Böcker i Springer Theses-serien

This book highlights the doctoral research of the author on electronic band structure engineering and ultrafast dynamics of Dirac semimetals. Dirac semimetals exhibit unique electronic band structure and novel physical properties with rich light-matter interaction, which inspires a wide range of potential applications. Enabling band engineering and revealing ultrafast dynamics of Dirac semimetals is therefore important. In the research work covered by the book, the first ultrafast time- and angle-resolved photoemission spectroscopy with tunable probe photon energy is developed, providing new opportunities for exploring ultrafast dynamics in 3D quantum materials. Using the spectroscopy, the author investigates the band structure engineering and ultrafast dynamics of Dirac semimetals, realizing the long-sought-after chiral symmetry breaking in a Kekulé-ordered graphene with flat band and revealing the ultrafast dynamics of Dirac fermions in 3D Dirac semimetal for the first time. The work advances the research of the electronic structure of Dirac semimetals in two aspects. Firstly, it identifies the Kekulé-ordered graphene as a new system for exploring chiral symmetry breaking- related physics and flat band- induced instability, providing a very rare system to investigate their interplay. Secondly, it solves the long-standing challenge of directly visualizing the non-equilibrium electronic structure of 3D Dirac semimetal and opens up new opportunities for exploring the light-matter interaction in 3D quantum materials, especially the light-induced topological phase transitions in 3D topological materials.

This thesis describes the development of iron-catalyzed thienyl C¿H/C¿H coupling. This is applied to the synthesis of highly conjugated and electron-rich thiophene compounds of interest in materials science by utilization of low redox potential of iron in combination with a mild oxalate oxidant.Transition-metal-catalyzed C(sp2)¿H/C(sp2)¿H coupling has attracted much attention as one of the most straightforward methods to construct C(sp2)¿C(sp2) bonds. However, application of this ideal transformation to the synthesis of redox-sensitive pi-materials was hindered by the requirement of a strong oxidant for catalyst turnover. This limitation originates primarily from the large redox potential of conventional transition-metal catalysts such as palladium and rhodium. This thesis shows that the efficiency of C¿H activation was significantly improved by introduction of a new conjugated tridentate phosphine ligand, giving direct access to polymeric thiophene materials from simple thiophene monomers. Considering the importance of environmentally friendly organic synthesis in terms of UN Sustainable Development Goals, the reactions described herein highlight the potential of iron, the most abundant transition-metal on earth, for the direct synthesis of functional small molecules and polymers of importance in energy device applications.

This thesis highlights research explorations in quantum contextuality with photons.Quantum contextuality is one of the most intriguing and peculiar predictions of quantum mechanics. It is also a cornerstone in modern quantum information science. It is the origin of the famous quantum nonlocality and various nonclassical paradoxes. It is also a resource for many quantum information processing tasks and even universal quantum computing. Therefore, the study of quantum contextuality not only advances the comprehension of the foundations of quantum physics, but also facilitates the practical applications of quantum information technology.In the last fifteen years, the study of quantum contextuality has developed from a purely theoretical level to a stage where direct experimental tests become amenable. However, the experimental research on contextuality at the current stage largely focuses on direct validations of some most famous predictions of contextuality, while other forms of contextuality and its practical applications in quantum information science are rarely involved. The research in this thesis is committed to bridge this gap from two directions: (1) to construct and test stronger forms of contextuality and relieve the requirements of contextuality experiments on experimental platforms, and (2) to explore the connections between contextuality and the other concepts in quantum information science and directly demonstrate the application of contextuality in broader scenarios. Specifically, the thesis have discussed the research topics about the relationship between quantum contextuality and nonlocality, the ¿all-versus-nothing¿ paradoxes from quantum contextuality, the ore- and post-selection paradoxes from quantum contextuality, and the topological protection and braiding dynamics of quantum contextuality in quasiparticle systems.

