In vitro reconstitution of light-harvesting POR-protochlorophyllide complex with protochlorophyllides a and b

NADPH:protochlorophyllide oxidoreductase (POR; EC1.1.33.1) is a key enzyme for the light-induced greening of angiosperms. In barley, two POR proteins exist, termed PORA and PORB. These have previously been proposed to form higher molecular weight light-harvesting complexes in the prolamellar body of etioplasts (Reinbothe, C., Lebedev, N., and Reinbothe, S. (1999)Nature 397, 80–84). Here we report the in vitro reconstitution of such complexes from chemically synthesized protochlorophyllides (Pchlides) a andb and galacto- and sulfolipids. Low temperature (77 K) fluorescence measurements revealed that the reconstituted, lipid-containing complex displayed the same characteristics of photoactive Pchlide 650/657 as the presumed native complex in the prolamellar body. Moreover, Pchlide F650/657 was converted to chlorophyllide (Chlide) 684/690 upon illumination of the reconstituted complex with a 1-ms flash of white light. Identification and quantification of acetone-extractable pigments revealed that only the PORB-bound Pchlide a had been photoactive and was converted to Chlide a, whereas Pchlide b bound to the PORA remained photoinactive. Nondenaturing PAGE of the reconstituted Pchlide a/b-containing complex further demonstrated a size similar to that of the presumed native complexin vivo, suggesting that both complexes may be identical.

LHPP, the light-harvesting NADPH:protochlorophyllide (Pchlide) oxido¬reductase:Pchlide complex of etiolated plants, is developmentally expressed across the barley leaf gradient

NADPH:protochlorophyllide oxidoreductase is a key enzyme for the light-induced greening of etiolated angiosperm plants. In barley, two POR proteins exist termed PORA and PORB that have previously been proposed to structurally and functionally cooperate in terms of a higher molecular mass light-harvesting complex named LHPP, in the prolamellar body of etioplasts [Nature 397 (1999) 80]. In this study we examined the expression pattern of LHPP during seedling etiolation and de-etiolation under different experimental conditions. Our results show that LHPP is developmentally expressed across the barley leaf gradient. We further provide evidence that LHPP operates both in plants that etiolate completely before being exposed to white light and in plants that etiolate only partially and begin light-harvesting as soon as traces of light become available in the uppermost parts of the soil. As a result of light absorption, in either case LHPP converts Pchlide a to chlorophyllide (Chlide) a and in turn disintegrates. The released Chlide a, as well as Chlide b produced upon LHPP’s light-dependent dissociation, which leads to the activation of the PORA as a Pchlide b-reducing enzyme, then bind to homologs of water-soluble chlorophyll proteins of Brassicaceae. We propose that these proteins transfer Chlide a and Chlide b to the thylakoids, where their esterification with phytol and assembly into the photosynthetic membrane complexes ultimately takes place. Presumably due to the tight coupling of LHPP synthesis and degradation, as well as WSCP formation and photosynthetic membrane assembly, efficient photo-protection is conferred onto the plant.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Efficient photo-induced dielectrophoretic particle trapping on Fe:LiNbO3 for arbitrary two dimensional patterning

1D and 2D patterning of uncharged micro- and nanoparticles via dielectrophoretic forces on photovoltaic z-cut Fe:LiNbO3 have been investigated for the first time. The technique has been successfully applied with dielectric micro-particles of CaCO3 (diameter d = 1-3 ?m) and metal nanoparticles of Al (d = 70 nm). At difference with previous experiments in x- and y-cut, the obtained patterns locally reproduce the light distribution with high fidelity. A simple model is provided to analyse the trapping process. The results show the remarkably good capabilities of this geometry for high quality 2D light-induced dielectrophoretic patterning overcoming the important limitations presented by previous configurations.

1D and 2D neutral particle patterning by dielectrophoretic forces on z-cut Fe:LiNbO3 crystals

1D and 2D patterning of uncharged micro- and nanoparticles via dielectrophoretic forces on photovoltaic z-cut Fe:LiNbO3 have been investigated for the first time. The technique has been successfully applied with dielectric micro-particles of CaCO3 (diameter d = 1-3 μm) and metal nanoparticles of Al (d = 70 nm). At difference with previous experiments in x- and y-cut, the obtained patterns locally reproduce the light distribution with high fidelity. A simple model is provided to analyse the trapping process. The results show the remarkably good capabilities of this geometry for high quality 2D light-induced dielectrophoretic patterning overcoming the important limitations presented by previous configurations.

Induced thermo-mechanical stress in CPV receivers with cycled high intensity light

CPV receivers are made of materials with very different lineal expansion coefficients. Strong variations in DNI due to the passage of clouds can cause sudden temperature changes that creates mechanical stress. For common solder and metal filled polymers the plastic limit could be reached causing substantial fatigue. The best forecast of receiver reliability is therefore achieved by applying an intermittent light source with nominal irradiance level and a number of cycles equal to the expected cloud passages for a given site. The UPM has developed specialized equipment, dubbed the LYSS (Light cYcling Stressing Source), for carrying out such experiments. The small thermal capacity of receivers allows simulating more than 25000 cycles per week. The number of deep transients expected for Madrid in 30 years operation, based on available data, is about 45000. We are currently using the system to cycle a ?Ge/Ag Epoxy/aluminum? receiver, which shows no degradation after 20000 cycles. The equipment can cast up to 200 and 70 W/cm2 on 0.1 and 1 cm2 cells, respectively.

