• La auto-modelación y el sujeto femenino en La Celestina de Fermando de Rojas y en La Farsa de la Costança de Cristóbal de Castillejo

      Piera, Montserrat; Pueyo Zoco, Víctor; Soufas, Teresa Scott; Delbrugge, Laura, 1968- (Temple University. Libraries, 2015)
      This thesis examines the concept of self-fashioning in the Spanish texts La Celestina and Farsa de Costança. Greenblatt's theory of self-fashioning in English Renaissance literature can also be applied to the analysis of these Medieval and Renaissance works of the Iberian Peninsula. Self-fashioning is a literary technique of constructing a public persona – that is perhaps different to one's true self, or private persona - in order to satisfy the demands imposed by society. This implies duplicity and disguise in the literary discourse. This study focuses mainly on the analysis of the female characters; special attention is given to the go-between. The characteristics of the medieval bawd and its Greco-Roman antecedents appear again in the new literary character of the female Spanish pícara of the XVI century. As in the case of the bawd, the pícara knows how to manipulate people regarding love, sex and greed. Through these marginal characters the authors voice their opinion regarding politics, religion and social conditions. Rojas, a converso living in Spain during the Inquisition, expresses his views in a veiled manner by criticizing and finding fault with Christian values. On the other hand, Castillejo, as in the case of Rojas, attacks the corruption of the Catholic Church and ridicules the sacrament of matrimony. Finally, these authors follow the traditional misogynistic views conceived by the church fathers.
    • La distopia en las novelas de Ana Maria Shua

      Morell, Hortensia R., 1951-; Lorenzino, Gerardo; Aldarondo, Hiram; Schmidt-Cruz, Cynthia (Temple University. Libraries, 2010)
      This dissertation focuses on the influence of political and social history in the novels of Ana María Shua, an Argentine author who critiques her own contemporary society based upon her nation’s history and her Jewish ancestry. It examines the relationships between individuals, such as parents and children, spouses, or friends to demonstrate that people are unable to change their own situation: the circularity of time and the repetition of the past will always haunt the inhabitants and marginalize them. This work analyzes Shua’s five novels: Soy paciente (1980), Los amores de Laurita (1984), El libro de los recuerdos (1994), La muerte como efecto secundario (1997), and El peso de la tentación (2007). These selected works explore the transformations of the protagonists through their interactions with their environment in order to prove that the individual will remain isolated within the hierarchies and institutions created by contemporary society. The introduction offers an overview of Shua’s biography and literary works as well as an exploration of the connections between the history of Argentina and the author’s novels. Chapter 1 focuses on the influence of history in the present and future of the protagonists in Los amores de Laurita, El libro de los recuerdos, and La muerte como efecto secundario. Chapter 2 makes use of Michel Foucault’s system of power to explore the way in which society victimizes the protagonists. The chapter studies: Los amores de Laurita, La muerte como efecto secundario, and El peso de la tentación. Chapter 3 analyzes the hierarchies established in the institutions and how they convert the body of the individual into a jail. The novels studied include: Soy paciente, La muerte como efecto secundario, and El peso de la tentación. Chapter 4 demonstrates how the history of Argentina is represented in the political and social institutions of El libro de los recuerdos, Soy paciente, and El peso de la tentación. It connects the contemporary desire of a utopian future with Jewish tradition and the hope of a messiah. The conclusions recapitulate the pessimistic, dystopian future that remains for each of the protagonists.
    • La novela erótica latinoamericana contemporánea: Cristina Peri Rossi, José Donoso, Griselda Gambaro y Mario Vargas Llosa

      Morell, Hortensia R., 1951-; Lorenzino, Gerardo; Piera, Montserrat; Ossa, Luisa Marcela, 1972- (Temple University. Libraries, 2013)
      Esta investigación examina cuatro novelas latinoamericanas de las últimas dos décadas del siglo XX con el fin de demostrar la forma en que establecen evidencia textual y contextual que valida su inclusión bajo la categoría de textos literarios eróticos y su exclusión de los "infiernos" eróticos.
    • Labeling Adult Sex Offenders and Sexually Violent Predators: The Impact of Registration and Community Notification

