Let It Fall // The Bath

Let it Fall “Let it Fall” was a senior concert in jazz voice and electronics comprised of original work and arrangements of jazz standards and pop songs. Inspired by the films of David Lynch, it was a work embracing disintegration and the unsettling. This concert was intended to combine my two academic focuses, jazz voice and electronic music, and evolved from a project in which I attempted to produce dream-pop covers of jazz standards. The concert took place in the Old Gym, which I designed to look like an amalgamation of venues featured in Lynch’s films, with eerie red and blue lighting and a red curtain. The band was a traditional jazz rhythm section consisting of piano, bass, drums, and guitar. Over the course of the concert, the music became increasingly distorted, as virtual synthesizers specially designed for this project, modeled after those used by Angelo Badalamenti in Twin Peaks, replaced the acoustic piano, and the effects on the guitar and voice built, becoming increasingly large and distorted. The final piece in the concert, and the culmination of the disintegration, was a solo electronic piece for voice, loop pedal, and Max. It used a quad speaker setup, filling the room with low frequencies from behind the audience, while the vocal loops I built with my loop pedal and in Max were presented in the front two speakers. This piece was intended to serve as the pivot point between my two senior projects, and the moment in the arc of my senior projects in which I stepped out of the traditional jazz singer role. The Bath “The Bath” is a work in eight parts for eight voices and electronics. It was originally intended to be a live performance, but this was not possible due to the pandemic. In lieu of the originally intended performance, I produced a recording of the piece, singing six out of the eight parts myself and using a synthesized organ for the bass parts. The piece was inspired by my practice of writing by constructing layered loops of my voice using a loop pedal, and then singing a melody line over them. This project was an effort to translate that practice into a live performance in which each “loop” is sung and repeated, creating the effect of looping without actually recording loops. I wanted to write a piece for non-classically trained singers that would use the voice as a serious and essential instrument, which I have not seen very often in jazz. This piece is, for me, an exploration of the voice: experimentation with extended vocal technique, playing with how voices can blend and separate, and diving into the unique ways in which the human voice interacts with audio effects. “The Bath” draws source material from hymns and folk songs. It is formed primarily around the idea of being a form of live vocal looping. The lyrical themes of the piece center around water: drowning, baptism, purification. These are themes I find myself continually drawn to in my writing, and have tried to reflect in the sonic environment of the piece through enveloping delays, cavernous reverb, and a general sense of being completely immersed in sound. I would like to keep working on this score, and eventually have it be performed live. In its live form, it will utilize a quad setup and Max. The vocalists will be in a circle in the center of the room, with the audience around them, and the speakers around them. I would also like to continue working on the recordings I made of this score for this senior project, and release the album as the solo form of this work

Use of heterocomplementary hydrogen bonding motifs for supramolecular materials chemistry

Hydrogen bonding is one of the most useful of the non-covalent interactions. Highly directional and easily tuneable, the strength of hydrogen bonded arrays enable controlled assembly of macromolecular structures. Because association can be designed to be selective, self-assembly involving low-molecular-weight amides and ureas has been expanded to higher order polymeric structures, so called ‘supramolecular polymers’. Chapter 1 introduces and develops upon the current themes of research in small-molecule hydrogen bonding, and the subsequent application towards the assembly of supramolecular polymers, in particular polyurethanes. The Wilson group is focused on the development of orthogonal recognition pathways, and their future application in the controlled assembly of polymers. The work presented in this thesis, therefore focuses on the development of self-sorting cascades- where molecules capable of hydrogen bonding have defined partners at specific stages of the cascade. Selecting two heterocomplementary hydrogen bonding arrays, and using them to form supramolecular polymers then advance this. Chapter 2 introduces the design and investigation of these self-sorting pathways involving hydrogen bonding arrays reported both in the literature and from within the Wilson group. The application of two of these hydrogen bonding motifs to assemble supramolecular polyurethanes is described in Chapter 3. The effect of the thermal history of supramolecular polyurethanes is then investigated, highlighting the change in response to thermal stimuli dependent on previous processing and treatment. The latter part of Chapter 3 introduces a ‘toolbox’ for supramolecular chemists, whereby components of the supramolecular polymer are changed systematically to gauge effect on subsequent mechanical properties. The synthetic route to supramolecular polymers is then discussed in Chapter 4, and the evolution of a solvent-free route to this particular class of polyurethanes is realised

«Малобюджетний» маркетинг

В умовах сьогоднішньої економічної кризи, яка зачепила всі вітчизняні підприємства, та постійного зниження української національної валюти актуальними стають питання пошуку способів економії коштів. Вирішенням таких проблем може стати «мало бюджетний» маркетинг, який допоможе розвиватися підприємству з використанням мінімальної кількості ресурсів. «Малобюджетний» маркетинг – це маркетингові інструменти залучення й утримання клієнтів, які припускають мінімальні витрати, а іноді можна взагалі обійтися без бюджету

Supercurrents through gated superconductor-normal-metal-superconductor contacts: the Josephson-transistor

