BODIPY-Porphyrazin-Hybride als panchromatische Lichtsammelsysteme für farbstoffsensibilisierte Solarzellen

In farbstoffsensibilisierten Solarzellen (DSSC) spielen Chromophore, die als Lichtsammel- und Energie-/Elektronentransfersysteme fungieren, eine zentrale Rolle. Phthalocyanine mit ihren intensiven Absorptionsbanden um 400 nm und 700 nm besitzen großes Potential für die effektive Sensibilisierung von Solarzellen. Trotz ihrer vielversprechenden physikochemischen Eigenschaften und intensiver Bemühungen erreichen Phthalocyanin-sensibilisierte Solarzellen nicht die Effizienzen, die bisher mit anderen Chromophorklassen erzielt werden konnten. In der vorliegenden Dissertation wurde die Entwicklung effizienter Lichtsammelsysteme für DSSC auf der Basis von Aza-substituierten Phthalocyaninen, sogenannten Pyrazinoporphyrazinen, verfolgt. Ein besonderer Fokus lag dabei auf einer Verbesserung der Absorptionseigenschaften der Chromophore im Bereich ihrer intrinsischen Absorptionslücke zwischen den Maxima um 400 nm und 700 nm. Um diese optische Lücke zu schließen wurden komplementär absorbierende BODIPY-Farbstoffe kovalent an synthetisch maßgeschneiderte Porphyrazine gebunden. Insgesamt wurden sechs neue Porphyrazin-Sensibilisatoren synthetisiert und photophysikalisch sowie elektrochemisch charakterisiert. Alle in dieser Arbeit untersuchten Porphyrazine tragen sterisch anspruchsvolle Tri(p-tolyl)propinyl-Gruppen um Agglomerationen zu vermeiden. Darüber hinaus wurden die Porphyrazine peripher entweder mit Hydroxy- oder Carboxygruppen als Bindungsstellen für oxidische Materialien ausgestattet sowie mit sechs BODIPY-Auxiliarfarbstoffen funktionalisiert, deren Substitutionsmuster variiert wurden. Zur Darstellung der komplexen Porphyrazine wurde eine Syntheseroute erarbeitet, die statistische Cyclisierungen unterschiedlicher Dinitril-Vorstufen beinhaltete und es ermöglichte, funktionelle Gruppen erst am vorgeformten Makrocyclus einzuführen. Die photophysikalische Untersuchung der hochfunktionalisierten Farbstoffe erfolgte über UV/Vis- und Fluoreszenzspektroskopie. Im Fall der BODIPY-Porphyrazin-Hybride schließt die zusätzliche Absorptionsbande der peripheren BODIPY-Einheiten die intrinsische Absorptionslücke der Porphyrazine. Die Hybride zeigen somit eine breite Absorption über den gesamten sichtbaren Spektralbereich mit hohen Extinktionskoeffizienten von ca. 4·10^5 M^−1cm^−1. Mittels Fluoreszenz- und Anregungsspektren wurde ein photoinduzierter Energie-transfer von den BODIPY-Einheiten auf den Porphyrazinkern nachgewiesen. Das elektrochemische Verhalten der BODIPY- und Porphyrazin-Verbindungen wurde mittels Cyclo- und Square-Wave-Voltammetrie untersucht. Die Effizienzen der Lichtenergieumwandlung wurden mit Hilfe von selbst-hergestellten und standardisierten farbstoffsensibilisierten Solarzellen bewertet. Alle Solarzellen zeigten eine messbare Photoaktivität unter Bestrahlung. Die Wirkungsgrade der Zellen lagen jedoch alle unter 1 %. Generell führten die Carboxyl-funktionalisierten Porphyrazine zu besseren Wirkungsgraden als die analogen, mit der tripodalen Ankergruppe ausgestatteten Derivate. Die mit Hilfe von Adsorptionsisothermen ermittelten Bindungskonstanten der Adsorption der Farbstoffe auf der TiO2-Oberfläche zeigten, dass beide Hafteinheiten eine feste Verankerung der Chromophore auf den TiO2-Elektroden ermöglichten. Insgesamt wirkte sich die Präsenz der peripheren BODIPY-Farbstoffe positiv auf die Wirkungsgrade der Solarzellen aus, jedoch nur in geringem Maß. Dieses Ergebnis wurde hauptsächlich auf die geringe Energiedifferenz zwischen der Leitungsbandkante des TiO2 und den LUMO-Energieniveaus der Chromophore zurückgeführt. Zusätzlich scheinen konkurrierende Prozesse wie die direkte Photoelektroneninjektion von den BODIPY-Einheiten in das TiO2 eine wichtige Rolle zu spielen. Neben der Anwendung in DSSC wurde die Wechselwirkung der Porphyrazine mit Graphen untersucht. Hierzu wurden A3B-Porphyrazine mit Pyrenyl-Seitenketten ausgestattet, die eine nicht-kovalente Verankerung des Chromophors auf Graphen ermöglichen. UV/Vis- und Fluoreszenzmessungen gaben u.a. erste Hinweise auf eine elektronische Kommunikation zwischen den beiden Hybridpartnern.