      Auerhahn, Kathleen, 1970-; Harris, Philip W.; Hiller, Matthew L.; Zakireh, Barry (Temple University. Libraries, 2009)
      When released from prison, sex offenders are typically required to register with designated law enforcement officials as a condition of their parole. These officials can warn local community members, organizations, and establishments of the offender's incoming presence. Research indicates that community notification can adversely affect sex offenders in terms of their interpersonal and family relationships, employment opportunities and housing, and can lead to offender harassment that extends to the family members of sex offenders (Burchfield & Mingus, 2008; Levenson & Cotter, 2005a, 2005b; Levenson, D'Amora, & Hern, 2007; Tewksbury, 2004, 2005; Tewksbury & Lees, 2007; Zevitz & Farkas, 2000b). The current analysis seeks to build on and extend the existing literature by investigating the consequences of sex offender registration and community notification from the perspective of registered sex offenders and sexually violent predators in Pennsylvania. Using multiple methods of data collection (i.e., survey and interview research) and analyses, the present study contributes to the current understanding of how sex offenders experience registration and community notification and focuses on the positive and negative effects (e.g., unintended and unanticipated consequences) of being labeled and subject to community notification. Data for the present study were collected in collaboration with four providers of sex offender treatment. These treatment facilities are non-profit mental health organizations that provide both outpatient examinations and treatment services for sex offenders. All treatment providers are located in Pennsylvania, and will remain anonymous in the current study. The survey sample consists of 200 adult male sex offenders. For the purposes of making comparisons, 181 of the sampled sex offenders were further classified as the following three subsamples: (1) registered sex offenders (RSOs) (n = 121), (2) sexually violent predators (SVPs) (n = 13), and (3) non-registered sex offenders (and non-sexually violent predators) (n = 47). Nine of the SVPs elected to participate in the face-to-face interview portion of this research where topics focused on the impact of active community notification, the process whereby the state police are required to mail out letters to community members about an offender's physical description and home address. The age of the interview sample ranged from 35 to 63, and the average was 49.22 years old. Descriptive results of the complete survey sample reveal that most sex offenders are White or African American, middle-aged, and not married, and have relatively little formal education. Most sex offenders are working in some capacity, self-identify as "working class," and earn less than $20,000 per year. The majority of the total sample of sex offenders has been convicted of indecent assault/indecent sexual assault (24.6%) followed by possession of child pornography (12%) and then rape (11.4%). Overall, most victims are minor-aged females who were known by - but not related to - the offender. Findings from the anonymous survey also indicate that over 40 percent of the sampled RSOs are restricted by a 1,000-foot-rule, have primary group members who sustained some type of harm, and have had meaningful, personal relationships severed. Sexually violent predators experienced job loss, denial of employment, loss of housing, and denial of a place to live, and were treated rudely in public, and had primary group members who experienced emotional harm and, separately, had personal relationships severed at a higher rate (i.e., at least 10 percentage points) than RSOs. None of the SVPs were physically assaulted, whereas six RSOs (i.e., 5 percent of 120 RSOs) were physically assaulted. Using only a combination of two of the three subsamples of sex offenders (i.e., RSOs and SVPs), the multivariate contingency table analyses assessed how sex offenders' selection of victim-type, relationship to victim, and race influenced the fifteen different economic, residency-related, and harassment outcomes. Specifically, if offenders victimized a child (i.e., victims from age 5 to 17), as opposed to an adult (i.e., 18 or older), they were significantly more likely to be restricted by a 1,000-foot-rule, as expected. Offenders who victimized children were also more likely than offenders who victimized adults (by at least 10 percentage points) to experience job loss and receive harassing telephone calls, and to have primary group members who sustained some form of emotional harm and, separately, have personal relationships severed. Findings gleaned from the interviews indicate that SVPs are experiencing several of the problems identified in the previous and related literature. Specifically, six of the interviewees (66.67 percent) indicated that, since the notification process began, they have had a difficult time locating and obtaining affordable housing. Analysis of covariance (ANCOVA) was used to examine the effect of sex offenders' socio-demographics, offender characteristics, victim characteristics, and negative experiences resulting from registration and/or notification on self-esteem (Rosenberg, 1965), mastery (Pearlin et al., 1981; Pearlin & Schooler, 1978), stigma (Link, 1987; Link et al., 1997), and depression using the Center for Epidemiologic Studies Depression Scale (CES-D). The multivariate regression results were quite unexpected. After controlling for sex offenders' sociodemographics, offender characteristics, and victim characteristics, none of the scales devised to measure the impact of registration and/or community notification significantly predicted any of the four outcomes. The significance of these findings for criminological theory, and offender rehabilitation and reintegration are discussed.

