Extended π‐Bridge in Organic Dye‐Sensitized Solar Cells: the Longer,the Better?

The elongation of π‐conjugated bridges between the donor (D) and the acceptor (A) represents a feasible strategy towards enhancement of light‐harvesting in both breadth and depth of organic D‐π‐A dyes suitable for nanocrystalline TiO₂‐based dye‐sensitized solar cells (DSSCs). Here, a series of organic dyes with elongating conjugated bridges is synthesized and characterized. DSSC devices employing a cobalt (II/III) redox electrolyte are fabricated using these dyes as light‐harvesting sensitizers. Compared to a dye with the 3,4‐ethylenedioxythiophene (EDOT) linker ( G188 ), the three counterparts with further extended π‐bridges present gradually red‐shifted electronic absorption spectra and a persistent decrease in oxidation potential. The photocurrent action spectra show that the extension of π‐conjugated bridges decreases the open‐circuit photovoltage. The best performance is shown in G268 with a short‐circuit photocurrent density (J_sc) of 16.27 mA cm², an open‐circuit photovoltage (V_oc) of 0.83 V, and a fill factor (FF) of 0.67, corresponding to an overall conversion efficiency of 9.24%. Unexpectedly, G270, which has with the longest π‐bridge , showed the lowest J_sc, V_oc, and efficiency.     

Bifunctional Moth‐Eye Nanopatterned Dye‐Sensitized Solar Cells: Light‐Harvesting and Self‐Cleaning Effects

A nanopatterning technique using nanostamps that provides a facile process to create a nature‐inspired moth‐eye structure achieving high transmittance in the visible range as well as a self‐cleaning effect is reported. Commercially available perfluoropolyether (PFPE) and NOA63 as the mold resin and second replica mold material, respectively, play an important role in fabricating the structure. The structure is found to increase transmittance up to 82% at 540 nm and contact angle up to 150°, representing superhydrophobicity even without the aid of a fluorinated self‐assembled monolayer (SAM) coating. The resulting solid‐state dye‐sensitized solar cells (ssDSSCs) with moth‐eye structures show enhancement of efficiency to 7.3% at 100 mW cm^?2, which is among the highest values reported to date for N719 dye‐based ssDSSCs. This nature‐inspired nanopatterning process could be used for improving light harvesting in any type of photovoltaic cell, and it produces superhydrophobic surfaces, which in turn lead to self‐cleaning for long‐term stability.     

Engineering Processes at the Interface of p‐Semiconductor for Enhancing the Open Circuit Voltage in p‐Type Dye‐Sensitized Solar Cells

To prevent the interfacial charge recombination between injected holes in the valence band and the redox mediator in the electrolyte in p‐type dye sensitized solar cells (p‐DSSC) the passivation of the recombination sites by organic insulator chenodeoxycholic acid (CDCA) layer is critically investigated in this study. Rather than classical coating of the semiconductor's surface by simultaneous co‐adsorption of CDCA during the dyeing step, two other methods are investigated. The first consists in dissolving CDCA in the electrolyte, while the second consists in spin coating an ethanol solution of CDCA onto the already dyed photocathode. In this study, different sensitizers, electrolytes, and p‐SCs, (NiO, CuGaO₂) are explored. Analysis of the current/voltage curves and electrochemical impedance spectroscopy provides evidence that the role of the CDCA layer is to create a physical barrier to prevent the approach of the redox mediator from the NiO surface and consequently raise the open circuit voltage (V_oc). The important finding of this study is the demonstration that the V_oc in p‐DSSC is heavily limited by interfacial charge recombination and that higher V_oc values much above 100 mV and as high as 500 mV can be attained with conventional materials (NiO) if this deleterious side reaction can be suppressed or diminished.     

