Norbornadienes for Solar Thermal Energy Storage and New Applications

The energy demand worldwide is steadily increasing, therefore it is fundamental to efficiently utilise renewable energy resources. Energy storage technologies are partic- ularly relevant in order to be able to exploit renewable energy resources such as solar energy, since these are typically intermittent and not evenly distributed. The work presen- ted in this thesis is focused on trying to optimise norbornadiene-quadricyclane systems to harness and store solar energy. Norbornadienes are able to absorb light, and undergo photoinduced isomerization to the high energy isomer quadricyclane, which is stable over time. When quadricyclanes back isomerise to norbornadienes they release the absorbed energy as heat. This technology is called “molecular solar thermal”, or MOST. Differ- ent features need to be optimised in order to utilise norbornadiene-quadricyclane pho- toswitches for MOST applications. In my work I focused on synthesising new norbor- nadienes, characterising their molecular and spectroscopic properties, and trying to op- timise them for energy storage purposes. In particular I focused on identifying specific structure-properties relationship that allow selectively engineering the kinetic stability of quadricyclanes, to achieve longer storage times. This was in fact achieved in a series of norbornadienes by selectively increasing the entropy of activation to the back isomeriza- tion. A small device was also built, in order to test a hybrid technology that would combine MOST and solar water heating. These laboratory-scale experiments were particularly in- structive in demonstrating the potential of MOST systems, and learning about the future challenges. Liquid, neat norbornadienes were also made, and their properties assessed. They retained the ability to photoisomerise and back convert in neat samples, but new challenges arose, such as stability over multiple cycles and storage times. Moreover, the use of a norbornadiene-quadriyclane photoswitch as a molecular keypad lock is demon- strated

Intramolecular Cyclization Reactions in Haloalkyl-Cobalt Complexes with Macrocyclic Equatorial Ligands

Organocobalt complexes containing axial haloalkyl groups afford metallacycles of different size by N or O alkylation of the macrocyclic equatorial ligands. The reaction mechanism involves the intra-molecular nucleophilic attack of a negatively charged atom of the equatorial ligand on the axial XCH2 haloalkyl group with simultaneous detachment of a halide ion, X−. In imino/oxime and amino/oxime derivatives, the generation of the negatively charged nitrogen requires the abstraction of a proton and the reaction occurs only in alkaline medium. In bis(dimethylglioximato) and Schiff base complexes, a negatively charged oxygen is present in the equatorial ligand and the reaction occurs even in neutral medium. Three-, six- and seven- membered metallacycles are obtained, with the common feature that the Co–C bond is shorter and more resistant toward homolysis than in parent complexes or in closely related derivatives. Keywords

Engineering of Norbornadiene/Quadricyclane Photoswitches for Molecular Solar Thermal Energy Storage Applications

ConspectusRenewable energy resources are mostly intermittent and not evenly distributed geographically; for this reason, the development of new technologies for energy storage is in high demand.Molecules that undergo photoinduced isomerization reactions that are capable of absorbing light, storing it as chemical energy, and releasing it as thermal energy on demand are referred to as molecular solar thermal energy storage (MOST) or solar thermal fuels (STF). Such molecules offer a promising solution for solar energy storage applications. Different molecular systems have been investigated for MOST applications, such as norbornadienes, azobenzenes, stilbenes, ruthenium derivatives, anthracenes, and dihydroazulenes. The polycyclic strained molecule norbornadiene (NBD), which photoconverts to quadricyclane (QC), is of great interest because it has a high energy storage density and the potential to store energy for a very long time. Unsubstituted norbornadiene has some limitations in this regard, such as poor solar spectrum match and low quantum yield. In the past decade, our group has developed and tested new NBD systems with improved characteristics. Moreover, we have demonstrated their function in laboratory-scale test devices for solar energy harnessing, storage, and release.This Account describes the most impactful recent findings on how to engineer key properties of the NBD/QC system (photochemistry, energy storage, heat release, stability, and synthesis) as well as examples of test devices for solar energy capture and heat release. While it was known that introducing donor-acceptor groups allows for a red-shifted absorption that better matches the solar spectrum, we managed to introduce donor and acceptor groups with very low molecular weight, which allowed for an unprecedented solar spectrum match combined with high energy density. Strategic steric hindrance in some of these systems dramatically increases the storage time of the photoisomer QC, and dimeric systems have independent energies barriers that lead to an improved solar spectrum match, prolonged storage times, and higher energy densities. These discoveries offer a toolbox of possible chemical modifications that can be used to tune the properties of NBD/QC systems and make them suitable for the desired applications, which can be useful for anyone wanting to take on the challenge of designing efficient MOST systems.Several test devices have been built, for example, a hybrid MOST device that stores sunlight energy and heat water at the same time. Moreover, we developed a device for monitoring catalyzed QC to NBD conversion resulting in the possibility to quantify a significant macroscopic heat generation. Finally, we tested different formulations of polymeric composites that can absorb light during the day and release the energy as heat during the night for possible use in future window coating applications. These lab-scale realizations are formative and contribute to pushing the field forward toward the real-life application of MOST systems

EPD and EPDnew, high-quality promoter resources in the next-generation sequencing era

The Eukaryotic Promoter Database (EPD), available online at http://epd.vital-it.ch, is a collection of experimentally defined eukaryotic POL II promoters which has been maintained for more than 25 years. A promoter is represented by a single position in the genome, typically the major transcription start site (TSS). EPD primarily serves biologists interested in analysing the motif content, chromatin structure or DNA methylation status of co-regulated promoter subsets. Initially, promoter evidence came from TSS mapping experiments targeted at single genes and published in journal articles. Today, the TSS positions provided by EPD are inferred from next-generation sequencing data distributed in electronic form. Traditionally, EPD has been a high-quality database with low coverage. The focus of recent efforts has been to reach complete gene coverage for important model organisms. To this end, we introduced a new section called EPDnew, which is automatically assembled from multiple, carefully selected input datasets. As another novelty, we started to use chromatin signatures in addition to mRNA 5′tags to locate promoters of weekly expressed genes. Regarding user interfaces, we introduced a new promoter viewer which enables users to explore promoter-defining experimental evidence in a UCSC genome browser windo

