267 research outputs found

    Echoes of the Past: Stylistic and Compositional Influences in the Music of Sergei Bortkiewicz

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    Despite the wide array of his compositional output in the first half of the twentieth century, the late Romantic composer, Sergei Bortkiewicz (1877-1952), remains relatively unknown. Bortkiewicz was born and raised near Kharkov, Ukraine, but considered himself Russian. Bortkiewicz studied in St. Petersburg and Leipzig, lived in Berlin, and later returned to Kharkov during World War I. During the Russian Revolution, he fled to Istanbul as a refugee. Eventually, he returned to Berlin and then to Vienna, where he would remain during World War II and for the rest of his life. Substantial modern-day recording efforts have rekindled interest in this composer who was faced with difficult circumstances throughout his life; however, a paucity of scholarly contributions exist. This project seeks to address some of these shortages. The first chapter provides historical perspective concerning Kharkov and Ukraine in the decades prior to the birth of Bortkiewicz. The second chapter presents a biography of Bortkiewicz against the backdrop of important events in world history. The third chapter contains commentary regarding Bortkiewicz’s compositional output which consisted primarily of works for the piano, but also included orchestral works, solo concerti, one opera, and several collections of songs. Unfortunately, some of these pieces have been lost as a result of World War II. The fourth chapter examines the compositional style of Sergei Bortkiewicz. Despite Bortkiewicz’s pro-Russian sentiments, some of his music appears to contain Ukrainian folk idioms. Other observations in this chapter supplement the work of Nils Franke regarding musical retrospection in Bortkiewicz’s works. These additional examples reaffirm harmonic and textural similarities and other stylistic connections in Bortkiewicz’s music. Ultimately, these similarities have pedagogical advantages notably through stylistic comparisons and might affect one’s approach to interpreting Bortkiewicz’s music

    Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications

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    The use of light to mediate controlled radical polymerization has emerged as a powerful strategy for rational polymer synthesis and advanced materials fabrication. This review provides a comprehensive survey of photocontrolled, living radical polymerizations (photo-CRPs). From the perspective of mechanism, all known photo-CRPs are divided into either (1) intramolecular photochemical processes or (2) photoredox processes. Within these mechanistic regimes, a large number of methods are summarized and further classified into subcategories based on the specific reagents, catalysts, etc., involved. To provide a clear understanding of each subcategory, reaction mechanisms are discussed. In addition, applications of photo-CRP reported so far, which include surface fabrication, particle preparation, photoresponsive gel design, and continuous flow technology, are summarized. We hope this review will not only provide informative knowledge to researchers in this field but also stimulate new ideas and applications to further advance photocontrolled reactions.National Science Foundation (U.S.) (CHE-1334703

    A novel mechanism of selectivity against AZT by the human mitochondrial DNA polymerase

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    Native nucleotides show a hyperbolic concentration dependence of the pre-steady-state rate of incorporation while maintaining concentration-independent amplitude due to fast, largely irreversible pyrophosphate release. The kinetics of 3′-azido-2′,3′-dideoxythymidine (AZT) incorporation exhibit an increase in amplitude and a decrease in rate as a function of nucleotide concentration, implying that pyrophosphate release must be slow so that nucleotide binding and incorporation are thermodynamically linked. Here we develop assays to measure pyrophosphate release and show that it is fast following incorporation of thymidine 5′-triphosphate (TTP). However, pyrophosphate release is slow (0.0009 s−1) after incorporation of AZT. Modeling of the complex kinetics resolves nucleotide binding (230 µM) and chemistry forward and reverse reactions, 0.38 and 0.22 s−1, respectively. This unique mechanism increases selectivity against AZT incorporation by allowing reversal of the reaction and release of substrate, thereby reducing kcat/Km (7 × 10−6 μ M−1 s−1). Other azido-nucleotides (AZG, AZC and AZA) and 8-oxo-7,8-dihydroguanosine-5′-triphosphate (8-oxo-dGTP) show this same phenomena

