Nitrate reductase 15N discrimination in Arabidopsis thaliana, Zea mays, Aspergillus niger, Pichea angusta, and Escherichia coli

Stable 15N isotopes have been used to examine movement of nitrogen (N) through various pools of the global N cycle. A central reaction in the cycle involves nitrate (NO3–) reduction to nitrite (NO2–) catalyzed via nitrate reductase (NR). Discrimination against 15N by NR is a major determinant of isotopic differences among N pools. Here, we measured in vitro 15N discrimination by several NRs purified from plants, fungi, and a bacterium to determine the intrinsic 15N discrimination by the enzyme and to evaluate the validity of measurements made using 15N-enriched NO3–. Observed NR isotope discrimination ranged from 22‰ to 32‰ (kinetic isotope effects of 1.022 to 1.032) among the different isozymes at natural abundance 15N (0.37%). As the fractional 15N content of substrate NO3– increased from natural abundance, the product 15N fraction deviated significantly from that expected based on substrate enrichment and 15N discrimination measured at natural abundance. Additionally, isotopic discrimination by denitrifying bacteria used to reduce NO3– and NO2– in some protocols became a greater source of error as 15N enrichment increased. We briefly discuss potential causes of artifactual results with enriched 15N and recommend against the use of highly enriched 15N tracers to study N discrimination in plants or soils

Correlating photovoltaic properties of PTB7-Th:PC71BM blend to photophysics and microstructure as a function of thermal annealing

We acknowledge support from EPSRC (grant number EP/L012294/1) and the European Research Council (grant number 321305). I.D.W.S. also acknowledges a Royal Society Wolfson Research Merit Award. VS acknowledges support from the Office of Naval Research NDSEG fellowship. Research data supporting this paper is available at doi http://dx.doi.org/10.17630/eadf56f3-8c70-47da-ac6d-67f2d78b3f74Selective optimisation of light harvesting materials and interface properties has brought breakthroughs in power conversion efficiency (11-12 %) of organic photovoltaics (OPVs). However to translate this promising efficiency to economically viable applications, long term stability is a fundamental requirement. A number of degradation pathways, both extrinsic and intrinsic, reduce the long term stability of OPVs. Here, the photovoltaic properties of a highly efficient bulk heterojunction PTB7-Th:PC71BM blend were investigated as a function of thermal annealing. The changes in charge generation, separation, and transport due to thermal annealing were measured and related to changes in the microstructure and photovoltaic performance. A 30 % drop in power conversion efficiency of PTB7-Th:PC71BM blends upon thermal annealing at 150 oC was identified as mainly due to morphological instability induced by strong phase separation of donor and acceptor molecules of the blend films. Based on the insight gained from these investigations, enhanced thermal stability was demonstrated by replacing the PC71BM fullerene acceptor with the non-fullerene acceptor ITIC, for which power conversion efficiency dropped only by 9 % upon thermal annealing at 150 oC.PostprintPeer reviewe

Triptycene as a supramolecular additive in PTB7:PCBM blends and its influence on photovoltaic properties

We acknowledge support from EPSRC (grant number EP/L012294/1) and the European Research Council (grant number 321305). I. D. W. S. also acknowledges a Royal Society Wolfson Research Merit Award.Additives play an important role in modifying the morphology and phase separation of donor and acceptor molecules in bulk heterojunction (BHJ) solar cells. Here, we report triptycene (TPC) as a small-molecule additive for supramolecular control of phase separation and concomitant improvement of the power conversion efficiency (PCE) of PTB7 donor and fullerene acceptor-based BHJ polymer solar cells. An overall 60% improvement in PCE is observed for both PTB7:PC61BM and PTB7:PC71BM blends. The improved photovoltaic (PV) performance can be attributed to three factors: (a) TPC-induced supramolecular interactions with donor:acceptor components in the blends to realize a nanoscale phase-separated morphology; (b) an increase in the charge transfer state energy that lowers the driving force for electron transfer from donor to acceptor molecules; and (c) an increase in the charge carrier mobility. An improvement in efficiency using TPC as a supramolecular additive has also been demonstrated for other BHJ blends such as PBDB-T:PC71BM and P3HT:PCBM, implying the wide applicability of this new additive molecule. A comparison of the photostability of TPC as an additive for PTB7:PCBM solar cells to that of the widely used 1,8-diiodooctane additive shows ∼30% higher retention of PV performance for the TPC-added solar cells after 34 h of AM 1.5G illumination. The results obtained suggest that the approach of using additives that can promote supramolecular interactions to modify the length scale of phase separation between donor and acceptor is very promising and can lead to the development of highly efficient and stable organic photovoltaics.PostprintPostprintPeer reviewe