      Garrett, Paul B., 1968-; Akinnaso, Festus Niyi; Romberg, Raquel; Williams-Witherspoon, Kimmika (Temple University. Libraries, 2009)
      Tucson, Arizona is a site of a lively Polish-American community. Initially associated with a political organization ("Solidarity Tucson"), which actively supported the Solidarity Movement throughout the 1980s, the Polish diaspora has gradually transformed into an ethnic community very much focused on maintaining its distinctive heritage. Recent formation of the Polish folkloric dance group Lajkonik was directly stimulated by the local multicultural establishment, which promotes ethnic diversity in the Old Pueblo. Having become an integral part of the Southwestern society, Lajkonik has developed a collection of identity practices, which despite diverse influences continues to reproduce Polish cultural traits. In my ethnographic account, I examine ways, by which members of the Lajkonik group construct their diasporic identities. First, I focus on the core activities of the group, which include the practice of Polish traditions, learning folk dances and songs in a wide cultural context, and negotiating the speaking of Polish. Additional analyses, based on video recordings, of Polish classes and dance rehearsals, which show the actual mechanics of the production processes, as well as the narratives of the teacher and parent of performers, further support the account of the ethnographer. Secondly, I look into the development of Polishness for public consumption, which involves negotiation of multiple images in accordance with specific cultural events, creation of engaging stage programs, and presenting the essence of Polishness to festival audiences in Tucson. Regardless of the particular purpose of identities' productions, either for integrating community or public display, these processes simultaneously involve the quest for authenticity, building ethnic pride, and negotiations of diverse traditions.
    • Land Acquisition for Special Economic Zones in India

      Chakravorty, Sanjoy; Kohl, Benjamin H. (Temple University. Libraries, 2011)
      This study is an exploration of land acquisition for Special Economic Zones (SEZs) in India. Land acquisition has become one of the most well known problems confronting the SEZ policy and other policies that encourage private investment in infrastructure. Land acquisition for SEZs has caused widespread popular mobilizations and resistance, which have in turn led to cost overruns, delays, and project failures. This study examines India's land acquisition framework, particularly the evolution of the Land Acquisition Act 1894, in order to understand the factors contributing to acquisition problems when the state uses its power of eminent domain, as well as when private developers attempt to acquire land through consensual market transactions. It uses two SEZs spanning over 14,000 hectares of land near Mumbai--Navi Mumbai SEZ and Mumbai SEZ--as cases through which to examine the land acquisition process.
    • Landscape Phenomics of the Human Face

      Rockwell, Christie; Weitz, Charles A.; Henry, Kevin A.; Nelson, Frank (Temple University. Libraries, 2021)
      The study of human cranial morphology has a long and contentious history. This study is the first large scale analysis of ecoregion specific human cranial modularity and integration. It utilizes an analysis of morphometric craniofacial variation and ecoregion affinity to better understand the environmental contribution to biological shape. This study tested three hypotheses. First, that there was variation in craniofacial shape that was linked to an individual’s ecoregion. Second, that there were ecoregion specific patterns of cranial modularity. And third, that the patterns of cranial integration (or the level of covariation between any two modules) were also associated with an individual’s ecoregion, and that different environments would result in different patterns of modular dependence and independence. Three-dimensional scans of 298 human crania were collected from museums, representing four higher level ecoregions and 11 lower-level ecoregions. Each cranium was mapped and placed within two hierarchical ecoregions. By examining ecoregions, instead of individual climatic variables, this analysis gives a more complete picture of how the environment is influencing cranial variation. Modules, or relatively independent morphological regions of the crania, were identified and their level of integration was assessed for every ecoregion. Modular integration is an analysis of the relative strength of the covariation between any two modules, and previous research theorized that changes in integration reflected changes in modular independence during development (Bastir and Rosas, 2005; Hall, 2005; Raff, 1996). The variation in strength between modules, both intrapopulation and interpopulation, were assessed and various explanations were explored. This analysis found that each ecoregion exhibited significantly different craniofacial shape from one another. Patterns of integration were also variable by ecoregion, suggesting that the ecological shape variation observed was solidified early in development. This study also identified the presence of a nasal module in each ecoregion. Overall, the findings of this study demonstrate that human crania are variable by ecoregion and that environmental conditions have led to ecoregion specific patterns of cranial modular integration.
    • Language and Identity among Adolescent Heritage Spanish Students

      Lorenzino, Gerardo; Holmquist, Jonathan Carl; Toth, Paul D.; Flores-Ferran, Nydia (Temple University. Libraries, 2013)
      This dissertation describes the language and identity trajectories of twelve purposefully selected heritage Spanish adolescents who were currently studying in a heritage language program within an urban high school in Bethlehem, Pennsylvania. These twelve students represented six sibling groups and five different nationalities, specifically Dominican, Ecuadorian, Puerto Rican, Salvadorian, and Venezuelan,. The research questions were: 1) How do Hispanic heritage students negotiate their bicultural/bilingual identities?; 2) What is the role of the heritage language in those negotiated identities?; 3) Do these negotiated identities influence their investment to maintain the heritage language?; 4) What are the linguistic manifestations of the Spanish spoken by these bilingual students? Findings of the study revealed that 1) the study participants negotiate their bicultural/bilingual identities in a variety of ways, 2) for some of these students, the heritage language is part of their `out of school' identities, 3) the dominant language ideologies of the school system have had a significant impact on the heritage students' investment in HL practice, and 4) although each participant's identity and linguistic trajectories are distinct, they each have maintained, to a greater or lesser degree, the aspectual preterit/imperfect contrast, and, at the same time have displayed some level of incomplete acquisition of the subjunctive mood. The implications of these findings as they relate to the fields of bilingualism, languages in contact and the developing theory of Heritage Language Acquisition are addressed in the concluding remarks.
    • Language Dominance and the Language, Literacy, and Early Math of Spanish-English Bilingual Preschoolers