Improving magnetic coupling for battery charging through 3D magnetic flux

The spatial distribution of the magnetic field and the coupling between the coils in the Wireless Power Transfer (WPT) systems is an important aspect to consider in the system design and efficiency optimization. The presented study in this paper is based on tests performed on a physical model. The transmitting (primary) equipment, is an electrical three-phase system, capable to be connected in star or delta (both electrically and geometrically). The measured results allow to describe graphically the magnetic field distribution in three dimensions. The analytical formulas aim to help to understand and to quantify the physical phenomena but they cannot be considered a universal approach and the measurement results help to understand better the observable facts. In the WPT, the key issues that will influence the efficiency, are the alignment of the coils, the spatial orientation of the magnetic field, the detachment and the tilt between the windings, all they changing the magnetic coupling between the transmitter and the receiver of energy. This research is directed not only to the magnetic field distribution but finally, to optimize the energy transfer efficiency.

Multiscale modeling of light-harvesting systems based on rhodamine B aggregates

Rhodamine B (RB) has been successfully exploited in the synthesis of light harvesting systems, but since RB is prone to form dimers acting as quenchers for the fluorescence, high energy transfer efficiencies can be reached only when using bulky and hydrophobic counterions acting as spacers between RBs. In this PhD thesis, a multiscale theoretical study aimed at providing insights into the structural, photophysical and optical properties of RB and its aggregates is presented. At the macroscopic level (no atomistic details) a phenomenological model describing the fluorescence decay of RB networks in presence of both quenching from dimers and exciton-exciton annihiliation is presented and analysed, showing that the quenching from dimers affects the decay only at long times, a feature that can be exploited in global fitting analysis to determine relevant chemical and photophysical information. At the mesoscopic level (atomistic details but no electronic structure) the RB aggregation in water in presence of different counterions is studied with molecular dynamics (MD) simulations. A new force field has been parametrized for describing the RB flexibility and the RB-RB interaction driving the dimerization. Simulations correctly predict the RB/counterion aggregation only in presence of bulky and hydrophobic counterion and its ability to prevent the dimerization. Finally, at the microscopic level, DFT calculations are performed to demonstrate the spacing action of bulky counterions, but standard TDDFT calculations are showed to fail in correctly describing the excited states of RB and its dimers. Moreover, also standard procedures proposed in literature for obtaining ad hoc functionals are showed to not work properly. A detailed analysis on the effect of the exact exchange shows that its short-range contribution is the crucial quantity for ameliorating results, and a new functional containing a proper amount of such an exchange is proposed and successfully tested.

