New indolium fluorofores for two-photon absortion (2PA) bioimaging applications

The development of organic materials with 2PA has attracted intensive attention in the past two decades [1]. In two-photon bio-imaging applications the design of the chromophore requires to have a good cross-section (σ2PA) and good biological compatibility which depends on the molecular volume and polarity [2]. In this work, we present the design, synthesis and characterization of new indolium derivatives. These compounds are easy to achieve with good yields and good photophysical properties. In addition, time-dependent density functional theory (TDDFT) has been carried out to investigate the energy level of the ground and excited state. Their spectral properties and assays performed on cultured cells, demonstrate the potential of these compounds as fluorescent probes with application in two-photon bio-imaging.

Slow passage through thresholds in quantum dot lasers

A turn on of a quantum dot (QD) semiconductor laser simultaneously operating at the ground state (GS) and excited state (ES) is investigated both experimentally and theoretically. We find experimentally that the slow passage through the two successive laser thresholds may lead to significant delays in the GS and ES turn ons. The difference between the turn-on times is measured as a function of the pump rate of change and reveals no clear power law. This has motivated a detailed analysis of rate equations appropriate for two-state lasing QD lasers. We find that the effective time of the GS turn on follows an -1/2 power law provided that the rate of change is not too small. The effective time of the ES transition follows an -1 power law, but its first order correction in ln is numerically significant. The two turn ons result from different physical mechanisms. The delay of the GS transition strongly depends on the slow growth of the dot population, whereas the ES transition only depends on the time needed to leave a repellent steady state.

Synthesis of Metal-Binding Ligand-Containing Copolymers, Nanoparticles and Blends

In this thesis we developed three copper-containing systems. Copper shows intriguing abilities in photocatalysis, however, one of the major limitations of many copper complexes is that photochemical properties might be quenched in solution caused by π-interactions between solvent and solute, due to Jahn-Teller distortion in the excited state. As such, we herein seek to synthesise copper heteroleptic complexes that will subsequently be nanoprecipitated with a polymer. This will allow the polymer to encase the complex and prevent the solvent-induced quenching. Subsequently, the preparation of blends of polymer with the aforementioned copper complexes, at different weight ratios is sought. The preparation of the blend is particularly interesting as the catalytic properties are anticipated to be inferior on account of the low surface area. However, owing to the polymer matrix better, mechanical properties are anticipated. The blends can combine the mechanical properties of the polymer and the luminescence of the complex, with the advantage that the polymer matrix can also prevent quenching from oxygen. As final task, we developed a copper-containing monomer. The synthesis of a monomer that contains copper and can be excited under ultraviolet (UV) light is particularly interesting.

Organic photosensitizers and nanostructured semiconductors for photoredox catalysis and artificial photosynthesis

Over the course of evolution, Nature has elegantly learned to use light to drive chemical reactions. On the other hand, humans have only recently started learning how to play with this powerful tool to carry out chemical transformations. In particular, a step forward was possible thanks to molecules and materials that can absorb light and trigger a series of processes that can drive chemical reactions. However, scarce elements are extensively employed in the design of most of these compounds and considerations on their scarcity and toxicity have sparked interest on alternatives based on earth-abundant elements. In this framework, the focus of this thesis has been the development and employment of heavy-metal free chromophores and of earth-abundant oxides. The first chapter regards the functionalization of boron-dipyrromethenes (BODIPYs) so as to allow access to their triplet excited state and tune their redox potentials, which was achieved thanks to the design of orthogonal donor-acceptor dyads. The BODIPY dyads were used to promote a photoredox reaction, and the mechanism of the reaction was clarified. In the second chapter, organic chromophores that display thermally-activated delayed fluorescence (TADF) were studied. These were used to perform enantioselective photoredox reactions, and a mechanistic investigation allowed to elucidate the fate of these photosensitizers in the reaction. Thanks to their stronger reducing power, it was possible to demonstrate the employability of TADF dyes in artificial photosynthesis, as well. Last, the oxidation of biomass-derived compounds was studied in a photoelectrochemical cell. For this purpose, hematite photoanodes were synthesized in collaboration with Prof. Caramori’s group at the University of Ferrara (Italy) and they were tested in the presence of a redox mediator. In addition to this, the possibility of repurposing a copper(II) water oxidation catalyst for the oxidation of biomass was investigated in collaboration with Prof. Llobet’s group at ICIQ (Tarragona, Spain).

