(+) gradient generated by CEF is essential to sustain nonphotochemical quenching, while an increase in the level of reduced plastoquinone would promote a state transition; both are necessary to down-regulate photosystem II activity. Moreover, stimulation of NDA2-dependent chlororespiration affords additional relief from the elevated reduction state associated with N deprivation through plastid terminal oxidase-dependent water synthesis. Overall, rerouting electrons through the NDA2 catalytic hub in response to photoautotrophic N deprivation sustains cell viability while promoting the dissipation of excess excitation energy through quenching and chlororespiratory processes.

Energy dissipation pathways in Photosystem 2 of the diatom, Phaeodactylum tricornutum, under high-light conditions.

To prevent photooxidative damage under supraoptimal light, photosynthetic organisms evolved mechanisms to thermally dissipate excess absorbed energy, known as non-photochemical quenching (NPQ). Here we quantify NPQ-induced alterations in light-harvesting processes and photochemical reactions in Photosystem 2 (PS2) in the pennate diatom Phaeodactylum tricornutum. Using a combination of picosecond lifetime analysis and variable fluorescence technique, we examined the dynamics of NPQ activation upon transition from dark to high light. Our analysis revealed that NPQ activation starts with a 2-3-fold increase in the rate constant of non-radiative charge recombination in the reaction center (RC); however, this increase is compensated with a proportional increase in the rate constant of back reactions. The resulting alterations in photochemical processes in PS2 RC do not contribute directly to quenching of antenna excitons by the RC, but favor non-radiative dissipation pathways within the RC, reducing the yields of spin conversion of the RC chlorophyll to the triplet state. The NPQ-induced changes in the RC are followed by a gradual ~ 2.5-fold increase in the yields of thermal dissipation in light-harvesting complexes. Our data suggest that thermal dissipation in light-harvesting complexes is the major sink for NPQ; RCs are not directly involved in the NPQ process, but could contribute to photoprotection via reduction in the probability of (3)Chl formation.