Spectroscopic Probes of Low-Barrier Proton-Transfer Dynamics

The diverse discipline of molecular spectroscopy, which has profited tremendously from the advent of tunable laser sources, has transformed the scientific community’s knowledge of the microscopic world, allowing the study of perplexing quantum-chemical phenomena. Classically-hindered proton transfer, a multidimensional process mediated by nuclear-quantum effects (e.g., potential-barrier tunneling), is a chemical transformation that forms the crux of all acid/base chemistry. Although extensive research efforts have aimed to establish the paradigms that govern this transformation, a full understanding has proven elusive with questions continuing to emerge.Exploring the proton-transfer reaction, and the related concept of hydrogen bonding, has benefitted greatly from investigations of model systems where the hydron migration is facilitated by a symmetric double-minimum potential well. In such molecular species, the spectroscopic signature of tunneling-induced bifurcations gives a direct measure of reaction rates, thus enabling the extraction of dynamical information. This thesis focuses on a relatively unexplored member of this group, 6-hydroxy-2- formylfulvene or HFF, which exhibits a quasi-linear reaction site on a conjugated framework – a structural arrangement that engenders a low-barrier hydrogen bonding (LBHBing) motif. Additionally, HFF has been suggested to experience a drastic quenching in dynamics accompanying π*←π electronic excitation that has been attributed to a substantial change in reaction mechanism whereby the strictly planar reaction coordinate in the X1A1 state transforms into an out-of-plane pathway involving substantial heavy- atom motion in the A1B2 (π∗π) state. The unique structural and dynamical characteristics of HFF create a potent platform for studying the effects of isotopic substitution and vibrational excitation on tunneling phenomena as presented in this thesis. The origin band of HFF and its monodeuterated isotopolog, HFF-d, were probed using polarization-resolved degenerate four-wave mixing (DFWM), an absorption-based technique that provides near-rotational resolution. This enabled the measurement of tunneling-induced bifurcations for the vibrationless A1B2 states of HFF and HFF-d, yielding Δ = 0.1009(43) cm-1 and Δ = 0.074(10) cm-1, respectively. These values imply a small deuterium kinetic isotope effect (DKIE) of Λ = 1.36 (relative to the analogous ground-state value of Λ = 3.44) that can be rationalized by considering the substantial heavy-atom motion (and the corresponding large effective mass) that is involved in the excited-state proton-transfer process, which dominates the reaction and makes the change in the mass of the shuttling hydron less consequential. Similar DFWM studies also were performed for two higher-energy vibronic bands of A1B2 (π∗π) HFF and HFF-d, ν4(a1), a chelate-ring breathing mode, and ν7(b2), a chelate-ring deformation mode. Although vibrational excitation can have a substantial effect on proton-transfer dynamics, the two studied modes did not couple effectively to the reaction coordinate and, therefore, resulted in minimal changes to measured tunneling splittings, thereby highlighting the distinct nature of the multidimensional out-of-plane tunneling mechanism that governs the π * ← π excited state

Extreme Hypoglycaemia in Anaplastic Large Cell Lymphoma

Introduction: Hypoglycaemia associated with non-islet cell tumours (NICTH) is a rare entity in patients with extra-pancreatic malignancies, mostly attributed to large mesenchymal or epithelial tumours. Anaplastic large cell lymphoma has not previously been associated with NICTH, making this the first publication of such a report. Patient and methods: A 22-year-old, non-diabetic patient was admitted to our department with malaise, itching, night sweats and weight loss. Serum glucose levels at presentation were extremely low, reaching 3 mg/dl at the lowest. Further investigations revealed undetectable blood insulin and C-peptide levels, together with low IGF-1 (34 ng/ml) levels. Inguinal lymph node biopsy showed anaplastic large cell lymphoma, and bone marrow biopsy along with supporting blood tests revealed haemophagocytic lymphohistiocytosis. Discussion: In conjunction with an adequate hyperglycaemic response to intravenous glucagon, all of the above findings indicate hypoglycaemia as a result of overproduction of high molecular weight IGF-2 precursor protein, generally referred to as ‘Big IGF-2’. Large solid tumours can occasionally produce loosely bound or free Big IGF-2 molecules which circulate throughout the plasma and bind to insulin as well as IGF receptors, thus increasing glucose intake by body tissues, decreasing the release of glucose to the bloodstream by the liver and causing feedback suppression of insulin, IGF-1 and growth hormone production. Therefore, it is exceptional to find Big IGF-2-related hypoglycaemia in non-solid tumours. Our case shows that, although extremely uncommon, rare instances of NICTH can be attributed to the production of Big IGF-2 in non-solid malignancies including anaplastic large cell lymphom