Diffusing alpha particles radiation treatment optimization in clinical settings

Alpha-particle emitters, notably used in 224Ra-DaRT, have emerged as effective in overcoming radiation resistance and providing targeted cancer therapy. These emitters cause DNA double-strand breaks, visualizable in human lymphocytes. The 224Ra DaRT technique, using a decay chain from seeds, extends alpha particle range, achieving complete tumor destruction while sparing healthy tissue. This thesis examines a biokinetic model, validated with patient data, and a feasibility study on skin squamous cell carcinomas are discussed. The study reports 75% tumor complete response rate and 48% patients experiencing acute grade 2 toxicity, resolving within a month. An observed abscopal effect (AE), where tumor regression occurs at non-irradiated sites, is examined, highlighting DaRT's potential in triggering anti-tumor immune responses. This effect, coupled with DaRT's high-linear energy transfer (LET), suggests its superiority over low-LET radiation in certain clinical scenarios. Improvements to DaRT, including the use of an external radio-opaque template for treatment planning, are explored. This advancement aids in determining source numbers for optimal tumor coverage, enhancing DaRT’s safety. The thesis outlines a typical DaRT procedure, from tumor measurements to source assessment and administration, emphasizing the importance of precise seed positioning. Furthermore, the thesis discusses DaRT's potential in treating prostate cancer, a prevalent global health issue, by offering an alternative to traditional salvage therapies. DaRT seeds, delivering alpha particle-based interstitial radiation, require precision in seed insertion due to their limited tissue range. In conclusion, the thesis advocates for DaRT's role in treating solid tumors, emphasizing its improved radiobiological potency and potential benefits over beta and gamma source-based therapies. Ongoing studies are assessing DaRT's feasibility in treating various solid tumors, including pancreatic, breast, prostate, and vulvar malignancies, suggesting a promising future in cancer treatment.

Modeling Ultrafast Spectroscopy of the NADH Dimer: From UV-VIS to X-rays

Ultrafast pump-probe spectroscopy is a conceptually simple and versatile tool for resolving photoinduced dynamics in molecular systems. Due to the fast development of new experimental setups, such as synchrotron light sources and X-ray free electron lasers (XFEL), new spectral windows are becoming accessible. On the one hand, these sources have enabled scientist to access faster and faster time scales and to reach unprecedent insights into dynamical properties of matter. On the other hand, the complementarity of well-developed and novel techniques allows to study the same physical process from different points of views, integrating the advantages and overcoming the limitations of each approach. In this context, it is highly desirable to reach a clear understanding of which type of spectroscopy is more suited to capture a certain facade of a given photo-induced process, that is, to establish a correlation between the process to be unraveled and the technique to be used. In this thesis, I will show how computational spectroscopy can be a tool to establish such a correlation. I will study a specific process, which is the ultrafast energy transfer in the nicotinamide adenine dinucleotide dimer (NADH). This process will be observed in different spectral windows (from UV-VIS to X-rays), accessing the ability of different spectroscopic techniques to unravel the system evolution by means of state-of-the-art theoretical models and methodologies. The comparison of different spectroscopic simulations will demonstrate their complementarity, eventually allowing to identify the type of spectroscopy that is best suited to resolve the ultrafast energy transfer.

