Fay Tincher

One of comedienne Fay Tincher’s few extant titles, Rowdy Ann (1919), has been described recently by Andrew Grossman, as “one of the first American films, comic or otherwise, to legitimately address the social psychology of gender construction.” But Tincher is barely mentioned, if at all, in histories of the silent era. Kalton C. Lahue and Samuel Gill are among the few to acknowledge her significance, writing that her work with Al Christie between 1919–1920 “ranked among the best on the screen at the time” (372). They suggest, as have others, that she had “some of the elusive qualities of Mabel Normand,” and conclude that her disappearance from the screen in 1928 remains a mystery (368). More recently, where she does receive a few lines, scholars selectively represent her career, as when Karen Mahar remarks that Tincher, whom she too sees as the closest to Normand in beauty and ability, reached fame between 1923 and 1928 playing the wife in the Andy Gump series (Mahar 2006, 130). Tincher did play Min Gump, although not in her wackiest phase during her peak, but rather at a time when her stardom was on a decline. Yes, the “Gump” series was very popular, but Tincher’s heyday was between 1914 and 1920 when, for one and a half years, between 1917 and 1919, she was reported as having had her own company, Fay Tincher Productions. Here, she invites comparison with other popular comediennes who gave their names to short-lived companies—Normand, Marie Dressler, Flora Finch, Gale Henry

Aqueous Photochemistry of α-Keto Acids: Building Complexity at Molecular and Supramolecular Scales

Sunlight-driven reactions of organic molecules contribute to the environmental processing of organic compounds, including the generation of molecular complexity via aqueous chemistry. This thesis focuses on the aqueous photochemistry of &alpha;-keto acids, and the implications of this reactivity for environmental chemistry of both the early and modern Earth. Beginning with pyruvic acid, the simplest &alpha;-keto acid, I have investigated the photochemical mechanisms governing their reactivity in aqueous solutions. Even in very dilute solutions with low concentrations of pyruvic acid, covalently-bonded dimers and trimers are formed from the recombination of photochemically-generated radical species. These mechanisms are readily generalizable to &alpha;-keto acids as a class of molecules, as shown for a series of alkyl &alpha;-keto acids. &alpha;-Keto acids are also shown to be capable of acting as photo-initiators, driving reactions of non-photoactive species. The photochemistry of &alpha;-keto acids is known to be particularly sensitive to reaction conditions. One example of this sensitivity is the observed pH dependence and its effects on relative product yields, which is due in part to changes in the extent of hydration and deprotonation. These observed changes are consistent within the expanded mechanistic framework for the reactivity of &alpha;-keto acids. Even simple starting solutions of a single alkyl &alpha;-keto acid species become a complex mixture of oligomeric species upon photolysis. This is due to the formation of reactive intermediate species, which can further react in solution. The oligomers formed from this photochemistry are amphiphiles, many of which have two or three alkyl chains. The photoproducts generated from these alkyl &alpha;-keto acids are surface-active and spontaneously self-assemble into monodisperse, spherical aggregates over the course of photolysis, which has important environmental implications both for today and the early Earth. In the modern environment, this chemistry may contribute to the abiotic processes by which surface-active species are formed at the sea surface microlayer. The formation of such multi-tailed lipids and aggregates on the early Earth may help answer questions about how the first protocells evolved.</p

A Critical Analysis of Electrospray Techniques for the Determination of Accelerated Rates and Mechanisms of Chemical Reactions in Droplets

Electrospray and Electrosonic Spray Ionization Mass Spectrometry (ESI-MS and ESSI-MS) have been widely used to report evidence that many chemical reactions in micro- and nano-droplets are dramatically accelerated by factors of ∼102 to 106 relative to macroscale bulk solutions. Despite electrospray\u27s relative simplicity to both generate and detect reaction products in charged droplets using mass spectrometry, substantial complexity exists in how the electrospray process itself impacts the interpretation of the mechanism of these observed accelerated rates. ESI and ESSI are both coupled multi-phase processes, in which analytes in small charged droplets are transferred and detected as gas-phase ions with a mass spectrometer. As such, quantitative examination is needed to evaluate the impact of multiple experimental factors on the magnitude and mechanisms of reaction acceleration. These include: (1) evaporative concentration of reactants as a function of droplet size and initial concentration, (2) competition from gas-phase chemistry and reactions on experimental surfaces, (3) differences in ionization efficiency and ion transmission and (4) droplet charge. We examine (1-4) using numerical models, new ESI/ESSI-MS experimental data, and prior literature to assess the limitations of these approaches and the experimental best practices required to robustly interpret acceleration factors in micro- and nano-droplets produced by ESI and ESSI