Excitonic properties of transition metal oxide perovskites and workflow automatization of GW schemes

The Many-Body-Perturbation Theory approach is among the most successful theoretical frameworks for the study of excited state properties. It allows to describe the excitonic interactions, which play a fundamental role in the optical response of insulators and semiconductors. The first part of the thesis focuses on the study of the quasiparticle, optical and excitonic properties of \textit{bulk} Transition Metal Oxide (TMO) perovskites using a G$_0$W$_0$+Bethe Salpeter Equation (BSE) approach. A representative set of 14 compounds has been selected, including 3d, 4d and 5d perovskites. An approximation of the BSE scheme, based on an analytic diagonal expression for the inverse dielectric function, is used to compute the exciton binding energies and is carefully bench-marked against the standard BSE results. In 2019 an important breakthrough has been achieved with the synthesis of ultrathin SrTiO3 films down to the monolayer limit. This allows us to explore how the quasiparticle and optical properties of SrTiO3 evolve from the bulk to the two-dimensional limit. The electronic structure is computed with G0W0 approach: we prove that the inclusion of the off-diagonal self-energy terms is required to avoid non-physical band dispersions. The excitonic properties are investigated beyond the optical limit at finite momenta. Lastly a study of the under pressure optical response of the topological nodal line semimetal ZrSiS is presented, in conjunction with the experimental results from the group of Prof. Dr. Kuntscher of the Augsburg University. The second part of the thesis discusses the implementation of a workflow to automate G$_0$W$_0$ and BSE calculations with the VASP software. The workflow adopts a convergence scheme based on an explicit basis-extrapolation approach [J. Klimeš \textit{et al.}, Phys. Rev.B 90, 075125 (2014)] which allows to reduce the number of intermediate calculations required to reach convergence and to explicit estimate the error associated to the basis-set truncation.

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2`-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E(a) = (54 +/- 8) kJ/mol, and chloroform cast film, E(a) = (69 +/- 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of similar to 10 degrees at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the inter-backbone planes reduces its intensity for higher temperatures. This last result Could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments. (C) 2008 Elsevier Ltd. All rights reserved.

The effects of anticalcification treatments and hydration on the molecular dynamics of bovine pericardium collagen as revealed by (13)C solid-state NMR

This article describes a solid-state NMR (SSNMR) investigation of the influence of hydration and chemical cross-linking on the molecular dynamics of the constituents of the bovine pericardium (BP) tissues and its relation to the mechanical properties of the tissue. Samples of natural phenetylamine-diepoxide (DE)- and glutaraldehyde (GL)-fixed BP were investigated by (13)C cross-polarization SSNMR to probe the dynamics of the collagen, and the results were correlated to the mechanical properties of the tissues, probed by dynamical mechanical analysis. For samples of natural BP, the NMR results show that the higher the hydration level the more pronounced the molecular dynamics of the collagen backbone and sidechains, decreasing the tissue`s elastic modulus. In contrast, in DE- and GL-treated samples, the collagen molecules are more rigid, and the hydration seems to be less effective in increasing the collagen molecular dynamics and reducing the mechanical strength of the samples. This is mostly attributed to the presence of cross-links between the collagen plates, which renders the collagen mobility less dependent on the water absorption in chemically treated samples. Copyright (C) 2010 John Wiley & Sons, Ltd.

Dynamics of Tm-Ho energy transfer and deactivation of the F-3(4) low level of thulium in fluorozirconate glasses