UV laser-induced high resolution cleaving of Si wafers for micro-nano devices and polymeric waveguide characterization

In this work we propose a method for cleaving silicon-based photonic chips by using a laser based micromachining system, consisting of a ND:YVO4laser emitting at 355 nm in nanosecond pulse regime and a micropositioning system. The laser makes grooved marks placed at the desired locations and directions where cleaves have to be initiated, and after several processing steps, a crack appears and propagate along the crystallographic planes of the silicon wafer. This allows cleavage of the chips automatically and with high positioning accuracy, and provides polished vertical facets with better quality than the obtained with other cleaving process, which eases the optical characterization of photonic devices. This method has been found to be particularly useful when cleaving small-sized chips, where manual cleaving is hard to perform; and also for polymeric waveguides, whose facets get damaged or even destroyed with polishing or manual cleaving processing. Influence of length of the grooved line and speed of processing is studied for a variety of silicon chips. An application for cleaving and characterizing sol–gel waveguides is presented. The total amount of light coupled is higher than when using any other procedure.

Ionoluminescence induced by swift heavy ions in silica and quartz: a comparative analysis

Ionoluminescence (IL) of the two SiO2 phases, amorphous silica and crystalline quartz, has been comparatively investigated in this work, in order to learn about the structural defects generated by means of ion irradiation and the role of crystalline order on the damage processes. Irradiations have been performed with Cl at 10 MeV and Br at 15 MeV, corresponding to the electronic stopping regime (i.e., where the electronic stopping power Se is dominant) and well above the amorphization threshold. The light-emission kinetics for the two main emission bands, located at 1.9 eV (652 nm) and 2.7 eV (459 nm), has been measured under the same ion irradiation conditions as a function of fluence for both, silica and quartz. The role of electronic stopping power has been also investigated and discussed within current views for electronic damage. Our experiments provide a rich phenomenological background that should help to elucidate the mechanisms responsible for light emission and defect creation.

Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.

Photoexcited-induced sensitivity of InGaAs surface QDs to environment

A detailed analysis of the impact of illumination on the electrical response of In0.5Ga0.5As surface nanostructures is carried out as a function of different relative humidity conditions. The importance of the surface-to-volume ratio for sensing applications is once more highlighted. From dark-to-photo conditions, the sheet resistance (SR) of a three-dimensional In0.5Ga0.5As nanostructure decays two orders of magnitude compared with that of a two-dimensional nanostructure. The electrical response is found to be vulnerable to the energy of the incident light and the external conditions. Illuminating with high energy light translates into an SR reduction of one order of magnitude under humid atmospheres, whereas it remains nearly unchanged under dry environments. Conversely, lighting with energy below the bulk energy bandgap, shows a negligible effect on the electrical properties regardless the local moisture. Both illumination and humidity are therefore needed for sensing. Photoexcited carriers can only contribute to conductivity if surface states are inactive due to water physisorption. The strong dependence of the electrical response on the environment makes these nanostructures very suitable for the development of highly sensitive and efficient sensing devices.

Induced Damping on Vibrating Circular Plates Submerged in still Fluid

When a structure vibrates immersed in a fluid it is known that the dynamic properties of the system are modified. The surrounding fluid will, in general, contribute to the inertia, the rigidity and the damping coefficient of the coupled fluid-structure system. For light structures, like spacecraft antennas, even when the fluid is air the contribution to the dynamic properties can be important. For not so light structures the ratio of the equivalent fluid/structure mass and rigidity can be very small and the fluid contribution could be neglected. For the ratio of equivalent fluid/structure damping both terms are of the same order and therefore the fluid contribution must be studied. The working life of the spacecraft structure would be on space and so without any surrounding fluid. The response of a spacecraft structure on its operational life would be attenuated by the structural damping alone but when the structure is dynamically tested on the earth the dynamic modal test is performed with the fluid surrounding it. The results thus are contaminated by the effects of the fluid. If the damping added by the fluid is of the same order as the structural damping the response of the structure in space can be quite different to the response predicted on earth. It is therefore desirable to have a method able to determine the amount of damping induced by the fluid and that should be subtracted of the total damping measured on the modal vibration test. In this work, a method for the determination of the effect of the surrounding fluid on the dynamic characteristics of a circular plate has been developed. The plate is assumed to vibrate harmonically with the vacuum modes and the generalized forces matrix due to the fluid is thus computed. For a compressible fluid this matrix is formed by complex numbers including terms of inertia, rigidity and damping. The matrix due to the fluid loading is determined by a boundary element method (BEM). The BEM used is of circular rings on the plate surface so the number of elements to obtain an accurate result is very low. The natural frequencies of the system are computed by an iteration procedure one by one and also the damping fluid contribution. Comparisons of the present method with various experimental data and other theories show the efficiency and accuracy of the method for any support condition of the plate.