Octanol-water partition coefficients of highly hydrophobic photodynamic therapy drugs: a computational study

Photodynamic therapy is a novel treatment for solid tumorsbased on the selective induction of cell death by the generation of cytotoxic reactive oxygen species within neoplastic tissues. Oxygen photosensitization is promoted as a consequence of the activation (using light) of a photosensitizer, which must reach the desired tissue by cellular transport. Hydrophobicity (expressed as the logarithm of octanol/water partition coefficient, logP), becomes a key factor in these processes. Unfortunately, there is no computational method to unambiguously predict the logP value for high hydrophobic photosensitizers. In this study, a total of 12 computational methods have been tested for predicting the logP value of tetrapyrrolic derivatives. Furthermore, in the attempt to correlate logP with experimental HPLC measurements (log(k’)), validation of the results leads to the proposal of a sigmoidal regression for the two parameters (log(k’) and logP)

Foliar photochemical processes and carbon metabolism under favourable and adverse winter conditions in a Mediterranean mixed forest, Catalonia (Spain)

Evergreen trees in the Mediterranean region must cope with a wide range of environmental stresses from summer drought to winter cold. The mildness of Mediterranean winters can periodically lead to favourable environmental conditions above the threshold for a positive carbon balance, benefitting evergreen woody species more than deciduous ones. The comparatively lower solar energy input in winter decreases the foliar light saturation point. This leads to a higher susceptibility to photoinhibitory stress especially when chilly (< 12 C) or freezing temperatures (< 0 C) coincide with clear skies and relatively high solar irradiances. Nonetheless, the advantage of evergreen species that are able to photosynthesize all year round where a significant fraction can be attributed to winter months, compensates for the lower carbon uptake during spring and summer in comparison to deciduous species. We investigated the ecophysiological behaviour of three co-occurring mature evergreen tree species (Quercus ilex L., Pinus halepensis Mill., and Arbutus unedo L.). Therefore, we collected twigs from the field during a period of mild winter conditions and after a sudden cold period. After both periods, the state of the photosynthetic machinery was tested in the laboratory by estimating the foliar photosynthetic potential with CO2 response curves in parallel with chlorophyll fluorescence measurements. The studied evergreen tree species benefited strongly from mild winter conditions by exhibiting extraordinarily high photosynthetic potentials. A sudden period of frost, however, negatively affected the photosynthetic apparatus, leading to significant decreases in key physiological parameters such as the maximum carboxylation velocity (Vc,max), the maximum photosynthetic electron transport rate (Jmax), and the optimal fluorometric quantum yield of photosystem II (Fv/Fm). The responses of Vc,max and Jmax were highly species specific, with Q. ilex exhibiting the highest and P. halepensis the lowest reductions. In contrast, the optimal fluorometric quantum yield of photosystem II (Fv/Fm) was significantly lower in A. unedo after the cold period. The leaf position played an important role in Q. ilex showing a stronger winter effect on sunlit leaves in comparison to shaded leaves. Our results generally agreed with the previous classifications of photoinhibition-tolerant (P. halepensis) and photoinhibitionavoiding (Q. ilex) species on the basis of their susceptibility to dynamic photoinhibition, whereas A. unedo was the least tolerant to photoinhibition, which was chronic in this species. Q. ilex and P. halepensis seem to follow contrasting photoprotective strategies. However, they seemed equally successful under the prevailing conditions exhibiting an adaptive advantage over A. unedo. These results show that our understanding of the dynamics of interspecific competition in Mediterranean ecosystems requires consideration of the physiological behaviour during winter which may have important implications for long-term carbon budgets and growth trends

Contrasting growth and water use strategies in four co-occurring Mediterranean tree species revealed by concurrent measurements of sap flow and stem diameter variations