Photosystem I-dependent cyclic electron transport is important in controlling Photosystem II activity in leaves under conditions of water stress

Leaves of the C₃ plant Brassica oleracea were illuminated with red and/or far-red light of different photon flux densities, with or without additional short pulses of high intensity red light, in air or in an atmosphere containing reduced levels of CO₂ and/or oxygen. In the absence of CO₂, far-red light increased light scattering, an indicator of the transthylakoid proton gradient, more than red light, although the red and far-red beams were balanced so as to excite Photosystem II to a comparable extent. On red background light, far-red supported a transthylakoid electrical field as indicated by the electrochromic P₅₁₅ signal. Reducing the oxygen content of the gas phase increased far-red induced light scattering and caused a secondary decrease in the small light scattering signal induced by red light. CO₂ inhibited the light-induced scattering responses irrespective of the mode of excitation. Short pulses of high intensity red light given to a background to red and/or far-red light induced appreciable additional light scattering after the flashes only, when CO₂ levels were decreased to or below the CO₂ compensation point, and when far-red background light was present. While pulse-induced light scattering increased, non-photochemical fluorescence quenching increased and F₀ fluorescence decreased indicating increased radiationless dissipation of excitation energy even when the quinone acceptor Q_A in the reaction center of Photosystem II was largely oxidized. The observations indicate that in the presence of proper redox poising of the chloroplast electron transport chain cyclic electron transport supports a transthylakoid proton gradient which is capable of controlling Photosystem II activity. The data are discussed in relation to protection of the photosynthetic apparatus against photoinactivation.Abbreviations F, F_M, F'_M, F"_M, F₀, F'₀ chlorophyll fluorescence levels - _exc quantum efficiency of excitation energy capture by open Photosystem II - _{PS II} quantum efficiency of electron flow through Photosystem II - P₅₁₅ field indicating rapid absorbance change peaking at 522 nm - P₇₀₀ primary donor of Photosystem I - Q_A primary quinone acceptor in Photosystem II - Q_N non-photochemical fluorescence quenching - Q_q photochemical quenching of chlorophyll fluorescence     

Interaction of lymphocytes and macrophage cell line cells (M1 cells). I. Functional maturation and appearance of Fc receptors im M1 cells

M₁ cells, which are cell line cells established from myeloid leukemia cells of the SL strain mouse, can differentiate from blast cells ($\text{M}{}_1{}^{\mathrm{?}}$) to mature macrophages ($\text{M}{}_1{}^{\mathrm{+}}$) within 48 hr, when they are cultured with conditioned medium (CM) obtained from murine embryonic fibroblasts. While $\text{M}{}_1{}^{\mathrm{?}}$ cells have no phagocytic activity nor Fc receptor (FcR), $\text{M}{}_1{}^{\mathrm{+}}$ cells possess both characteristics. The appearance of FcR is temperature-dependent and inhibited by a metabolic inhibitor, cycloheximide. FcR on $\text{M}{}_1{}^{\mathrm{+}}$ cells is resistant to trypsin and pronase. $\text{M}{}_1{}^{\mathrm{+}}$ cells improve the viability of macrophage-depleted SL splenic lymphocytes and restore the in vitro secondary plaque forming cell response of macrophage-depleted spleen cells to particulate and soluble antigens. $\text{M}{}_1{}^{\mathrm{?}}$ cells lack this macrophage-substituting capacity. Mm₁ cells, mutant cells from M₁ cells, having FcR and higher phagocytic activity than $\text{M}{}_1{}^{\mathrm{+}}$ cells, are also devoid of this capacity.     

Highly Efficient Perovskite Solar Cell Photocharging of Lithium Ion Battery Using DC–DC Booster

Solar cells become a viable energy source to charge lithium ion batteries. Here a simple and efficient photocharging design approach is demonstrated, where a promising low cost single junction solar cell such as perovskite solar cell or dye sensitized solar cell efficiently charges a Li₄Ti₅O₁₂‐LiCoO₂ Li‐ion cell using a DC–DC voltage boost converter. The converter boosts the low input voltage of a single junction solar cell to charge a lithium ion cell and offers advantages including maximum power point tracking of solar photovoltaics and overvoltage protection for the lithium ion cell. This is the first demonstration of this technology. This approach leads to the highest reported overall efficiency of 9.36% and average storage efficiency of 77.2% at 0.5 C discharge for a perovskite solar cell‐converter charging. The high efficiency for the perovskite solar cell‐converter charging is attributed to maximum power harvesting along with high power conversion efficiency of the perovskite solar cell and low potential polarization between the charge and discharge voltage plateaus for the Li₄Ti₅O₁₂‐LiCoO₂ Li‐ion cell.     