JOINT ENERGY BEAMFORMING AND TIME ASSIGNMENT FOR COOPERATIVE WIRELESS POWERED NETWORKS

Wireless power transfer (WPT) and radio frequency (RF)-based energy har- vesting arouses a new wireless network paradigm termed as wireless powered com- munication network (WPCN), where some energy-constrained nodes are enabled to harvest energy from the RF signals transferred by other energy-sufficient nodes to support the communication operations in the network, which brings a promising approach for future energy-constrained wireless network design. In this paper, we focus on the optimal WPCN design. We consider a net- work composed of two communication groups, where the first group has sufficient power supply but no available bandwidth, and the second group has licensed band- width but very limited power to perform required information transmission. For such a system, we introduce the power and bandwidth cooperation between the two groups so that both group can accomplish their expected information delivering tasks. Multiple antennas are employed at the hybrid access point (H-AP) to en- hance both energy and information transfer efficiency and the cooperative relaying is employed to help the power-limited group to enhance its information transmission throughput. Compared with existing works, cooperative relaying, time assignment, power allocation, and energy beamforming are jointly designed in a single system. Firstly, we propose a cooperative transmission protocol for the considered system, where group 1 transmits some power to group 2 to help group 2 with information transmission and then group 2 gives some bandwidth to group 1 in return. Sec- ondly, to explore the information transmission performance limit of the system, we formulate two optimization problems to maximize the system weighted sum rate by jointly optimizing the time assignment, power allocation, and energy beamforming under two different power constraints, i.e., the fixed power constraint and the aver- age power constraint, respectively. In order to make the cooperation between the two groups meaningful and guarantee the quality of service (QoS) requirements of both groups, the minimal required data rates of the two groups are considered as constraints for the optimal system design. As both problems are non-convex and have no known solutions, we solve it by using proper variable substitutions and the semi-definite relaxation (SDR). We theoretically prove that our proposed solution method can guarantee to find the global optimal solution. Thirdly, consider that the WPCN has promising application potentials in future energy-constrained net- works, e.g., wireless sensor network (WSN), wireless body area network (WBAN) and Internet of Things (IoT), where the power consumption is very critical. We investigate the minimal power consumption optimal design for the considered co- operation WPCN. For this, we formulate an optimization problem to minimize the total consumed power by jointly optimizing the time assignment, power allocation, and energy beamforming under required data rate constraints. As the problem is also non-convex and has no known solutions, we solve it by using some variable substitutions and the SDR method. We also theoretically prove that our proposed solution method for the minimal power consumption design guarantees the global optimal solution. Extensive experimental results are provided to discuss the system performance behaviors, which provide some useful insights for future WPCN design. It shows that the average power constrained system achieves higher weighted sum rate than the fixed power constrained system. Besides, it also shows that in such a WPCN, relay should be placed closer to the multi-antenna H-AP to achieve higher weighted sum rate and consume lower total power.

Advanced Nuclear Energy Systems: Heat Transfer Issues and Trends

Almost 450 nuclear power plants are currently operating throughout the world and supplying about 17% of the world’s electricity. These plants perform safely, reliably, and have no free-release of byproducts to the environment. Given the current rate of growth in electricity demand and the ever growing concerns for the environment, the US consumer will favor energy sources that can satisfy the need for electricity and other energy-intensive products (1) on a sustainable basis with minimal environmental impact, (2) with enhanced reliability and safety and (3) competitive economics. Given that advances are made to fully apply the potential benefits of nuclear energy systems, the next generation of nuclear systems can provide a vital part of a long-term, diversified energy supply. The Department of Energy has begun research on such a new generation of nuclear energy systems that can be made available to the market by 2030 or earlier, and that can offer significant advances toward these challenging goals [1]. These future nuclear power systems will require advances in materials, reactor physics as well as heat transfer to realize their full potential. In this paper, a summary of these advanced nuclear power systems is presented along with a short synopsis of the important heat transfer issues. Given the nature of research and the dynamics of these conceptual designs, key aspects of the physics will be provided, with details left for the presentation.

Midday auroral breakup events and related energy and momentum transfer from the magnetosheath