      Hammer, Carol Scheffner; Krakow, Rena A.; Reich, Jodi; Wasik, Barbara A.; Hindman, Annemarie H. (Temple University. Libraries, 2016)
      There is a growing need for more information regarding the early academic development of preschool-age children who are learning to speak Spanish and English. To achieve this, studies are needed that acknowledge the heterogeneity of language abilities within bilingual preschool children, and that these variations in language abilities may impact children’s early academic skills. This two-study dissertation investigated how four foundational skills: narrative production, phonological awareness, letter-word identification, and early math, differed depending on the language dominance Spanish-English bilingual children possessed at preschool entry. The studies used data from a larger language, literacy, and self-regulation project entitled Tools of the Mind: Promoting ELLs’ Language, Self-Regulation & School-Readiness. Participants were typically-developing children of Latino heritage recruited from early childhood centers with primarily English instruction. Performance on a standardized language battery given in English and Spanish was used to assign children to one of three language-dominance groups (i.e., stronger-English, balanced abilities, stronger-Spanish). Both studies yielded several findings that make unique contributions to research on bilingual preschoolers. The first study underscored the important relations of both lexical diversity and grammatical production abilities to bilingual preschoolers’ narrative macrostructure. The second study identified specific areas of school readiness strengths for each language dominance group and identified areas that may need additional support. Implications of interest to speech-language pathologists and other early childhood professionals are discussed, including implications for assessment and differential instruction.
    • Language Expertise as a Source of Dispute in Bilingual Couple Talk

      Carroll, Donald; Houck, Nöel, 1942-; Hosoda, Yuri; Childs, Marshall; Beglar, David J. (Temple University. Libraries, 2010)
      This study explores dispute sequences in talk between bilingual couples communicating in Japanese. Specifically I examine naturally occurring face-to-face talk between Japanese wives and their American husbands who communicate primarily in Japanese at home. Conversation analysis (CA) is employed to document occasions where the talk between these couples evolves into problematic talk such as disputes. The analytical focus is on sequences where problematic talk is related to the participants' orientation to such contrasting identities as native/non-native speaker and expert/novice categories. A total of 16 hours of conversations were audio-recorded in the couples' homes while they were engaged in everyday activities such as eating meals. The analysis of the data revealed several separate but related issues. First, the couples made their language expert and novice identities relevant in their talk when they conducted metalingual talk, i.e., talk about the Japanese language. Specifically, these identities emerged through repair sequences on occasions when one person had difficulty understanding or producing a lexical item and his or her spouse provided assistance with the problematic item. Second, problematic episodes, such as dispute sequences, were often occasioned by metalingual talk. Third, Japanese native and non-native speaker identities were sometimes separated from differential language expertise. When this happens, the native speaker disputes it and problematic talk occurs. The findings indicated that language expertise should be thought of as something that is independent to being a "native speaker" of a language. Being a language expert is locally situated in and negotiated through the ongoing talk and non-native speakers can be language experts as well. However, the data in this study show that the native speakers of Japanese, Japanese wives, sometimes perceived their non-native American husbands as disputing their expertise when they were engaged in metalingual talk. The American husbands occasionally displayed their expertise and argued against their Japanese wives on linguistic issues or did not acknowledge the expert information provided by the wives. When that happened, their talk became problematic, as the native speaker wives claimed that they were the experts and not the non-native husbands. In sum, this study revealed that dispute in intercultural marriage is in some cases due to language expertise displayed in the interactions. Dispute emerges through the on-going talk and is not determined based on the second language speaker's disfluency or differences between the speakers' cultural backgrounds, a claim that is frequently made in other fields such as intercultural communication, second language studies, and sociolinguistics. This newly identified phenomena based on language expertise is at the root of dispute in bilingual couple talk.
    • Language Learners' Beliefs: Development and Change