Entwicklung von Effizienzindexen im Basketball: mit den Trainern auf ihrer Sprache kommunizieren

Achieving a high level of performance in ball-game activities such as basketball depends upon (a) the technical skill level of the player within the team and of the whole team, and (b) the psychological, mental, and emotional edge over the opposing team. However, bothcoaches and players seem to emphasise the technical aspects of the game when preparing for a long-duration championship, a tournament, or a single game. The purpose of this study was to examine the correlational relationship among indexes of efficiency, technical and height variables and the final placing of a team in a 9-day championship. More specifically, two questions were raised in this study: (a) Is it possible to predict the final placing of a team based on its technical playing ability? and, (b) Is it possible to develop appropriate indexes to measure team ability and predict its final success? Based on the data obtained in the European Basketball Championship for teams under 19 years of age, two indexes of efficiency were developed. In addition, nine technical variables of the game of basketball were analyzed. Spearman rank-order and Pearson product moment correlations were used to examine the relationship between each index and variable and the final placing of a team, and the relationships between all variables. It was concluded that it was possible to use indexes of efficiency such as index of playing ability, and technical variables such as final scores and 2-point percentages, to predict the final ranking of a team. However, in order to promote the prediction process in ball-game activities it is recommended that researchers and practitioners develop multi-face indexes in which psychological, as well as technical, variables are considered.Um ein hohes Aufführungsniveau in einem Ballspiel wie Basketball zu erreichen, sollen die folgenden Bedingungen erfüllt werden: a) ein hoher Grad der technischen, Fähigkeiten einzelner Spieler, sowie der ganzen Mannschaft, und b) ein höherer psychologischer, mentaler und emotionaler Rand als die Gegnermannschaft. Doch, in der Vorbereitung auf einen längeren Wettkampf, oder ein Match, betonen Trainer, sowie die Spieler, vor allem die technischen Spielaspekte. Das Ziel dieser Studie war, die Korrelationen zwischen den Effizienzindexen, technischen sowie Variablen der Spieler, größe und der Tabellenposition einer Mannschaft am Ende eines 9-tigigen Wettbewerbs festzustellen. Die Studie befasste sich vor allem mit zwei Fragen: a) ob es möglich sei, aufgrund technischer Fähigkeiten einer Mannschaft, ihre Endtabellenposition vorauszusehen und b) ob es möglich sei, die zum Messen der Teamfähigkeiten geeigneten Indexe zu entwickeln und damit das Endresultat voraussehen zu können. Aufgrund der Daten von der Basketballmeisterschaft Europas für Spieler unter 19 Jahren wurden zwei Effizienzindexe entwickelt. Außerdem wurden 9 technischen Spielvariablen im Basketball analysiert. Mittels der Spearmanschen Rangliste und Pearsonschen Produkt-Moment- Korrelationen wurde die Beziehung zwischen jedem Index, bzw. jeder Variable, und der Endposition, sowie die Beziehung unter allen Variablen geprüft. Es wurde festgestellt, dass es möglich sei, die Effizienzindexe (z.B. den Spielfähigkeitsindex) und die technischen Variablen (z.B. das Endresultat und das 2- Punkt-Prozent) zu gebrauchen, um die Endposition einer Mannschaft vorauszusehen. Doch, um die Resultate eines Ballspieles besser voraussehen zu können, wird es vorgeschlagen, dass Forscher und Trainer multiple Indexe entwickeln, die die psychologischen, sowie technischen Variablen in Betracht nehmen würden

