Photoelectrochemical behavior of coupled SnO2|CdSe nanocrystalline semiconductor films

A photoelectrochemical cell with a coupled SnO₂|CdSe nanocrystalline semiconductor electrode has been prepared by sequential deposition of SnO₂ and CdSe films onto an optically transparent electrode (OTE), and its photoelectrochemical behavior has been studied. The results show that the coupling of CdSe with SnO₂ leads to an improvement in the performance of OTE|SnO₂|CdSe over OTE|CdSe cells in terms of increased incident photon-to-current conversion efficiency, increased stability and smaller reversal of current. The favorable positioning of the energy bands of SnO₂ and CdSe is responsible for the above observations. Various photoelectrochemical parameters of the OTE|SnO₂|CdSe cell obtained for an incident light power of 0.31 mW cm⁻² at 470nm, are as follows: I_sc ≈ 25–30 μA cm⁻², V_oc ≈ 0.5–0.6 V, ƒƒ = 0.47 and a power conversion efficiency of about 2.25%.     

Characterization of the Photosynthetic Activity of Platinized Chloroplasts: A Study Using Fluorescence and Photoacoustic Techniques

In this report, the effect of platinization on the photosynthetic activity of the chloroplast membranes is studied. Oxygen evolution, fluorescence emission and thermal de-activation processes are modified after platinization. It is shown that photosystem II activity is affected by the hydrogen purging involved in the platinization procedure as seen by the reduced rates of oxygen evolution and a decrease in variable fluorescence. Depletion of bicarbonate from photosystem II during purging is suggested to be responsible partly for the decreased electron transfer rates and for a lower half-saturation light intensity required for energy storage as measured by photoacoustic spectroscopy. On the other hand, the electron sink created by the reduction of hydrogen at the acceptor side of photosystem I is shown to reoxidize efficiently the plas-toquinone pool of photosystem II.     

POLARIZED PHOTOACOUSTIC SPECTRA OF PHYCOERYTHRIN and PHYCOCYANIN IN ANISOTROPIC POLYMER FILMS

Abstract— Photoacoustic spectra (PAS) of biliproteins, namely, R-phycoerythrin (PE) and C-phycocyanin (PC) and their mixture in anisotropic and isotropic polyvinylalcohol (PVA) films were measured under the illumination with polarized and natural light. Also samples in deuterated PVA were investigated. The yields of fluorescence of various chromophores of investigated biliproteins were obtained from PAS, absorption, fluorescence and fluorescence lifetime measurements. The deuteration of samples causes different changes in thermal deactivation of excitation of various chromophores. Ratios of PAS to absorption of the light polarized parallel and perpendicular to the direction of film stretching are different. The PAS amplitude of deuterated samples is higher than that for undeuterated.     

Photoinduced electron transfer between chlorophyll a and gold nanoparticles

Excited-state interactions between chlorophyll a (Chla) and gold nanoparticles have been studied. The emission intensity of Chla is quenched by gold nanoparticles. The dominant process for this quenching has been attributed to the process of photoinduced electron transfer from excited Chla to gold nanoparticles, although because of a small overlap between fluorescence of Chla and absorption of gold nanoparticles, the energy-transfer process cannot be ruled out. Photoinduced electron-transfer mechanism is supported by the electrochemical modulation of fluorescence of Chla. In absence of an applied bias, Chla cast on gold film, as a result of electron transfer, exhibits a very weak fluorescence. However, upon negatively charging the gold nanocore by external bias, an increase in fluorescence intensity is observed. The negatively charged gold nanoparticles create a barrier and suppress the electron-transfer process from excited Chla to gold nanoparticles, resulting in an increase in radiative process. Nanosecond laser flash experiments of Chla in the presence of gold nanoparticles and fullerene (C60) have demonstrated that Au nanoparticles, besides accepting electrons, can also mediate or shuttle electrons to another acceptor. Taking advantage of these properties of gold nanoparticles, a photoelectrochemical cell based on Chla and gold nanoparticles is constructed. A superior performance of this cell compared to that without the gold film is due to the beneficial role of gold nanoparticles in accepting and shuttling the photogenerated electrons in Chla to the collecting electrode, leading to an enhancement in charge separation efficiency.     