High‐Surface‐Area Porous Platinum Electrodes for Enhanced Charge Transfer

Cobalt‐based electrolytes are highly tunable and have pushed the limits of dye‐sensitized solar cells, enabling higher open‐circuit voltages and new record efficiencies. However, the performance of these electrolytes and a range of other electrolytes suffer from slow electron transfer at platinum counter electrodes. High surface area platinum would enhance catalysis, but pure platinum structures are too expensive in practice. Here, a material‐efficient host‐guest architecture is developed that uses an ultrathin layer of platinum deposited upon an electrically conductive scaffold, niobium‐doped tin oxide (NTO). This nanostructured composite enhances the counter electrode performance of dye‐sensitized solar cells (DSCs) using a Co^(II/III)BPY₃ electrolyte with an increased fill factor and power conversion efficiency (11.26%), compared to analogous flat films. The modular strategy is elaborated by integrating a light scattering layer onto the counter electrode to reflect unabsorbed light back to the photoanode to improve the short‐circuit current density and power conversion efficiency.     

Photoinactivation of Photosystem II by flashing light

Inhibition of Photosystem II (PS II) activity by single turnover visible light flashes was studied in thylakoid membranes isolated form spinach. Flash illumination results in decreased oxygen evolving activity of PS II, which effect is most pronounced when the water-oxidizing complex is in the S₂ and S₃ states, and increases with increasing time delay between the subsequent flashes. By applying the fluorescent spin-trap DanePy, we detected the production of singlet oxygen, whose amount was increasing with increasing flash spacing. These findings were explained in the framework of a model, which assumes that recombination of the S₂Q_B⁻ and S₃Q_B⁻ states generate the triplet state of the reaction center chlorophyll and lead to the production of singlet oxygen.     

Acceptor side photoinhibition in PS II: On the possible effects of the functional integrity of the PS II donor side on photoinhibition of stable charge separation

Photoinhibition under aerobic and anaerobic conditions was analyzed in O₂-evolving and in Tris-treated PS II-membrane fragments from spinach by measuring laser-flash-induced absorption changes at 826 nm reflecting the transient P680⁺ formation and the chlorophyll fluorescence lifetime. It was found that anaerobic photoinhibitory treatment leads in both types of samples to the appearence of two long-lived fluorescence components with lifetimes of 7 ns and 16 ns, respectively. The extent of these fluorescence kinetics depends on the state of the reaction center (open/closed) during the fluorescence measurements: it is drastically higher in the closed state. It is concluded that this long-lived fluorescence is mainly emitted from modified reaction centers with singly reduced Q_A(Q_A ^-). This suggests that the observation of long-lived fluorescence components cannot necessarily be taken as an indicator for reaction centers with missing or doubly reduced and protonated Q_A (Q_AH₂). Time-resolved measurements of 826 nm absorption changes show that the rate of photoinhibition of the stable charge separation (P680^*Q_A P680⁺Q_A ^-), is nearly the same in O₂-evolving and in Tris-treated PS II-membrane fragments. This finding is difficult to understand within the framework of the Q_AH₂-mechanism for photoinhibition of stable charge separation because in that case the rate of photoinhibition should strongly depend on the functional integrity of the donor side of PS II. Based on the results of this study it is inferred, that several processes contribute to photoinhibition within the PS II reaction center and that a mechanism which comprises double reduction and protonation of Q_A leading to Q_AH₂ formation is only of marginal – if any – relevance for photoinhibition of PS II under both, aerobic and anaerobic, conditions.