      Childs, Marshall; Beglar, David; Sawyer, Mark; Murphey, Tim; Sakamoto, Masako (Temple University. Libraries, 2012)
      This longitudinal study was designed to provide an orderly account of how beliefs about English language learning develop among seven Japanese high school students, identify beliefs that are beneficial and interfering for language learning and the routes by which these beliefs are reached, and identify belief changes and their sources. Beliefs are defined as a cognitive representation about self and the world. They are situated in experiences and social context. Learner beliefs pertain to many aspects of language learning and come from multiple sources, including educational background, experience living overseas, peers, teachers, and persons met in chance encounters. The data for the study were collected from seven students attending a Japanese public high school. Beginning when the students were first-year high school students (10th graders), the data, which were drawn from in-depth interviews, journals, written reports, observations, and school records, form a qualitative multiple-case-study. Data gathering ended when the students chose a university in the third year of high school. There were five major findings. First, learners develop and modify their beliefs based on their life experiences inside and outside the classroom. This finding suggests that providing learning experiences is important, but teachers should be aware that learners with different learning backgrounds and personal traits will likely respond to those experiences differently. Experiences that most influence learners’ beliefs seem to be those that learners choose themselves. Second, beliefs are usually implicit, and thus, learners are not always aware of their beliefs until they are asked to verbalize them. Thus, one role for researchers and teachers is to find effective ways to elicit learner beliefs and make them explicit. Third, beliefs can be placed in three categories: beneficial beliefs, indeterminate beliefs, and interfering beliefs. Beneficial beliefs enhance learners’ motivation to learn, while interfering beliefs concern negative thoughts that hinder them from learning and from engaging in challenging tasks. Indeterminate beliefs can be either beneficial or interfering depending on the context in which they occur. Those beliefs are context-sensitive; thus, they are not necessarily shared by all learners. Individual learners have different beneficial and interfering beliefs depending on their learning context. Fourth, adolescent learners’ beliefs change over time because adolescents are in the process of growing and changing physically and mentally. This suggests that there is great potential for modifying their beliefs in positive ways. Fifth, learners develop personal theories about learning based on their beliefs. Considering that learners behave according to their theories of learning, eliciting learners’ beliefs can bring benefits for researchers and teachers because they can anticipate learners’ behavior by knowing their beliefs.
    • Large Scale Multiple Testing for High-Dimensional Nonparanormal Data

      Sarkar, S. K. (Sanat K.); Han, Xu (Temple University. Libraries, 2019)
      False discovery control in high dimensional multiple testing has been frequently encountered in many scientific research. Under the multivariate normal distribution assumption, \cite{fan2012} proposed an approximate expression for false discovery proportion (FDP) in large-scale multiple testing when a common threshold is used and provided a consistent estimate of realized FDP when the covariance matrix is known. They further extended their study when the covariance matrix is unknown \citep{fan2017}. However, in reality, the multivariate normal assumption is often violated. In this paper, we relaxed the normal assumption by developing a testing procedure on nonparanormal distribution which extends the Gaussian family to a much larger population. The nonparanormal distribution is indeed a high dimensional Gaussian copula with nonparametric marginals. Estimating the underlying monotone functions is key to good FDP approximation. Our procedure achieved minimal mean error in approximating the FDP compared with other methods in simulation studies. We gave theoretical investigations regarding the performance of estimated covariance matrix and false rejections. In real dataset setting, our method was able to detect more differentiated genes while still maintaining the FDP under a small level. This thesis provides an important tool for approximating FDP in a given experiment where the normal assumption may not hold. We also developed a dependence-adjusted procedure which provides more power than fixed-threshold method. Our procedure also show robustness for heavy-tailed data under a variety of distributions in numeric studies.