PHOTO ACOUSTIC SPECTRA OF PHYCOBILIPROTEINS and CHLOROPHYLLIN IN ISOTROPIC and ANISOTROPIC POLYVINYL ALCOHOL FILMS

Abstract— Photoacoustic spectra (PAS) of biliproteins: R-phycoerythrin (PE) with R-phycocyanin (PC) admixture in isotropic and anisotropic polyvinyl-alcohol (PVA) films were measured. The mixtures of biliproteins and chlorophyllin (Chllin) in PVA were also investigated. In order to establish the influence of PVA anisotropy on PAS amplitude, the stretched and unstretched PVA films colored by Congo red were studied. The films with PE and Chllin mixture when illuminated in the region of PE absorption, show higher PAS signals than the films with PE alone. This is explained by the excitation energy transfer from efficiently fluorescent PE to Chllin that has much lower yield of fluorescence. The stretched films always show a higher PAS signal than isotropic films because of the increase in the thermal conductivity of PVA. But normalized PAS of Congo red and Chllin in stretched PVA are similar to those in unstretched films.
Pigment molecules oriented parallel to the direction of film stretching have a lower rate of thermal deactivation compared to that of unoriented molecules as has been found by comparing PAS of differently oriented Congo red molecules using photoselection by polarized light. The same result was obtained for various PE chromophores which are differently oriented in anisotropic films.     

Afterglow thermoluminescence measured in isolated chloroplasts

The thermoluminescence afterglow (AG) measured in plant leaves originates from the S(2)/S(3)Q(B)(-) charge pair recombination in photosystem II (PSII) initiated by reverse electron flow from stromal reductants to PQ and then to the Q(B) site in PSII centers that are in the S(2)/S(3)Q(B) state. In this study, we show that this luminescence, absent in isolated thylakoid membranes, can be measured in intact chloroplasts that retain their stromal content including the electron acceptor pool (oxidized ferredoxin/NADP(+)) of photosystem I. The properties of the chloroplasts AG emission is similar to the AG in leaves in terms of temperature maximum, period-four modulation, far-red light stimulation, and antimycin A inhibition.     

Interaction of semiconductor colloids with J-aggregates of a squaraine dye and its role in sensitizing nanocrystalline semiconductor films

The role of bis(2,4,6-trihydroxyphenyl)squaraine, Sq, in sensitizing large bandgap semiconductors has been investigated in the present study. The dye in its aggregate form readily interacts with the TiO₂ colloids giving rise to a new charge transfer band in the red region. The apparent association constant for the dye aggregate and TiO₂ colloid as determined from a Benesi-Hildebrand plot is 1600 M^-1. Nanocrystalline semiconductor films prepared from TiO₂, ZnO, and SnO₂ colloids have been modified with Sq to probe the photosensitization effects. Both dye monomers and aggregates were found to participate in the charge injection process. An incident photon-to-photocurrent efficiency up to 0.7% has been observed.     

POLARIZED PHOTO ACOUSTIC SPECTRA OF PHYCOBILISOMES IN POLYVINYL ALCOHOL FILMS

Abstract— Phycobilisomes from Porphyridium cruentum , suspended in polyvinyl alcohol were found to be highly stable, and had normal absorption and fluorescence spectra. Intact phycobilisomes had a major emission peak at 680 nm, whereas upon partial dissociating the major emission was at 580 nm. Incorporation of phycobilisomes in thin polyvinyl alcohol films facilitated examination by photoacoustic spectroscopy. The photoacoustic spectra had a broad absorption maximum at 545–565 nm (phycoerythrin), which resolved as two peaks (545 and 563 nm) in absorption spectra. Stretching of films resulted in apparent chromophore reorientation in partially dissociated, but not in intact phycobilisomes. Only in dissociated phycobilisomes was observed a differential chromophore orientation at 685 nm by polarized fluorescence, which is attributed to a change in orientation of the terminal phycobilisome pigment relative to phycoerythrin.     

SPECTROSCOPIC BEHAVIOUR OF RETINYL POLYENES IN SOLID FILMS

Abstract— The absorption spectroscopic study of retinyl polyenes, i.e. all- trans retinal, 9- cis retinal, 13- cis retinal, all- trans retinol, 13- cis retinol and all- trans retinyl acetate in solid films is discussed. The spectra of the films with low surface coverages obtained from dilute solutions are red shifted relative to their solution spectra. This shift is interpreted as due to the weak interaction between the surface and polyene molecules. With increased surface coverages, i.e. the films obtained from concentrated solutions, the retinals show a large red shift whereas a blue shift is observed with the retinols. Chromophore–chromophore interactions in addition to the surface effects are believed to be responsible for such observations. Effect of surface causing permanent changes in molecule is also discussed.