Drought limits tree water use and growth of Mediterranean trees. However, growth and water use strate-gies are rarely addressed simultaneously across species and drought conditions. Here, we investigatethe link between stem diameter variations and sap flow in four co-existing Mediterranean trees (Pinushalepensis Mill., Quercus pubescens Willd., Quercus ilex L. and Arbutus unedo L.), under relatively wet (2011)and dry (2012) conditions. Continuous stem diameter variations were converted to basal area increment(BAI) and de-trended to estimate tree water deficit ( W), an indicator of stem hydration. P. halepensis andQ. pubescens showed the most and the least conservative sap flow density (JS) regulation under drought,respectively, with Q. ilex and A.unedo showing intermediate drought responses. All species, except A.unedo, showed some between-year variability in the environmental control of JS. Seasonal stem shrink-age in response to drought (i.e., increasing W) and subsequent trunk rehydration after rainfall (i.e.,decreasing W) occurred in all species. Vapor pressure deficit (VPD) and soil moisture ( ) interacted todetermine seasonal variation in W. Interestingly, in the dry year, 2012, more species-specific differ-ences were found in the responses of W to and VPD. Across species, JSand W began to decline atsimilar soil moisture thresholds, underpinning the tight link between JSand W under varying droughtconditions. Annual BAI decreased proportionally more than tree-level transpiration (JT) between the wet(2011) and the dry (2012) year, hence growth-based WUE (WUEBAI= BAI/JT) decreased for all species,albeit less acutely for P. halepensis. Overall, despite their contrasting leaf habit and wood type, the stud-ied Mediterranean tree species show coordinated responses of transpiration, water storage dynamicsand growth-based WUE which allow them to cope with seasonal and interannual drought

Foliar photochemical processes and carbon metabolism under favourable and adverse winter conditions in a Mediterranean mixed forest, Catalonia (Spain)

Evergreen trees in the Mediterranean region must cope with a wide range of environmental stresses from summer drought to winter cold. The mildness of Mediterranean winters can periodically lead to favourable environmental conditions above the threshold for a positive carbon balance, benefitting evergreen woody species more than deciduous ones. The comparatively lower solar energy input in winter decreases the foliar light saturation point. This leads to a higher susceptibility to photoinhibitory stress especially when chilly (< 12 °C) or freezing temperatures (< 0 °C) coincide with clear skies and relatively high solar irradiances. Nonetheless, the advantage of evergreen species that are able to photosynthesize all year round where a significant fraction can be attributed to winter months, compensates for the lower carbon uptake during spring and summer in comparison to deciduous species. We investigated the ecophysiological behaviour of three co-occurring mature evergreen tree species (Quercus ilex L., Pinus halepensis Mill., and Arbutus unedo L.). Therefore, we collected twigs from the field during a period of mild winter conditions and after a sudden cold period. After both periods, the state of the photosynthetic machinery was tested in the laboratory by estimating the foliar photosynthetic potential with CO² response curves in parallel with chlorophyll fluorescence measurements. The studied evergreen tree species benefited strongly from mild winter conditions by exhibiting extraordinarily high photosynthetic potentials. A sudden period of frost, however, negatively affected the photosynthetic apparatus, leading to significant decreases in key physiological parameters such as the maximum carboxylation velocity (V_(c,max)), the maximum photosynthetic electron transport rate (J(max)), and the optimal fluorometric quantum yield of photosystem II (F_v/F_m). The responses of V_(c,max) and J(max) were highly species specific, with Q. ilex exhibiting the highest and P. halepensis the lowest reductions. In contrast, the optimal fluorometric quantum yield of photosystem II (F_v/_Fm) was significantly lower in A. unedo after the cold period. The leaf position played an important role in Q. ilex showing a stronger winter effect on sunlit leaves in comparison to shaded leaves. Our results generally agreed with the previous classifications of photoinhibition-tolerant (P. halepensis) and photoinhibition-avoiding (Q. ilex) species on the basis of their susceptibility to dynamic photoinhibition, whereas A. unedo was the least tolerant to photoinhibition, which was chronic in this species. Q. ilex and P. halepensis seem to follow contrasting photoprotective strategies. However, they seemed equally successful under the prevailing conditions exhibiting an adaptive advantage over A. unedo. These results show that our understanding of the dynamics of interspecific competition in Mediterranean ecosystems requires consideration of the physiological behaviour during winter which may have important implications for long-term carbon budgets and growth trends

