Nonabelian Hodge theory and vector valued modular forms

We examine the relationship between nonabelian Hodge theory for Riemann surfaces and the theory of vector valued modular forms. In particular, we explain how one might use this relationship to prove a conjectural three-term inequality on the weights of free bases of vector valued modular forms associated to complex, finite dimensional, irreducible representations of the modular group. This conjecture is known for irreducible unitary representations and for all irreducible representations of dimension at most 12. We prove new instances of the three-term inequality for certain nonunitary representations, corresponding to a class of maximally-decomposed variations of Hodge structure, by considering the same inequality with respect to a new type of modular form, called a "Higgs form", that arises naturally on the Dolbeault side of nonabelian Hodge theory. The paper concludes with a discussion of a strategy for reducing the general case of nilpotent Higgs bundles to the case under consideration in our main theorem.Comment: 22 pages, 1 tabl

Synthèse et étude de cages moléculaires photo-modulables et génération de nano-cristaux d'or par photo-catalyse supramoléculaire

Les objectifs de cette thèse sont articulés autour de deux axes principaux : la synthèse et l étude de cages moléculaires photo-modulables, et la génération de nano-cristaux d or par photo-catalyse supramoléculaire. Ces deux thématiques sont reliées entre elles par l exploitation des propriétés photophysiques et photochimiques d un motif commun, le 9,10-diphénylanthracène (DPA). Dans un premier temps, de nouvelles architectures tridimensionnelles photo-modulables de type cage moléculaire ont été conçues et étudiées. En présence d oxygène, l irradiation directe ou sensibilisée du DPA permet de former réversiblement le dérivé endoperoxyde et ainsi moduler les propriétés de complexation de la cage. Les différentes stratégies de synthèse mises en place reposent sur l exploitation conjuguée de la réactivité de la 2,4,6-trichloro-1,3,5-triazine, et de réactions de chimie click (métathèse des oléfines, cycloaddition de Huisgen). L étude et la modulation des propriétés des reconnaissances ont été effectuées sur des sels de cations alcalins (sodium et césium) et suivies par émission de fluorescence et spectroscopie d absorption UV-visible. Les résultats obtenus avec deux cages possédant des constantes d'associations élevées (logK = 8,7 pour le cation sodium) montrent une augmentation de la constante d association d un facteur 10 et 20 pour respectivement le sodium et le césium entre la forme DPA et la forme endoperoxyde. Dans un second temps, des photocatalyseurs supramoléculaires basés sur le chromophore DPA ont été étudiés en vue de la synthèse de nano-cristaux d or nus. L association du chromophore avec des thioéthers permet de former un complexe en phase organique par extraction de sels d or(III) depuis une phase aqueuse. L irradiation à 400nm permet la réduction de l or(III) par transfert d énergie depuis le 9,10-diphénylanthracène. Les atomes d or sont ensuite relargués en phase aqueuse pour former des nano-cristaux nus qui ont pu être caractérisés par MET, XPS, AFM et DLS. Par ailleurs, ce procédé est catalytique dans le toluène et un système de réduction en flux continu a été mis au point permettant un turnover moyen de 150.The goals of this thesis are organized around two major axes: the synthesis and study of photo-gated molecular cages, and the generation of gold nanocrystals by supramolecular photocatalysis. These two themes are connected by the use of the photochemical and photophysical properties of a common chromophore, 9,10-diphenylanthracene (DPA). Three-dimensional photo-gated cage-like architectures were designed and synthesized. Various synthetic strategies based on the combined use of the 2,4,6-trichloro-1,3,5-triazine unit and "click" chemistry reactions (olefin metathesis, Huisgen cycloaddition) were employed for the synthesis. In the presence of oxygen, sensitized or direct irradiation of the DPA chromophore forms the corresponding endoperoxide derivative, thereby modulating the binding properties of the cage. The study and the modulation of the recognition properties were performed on various alkali metal cations and a strong binding of sodium and cesium was evidenced by fluorescence emission and UV-visible absorption spectroscopy. The cages investigated possessed high association constants towards sodium and cesium cations (logK = 8.7 for the sodium cation) which could be reversibly increased by a factor 10 and 20 for sodium and cesium, respectively, upon formation of the endoperoxide. Supramolecular photocatalysis of gold(III) reduction based on the DPA chromophore was also studied for the preparation of uncapped gold nanocrystals. The combination of the DPA chromophore with thioether chains allows the formation of a complex in the organic phase by extraction of gold(III) chloride from an aqueous phase. Irradiation at 400 nm enables the reduction gold(III) by energy transfer from the 9,10-diphenylanthracene followed by oxidation of the solvent. The gold atoms are subsequently released in the aqueous phase to form uncapped nanocrystals characterized using TEM, XPS, AFM, and DLS techniques. Furthermore, the process is catalytic in toluene, where a continuous flow reactor was developed. The latter allowed an average catalytic turnover of 150 to be determined.BORDEAUX1-Bib.electronique (335229901) / SudocSudocFranceF

Direct formation of fullerene monolayers using [4+2] Diels-Alder cycloaddition.