The Eukaryotic Promoter Database: expansion of EPDnew and new promoter analysis tools

We present an update of EPDNew (http://epd.vital-it.ch), a recently introduced new part of the Eukaryotic Promoter Database (EPD) which has been described in more detail in a previous NAR Database Issue. EPD is an old database of experimentally characterized eukaryotic POL II promoters, which are conceptually defined as transcription initiation sites or regions. EPDnew is a collection of automatically compiled, organism-specific promoter lists complementing the old corpus of manually compiled promoter entries of EPD. This new part is exclusively derived from next generation sequencing data from high-throughput promoter mapping experiments. We report on the recent growth of EPDnew, its extension to additional model organisms and its improved integration with other bioinformatics resources developed by our group, in particular the Signal Search Analysis and ChIP-Seq web server

The Weak Metal-Water Bond in Diphenylborylated Organoaquacobaloximes and Rhodoximes Leads to the Formation of an Unusual Dinuclear Rh(III) Complex

The synthesis and characterization of a series of RM(DBPh2)2(H2O) complexes (M = Co and Rh) and the X-ray structure of the dinuclear [n-PrRh(DH)(DBPh2)]2 (1) obtained by recrystallization of n-PrRh(DBPh2)2(H2O) in non coordinating solvent are reported. The crystals of (1) are built up by neutral centrosymmetric dinuclear [n-PrRh(DH)(DBPh2)]2 units and CH2Cl2 crystallization molecules in the ratio 1:1. The Rh ion of one n-PrRh(DH)(DBPh2) unit achieves hexacoordination by coordination of one of the oxime O at-oms of the other unit. The formation of the dimer by recrystallization of n-PrRh(DBPh2)2(H2O) in non coordinating solvent may be ascribed to the concomitant effect of the weak metal-water bond in the monomeric aqua complex, the strong tendency of Rh to achieving hexacoordination in such organo derivatives, and the ease of losing a BPh2 bridge of the diphenylborylated organorhodoximes

Genetic and physiological analysis of Rht8 in bread wheat: an alternative source of semi-dwarfism with a reduced sensitivity to brassinosteroids

Over the next decade, wheat grain production must increase to meet the demand of a fast growing human population. One strategy to meet this challenge is to raise wheat productivity by optimizing plant stature. The Reduced height 8 (Rht8) semi-dwarfing gene is one of the few, together with the Green Revolution genes, to reduce stature of wheat (Triticum aestivum L.), and improve lodging resistance, without compromising grain yield. Rht8 is widely used in dry environments such as Mediterranean countries where it increases plant adaptability. With recent climate change, its use could become increasingly important even in more northern latitudes. In the present study, the characterization of Rht8 was furthered. Morphological analyses show that the semi-dwarf phenotype of Rht8 lines is due to shorter internodal segments along the wheat culm, achieved through reduced cell elongation. Physiological experiments show that the reduced cell elongation is not due to defective gibberellin biosynthesis or signalling, but possibly to a reduced sensitivity to brassinosteroids. Using a fine-resolution mapping approach and screening 3104 F2 individuals of a newly developed mapping population, the Rht8 genetic interval was reduced from 20.5 cM to 1.29 cM. Comparative genomics with model genomes confined the Rht8 syntenic intervals to 3.3 Mb of the short arm of rice chromosome 4, and to 2 Mb of Brachypodium distachyon chromosome 5. The very high resolution potential of the plant material generated is crucial for the eventual cloning of Rht

Readthrough of stop codons under limiting ABCE1 concentration involves frameshifting and inhibits nonsense-mediated mRNA decay

To gain insight into the mechanistic link between translation termination and nonsense-mediated mRNA decay (NMD), we depleted the ribosome recycling factor ABCE1 in human cells, resulting in an upregulation of NMD-sensitive mRNAs. Suppression of NMD on these mRNAs occurs prior to their SMG6-mediated endonucleolytic cleavage. ABCE1 depletion caused ribosome stalling at termination codons (TCs) and increased ribosome occupancy in 3' UTRs, implying enhanced TC readthrough. ABCE1 knockdown indeed increased the rate of readthrough and continuation of translation in different reading frames, providing a possible explanation for the observed NMD inhibition, since enhanced readthrough displaces NMD activating proteins from the 3' UTR. Our results indicate that stalling at TCs triggers ribosome collisions and activates ribosome quality control. Collectively, we show that improper translation termination can lead to readthrough of the TC, presumably due to ribosome collisions pushing the stalled ribosomes into the 3' UTR, where it can resume translation in-frame as well as out-of-frame

Exploring the potential of a hybrid device combining solar water heating and molecular solar thermal energy storage

A hybrid solar energy system consisting of a molecular solar thermal energy storage system (MOST) combined with a solar water heating system (SWH) is presented. The MOST chemical energy storage system is based on norbornadiene–quadricyclane derivatives allowing for conversion of solar energy into stored chemical energy at up to 103 kJ mol1 (396 kJ kg1 ). It is demonstrated that 1.1% of incoming solar energy can be stored in the chemical system without significantly compromising the efficiency of the solar water heating system, leading to efficiencies of combined solar water heating and solar energy storage of up to 80%. Moreover, prospects for future improvement and possible applications are discussed