Improved understanding of drought controls on seasonal variation in Mediterranean forest canopy CO2 and water fluxes through combined in situ measurements and ecosystem modelling

Water stress is a defining characteristic of Mediterranean ecosystems, and is likely to become more severe in the coming decades. Simulation models are key tools for making predictions, but our current understanding of how soil moisture controls ecosystem functioning is not sufficient to adequately constrain parameterisations. Canopy-scale flux data from four forest ecosystems with Mediterranean-type climates were used in order to analyse the physiological controls on carbon and water flues through the year. Significant non-stomatal limitations on photosynthesis were detected, along with lesser changes in the conductance-assimilation relationship. New model parameterisations were derived and implemented in two contrasting modelling approaches. The effectiveness of two models, one a dynamic global vegetation model ('ORCHIDEE'), and the other a forest growth model particularly developed for Mediterranean simulations ('GOTILWA+'), was assessed and modelled canopy responses to seasonal changes in soil moisture were analysed in comparison with in situ flux measurements. In contrast to commonly held assumptions, we find that changing the ratio of conductance to assimilation under natural, seasonally-developing, soil moisture stress is not sufficient to reproduce forest canopy CO2 and water fluxes. However, accurate predictions of both CO2 and water fluxes under all soil moisture levels encountered in the field are obtained if photosynthetic capacity is assumed to vary with soil moisture. This new parameterisation has important consequences for simulated responses of carbon and water fluxes to seasonal soil moisture stress, and should greatly improve our ability to anticipate future impacts of climate changes on the functioning of ecosystems in Mediterranean-type climates

Balance between carbon gain and loss under long-term drought: impacts on foliar respiration and photosynthesis in Quercus ilex L

Terrestrial carbon exchange is a key process of the global carbon cycle consisting of a delicate balance between photosynthetic carbon uptake and respiratory release. We have, however, a limited understanding how long-term decreases in precipitation induced by climate change affect the boundaries and mechanisms of photosynthesis and respiration. We examined the seasonality of photosynthetic and respiratory traits and evaluated the adaptive mechanism of the foliar carbon balance of Quercus ilex L. experiencing a long-term rainfall-exclusion experiment. Day respiration (R d) but not night respiration (R n) was generally higher in the drought treatment leading to an increased R d/R n ratio. The limitation of mesophyll conductance (g m) on photosynthesis was generally stronger than stomatal limitation (g s) in the drought treatment, reflected in a lower g m/g s ratio. The peak photosynthetic activity in the drought treatment occurred in an atypical favourable summer in parallel with lower R d/R n and higher g m/g s ratios. The plant carbon balance was thus strongly improved through: (i) higher photosynthetic rates induced by g m; and (ii) decreased carbon losses mediated by R d. Interestingly, photosynthetic potentials (V c,max, J max, and TPU) were not affected by the drought treatment, suggesting a dampening effect on the biochemical level in the long term. In summary, the trees experiencing a 14-year-long drought treatment adapted through higher plasticity in photosynthetic and respiratory traits, so that eventually the atypical favourable growth period was exploited more efficiently

Contrasting growth and water use strategies in four co-occurring Mediterranean tree species revealed by concurrent measurements of sap flow and stem diameter variations