International audienceThe formation of covalent C(60) monolayers through [4+2] Diels-Alder cycloaddition between C(60) and anthracene monolayers grafted onto a silicon oxide surface was investigated by ellipsometry, fluorescence and by atomic force microscopy

Evidence of Band Bending Induced by Hole Trapping at MAPbI3 Perovskite / Metal Interface

International audienceElectron injection by tunneling from a gold electrode and hole transport properties in polycrystalline MAPbI3 has been investigated using variable temperature experiments and numerical simulations. The presence of a large and unexpected band bending at the Au/MAPbI3 interface is revealed and attributed to the trapping of holes, which enhances the injection of electrons via tunneling. These results elucidate the role of volume and interface defects in state-of-the-art hybrid perovskite semiconductors

Common mechanism for helical nanotube formation by anodic polymerization and by cathodic deposition using helical pores on silicon electrodes

We report that platinum-assisted chemical etching formed self-organized helical pores in silicon substrates can be utilized as platforms for the electrochemical production of nanohelices of conducting polymers (polypyrrole) and metals (gold). Surprisingly, the nanohelices thus created are tubes although the polymerization and deposition were carried out by anodic and cathodic reactions, respectively. Based on our results, we propose a common mechanism for the formation of tubular nanohelices by both anodic polymerization and cathodic deposition through the accumulation of reactants in microporous silicon which covers the wall surface of the helical pores

Influence of anions and solvent molecules on the packing and emission spectra of coordination polymers based on silver ions and an anthracene derivative

Luminescence between green and blue was observed in the solid state for the free ligand L (anthracene-9,10-diylbis(methylene) dinicotinate) and five different Ag-L coordination polymers upon excitation at 344 nm. Depending on the packing of the anthracene moieties due to coordinating anions and the presence or absence of solvent molecules, the emission maximum is shifted

“Innovative high pressure/high temperature, multi-sensing bioreactors system for microbial risk assessment in underground hydrogen storage”

This study addresses the microbial risks associated with Underground Hydrogen Storage (UHS), a critical component in the transition towards renewable energy systems, by employing an innovative multi-reactor system (Bio-xplorer) to simulate UHS conditions in two Italian reservoirs. The microbiological risk assessment (MRA) of Reservoir A and B was evaluated by subjecting them to gas mixtures of 10 % H2 and 90 % CH4, and 99 % H2 and 1 % CO2, respectively. In Reservoir A, the stability of pressure and temperature, the negligible optical density, and lack of microbial metabolites suggested a low risk of microbial activation. Molecular analyses confirmed the absence of sulphate- reducing bacteria (SRB) and limited growth of hydrogenotrophic methanogens (HM). Similarly, in Reservoir B, the absence of SRB and limited occurrence of HM indicated a low microbiological risk. Overall, the present work supports the safe and efficient implementation of UHS, a promising mitigation technique for climate change, using an innovative tool for MRA

Narcissistic self-sorting of n-acene nano-ribbons yielding energy-transfer and electroluminescence at p-n junctions

The 2,3-didecyloxy derivative of an n-type anthracene (n-BG) and a p-type tetracene (p-R) have been synthesized and their self-assembly into nano-ribbons studied. Hyperspectral fluorescence imaging revealed their narcissistic self-sorting, leading to separated nanoribbons emitting with very different colors (blue or green for n-BG, depending on the growth solvent, and red for p-R). It is unique that the usual origins of self-sorting, such as specific H-bonding, different growth kinetics, or incompatible steric hindrance can be ruled out. Hence, the narcissistic behaviour is herein proposed to originate from a sofar unconsidered cause: the discrepancy between the quadrupolar character of n-BG and dipolar character of p-R. At the p-n junctions of these nanoribbons, inter-ribbon FRET and electro-luminescence switch-on were observed by fluorescence/luminescence microscopy.The authors acknowledge the financial support of the European Research Council Marie Curie Actions (FP7-PEOPLE-2012-ITN SMARTNET Grant agreement Nr 316656); the CNRS; the French Ministry of Education and Research; the Region Aquitaine; the ANR-06-JCJC-0030; the Department of Education, Science and Universities of the Basque Country Government (postdoctoral grant and project IT1639-22); the "Arina" informatic cluster of UPV/EHU; the facilities ELORGA of UB; and the ANR-17-CE24-0033-01 RESOLVE. The authors thank Dr A. Mendez-Ardoy for the CV measurements and CESAMO for structural analyses (ISM, Univ. Bordeaux)

Loading linear arrays of Cu(II) inside aromatic amide helices

The very stable helices of 8-amino-2-quinolinecar-boxylic acid oligoamides are shown to uptake CuIIions in theircavity through deprotonation of their amide functions with minimal alteration of their shape, unlike most metallo-organicstructures which generally differ from their organic precursors.The outcome is the formation of intramolecular linear arrays of a defined number of CuIIcenters (up to sixteen in this study)at a 3 distance, forming a molecular mimic of a metal wirecompletely surrounded by an organic sheath. The helices packin the solid state so that the arrays of CuIIextend intermolecularly. Conductive-AFM and cyclic voltammetry suggest thatelectrons are transported throughout the metal-loaded helices in contrast with hole transport observed for analogous foldamers devoid of metal ions.Les voies de signalisation du récepteur 5-HT6: de nouvelles cibles pour le traitement de la douleur neuropathique