The mechanism involved in the Tm3+ (F-3(4))-->Ho3+ (I-5(7)) energy transfer and Tm3+ (H-3(4), H-3(6))-->Tm3+ (F-3(4), F-3(4)) cross relaxation as a function of the donor and acceptor concentrations was investigated in Tm-Ho-codoped fluorozirconate glasses. The experimental transfer rates were determined for the Tm-->Ho energy transfer from the best fit of the acceptor luminescence decay using an expression which takes into account the Inokuti-Hirayama model and localized donor-to-acceptor interaction solution. The original acceptor solution derived from the Inokuti-Hirayama model fits well the acceptor luminescence transient only for low-concentrated systems. The results showed that a fast excitation diffusion that occurs in a very short time (t<excited donor (D-*) and the acceptor (A). A localized donor-to-acceptor interaction takes place, leading to an exponential decay of donors as an average of the microscopic rate equation solution of each D-*-A pair separated by distance R that contributes in addition to the Inokuti-Hirayama solution. The observation that the experimental transfer rates were always much bigger than the one predicted by the diffusion model, in which the energy transfer process is assisted by excitation migration among donors state, reinforces the existence of a fast excitation diffusion among donor ions before the energy transfer to acceptor already observed in Yb:Er:ZBLAN. The fast excitation diffusion effect was observed to dominate both the Tm-->Tm cross relaxation and Tm-->Ho energy transfer ions from H-3(4) and F-3(4) thulium states, respectively. (C) 2004 American Institute of Physics.

On Nonlinear Dynamics and Control of A Particular Portal Frame Foundation Model, Excited by a Non-Ideal Motor

The nonlinear dynamic response and a nonlinear control method of a particular portal frame foundation for an unbalanced rotating machine with limited power (non-ideal motor) are examined. Numerical simulations are performed for a set of control parameters (depending on the voltage of the motor) related to the static and dynamic characteristics of the motor. The interaction of the structure with the excitation source may lead to the occurrence of interesting phenomena during the forward passage through the several resonance states of the systems. A mathematical model having two degrees of freedom simplifies the non-ideal system. The study of controlling steady-state vibrations of the non-ideal system is based on the saturation phenomenon due to internal resonance.

Spin coherence generation in negatively charged self-assembled (In,Ga)As quantum dots by pumping excited trion states

Spin coherence generation in an ensemble of negatively charged (In,Ga)As/GaAs quantum dots was investigated by picosecond time-resolved pump-probe spectroscopy measuring ellipticity. Robust coherence of the ground-state electron spins is generated by pumping excited charged exciton (trion) states. The phase of the coherent state, as evidenced by the spin ensemble precession about an external magnetic field, varies relative to spin coherence generation resonant with the ground state. The phase variation depends on the pump photon energy. It is determined by (a) pumping dominantly either singlet or triplet excited states, leading to a phase inversion, and (b) the subsequent carrier relaxation into the ground states. From the dependence of the precession phase and the measured g factors, information about the quantum dot shell splitting and the exchange energy splitting between triplet and singlet states can be extracted in the ensemble.

Influence of spatial constraints in non-crystalline regions on the polymer dynamics in semi-crystalline polyethylene: a solid state NMR study

A broad variety of solid state NMR techniques were used to investigate the chain dynamics in several polyethylene (PE) samples, including ultrahigh molecular weight PEs (UHMW-PEs) and low molecular weight PEs (LMW-PEs). Via changing the processing history, i.e. melt/solution crystallization and drawing processes, these samples gain different morphologies, leading to different molecular dynamics. Due to the long chain nature, the molecular dynamics of polyethylene can be distinguished in local fluctuation and long range motion. With the help of NMR these different kinds of molecular dynamics can be monitored separately. In this work the local chain dynamics in non-crystalline regions of polyethylene samples was investigated via measuring 1H-13C heteronuclear dipolar coupling and 13C chemical shift anisotropy (CSA). By analyzing the motionally averaged 1H-13C heteronuclear dipolar coupling and 13C CSA, the information about the local anisotropy and geometry of motion was obtained. Taking advantage of the big difference of the 13C T1 relaxation time in crystalline and non-crystalline regions of PEs, the 1D 13C MAS exchange experiment was used to investigate the cooperative chain motion between these regions. The different chain organizations in non-crystalline regions were used to explain the relationship between the local fluctuation and the long range motion of the samples. In a simple manner the cooperative chain motion between crystalline and non-crystalline regions of PE results in the experimentally observed diffusive behavior of PE chain. The morphological influences on the diffusion motion have been discussed. The morphological factors include lamellar thickness, chain organization in non-crystalline regions and chain entanglements. Thermodynamics of the diffusion motion in melt and solution crystallized UHMW-PEs is discussed, revealing entropy-controlled features of the chain diffusion in PE. This thermodynamic consideration explains the counterintuitive relationship between the local fluctuation and the long range motion of the samples. Using the chain diffusion coefficient, the rates of jump motion in crystals of the melt crystallized PE have been calculated. A concept of "effective" jump motion has been proposed to explain the difference between the values derived from the chain diffusion coefficients and those in literatures. The observations of this thesis give a clear demonstration of the strong relationship between the sample morphology and chain dynamics. The sample morphologies governed by the processing history lead to different spatial constraints for the molecular chains, leading to different features of the local and long range chain dynamics. The knowledge of the morphological influence on the microscopic chain motion has many implications in our understanding of the alpha-relaxation process in PE and the related phenomena such as crystal thickening, drawability of PE, the easy creep of PE fiber, etc.