Mechanistic description of photochemical oligomer formation from aqueous pyruvic acid

The aqueous phase photochemistry of pyruvic acid, an important oxidation product of isoprene, is known to generate larger oligomeric species that may contribute to the formation of secondary organic aerosol in the atmosphere. Using high resolution negative mode electrospray ionization mass spectrometry, the aqueous photochemistry of dilute solutions of pyruvic acid (10, 1, and 0.5 mM) under anaerobic conditions was investigated. Even at the lowest concentration, covalently bonded dimers and trimers of pyruvic acid were observed as photochemical products. We calculate that it is energetically possible to photochemically generate parapyruvic acid, a dimer of pyruvic acid that is known to form via dark oligomerization processes. Subsequent photochemical reactions of parapyruvic acid with pyruvic acid form larger oligomeric products, such as 2,4-dihydroxy-2-methyl-5-oxohexanoic acid. A robust and relatively simple photochemical mechanism is discussed that explains both the conditional dependence and wide array of products that are observed

Compression of a Stearic Acid Surfactant Layer on Water Investigated by Ambient Pressure X-ray Photoelectron Spectroscopy

We present a combined Langmuir-Pockels trough and ambient pressure X-ray photoelectron spectroscopy (APXPS) study of the compression of stearic acid surfactant layers on neat water. Changes in the packing density of the molecules are directly determined from C 1s and O 1s APXPS data. The experimental data are fit with a 2D model for the stearic acid coverage. Based on the results of these proof-of-principle experiments, we discuss the remaining challenges that need to be overcome for future investigations of the role of surfactants in heterogeneous chemical reactions at liquid-vapor interfaces in combined Langmuir-Pockels trough and APXPS measurements

Regensburger Land. Der Landkreis Regensburg in Geschichte und Gegenwart 1 (2008)

Die neue Schriftenreihe „Regensburger Land. Der Landkreis Regensburg in Geschichte und Gegenwart“ soll im Stile eines Almanachs möglichst jährlich mit einem Band erscheinen und informative Beiträge zur regionalen Geschichte und Kultur enthalten. Ansprechend aufgemacht und reich bebildert, ist sie an eine breite Leserschaft gerichtet

Environmental processing of lipids driven by aqueous photochemistry of α-Keto acids

Sunlight can initiate photochemical reactions of organic molecules though direct photolysis, photosensitization, and indirect processes, often leading to complex radical chemistry that can increase molecular complexity in the environment. α-Keto acids act as photoinitiators for organic species that are not themselves photoactive. Here, we demonstrate this capability through the reaction of two α-keto acids, pyruvic acid and 2-oxooctanoic acid, with a series of fatty acids and fatty alcohols. We show for five different cases that a cross-product between the photoinitiated α-keto acid and non-photoactive species is formed during photolysis in aqueous solution. Fatty acids and alcohols are relatively unreactive species, which suggests that α-keto acids are able to act as radical initiators for many atmospherically relevant molecules found in the sea surface microlayer and on atmospheric aerosol particles

Compression of a Stearic Acid Surfactant Layer on Water Investigated by Ambient Pressure X-ray Photoelectron Spectroscopy

We present a combined Langmuir–Pockels trough and ambient pressure X-ray photoelectron spectroscopy (APXPS) study of the compression of stearic acid surfactant layers on neat water. Changes in the packing density of the molecules are directly determined from C 1s and O 1s APXPS data. The experimental data are fit with a 2D model for the stearic acid coverage. Based on the results of these proof-of-principle experiments, we discuss the remaining challenges that need to be overcome for future investigations of the role of surfactants in heterogeneous chemical reactions at liquid–vapor interfaces in combined Langmuir–Pockels trough and APXPS measurements