      Megalooikonomou, Vasilis; Obradovic, Zoran; Ling, Haibin; Faro, Scott H. (Temple University. Libraries, 2012)
      Gene expression signatures in the mammalian brain hold the key to understanding neural development and neurological diseases, and gene expression profiles have been widely used in functional genomic studies. However, not much work in traditional gene expression profiling takes into account the location information of a gene's expressions in the brain. Gene expression maps, which are obtained by combining voxelation and microarrays, contain spatial information regarding the expression of genes in mice's brain. We study approaches for identifying the relationship between gene expression maps and gene functions, for mining association rules, and for predicting certain gene functions and functional similarities based on the gene expression maps obtained by voxelation. First, we identified the relationship between gene functions and gene expression maps. On one side, we chose typical genes as queries and aimed at discovering the groups of the genes which have similar gene expression maps to the queries. Then we study the relationship between functions and maps by checking the similarities of gene functions in the detected gene groups. The similarity between a pair of gene expression maps was identified by calculating the Euclidean Distance between the pair of feature vectors which were extracted by wavelet transformation from the hemispheres averaged gene expression maps. Similarities of gene functions were identified by Lin's method based on gene ontology structures. On the other side, we proposed a multiple clustering approach, combined with hierarchical clustering method to detect significant clusters of genes which have both similar gene functions and similar gene expression maps. Among each group of similar genes, the gene function similarity was measured by calculating the average pair-wise gene function distance in the group and then ranking it in random cases. By finding groups of similar genes toward typical genes, we were able to improve our understanding of gene expression patterns and gene functions. By doing the multiple clustering, we obtained significant clusters of similar genes and very similar gene functions respectively to their corresponding gene ontologies. The cellular component ontology resulted in prominent clusters expressed in cortex and corpus callosum. The molecular function ontology gave prominent clusters in cortex, corpus callosum and hypothalamus. The biological process ontology resulted in clusters in cortex, hypothalamus and choroid plexus. Clusters from all three ontologies combined were most prominently expressed in cortex and corpus callosum. The experimental results confirm the hypothesis that genes with similar gene expression maps have similar gene functions for certain genes. Based on the relationship between gene functions and expression maps, we developed a modified Apriori algorithm to mine association rules among gene functions in the significant clusters. The experimental results show that the detected association rules (frequent itemsets of gene functions) make sense biologically. By inspecting the obtained clusters and the genes having the same frequent itemsets of functions, interesting clues were discovered that provide valuable insight to biological scientists. The discovered association rules can be potentially used to predict gene functions based on similarity of gene expression maps. Moreover, proposed an efficient approach to identify gene functions. A gene function or a set of certain gene functions can potentially be associated with a specific gene expression profile. We named this specific gene expression profile, Functional Expression Profile (FEP) for one function, or Multiple Functional Expression Profile (MFEP) for a set of functions. We suggested two different ways of finding (M)FEPS, a cluster-based and a non-cluster-based method. Both of these methods achieved high accuracy in predicting gene functions, each for different kinds of gene functions. Compared to the traditional K-nearest neighbor method, our approach shows higher accuracy in predicting functions. The visualized gene expression maps of (M)FEPs were in good agreement with anatomical components of mice's brain Furthermore, we proposed a supervised learning methodology to predict pair-wise gene functional similarity from gene expression maps. By using modified AdaBoost algorithm coupled with our proposed weak classifier, we predicted the gene functional similarities between genes to a certain degree. The experimental results showed that with increasing similarities of gene expression maps, the functional similarities were increased too. The weights of the features in the model indicated the most significant single voxels and pairs of neighboring voxels which can be visualized in the expression map image of a mouse brain.
    • Laser (Cooling) Refrigeration in Erbium Based Solid State Materials

      Hasan, Zameer U.; Riseborough, Peter; Iavarone, Maria; Perdew, John P. (Temple University. Libraries, 2015)
      The objective of this study was to investigate the potential of erbium based solid state materials for laser refrigeration in bulk material. A great deal of work in the field has been focused on the use of ytterbium based ZBLAN glass. Some experiments have also reported cooling in thulium based solid state materials but with considerably less success. We proposed that erbium had many attractive features compared to ytterbium and therefore should be tried for cooling. The low lying energy level structure of erbium provides energy levels that could bring obtainable temperatures two orders of magnitude lower. Erbium transitions of interest for cooling fall in the near IR region (0.87 microns and 1.5 microns). Lasers for one of these transitions, in the 1.5 micron region, are well developed for communication and are in the eye-safe and water and atmosphere transparent region. Theoretical calculations are also presented so as to identify energy levels of the eleven 4f electrons in Er3+ in Cs2NaYCl6:Er3+ and the transitions between them. The strengths of the optical transitions between them have been calculated. Knowledge of such energy levels and the strength of the laser induced transitions between them is crucial for understanding the refrigeration mechanisms and different energy transfer pathways following the laser irradiation. The crystal host for erbium was a hexa-chloro-elpasolite crystal, Cs2NaYCl6:Er3+ with an 80% (stoichiometric) concentration of erbium. The best cooling results were obtained using the 0.87 micron transition. We have demonstrated bulk cooling in this crystal with a temperature difference of ~6.2 K below the surrounding temperature. The temperatures of the crystal and its immediate surrounding environment were measured using differential thermometry. Refrigeration experiments using the 1.5 micron transition were performed and the results are presented. The demonstrated temperature difference was orders of magnitude smaller. Only a temperature of ~0.015 K below the temperature of the surrounding environment was observed in this case. These results are in agreement with another group’s that has observed cooling, though a slightly poorer temperature difference, using this transition of erbium (Condon et. al., 2009). Cooling was also attempted in the 0.87 micron transition of another crystal host, KPb2Cl5:Er, which has a concentration of about one percent of erbium. We did not observe any cooling in this crystal. However, the first cooling reports in erbium based systems were with this crystal where another group observed cooling by 0.7 K using the same transition (Fernández, García-Adeva, & Balda, 2006).

