Filtern
Dokumenttyp
- Wissenschaftlicher Artikel (5)
- Postprint (2)
- Dissertation (1)
Gehört zur Bibliographie
- ja (8)
Schlagworte
- recombination (8) (entfernen)
Institut
Nonribosomal peptides (NRP) are crucial molecular mediators in microbial ecology and provide indispensable drugs. Nevertheless, the evolution of the flexible biosynthetic machineries that correlates with the stunning structural diversity of NRPs is poorly understood. Here, we show that recombination is a key driver in the evolution of bacterial NRP synthetase (NRPS) genes across distant bacterial phyla, which has guided structural diversification in a plethora of NRP families by extensive mixing andmatching of biosynthesis genes. The systematic dissection of a large number of individual recombination events did not only unveil a striking plurality in the nature and origin of the exchange units but allowed the deduction of overarching principles that enable the efficient exchange of adenylation (A) domain substrates while keeping the functionality of the dynamic multienzyme complexes. In the majority of cases, recombination events have targeted variable portions of the A(core) domains, yet domain interfaces and the flexible A(sub) domain remained untapped. Our results strongly contradict the widespread assumption that adenylation and condensation (C) domains coevolve and significantly challenge the attributed role of C domains as stringent selectivity filter during NRP synthesis. Moreover, they teach valuable lessons on the choice of natural exchange units in the evolution of NRPS diversity, which may guide future engineering approaches.
Plant X-tender
(2018)
Cloning multiple DNA fragments for delivery of several genes of interest into the plant genome is one of the main technological challenges in plant synthetic biology. Despite several modular assembly methods developed in recent years, the plant biotechnology community has not widely adopted them yet, probably due to the lack of appropriate vectors and software tools. Here we present Plant X-tender, an extension of the highly efficient, scarfree and sequence-independent multigene assembly strategy AssemblX,based on overlapdepended cloning methods and rare-cutting restriction enzymes. Plant X-tender consists of a set of plant expression vectors and the protocols for most efficient cloning into the novel vector set needed for plant expression and thus introduces advantages of AssemblX into plant synthetic biology. The novel vector set covers different backbones and selection markers to allow full design flexibility. We have included ccdB counterselection, thereby allowing the transfer of multigene constructs into the novel vector set in a straightforward and highly efficient way. Vectors are available as empty backbones and are fully flexible regarding the orientation of expression cassettes and addition of linkers between them, if required. We optimised the assembly and subcloning protocol by testing different scar-less assembly approaches: the noncommercial SLiCE and TAR methods and the commercial Gibson assembly and NEBuilder HiFi DNA assembly kits. Plant X-tender was applicable even in combination with low efficient homemade chemically competent or electrocompetent Escherichia coli. We have further validated the developed procedure for plant protein expression by cloning two cassettes into the newly developed vectors and subsequently transferred them to Nicotiana benthamiana in a transient expression setup. Thereby we show that multigene constructs can be delivered into plant cells in a streamlined and highly efficient way. Our results will support faster introduction of synthetic biology into plant science.
Doped spiro-OMeTAD at present is the most commonly used hole transport material (HTM) in n-i-p-type perovskite solar cells, enabling high efficiencies around 22%. However, the required dopants were shown to induce nonradiative recombination of charge carriers and foster degradation of the solar cell. Here, in a novel approach, highly conductive and inexpensive water-free poly(3,4-ethylenedioxythiophene) (PEDOT) is used to replace these dopants. The resulting spiro-OMeTAD/PEDOT (SpiDOT) mixed films achieve higher lateral conductivities than layers of doped spiro-OMeTAD. Furthermore, combined transient and steady-state photoluminescence studies reveal a passivating effect of PEDOT, suppressing nonradiative recombination losses at the perovskite/HTM interface. This enables excellent quasi-Fermi level splitting values of up to 1.24 eV in perovskite/SpiDOT layer stacks and high open-circuit voltages (V-OC) up to 1.19 V in complete solar cells. Increasing the amount of dopant-free spiro-OMeTAD in SpiDOT layers is shown to enhance hole extraction and thereby improves the fill factor in solar cells. As a consequence, stabilized efficiencies up to 18.7% are realized, exceeding cells with doped spiro-OMeTAD as a HTM in this study. Moreover, to the best of our knowledge, these results mark the lowest nonradiative recombination loss in the V-OC (140 mV with respect to the Shockley-Queisser limit) and highest efficiency reported so far for perovskite solar cells using PEDOT as a HTM.
Open-circuit voltages of lead-halide perovskite solar cells are improving rapidly and are approaching the thermodynamic limit. Since many different perovskite compositions with different bandgap energies are actively being investigated, it is not straightforward to compare the open-circuit voltages between these devices as long as a consistent method of referencing is missing. For the purpose of comparing open-circuit voltages and identifying outstanding values, it is imperative to use a unique, generally accepted way of calculating the thermodynamic limit, which is currently not the case. Here a meta-analysis of methods to determine the bandgap and a radiative limit for open-circuit voltage is presented. The differences between the methods are analyzed and an easily applicable approach based on the solar cell quantum efficiency as a general reference is proposed.