Drought limits tree water use and growth of Mediterranean trees. However, growth and water use strategies are rarely addressed simultaneously across species and drought conditions. Here, we investigate the link between stem diameter variations and sap flow in four co-existing Mediterranean trees (Pinus halepensis Mill., Quercus pubescens Willd., Quercus ilex L. and Arbutus unedo L.), under relatively wet (2011) and dry (2012) conditions. Continuous stem diameter variations were converted to basal area increment (BAI) and de-trended to estimate tree water deficit (ΔW), an indicator of stem hydration. P. halepensis and Q. pubescens showed the most and the least conservative sap flow density (Js) regulation under drought, respectively, with Q. ilex and A.unedo showing intermediate drought responses. All species, except A. unedo, showed some between-year variability in the environmental control of Js. Seasonal stem shrinkage in response to drought (i.e., increasing ΔW) and subsequent trunk rehydration after rainfall (i.e., decreasing ΔW) occurred in all species. Vapor pressure deficit (VPD) and soil moisture (θ) interacted to determine seasonal variation in ΔW. Interestingly, in the dry year, 2012, more species-specific differences were found in the responses of ΔW to θ and VPD. Across species, Js and ΔW began to decline at similar soil moisture thresholds, underpinning the tight link between Js and ΔW under varying drought conditions. Annual BAI decreased proportionally more than tree-level transpiration (JT) between the wet (2011) and the dry (2012) year, hence growth-based WUE (WUEBAI = BAI/JT) decreased for all species, albeit less acutely for P. halepensis. Overall, despite their contrasting leaf habit and wood type, the studied Mediterranean tree species show coordinated responses of transpiration, water storage dynamics and growth-based WUE which allow them to cope with seasonal and interannual drought

Does soil moisture overrule temperature dependence of soil respiration in Mediterranean riparian forests?

Soil respiration (SR) is a major component of ecosystems' carbon cycles and represents the second largest CO2 flux in the terrestrial biosphere. Soil temperature is considered to be the primary abiotic control on SR, whereas soil moisture is the secondary control factor. However, soil moisture can become the dominant control on SR in very wet or dry conditions. Determining the trigger that makes soil moisture as the primary control factor of SR will provide a deeper understanding on how SR changes under the projected future increase in droughts. Specific objectives of this study were (1) to investigate the seasonal variations and the relationship between SR and both soil temperature and moisture in a Mediterranean riparian forest along a groundwater level gradient; (2) to determine soil moisture thresholds at which SR is controlled by soil moisture rather than by temperature; (3) to compare SR responses under different tree species present in a Mediterranean riparian forest (Alnus glutinosa, Populus nigra and Fraxinus excelsior). Results showed that the heterotrophic soil respiration rate, groundwater level and 30 cm integral soil moisture (SM30) decreased significantly from the riverside moving uphill and showed a pronounced seasonality. SR rates showed significant differences between tree species, with higher SR for P. nigra and lower SR for A. glutinosa. The lower threshold of soil moisture was 20 and 17% for heterotrophic and total SR, respectively. Daily mean SR rate was positively correlated with soil temperature when soil moisture exceeded the threshold, with Q10 values ranging from 1.19 to 2.14; nevertheless, SR became decoupled from soil temperature when soil moisture dropped below these thresholds

Seasonal variability of foliar photosynthetic and morphological traits and drought impacts in a Mediterranean mixed forest

The Mediterranean region is a hot spot of climate change vulnerable to increased droughts and heat waves. Scaling carbon fluxes from leaf to landscape levels is particularly challenging under drought conditions. We aimed to improve the mechanistic understanding of the seasonal acclimation of photosynthesis and morphology in sunlit and shaded leaves of four Mediterranean trees (Quercus ilex L., Pinus halepensis Mill., Arbutus unedo L. and Quercus pubescens Willd.) under natural conditions. Vc,max and Jmax were not constant, and mesophyll conductance was not infinite, as assumed in most terrestrial biosphere models, but varied significantly between seasons, tree species and leaf position. Favourable conditions in winter led to photosynthetic recovery and growth in the evergreens. Under moderate drought, adjustments in the photo/biochemistry and stomatal/mesophyllic diffusion behaviour effectively protected the photosynthetic machineries. Severe drought, however, induced early leaf senescence mostly in A. unedo and Q. pubescens, and significantly increased leaf mass per area in Q. ilex and P. halepensis. Shaded leaves had lower photosynthetic potentials but cushioned negative effects during stress periods. Species-specificity, seasonal variations and leaf position are key factors to explain vegetation responses to abiotic stress and hold great potential to reduce uncertainties in terrestrial biosphere models especially under drought conditions