In this thesis, attention was paid to several novel oxygenated fuels¿carbonates, polyethers and ketones. Combustion kinetic investigations were performed for typical representative compounds, including dimethyl carbonate, diethyl carbonate, cyclopentanone, 3-pentanone, 1,2-dimethoxyethane and dimethoxymethane. For experiments, suitable diagnostic techniques were used to measure the detailed speciation information of the target fuels under different conditions. For kinetic modeling, rate coefficients for crucial elementary reactions were obtained through high-level theoretical calculations. Based on that, validated kinetic models with good predictive performances were developed. On the basis of experimental measurements and model interpretations, this work highlighted two important combustion characteristics regarding the practical use: the pollutant formation and the ignition performance. Besides, the correlation between oxygen-containing functional groups and the aforementioned combustion characteristics was revealed. To reveal the potential interactions between the reaction networks of oxygenated additives and the hydrocarbon base fuels during combustion. Chemical structures of laminar premixed flames fueled by binary fuels were measured, and by changing the initial fuel compositions, the addition effects of the oxygenates on the fuel consumption and pollutant formation behaviors were explored. It was found that complicated chemical interactions do not exist in the reaction networks under the investigated conditions.

This book presents innovative laser desorption ionization (LDI)-active nanophotonic structures for addressing the challenges that matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) is currently facing and for enhancing LDI efficiency. It presents a variety of cutting-edge nanophotonic structures to satisfy the mass-analytical needs of sensitivity, reproducibility, and quantification. As opposed to the commercialized, conventional organic matrix used in MALDI-MS, these nanostructures are validated to be highly effective in detecting small metabolites and drugs, highlighting their considerable potential in the mass spectrometry field. It also systematically elucidates fundamental LDI processes in terms of the photo-thermal, electronic, and structural characteristics of nanophotonic structures, offering mechanistic knowledge of LDI-MS. Even though LDI-MS performance is heavily influenced by a number of nanostructure parameters, relatively little is known about the LDI processes associated with those characteristics. An in-depth understanding of nanostructure characteristics and LDI mechanisms thus paves the way for more effective, rational design and development of nanostructures with improved LDI capabilities. Further, with a focus on multiple cascades in nanostructure functions in response to laser pulse stimuli, this book provides detailed, step-by-step procedures to design and construct a nanophotonic, LDI-active platform, which may serve as a roadmap for graduate students in the field of mass spectrometry. Readers, including graduate students, researchers, and experts working in the related areas of mass spectrometry, nanophotonics, and material science and material engineering, will find a wealth of useful information in this book.

This thesis addresses the design of crystal structures using hydrogen bonds. In particular, it focuses on the design of functionalities and the control over the packing of molecular assemblies, based on molecular designs.Firstly, the synthesis and evaluation of a proton¿electron mixed conducting charge transfer salt is reported. Focusing on the difference in the strength of hydrogen bonds and weaker intermolecular interactions, a system was rationally designed and constructed where electron-conducting molecular wires were encapsulated within a proton-conducting matrix. Next, the investigation of structural phase transitions in a cocrystal consisting of hydrogen-bonded two-dimensional molecular assemblies is reported. Drastic rearrangements of hydrogen-bonded molecular assemblies in the cocrystal led to single-crystal-to-single-crystal phase transitions, resulting in anisotropic changes in the crystal shape. Furthermore, chemical modification of a component molecule in the cocrystal is reported. The modification afforded control over the stacking patterns of the two-dimensional molecular assemblies, i.e., sheets, and the mechanism was discussed considering the intersheet intermolecular interactions and molecular motion.It is suggested that hydrogen bonds are beneficial to construct molecular assemblies in molecular crystals because of their strength and well-defined directionality, and the consideration of coexisting weaker intermolecular interactions can lead to the design of whole crystal structures and, hence, functionalities. This thesis benefits students and researchers working on solid-state chemistry by presenting various methods for characterizing and evaluating the properties of molecular solids.

This Ph.D. book develops nanowire-assisted electroporation disinfection technology based on the flow-through porous electrode. The author presents pioneering results on theoretical modeling, experimental realization, and selected applications, showing the novel disinfection mechanism of electroporation guarantees an exceedingly low level of energy consumption. In this regard, three classes of novel dynamic behavior are investigated: (i) The developed nanowire-assisted flow-through electroporation disinfection technology enables great microbial disinfection performance with extremely low voltage (1V), which significantly reduce the formation potential of harmful disinfection by-products during the treatment process. (ii) The nanowire-assisted flow-through electroporation disinfection technology ensures no reactivation/regrowth of inactivated bacteria and meanwhile promotes the gradual death of damaged bacteria during the storage process. (iii) The application of high-frequency AC power supply (106 Hz) ensures the high microbial disinfection efficiency while suppressing the occurrence of electrochemical reactions and extending the electrode lifetime effectively.