    BRUSH-ARM STAR POLYMER IMAGING AGENTS AND USES THEREOF

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    Disclosed are methods, compositions, reagents, systems, and kits to prepare nitroxide-functionalized brush-arm star polymer organic radical contrast agent (BASP-ORCA) as well as compositions and uses thereof. Various embodiments show that BASP-ORCA display unprecedented per-nitrox-ide and per-molecule transverse relaxivities for organic radical contrast agents, exceptional stability, high water solubility, low in vitro and in vivo toxicity, and long blood compartment half-life. These materials have the potential to be adopted for tumor imaging using clinical high-field 1H MRI techniques

    The PAS Domain-Containing Protein HeuR Regulates Heme Uptake in Campylobacter jejuni

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    Campylobacter jejuni is a leading cause of bacterially derived gastroenteritis. A previous mutant screen demonstrated that the heme uptake system (Chu) is required for full colonization of the chicken gastrointestinal tract. Subsequent work identified a PAS domain-containing regulator, termed HeuR, as being required for chicken colonization. Here we confirm that both the heme uptake system and HeuR are required for full chicken gastrointestinal tract colonization, with the hour mutant being particularly affected during competition with wild-type C. jejuni. Transcriptomic analysis identified the chu genes—and those encoding other iron uptake systems—as regulatory targets of HeuR. Purified HeuR bound the chuZA promoter region in electrophoretic mobility shift assays. Consistent with a role for HeuR in chu expression, heuR mutants were unable to efficiently use heme as a source of iron under iron-limiting conditions, and mutants exhibited decreased levels of cell-associated iron by mass spectrometry. Finally, we demonstrate that an heuR mutant of C. jejuni is resistant to hydrogen peroxide and that this resistance correlates to elevated levels of catalase activity. These results indicate that HeuR directly and positively regulates iron acquisition from heme and negatively impacts catalase activity by an as yet unidentified mechanism in C. jejuni

    EPR Study of Spin Labeled Brush Polymers in Organic Solvents

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    Spin-labeled polylactide brush polymers were synthesized via ring-opening metathesis polymerization (ROMP), and nitroxide radicals were incorporated at three different locations of brush polymers: the end and the middle of the backbone, and the end of the side chains (periphery). Electron paramagnetic resonance (EPR) was used to quantitatively probe the macromolecular structure of brush polymers in dilute solutions. The peripheral spin-labels showed significantly higher mobility than the backbone labels, and in dimethylsulfoxide (DMSO), the backbone end labels were shown to be more mobile than the middle labels. Reduction of the nitroxide labels by a polymeric reductant revealed location-dependent reactivity of the nitroxide labels: peripheral nitroxides were much more reactive than the backbone nitroxides. In contrast, almost no difference was observed when a small molecule reductant was used. These results reveal that the dense side chains of brush polymers significantly reduce the interaction of the backbone region with external macromolecules, but allow free diffusion of small molecules

    Decision Support Algorithm for Evaluating Carbon Dioxide Emissions from Electricity Generation in the United States

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    Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/146433/1/jiec12708.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/146433/2/jiec12708-sup-0001-SuppMat.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/146433/3/jiec12708_am.pd

    Core-Clickable PEG-Branch-Azide Bivalent-Bottle-Brush Polymers by ROMP: Grafting-Through and Clicking-To

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    The combination of highly efficient polymerizations with modular "click" coupling reactions has enabled the synthesis of a wide variety of novel nanoscopic tructures. Here we demonstrate the facile synthesis of a new class of clickable, branched nanostructures, polyethylene glycol (PEG)-branch-azide bivalent-brush polymers, facilitated by "graft-through" ring-opening metathesis polymerization of a branched norbornene-PEG-chloride macromonomer followed by halide-azide exchange. The resulting bivalent-brush polymers possess azide groups at the core near a polynorbornene backbone with PEG chains extended into solution; the structure resembles a unimolecular micelle. We demonstrate copper-catalyzed azide-alkre cycloaddition (CuAAC) "click-to" coupling of a photocleavable doxorubicin (DOX)-alkyne derivative to the azide core. The CuAAC coupling was quantitative across a wide range of nanoscopic sizes (similar to 6-similar to 50 nrn); UV photolysis of the resulting DOX-loaded materials yielded free DOX that was therapeutically effective against human cancer cells
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