Including Students with Disabilities in a Physical Education Teacher Preparation Program: An Institutional Perspective

The increasing number of students with disabilities who have the goal of becoming a teacher in either elementary or high school is one of the challenges we are currently facing at the academic colleges of education in Israel. In this chapter, we address the inclusion challenge, namely how we have taken up the challenge to modify one existing teacher preparation program (TPP) in physical education (PE) to enable students with disabilities to study at the same level as the other students who are enrolled in the program. The chapter is composed of four sections. In the first section, we introduce the term inclusive education, elaborate upon its concepts, and highlight a number of developmental phases associated with this term. In the second section, we present the theoretical background and the practical frameworks of an inclusive pedagogy. In the third section, we describe a number of actions taken in one college that enabled students with disabilities to enroll in a PE TPP. In the fourth section, we conclude our discussion and provide a number of ideas for future research, in order to strengthen the understanding of how to integrate students with disabilities in PE TPP

Entwicklung von Effizienzindexen im Basketball: mit den Trainern auf ihrer Sprache kommunizieren

Achieving a high level of performance in ball-game activities such as basketball depends upon (a) the technical skill level of the player within the team and of the whole team, and (b) the psychological, mental, and emotional edge over the opposing team. However, bothcoaches and players seem to emphasise the technical aspects of the game when preparing for a long-duration championship, a tournament, or a single game. The purpose of this study was to examine the correlational relationship among indexes of efficiency, technical and height variables and the final placing of a team in a 9-day championship. More specifically, two questions were raised in this study: (a) Is it possible to predict the final placing of a team based on its technical playing ability? and, (b) Is it possible to develop appropriate indexes to measure team ability and predict its final success? Based on the data obtained in the European Basketball Championship for teams under 19 years of age, two indexes of efficiency were developed. In addition, nine technical variables of the game of basketball were analyzed. Spearman rank-order and Pearson product moment correlations were used to examine the relationship between each index and variable and the final placing of a team, and the relationships between all variables. It was concluded that it was possible to use indexes of efficiency such as index of playing ability, and technical variables such as final scores and 2-point percentages, to predict the final ranking of a team. However, in order to promote the prediction process in ball-game activities it is recommended that researchers and practitioners develop multi-face indexes in which psychological, as well as technical, variables are considered.Um ein hohes Aufführungsniveau in einem Ballspiel wie Basketball zu erreichen, sollen die folgenden Bedingungen erfüllt werden: a) ein hoher Grad der technischen, Fähigkeiten einzelner Spieler, sowie der ganzen Mannschaft, und b) ein höherer psychologischer, mentaler und emotionaler Rand als die Gegnermannschaft. Doch, in der Vorbereitung auf einen längeren Wettkampf, oder ein Match, betonen Trainer, sowie die Spieler, vor allem die technischen Spielaspekte. Das Ziel dieser Studie war, die Korrelationen zwischen den Effizienzindexen, technischen sowie Variablen der Spieler, größe und der Tabellenposition einer Mannschaft am Ende eines 9-tigigen Wettbewerbs festzustellen. Die Studie befasste sich vor allem mit zwei Fragen: a) ob es möglich sei, aufgrund technischer Fähigkeiten einer Mannschaft, ihre Endtabellenposition vorauszusehen und b) ob es möglich sei, die zum Messen der Teamfähigkeiten geeigneten Indexe zu entwickeln und damit das Endresultat voraussehen zu können. Aufgrund der Daten von der Basketballmeisterschaft Europas für Spieler unter 19 Jahren wurden zwei Effizienzindexe entwickelt. Außerdem wurden 9 technischen Spielvariablen im Basketball analysiert. Mittels der Spearmanschen Rangliste und Pearsonschen Produkt-Moment- Korrelationen wurde die Beziehung zwischen jedem Index, bzw. jeder Variable, und der Endposition, sowie die Beziehung unter allen Variablen geprüft. Es wurde festgestellt, dass es möglich sei, die Effizienzindexe (z.B. den Spielfähigkeitsindex) und die technischen Variablen (z.B. das Endresultat und das 2- Punkt-Prozent) zu gebrauchen, um die Endposition einer Mannschaft vorauszusehen. Doch, um die Resultate eines Ballspieles besser voraussehen zu können, wird es vorgeschlagen, dass Forscher und Trainer multiple Indexe entwickeln, die die psychologischen, sowie technischen Variablen in Betracht nehmen würden