This book elucidates fascinating electronic phenomena of unusual Bi2-square net in layered R2O2Bi (R: rare earth) compounds using two approaches: the fabrication of epitaxial thin films and the synthesis of bulk polycrystalline powders. The Bi2-square net compounds are a promising platform to explore exotic physical properties originating from the interplay between a two-dimensional electronic state and strong spin¿orbit coupling; however, there are few reports on Bi2-square net compounds due to the instability of unusual electronic configurations. The book presents the development of synthetic routes for R2O2Bi compounds, such as novel solid phase epitaxy techniques and chemical control of crystal structure, demonstrating the intrinsic physical properties of Bi2-square net for the first time. The most notable finding is the successful induction of two-dimensional superconductivity in Bi2-square net with the coexistence of rich electronic phases. The book also discusses the superconducting mechanisms and the effect of R cation substitution in detail and describes the mechanical properties of Bi2-square net. These findings overturn the results of previous studies of R2O2Bi. The book sheds light on hidden layered compounds, representing a significant advance in the field.

This book focuses on the development of high-performance carbon electrodes for sodium ion batteries (SIBs). By proposing folded-graphene as the high-density cathode with excellent rate capability, it provides insight into the interplay between oxygen functional groups and folded texture. It also highlights the superiority of ether electrolytes matching with carbon anodes, which are shown to deliver largely improved electrochemical performance. The achievements presented offer a valuable contribution to the carbon-based electrodes in SIBs.

This thesis presents the first realization of non-reciprocal energy transfer between two cantilevers by quantum vacuum fluctuations. According to quantum mechanics, vacuum is not empty but full of fluctuations due to zero-point energy. Such quantum vacuum fluctuations can lead to an attractive force between two neutral plates in vacuum ¿ the so-called Casimir effect ¿ which has attracted great attention as macroscopic evidence of quantum electromagnetic fluctuations, and can dominate the interaction between neutral surfaces at small separations. The first experimental demonstration of diode-like energy transport in vacuum reported in this thesis is a breakthrough in Casimir-based devices. It represents an efficient and robust way of regulating phonon transport along one preferable direction in vacuum. In addition, the three-body Casimir effects investigated in this thesis were used to realize a transistor-like three-terminal device with quantum vacuum fluctuations. These two breakthroughs pave the way for exploring and developing advanced Casimir-based devices with potential applications in quantum information science. This thesis also includes a study of the non-contact Casimir friction, which will enrich the understanding of quantum vacuum fluctuations.

This thesis makes significant advances in the use of microspheres in optical traps as highly precise sensing platforms. While optically trapped microspheres have recently proven their dominance in aqueous and vacuum environments, achieving state-of-the-art measurements of miniscule forces and torques, their sensitivity to perturbations in air has remained relatively unexplored. This thesis shows that, by uniquely operating in air and measuring its thermally-fluctuating instantaneous velocity, an optically trapped microsphere is an ultra-sensitive probe of both mass and sound. The mass of the microsphere is determined with similar accuracy to competitive methods but in a fraction of the measurement time and all while maintaining thermal equilibrium, unlike alternative methods. As an acoustic transducer, the air-based microsphere is uniquely sensitive to the velocity of sound, as opposed to the pressure measured by a traditional microphone. By comparison to state-of-the-art commercially-available velocity and pressure sensors, including the world¿s smallest measurement microphone, the microsphere sensing modality is shown to be both accurate and to have superior sensitivity at high frequencies. Applications for such high-frequency acoustic sensing include dosage monitoring in proton therapy for cancer and event discrimination in bubble chamber searches for dark matter. In addition to reporting these scientific results, the thesis is pedagogically organized to present the relevant history, theory, and technology in a straightforward way.