We analyze the transport through a narrow ballistic superconductor-normal- metal-superconductor Josephson contact with non-ideal transmission at the superconductor-normal-metal interfaces, e.g., due to insulating layers, effective mass steps, or band misfits (SIN interfaces). The electronic spectrum in the normal wire is determined through the combination of Andreev- and normal reflection at the SIN interfaces. Strong normal scattering at the SIN interfaces introduces electron- and hole-like resonances in the normal region which show up in the quasi-particle spectrum. These resonances have strong implications for the critical supercurrent $I_c$ which we find to be determined by the lowest quasi-particle level: tuning the potential $\mu_{x0}$ to the points where electron- and hole-like resonances cross, we find sharp peaks in $I_{\rm c}$, resulting in a transitor effect. We compare the performance of this Resonant Josephson-Transistor (RJT) with that of a Superconducting Single Electron Transistor (SSET).Comment: to appear in PRB, 11 pages, 9 figure

The effect of solvent choice on the gelation and final hydrogel properties of Fmoc–diphenylalanine

Gels can be formed by dissolving Fmoc–diphenylalanine (Fmoc–PhePhe or FmocFF) in an organic solvent and adding water. We show here that the choice and amount of organic solvent allows the rheological properties of the gel to be tuned. The differences in properties arise from the microstructure of the fibre network formed. The organic solvent can then be removed post-gelation, without significant changes in the rheological properties. Gels formed using acetone are meta-stable and crystals of FmocFF suitable for X-ray diffraction can be collected from this gel

A dynamic supramolecular polyurethane network whose mechanical properties are kinetically controlled

We report the synthesis and characterization of a kinetically controlled, thermoreversible supramolecular polyurethane whose mechanical properties depend unusually strongly on the processing history. Materials were prepared by solution casting, quenching and annealing of quenched material, allowing pronounced micro-structural evolution, which leads to rapid increases in modulus as determined by rheological analysis. Tensile tests showed that the quenched material is soft, weak and ductile (shear modulus ~ 5 MPa, elongation ~ 250 %), but after annealing, at 70 °C for one hour, it becomes stiffer, stronger and more brittle (~ 20 MPa, ~ 20 %). FTIR and NMR spectroscopic analysis, coupled with MDSC and SAXS, were performed to investigate the network’s dynamic structural changes. SAXS results suggest the presence of a lamellar structure in the sample when solution cast at high temperature, or annealed. This ordering is unique when compared to structurally-related supramolecular bisurethane and bisurea polymers, and may be the cause of the observed path dependence. These mechanical properties, which can be switched repeatedly by simple thermal treatments, coupled with its adhesion properties as determined from peel and tack tests, make it an excellent candidate as a recyclable material for adhesives and coatings

Using solution state NMR spectroscopy to probe NMR invisible gelators

Supramolecular hydrogels are formed via the self-assembly of gelator molecules upon application of a suitable trigger. The exact nature of this self-assembly process has been widely investigated as a practical understanding is vital for the informed design of these materials. Solution-state NMR spectroscopy is an excellent non-invasive tool to follow the self-assembly of supramolecular hydrogels. However, in most cases the self-assembled aggregates are silent by conventional 1H NMR spectroscopy due to the low mobility of the constituent molecules, limiting NMR spectroscopy to following only the initial assembly step(s). Here, we present a new solution-state NMR spectroscopic method which allows the entire self-assembly process of a dipeptide gelator to be followed. This gelator forms transparent hydrogels by a multi-stage assembly process when the pH of an initially alkaline solution is lowered via the hydrolysis of glucono-δ-lactone (GdL). Changes in the charge, hydrophobicity and relative arrangement of the supramolecular aggregates can be followed throughout the assembly process by measuring the residual quadrupolar couplings (RQCs) of various molecular probes (here, 14NH4+ and isopropanol-d8), along with the NMR relaxation rates of 23Na+. The initially-formed aggregates comprise negatively charged fibrils which gradually lose their charge and become increasingly hydrophobic as the pH falls, eventually resulting in a macroscopic contraction of the hydrogel. We also demonstrate that the in situ measurement of pH by NMR spectroscopy is both convenient and accurate, representing a useful tool for the characterisation of self-assembly processes by NMR

An adhesive elastomeric supramolecular polyurethane healable at body temperature

In this paper, we report the synthesis and healing ability of a non-cytotoxic supramolecular polyurethane network whose mechanical properties can be recovered efficiently (> 99%) at the temperature of the human body (37 ºC). Rheological analysis revealed an acceleration in the drop of the storage modulus above 37 ºC, on account of the dissociation of the supramolecular polyurethane network, and this decrease in viscosity enables the efficient recovery of the mechanical properties. Microscopic and mechanical characterisation has shown that this material is able to recover mechanical properties across a damage site with minimal contact required between the interfaces and also demonstrated that the mechanical properties improved when compared to other low temperature healing elastomers or gel-like materials. The supramolecular polyurethane was found to be non-toxic in a cytotoxicity assay carried out in human skin fibroblasts (cell viability > 94% and non-significantly different compared to the untreated control). This supramolecular network material also exhibited excellent adhesion to pig skin and could be healed completely in situ post damage indicating that biomedical applications could be targeted, such as artificial skin or wound dressings with supramolecular materials of this type