Combined observations by meridian-scanning photometers, all-sky auroral TV camera and the EISCAT radar permitted a detailed analysis of the temporal and spatial development of the midday auroral breakup phenomenon and the related ionospheric ion flow pattern within the 71°–75° invariant latitude radar field of view. The radar data revealed dominating northward and westward ion drifts, of magnitudes close to the corresponding velocities of the discrete, transient auroral forms, during the two different events reported here, characterized by IMF |BY/BZ| < 1 and > 2, respectively (IMF BZ between −8 and −3 nT and BY > 0). The spatial scales of the discrete optical events were ∼50 km in latitude by ∼500 km in longitude, and their lifetimes were less than 10 min. Electric potential enhancements with peak values in the 30–50 kV range are inferred along the discrete arc in the IMF |BY/BZ| < 1 case from the optical data and across the latitudinal extent of the radar field of view in the |BY/BZ| > 2 case. Joule heat dissipation rates in the maximum phase of the discrete structures of ∼ 100 ergs cm−2 s−1 (0.1 W m−2) are estimated from the photometer intensities and the ion drift data. These observations combined with the additional characteristics of the events, documented here and in several recent studies (i.e., their quasi-periodic nature, their motion pattern relative to the persistent cusp or cleft auroral arc, the strong relationship with the interplanetary magnetic field and the associated ion drift/E field events and ground magnetic signatures), are considered to be strong evidence in favour of a transient, intermittent reconnection process at the dayside magnetopause and associated energy and momentum transfer to the ionosphere in the polar cusp and cleft regions. The filamentary spatial structure and the spectral characteristics of the optical signature indicate associated localized ˜1-kV potential drops between the magnetopause and the ionosphere during the most intense auroral events. The duration of the events compares well with the predicted characteristic times of momentum transfer to the ionosphere associated with the flux transfer event-related current tubes. It is suggested that, after this 2–10 min interval, the sheath particles can no longer reach the ionosphere down the open flux tube, due to the subsequent super-Alfvénic flow along the magnetopause, conductivities are lower and much less momentum is extracted from the solar wind by the ionosphere. The recurrence time (3–15 min) and the local time distribution (∼0900–1500 MLT) of the dayside auroral breakup events, combined with the above information, indicate the important roles of transient magnetopause reconnection and the polar cusp and cleft regions in the transfer of momentum and energy between the solar wind and the magnetosphere.

Intrachain Energy Migration to Weak Charge-Transfer State in Polyfluorene End-Capped with Naphthalimide Derivative

Polyfluorene end-capped with N-(2-benzothiazole)-1 8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CI) of the end group BNI The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state polyfluorene backbone decay and ICCT deactivation Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0 8-1 4 ns depending on the solvent showing that depolarization occurs from two different processes energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF BNI ascribed to the conversion of S(1) to the ICCT excited state From the ratio of asymptotic and initial amplitudes of the transient absorption measurement the efficiency of intrachain ICCT formation is estimated in 0 5 which means that on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state

Low-energy three-body charge transfer reactions with Coulomb interaction in the final state

Three-body charge transfer reactions with Coulomb interaction in the final state are considered within the framework of coordinate-space integro-differential Faddeev-Hahn-type equations within two- and six-state close-coupling approximations. The method is employed to study direct muon transfer in low-energy collisions of the muonic hydrogen H-mu by helium (He2+) and lithium (Li3+) nuclei. The experimentally observed isotopic dependence is reproduced.

Low-energy direct muon transfer from H to Ne10+, S16+ and Ar18+ using the two-state close-coupling approximation to the Faddeev-Hahn-type equation

We perform a three-body calculation of direct muon-transfer rates from thermalized muonic hydrogen isotopes to bare nuclei Ne10+, S16+ and Ar18+ employing integro-differential Faddeev-Hahn-type equations in configuration space with a two-state close-coupling approximation scheme. All Coulomb potentials including the strong final-state Coulomb repulsion are treated exactly. A long-range polarization potential is included in the elastic channel to take into account the high polarizability of the muonic hydrogen. The transfer rates so-calculated are in good agreement with recent experiments. We find that the muon is captured predominantly in the n = 6, 9 and 10 states of muonic Ne10+, S16+ and Ar18+, respectively.

The energy landscape for solvent dynamics in electron transfer reactions: A minimalist model

Energy fluctuations of a solute molecule embedded in a polar solvent are investigated to depict the energy landscape for solvation dynamics. The system is modeled by a charged molecule surrounded by two layers of solvent dipolar molecules with simple rotational dynamics. Individual solvent molecules are treated as simple dipoles that can point toward or away from the central charge (Ising spins). Single-spin-flip Monte Carlo kinetics simulations are carried out in a two-dimensional lattice for different central charges, radii of outer shell, and temperatures. By analyzing the density of states as a function of energy and temperatures, we have determined the existence of multiple freezing transitions. Each of them can be associated with the freezing of a different layer of the solvent. (C) 2002 American Institute of Physics.

Pareto Frontier for the time-energy cost vector to an Earth-Moon transfer orbit using the patched-conic approximation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)