      Levis, Robert J.; Strongin, Daniel R.; Schafmeister, Christian; Amini, Shohreh (Temple University. Libraries, 2011)
      The use of femtosecond (fs) laser pulses in laser-induced breakdown spectroscopy (LIBS) and for chemical analysis using mass spectrometry is explored. A comparison of fs-LIBS and remote filament-induced breakdown spectroscopy (R-FIBS) in the analysis of graphite composites yielded more accurate results with filaments due to intensity clamping within the filament. The investigation of fs-LIBS and R-FIBS in the detection of explosives led to the discovery of femtosecond vaporization of intact molecules under ambient conditions. This knowledge was then used in the development of a new ambient laser-based mass analysis technique. The combination of nonresonant femtosecond laser vaporization with electrospray post-ionization called laser electrospray mass spectrometry (LEMS) was investigated as a universal detection method of pharmaceuticals, biological macromolecules and plant tissues. We show the capability of femtosecond lasers to desorb sample without any sample preparation or resonant transition in the sample or substrate. Ambient mass spectral imaging and tissue type classification is also demonstrated.
    • Laser Electrospray Mass Spectrometry for Structural Analysis of Biomolecules

      Levis, Robert J.; Levis, Robert J.; Valentine, Ann M.; Zdilla, Michael J., 1978-; McEwen, Charles N., 1942- (Temple University. Libraries, 2017)
      This dissertation elucidates a greater understanding of protein folding and unfolding processes during the lifetimes of electrospray and nano-spray droplets in laser electrospray mass spectrometry (LEMS) and nano-laser electrospray mass spectrometry (nano-LEMS) measurements, respectively. The similarity in mass spectral features obtained from conventional electrospray measurements for supercharged proteins with those of LEMS measurements suggested that supercharging phenomena occurs in the electrospray droplets during the droplet desolvation process. It was observed that the laser vaporization of protein from condensed phase into the electrospray droplets containing denaturing electrospray solution and a supercharging reagent resulted in the increase in ion abundance of higher charge states in comparison with electrospray measurements. Conversely, the addition of solution additives with varying gas phase basicity in the electrospray solvent resulted in charge reduction for unfolded protein upon laser vaporization from condensed phase into the charged electrospray droplets. The extent of charge reduction and the fraction of folded protein within the electrospray droplets was found to be dependent upon both the extent of protein denaturation in the solution prior to laser vaporization and the gas phase basicity of solution additives. The ability of the LEMS technique to analyze molecules from solution with high matrix effects was established by the successful detection of protein molecules from solution with high salt concentration. Experiments with LEMS enabled the detection of a protonated protein feature as the dominating peak in the mass spectra for up to 250 mM sodium chloride while conventional electrospray resulted in predominantly salt-adducted features, with suppression of the protonated protein ions for the salt concentration of 5 mM. This dissertation also expanded upon the use of a reaction system to measure the lifetimes of laser vaporized liquid droplets coupled with electrospray and nano-spray postionization mass spectrometry. Electrospray and nanospray droplet lifetimes were measured to be 4.5±0.6 ms and 1.4±0.3 ms using LEMS and nano-LEMS measurements, respectively. Time dependent protein folding measurements using LEMS revealed intermediate states during protein folding processes which are often limited in conventional electrospray measurements where bulk solution in manipulated (change in pH) to achieve protein folding.