Assembly of Ordered Polystyrene Nanoparticles on Self- Assembled Monolayers

Spontaneous assembly of nanoparticles onto a surface is a promising bottom-up concept for the fabrication of new functional materials that can be used for various applications in the nanotechnology. In this paper, we describe a system based on gold/polystyrene (Au/PS) Janus particles arranged onto Au self-assembled monolayer (SAM) of 1-dodecanthiol (NDA). The micro-size Au/PS Janus particles are self-assembled onto Au surface and are dissolved into polystyrene (PS) nanoparticles. The SAM of NDA plays two different roles; it dissolves the original Au/PS Janus particles and organizes the PS nanoparticles onto the Au surface. Overall, our proposed method for the assembly of large-scale area nanoparticles can be extended for further uses in the surface science

VIBRATIONAL SPECIFICITY AND ISOTOPIC DEPENDENCE OF PROTON-TRANSFER DYNAMICS IN ELECTRONICALLY EXCITED 6-HYDROXY-2-FORMYLFULVENE

The vibrational specificity and isotopic dependence of hindered proton-transfer dynamics have been explored in the lowest-lying singlet excited state, \textit{\~{A}}$^{1}$B$_{2}$ ($\pi$$^{*}$$\pi$), of 6-hydroxy-2-formylfulvene (HFF) and its monodeuterated isotopolog (HFF-\textit{d}). Both systems have been probed under bulk-gas conditions by employing polarization-resolved degenerate four-wave mixing (DFWM) spectroscopy, where judicious selection of incident and detected polarization geometries served to alleviate spectral complexity and to allow for the quantitative extraction of rotation-tunneling information. The observed $>$1000-fold decrease in tunneling rate that accompanies the $\pi$$^{*}$$\leftarrow$ $\pi$ electron promotion (transitioning from ultrafast ground-state dynamics\footnote{Z. N. Vealey, L. Foguel and P. H. Vaccaro, \textit{J. Phys. Chem. Lett.} \textbf{9}, 4949 (2018)} to near-complete quenching of analogous excited-state behavior) makes HFF a compelling model system for investigating the nuanced nature of low-barrier hydrogen bonding and its ability to regulate attendant hydron-migration events. A thorough analysis of low-energy vibronic bands in the \textit{\~{A}}$^{1}$B$_{2}$ manifold will be presented, with the dependence of unimolecular reactivity on heavy atom motion and isotopic modification being discussed in the context of structural predictions emerging from high-level quantum-chemical calculations

Physical and physiological attributes of soccer goalkeepers - Should we rely only on means and standard deviations?

The purpose of this study was twofold: (a) to profile physical characteristics and physiological attributes of soccer goalkeepers (GKs) who were divided into three age groups – under 16 years, 16-19, and over 19, and (b) to examine the intra-individual variability among the GKs in each age group on all physical and physiological measurements performed in the study. The GKs underwent a series of physical (e.g., height, body mass, and percentage of body fat) and physiological (e.g., anaerobic profile, power and strength, and flexibility) tests. The three main findings of the current study were: (a) differences in physical characteristics and physiological attributes existed between GKs in the three age groups, (b) intra-individual variability can be found in most physical characteristics and physiological attributes of the GKs, and (c) the intra-individual variability was observed in all three groups. These findings emphasize the need for coaches to examine the intra-individual variability in GKs on their teams. These findings can be used by coaches when planning specific training programs for GKs of different age and skill levels