Metastability exchange optical pumping in 3 He gas up to 30 mT: Efficiency measurements and evidence of laser-induced nuclear relaxation

Advances in metastability exchange optical pumping (MEOP) of 3He at high laser powers, with its various applications, but also at high gas pressures p3 and high magnetic field strengths B, have provided strong motivation for revisiting the understanding and for investigating the limitations of this powerful technique. For this purpose, we present systematic experimental and theoretical studies of efficiency and of relaxation mechanisms in B≤30 mT and p3=0.63−2.45 mbar. 3He nuclear polarisation is measured by light absorption in longitudinal configuration where weak light beams at 1083 nm parallel to magnetic field and cell axis with opposite circular polarisations are used to probe the distribution of populations in the metastable state. This method is systematically tested to evaluate potential systematic biases and is shown to be reliable for the study of OP dynamics despite the redistribution of populations by OP light. Nuclear polarisation loss associated to the emission of polarised light by the plasma discharge used for MEOP is found to decrease above 10 mT, as expected, due to hyperfine decoupling in highly excited states. However, this does not lead to improved MEOP efficiency at high laser power. We find clear evidence of additional laser-induced relaxation instead. The strong OP-enhanced polarisation losses, currently limiting MEOP performances, are quantitatively investigated using an angular momentum budget approach and a recently developed comprehensive model that describes the combined effects of OP, ME and relaxation, validated by comparison to experimental results.

Impact of the carrier relaxation paths on two-state operation in quantum dot lasers

We study InGaAs QD laser operating simultaneously at ground (GS) and excited (ES) states under 30ns pulsed-pumping and distinguish three regimes of operation depending on the pump current and the carrier relaxation pathways. An increased current leads to an increase in ES intensity and to a decrease in GS intensity (or saturation) for low pump range, as typical for the cascade-like pathway. Both the GS and ES intensities are steadily increased for high current ranges, which prove the dominance of the direct capture pathway. The relaxation oscillations are not pronounced for these ranges. For the mediate currents, the interplay between the both pathways leads to the damped large amplitude relaxation oscillations with significant deviation of the relaxation oscillation frequency from the initial value during the pulse.

Site Specific Spin Dynamics In Bafe2as2: Tuning The Ground State By Orbital Differentiation.

The role of orbital differentiation on the emergence of superconductivity in the Fe-based superconductors remains an open question to the scientific community. In this investigation, we employ a suitable microscopic spin probe technique, namely Electron Spin Resonance (ESR), to investigate this issue on selected chemically substituted BaFe2As2 single crystals. As the spin-density wave (SDW) phase is suppressed, we observe a clear increase of the Fe 3d bands anisotropy along with their localization at the FeAs plane. Such an increase of the planar orbital content is interestingly independent of the chemical substitution responsible for suppressing the SDW phase. As a consequence, the magnetic fluctuations in combination with this particular symmetry of the Fe 3d bands are propitious ingredients for the emergence of superconductivity in this class of materials.

Generation of nonground-state Bose-Einstein condensates by modulating atomic interactions

A technique is proposed for creating nonground-state Bose-Einstein condensates in a trapping potential by means of the temporal modulation of atomic interactions. Applying a time-dependent spatially homogeneous magnetic field modifies the atomic scattering length. A modulation of the scattering length excites the condensate, which, under special conditions, can be transferred to an excited nonlinear coherent mode. It is shown that a phase-transition-like behavior occurs in the time-averaged population imbalance between the ground and excited states. The application of the technique is analyzed and it is shown that the considered effect can be realized for experimentally available condensates.