Open-circuit voltages of lead-halide perovskite solar cells are improving rapidly and are approaching the thermodynamic limit. Since many different perovskite compositions with different bandgap energies are actively being investigated, it is not straightforward to compare the open-circuit voltages between these devices as long as a consistent method of referencing is missing. For the purpose of comparing open-circuit voltages and identifying outstanding values, it is imperative to use a unique, generally accepted way of calculating the thermodynamic limit, which is currently not the case. Here a meta-analysis of methods to determine the bandgap and a radiative limit for open-circuit voltage is presented. The differences between the methods are analyzed and an easily applicable approach based on the solar cell quantum efficiency as a general reference is proposed.
Die heutige optische Informationsverarbeitung erfordert neue Materialien, die Licht effektiv verarbeiten, steuern und speichern können. Photorefraktive (PR) Materialien sind dafür sehr interessant. In diesen Materialien entsteht bei inhomogener Beleuchtung (z.B. mit einem Intererenzmuster) über Ladungsträgergenerierung und Einfang der Ladungsträger in Fallen ein Raumladungsfeld. Dieses wird über den elektrooptischen Effekt in eine räumliche Modulation des Brechungsindex umgesetzt. Letztendlich führt somit die inhomogene Beleuchtung eines PR-Materials zu einer räumlich variierenden Änderung des Brechungsindex. Vor ca. 10 Jahren wurde entdeckt, dass auch Polymere einen PR-Effekt aufweisen können. Die Ansprechzeit dieser Materialien wird dabei wesentlich durch die Dynamik der Ladungsträger (bestimmt durch Erzeugung, Transport, Einfang in Fallen etc.) begrenzt. Bis zu Beginn dieser Arbeit war es noch nicht gelungen, einen quantitativen Zusammenhang zwischen der Ladungsträgerdynamik und der Ansprechzeit des PR-Effekts experimentell nachzuweisen. In dieser Arbeit wird ein Weg aufgezeigt, durch photophysikalische Experimente unter verschiedenen Beleuchtungsbedingungen alle photophysikalischen Größen experimentell zu bestimmen, die den Aufbau des Raumladungsfelds in organischen photorefraktiven Materialien bestimmen. So konnte durch Experimente unter Beleuchtung mit kurzen Einzelpulsen sowohl die Beweglichkeit der freien Ladungsträger als auch die charakteristischen Parameter flacher Fallen ermittelt werden. Zur Bestimmung der Dichte tiefer Fallen wurde die Intensitätsabhängigkeit des stationären Photostroms untersucht. Durch die analytische Lösung des bestimmenden Gleichungssystems konnte gezeigt werden, dass die Sublinearität der Intensitätsabhängigkeit des Photostroms primär mit dem Verhältnis zwischen Entleerungs- und Einfangkoeffizienten tiefer Fallen korreliert. Zur unabhängigen Bestimmung des Entleerungskoeffizienten der tiefen Fallen wurden Doppelpulsexperimente mit variabler Verzögerungszeit zwischen den Pulsen verwendet. Mit den erhaltenen Parametern konnte dann das untere Limit der zum Aufbau des Raumladungsfelds notwendigen Zeit abgeschätzt werden. Diese Werte wurden mit den gemessenen photorefraktiven Ansprechzeiten verglichen. Es zeigt sich, dass weder die Photogeneration noch der Transport der Ladungsträger die Geschwindigkeit des Aufbaus des Raumladungsfeldes limitiert. Stattdessen konnte erstmals quantitativ nachgewiesen werden, dass die Dynamik des Raumladungsfelds in den hier untersuchten PR-Materialien durch das Füllen tiefer Fallen mit photogenerierten Ladungsträgern bestimmt wird. Dabei spielt das Verhältnis zwischen dem Einfang- und dem Rekombinationskoeffizienten eine wesentliche Rolle. Weiterhin wurde die Dynamik des Aufbaus des Raumladungsfelds bei unterschiedlichen Vorbeleuchtungsbedingungen quantitativ simuliert und mit den experimentellen PR-Transienten verglichen. Die gute Übereinstimmung zwischen den simulierten und gemessenen Transienten erlaubte es abschließend, die kritischen Parameter, die die Dynamik des PR-Effekts in den untersuchten Polymeren begrenzen, zu identifizieren.
Organic bulk heterojunction (BHJ) solar cells require energetic offsets between the donor and acceptor to obtain high short-circuit currents (J(SC)) and fill factors (FF). However, it is necessary to reduce the energetic offsets to achieve high open-circuit voltages (V-OC). Recently, reports have highlighted BHJ blends that are pushing at the accepted limits of energetic offsets necessary for high efficiency. Unfortunately, most of these BHJs have modest FF values. How the energetic offset impacts the solar cell characteristics thus remains poorly understood. Here, a comprehensive characterization of the losses in a polymer:fullerene BHJ blend, PIPCP:phenyl-C61-butyric acid methyl ester (PC61BM), that achieves a high V-OC (0.9 V) with very low energy losses (E-loss = 0.52 eV) from the energy of absorbed photons, a respectable J(SC) (13 mA cm(-2)), but a limited FF (54%) is reported. Despite the low energetic offset, the system does not suffer from field-dependent generation and instead it is characterized by very fast nongeminate recombination and the presence of shallow traps. The charge-carrier losses are attributed to suboptimal morphology due to high miscibility between PIPCP and PC61BM. These results hold promise that given the appropriate morphology, the J(SC), V-OC, and FF can all be improved, even with very low energetic offsets.