Search results for "Photochemical"
showing 10 items of 108 documents
A systems-wide understanding of photosynthetic acclimation in algae and higher plants
2017
The ability of phototrophs to colonise different environments relies on robust protection against oxidative stress, a critical requirement for the successful evolutionary transition from water to land. Photosynthetic organisms have developed numerous strategies to adapt their photosynthetic apparatus to changing light conditions in order to optimise their photosynthetic yield, which is crucial for life on Earth to exist. Photosynthetic acclimation is an excellent example of the complexity of biological systems, where highly diverse processes, ranging from electron excitation over protein protonation to enzymatic processes coupling ion gradients with biosynthetic activity, interact on drasti…
Hydrogen Bond Fluctuations Control Photochromism in a Reversibly Photo-Switchable Fluorescent Protein
2015
Reversibly switchable fluorescent proteins (RSFPs) are essential for high-resolution microscopy of biological samples, but the reason why these proteins are photochromic is still poorly understood. To address this problem, we performed molecular dynamics simulations of the fast switching Met159Thr mutant of the RSFP Dronpa. Our simulations revealed a ground state structural heterogeneity in the chromophore pocket that consists of three populations with one, two, or three hydrogen bonds to the phenolate moiety of the chromophore. By means of non-adiabatic quantum mechanics/molecular dynamics simulations, we demonstrated that the subpopulation with a single hydrogen bond is responsible for of…
Ring splitting of azetidin-2-ones via radical anions
2012
The radical anions of azetidin-2-ones, generated by UV-irradiation in the presence of triethylamine, undergo ring-splitting via N-C4 or C3-C4 bond breaking, leading to open-chain amides. This reactivity diverges from that found for the neutral excited states, which is characterised by alpha-cleavage. The preference for beta-cleavage is supported by DFT theoretical calculations on the energy barriers associated with the involved transition states. Thus, injection of one electron into the azetidin-2-one moiety constitutes a complementary activation strategy which may be exploited to produce new chemistry.
Remote sensing of solar-induced chlorophyll fluorescence: Review of methods and applications
2009
Interest in remote sensing (RS) of solar-induced chlorophyll fluorescence (F) by terrestrial vegetation is motivated by the link of F to photosynthetic efficiency which could be exploited for large scale monitoring of plant status and functioning. Today, passive RS of F is feasible with different prototypes and commercial ground-based, airborne, and even spaceborne instruments under certain conditions. This interest is generating an increasing number of research projects linking F and RS, such as the development of new F remote retrieval techniques, the understanding of the link between the F signal and vegetation physiology and the feasibility of a satellite mission specifically designed f…
Influence of clouds on the spectral actinic flux density in the lower troposphere (INSPECTRO): overview of the field campaigns
2008
Ultraviolet radiation is the key factor driving tropospheric photochemistry. It is strongly modulated by clouds and aerosols. A quantitative understanding of the radiation field and its effect on photochemistry is thus only possible with a detailed knowledge of the interaction between clouds and radiation. The overall objective of the project INSPECTRO was the characterization of the three-dimensional actinic radiation field under cloudy conditions. This was achieved during two measurement campaigns in Norfolk (East Anglia, UK) and Lower Bavaria (Germany) combining space-based, aircraft and ground-based measurements as well as simulations with the one-dimensional radiation transfer model UV…
Hyperspectral response of agronomic variables to background optical variability: Results of a numerical experiment
2022
Understanding how biophysical and biochemical variables contribute to the spectral characteristics of vegetation canopies is critical for their monitoring. Quantifying these contributions, however, remains difficult due to extraneous factors such as the spectral variability of canopy background materials, including soil/crop-residue moisture, soil-type, and non-photosynthetic vegetation (NPV). This study focused on exploring the spectral response of two important agronomic variables (1) leaf chlorophyll content (Cab ) and (2) leaf area index (LAI) under various canopy backgrounds through a global sensitivity analysis of wheat-like canopy spectra simulated using the physically-based PROSAIL …
Experimental and DFT studies on competitive heterocyclic rearrangements. part 2: A one-atom side-chain versus the classic three-atom side-chain (Boul…
2007
The experimental investigation of the base-catalyzed rearrangements of 3-acylamino-1,2,4-oxadiazoles evidenced a new reaction pathway which competes with the well-known ring-degenerate Boulton- Katritzky rearrangement (BKR). The new reaction consists of a one-atom side-chain rearrangement that is base-activated, occurs at a higher temperature than the BKR, and irreversibly leads to the corresponding 2-acylamino-1,3,4-oxadiazoles. An extensive DFT study is reported to elucidate the proposed reaction mechanism and to compare the three possible inherent routes: (i) the reversible three-atom side-chain ring-degenerate BKR, (ii) the ring contraction-ring expansion route (RCRE), and (iii) the one…
Photoreduction of carbon dioxide to formic acid in aqueous suspension: a comparison between phthalocyanine/TiO2 and porphyrin/TiO2 catalysed processes
2014
Composite materials prepared by loading polycrystalline TiO2 powders with lipophilic highly branched Cu(II)- and metal-free phthalocyanines or porphyrins, which have been used in the past as photocatalysts for photodegradative processes, have been successfully tested for the efficient photoreduction of carbon dioxide in aqueous suspension affording significant amounts of formic acid. The results indicated that the presence of the sensitizers is beneficial for the photoactivity, confirming the important role of Cu(II) co-ordinated in the middle of the macrocycles. A comparison between Cu(II) phthalocyanines and Cu(II) porphyrins indicated that the Cu(II)- phthalocyanine sensitizer was more e…
Diurnal and Seasonal Solar Induced Chlorophyll Fluorescence and Photosynthesis in a Boreal Scots Pine Canopy
2019
Solar induced chlorophyll fluorescence has been shown to be increasingly an useful proxy for the estimation of gross primary productivity (GPP), at a range of spatial scales. Here, we explore the seasonality in a continuous time series of canopy solar induced fluorescence (hereafter SiF) and its relation to canopy gross primary production (GPP), canopy light use efficiency (LUE), and direct estimates of leaf level photochemical efficiency in an evergreen canopy. SiF was calculated using infilling in two bands from the incoming and reflected radiance using a pair of Ocean Optics USB2000+ spectrometers operated in a dual field of view mode, sampling at a 30 min time step using custom written …
Tracking seasonal drought effects on ecosystem light use efficiency in a mediterranean forest using climatic and remote sensing data
2012
Daily values of light use efficiency (LUE) of a Mediterranean forest throughout five years have been analyzed in terms of different spectral indices obtained from MODIS products and which are informative on the water stress conditions. Although correlations between LUE and the different indices are rather high, the inter-annual variation of LUE due to the summer water stress is not well identified in most of them. In particular, the PRI (photochemical reflectance index) inter-annual variation has been found to be mostly attributable to concurrent variations in sun and view zenith angles. For the study area and at MODIS spatial resolution, the different indices are informative on changes in …