Tuning the Properties of Polymer Bulk Heterojunction Solar Cells by Adjusting Fullerene Size to Control Intercalation

Pour la France contemporaine, René Lévy notait en 1996, l’hétérogénéité des recherches d’histoire du crime produites depuis le milieu des années 1980. Il en soulignait les raisons d’ordres divers : approche peu critique des sources, absence de dialogue entre deux pans de la corporation historienne : historiens de lettres et historiens du droit, faible spécialisation du domaine, difficultés de publication. Près d’une décennie plus tard, l’évolution est nette. Les deux derniers siècles ont fait..

Morphological, chemical, and electronic changes of the conjugated polymer PTB7 with thermal annealing

This work was supported by the Office of Naval Research NDSEG fellowship (V.S.) and the Department of Energy SCGSR Program (L.J.P.). Work was partially supported by the Department of the Navy, Office of Naval Research Award No. N00014-14-1-0580 (S.D.O., M.F.T.). L.K.J., I.R., and I.D.W.S. were supported by the Engineering and Physical Sciences Research Council (grants EP/L017008/1 and EP/L012294/1 ). I.D.W.S. also acknowledges support from a Royal Society Wolfson Research Merit Award. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.There is considerable interest in improving the performance of organic optoelectronic devices through processing techniques. Here, we study the effect of high-temperature annealing on the properties of the semiconducting polymer PTB7 and PTB7:fullerene blends, of interest as efficient organic photovoltaic (OPV) devices. Annealing to moderate temperature improves the PTB7 morphology and optoelectronic properties. High-temperature annealing also improves morphology but results in poorer optoelectronic properties. This is a result of side chain cleavage that creates by-products that act as trap states, increasing electronic disorder and decreasing mobility. We further observe changes to the PTB7 chemical structure after thermal cleavage that are similar to those following solar irradiation. This implies that side chain cleavage is an important mechanism in device photodegradation, which is a major ?burn-in? loss mechanism in OPV. These results lend insight into side chain cleavage as a method of improving optoelectronic properties and suggest strategies for improvement in device photostability.Publisher PDFPeer reviewe

Effects of Odd–Even Side Chain Length of Alkyl-Substituted Diphenylbithiophenes on First Monolayer Thin Film Packing Structure

Because of their preferential two-dimensional layer-by-layer growth in thin films, 5,5′bis(4-alkylphenyl)-2,2′-bithiophenes (P2TPs) are model compounds for studying the effects of systematic chemical structure variations on thin-film structure and morphology, which in turn, impact the charge transport in organic field-effect transistors. For the first time, we observed, by grazing incidence X-ray diffraction (GIXD), a strong change in molecular tilt angle in a monolayer of P2TP, depending on whether the alkyl chain on the P2TP molecules was of odd or even length. The monolayers were deposited on densely packed ultrasmooth self-assembled alkane silane modified $SiO_2$ surfaces. Our work shows that a subtle change in molecular structure can have a significant impact on the molecular packing structure in thin film, which in turn, will have a strong impact on charge transport of organic semiconductors. This was verified by quantum-chemical calculations that predict a corresponding odd–even effect in the strength of the intermolecular electronic coupling.Chemistry and Chemical BiologyEngineering and Applied Science

Impact of regioregularity on thin-film transistor and photovoltaic cell performances of pentacene-containing polymers

Regioregular pentacene-containing polymers were synthesized with alkylated bithiophene (BT) and cyclopentadithiophene (CPDT) as comonomers. Among them, 2,9-conjugated polymers PnBT-2,9 and PnCPDT-2,9 achieved the best performance in transistor and photovoltaic devices respectively. The former achieved the most highly ordered structures in thin films, yielding ambipolar transistor behavior with hole and electron mobilities up to 0.03 and 0.02 cm(2) V-1 s(-1) on octadecylsilane-treated substrates. The latter achieved photovoltaic power conversion efficiencies up to 0.33%. The impact of regioregularity and direction of conjugation-extension (2,9 vs. 2,10), on thin-film order and device performance has been demonstrated for the pentacene-containing polymers for the first time, providing insight towards future functional material design.close101