This book describes the development of novel protein¿RNA-binding assays and their applications in a high-throughput manner for the identification of small-molecule modulators of protein¿RNA interactions to treat cancer and COVID-19.Modulating protein¿RNA interactions with small molecules is expected to provide novel biological insights of the interrelation of diseases with the protein¿RNA interactome. The modulations may also be exploited therapeutically. For these reasons, the development of a simple, reliable, and sensitive protein¿RNA-binding assay is necessary for high-throughput screening to discover new effective chemical entities capable of acting on diverse protein¿RNA interactions. This book discusses the discovery of small-molecule modulators targeting protein¿RNA interactions that are potentially valuable to treat cancer and COVID-19 by constructing novel high-throughput screening methods. The results of this dissertation provide valuable insights into the regulation of protein¿RNA interactions in chemical biology and drug development.

This thesis describes how the rich internal degrees of freedom of molecules can be exploited to construct the first ¿clock¿ based on ultracold molecules, rather than atoms. By holding the molecules in an optical lattice trap, the vibrational clock is engineered to have a high oscillation quality factor, facilitating the full characterization of frequency shifts affecting the clock at the hertz level. The prototypical vibrational molecular clock is shown to have a systematic fractional uncertainty at the 14th decimal place, matching the performance of the earliest optical atomic lattice clocks. As part of this effort, deeply bound strontium dimers are coherently created, and ultracold collisions of these Van der Waals molecules are studied for the first time, revealing inelastic losses at the universal rate. The thesis reports one of the most accurate measurements of a molecule¿s vibrational transition frequency to date. The molecular clock lays the groundwork for explorations into terahertz metrology, quantum chemistry, and fundamental interactions at atomic length scales.

This book provides a comprehensive overview of Nuclear Magnetic Resonance (NMR) theory, its applications, and advanced techniques to improve the quality and speed of NMR data acquisition. In this book, the author expands his outstanding Ph.D. thesis and provides a valuable resource for researchers, professionals, and students in the field of NMR spectroscopy.The book covers quantum mechanics basics, and topics like density operators, pulse sequences, 1D pulse acquisition, INEPT (Insensitive nuclei enhancement by polarization transfer), product operators, and 2D NMR principles. It also explores innovative experiments like States HSQC (Heteronuclear Single Quantum Coherence) and echo-antiecho HSQC with gradients.In the subsequent chapters, the author discusses Pure Shift NMR, including PSYCHE (Pure Shift Yielded by Chirp Excitation) and its optimizations, such as waveform parameterization and time-reversal methods. The 'Discrete PSYCHE' approach and Ultrafast PSYCHE-iDOSY (Diffusion-ordered spectroscopy) are also highlighted.This book presents the POISE (Parameter Optimisation by Iterative Spectral Evaluation) software for real-time NMR experiment optimization, including pulse width calibration and Ernst angle optimization, and demonstrates applications across various NMR experiments.Lastly, the book examines accelerated 2D NMR data collection and the NOAH (NMR by Ordered Acquisition using 1H detection) supersequences, emphasizing automated pulse program creation using GENESIS (GENEration of Supersequences In Silico). Covered NMR experiments include 13C sensitivity-enhanced HSQC, 15N HMQC (Heteronuclear Multiple Quantum Coherence), dual HSQC, HSQC-TOCSY (Total Correlation Spectroscopy), HMBC (Heteronuclear Multiple Bond Correlation), and ADEQUATE (Adequate Sensitivity Double-Quantum Spectroscopy).

One of the main unanswered question of modern Physics is "How does gravity behave at small scales?". The aim of this thesis is to illustrate in a comprehensive but accessible way how to look for deviations from Einstein's theory of General Relativity in this regime, looking at the simplest celestial bodies: static and spherically symmetric ones.With a conservative and bottom-up approach, at smaller scales the first corrections to the action of General Relativity are generally considered to be terms quadratic in the curvature tensors; while these modifications do not cure the inconsistency between gravity and quantum mechanics, the solutions of this theory are plausible candidates to be the first-order corrections of the classical ones.Even with such simple modifications, a striking picture emerges from the study of isolated objects: the unique Schwarzschild solution of General Relativity is only a rare bird in the set of solutions, with non-Schwarzschild black holes, wormholes and naked singularities appearing as possible substitutes.Tailored to graduate students and researchers entering this field, this thesis shows how to construct these new solutions from action principles, how to characterize their metric, how to study their physical properties, such as their stability or Thermodynamics, and how to look for phenomenological signatures.