      Levis, Robert J.; Levis, Robert J.; Valentine, Ann M.; Strongin, Daniel R.; McEwen, Charles N., 1942- (Temple University. Libraries, 2017)
      This dissertation elucidates the instrumentation and application of a hybrid ambient ionization source, laser electrospray mass spectrometry (LEMS), for the direct analysis and molecular imaging of biological tissue without matrix deposition. In LEMS, laser pulses from a Ti:Sapphire laser amplifier (60 fs, 800 nm, and 1 mJ) interact with surface analytes and transfer them from the condensed phase into the gas phase without the requirement of either exogenous matrix or endogenous water in the sample. The laser vaporized analytes are captured and ionized by an electrospray source, and finally detected by a mass analyzer. It was found that a turn-key, robust femtosecond fiber laser with longer wavelength, longer duration, and lower pulse energy at 1042 nm, 425 fs, and 50 µJ, respectively, provided comparable results with the Ti:Sapphire laser. Vaporization of intact, dried or aqueous cytochrome c and lysozyme samples was demonstrated by the fiber laser. A charge states distribution at lower charge states indicating folded conformation of proteins and the hemoglobin α subunit-heme complex from whole blood was observed. Endogenous anthocyanins, sugars, and other metabolites were detected and revealed the anticipated metabolite profile for the flower petal and leaf samples by the fiber laser. Phospholipids, especially phosphatidylcholine, were identified from a fresh mouse brain section sample. These lipid features were suppressed in both the fiber laser and Ti:Sapphire LEMS measurement in the presence of optimal cutting temperature compounds which are commonly used in animal tissue cryosectioning. This dissertation also details the design of an automated mass spectrometry imaging source based on the Ti:Sapphire LEMS. The laser, translation stage, and mass analyzer are synchronized and controlled using a customized user interface to enable step-by-step scanning of the area of interest on a given tissue sample. The imaging source is coupled with a high resolution accurate mass quadrupole time-of-flight (QTOF) mass analyzer with tandem mass analysis capability. A lateral resolution of 60 µm was demonstrated on a patterned ink film by LEMS imaging. Plant metabolites including sugar and anthocyanins were directly imaged from a leaf sample. Small metabolites, lipids and proteins were simultaneously imaged from a single tissue section of a pig liver sample. Biomarkers of blood-brain barrier damage and traumatic brain injury (TBI) that occurred during the injury were detected and imaged from a TBI mouse brain. The loading values from principal component analysis (PCA) were shown to be useful for identification of features of interest from the large LEMS imaging dataset.
    • Laser Electrospray Mass Spectrometry: Mechanistic Insights and Classification of Inorganic-Based Explosives and Tissue Phenotypes Using Multivariate Statistics

      Levis, Robert J.; Strongin, Daniel R.; Schafmeister, Christian; Owens, Kevin Glenn, 1960- (Temple University. Libraries, 2014)
      This dissertation elucidates a greater understanding of the vaporization and electrospray post-ionization mechanisms when using femtosecond laser pulses for desorption of surface molecules and electrospray ionization for capture and mass analysis of the gas phase ions. The internal energy deposition from nonresonant vaporization with femtosecond laser pulses was measured using dried and liquid samples of p-substituted benzylpyridinium ions and peptides. In the comparison of the experiments of using 800 nm and 1042 nm laser pulses, it was found that there are different vaporization mechanisms for dried and liquid samples. It was established that LEMS is a "soft" mass analysis technique as it resulted in comparable internal energy distributions to ESI-MS with one caveat; multiphoton excitation of dried samples results in extensive fragmentation at higher pulse energies. The quantitative aspects of the laser electrospray mass spectrometry (LEMS) technique were established using various multicomponent mixtures of small biomolecules. Experiments with LEMS resulted in similar quantitative characteristics to ESI-MS except that ESI-MS demonstrated a greater degree of ion suppression when using higher concentrations, particularly in the four-component mixture. The lack of ion suppression in the LEMS measurements was due to the ~1% neutral capture efficiency and most likely not a result of nonequilibrium partitioning. This was supported by the excess charge limit not being surpassed in the LEMS experiments and the quantitative analysis requiring the use of response factors. This dissertation also expanded upon the use of multivariate analysis for the classification of samples that were directly mass analyzed without any sample preparation using LEMS. A novel electrospray complexation mixture using cationic pairing agents, a lipid, and sodium acetate enabled the simultaneous detection of positive, neutral and negative charged features of inorganic-based explosive residues in a single experiment. This complexation mixture also enabled the detection of new features from an RDX-based propellant mixture. Principal component analysis (PCA) proved reliable for accurate classifications of the explosive mixtures. PCA was also used for accurate classification of eight phenotypes of Impatiens plant flower petals after mass analysis with LEMS. The PCA loading values were used to identify the key biomarkers in the classification. These important mass spectral features were identified as the biologically-relevant anthocyanins, which are phytochemicals that are responsible for the color of the flower petals.
    • Late Eocene Terrestrial Paleoclimatie Record From The White River Formation At Flagstaff Rim, Wyoming, USA

      Terry, Dennis O., 1965-; Grandstaff, David E.; Tumarkin-Deratzian, Allison (Temple University. Libraries, 2011)
      Flagstaff Rim near Casper, WY preserves the most complete late Eocene section of the White River Group with over 219 m of late Eocene age sediment compared to 35 m preserved at Toadstool Park, NE. While Flagstaff Rim does not span the Eocene-Oligocene transition, it holds the earliest clues in the White River Group of a late Eocene (37-34 Ma) climatic deterioration. In this study 8 paleosols were collected, described and analyzed based on pedogenic features, mineralogy, and geochemistry, above and below dated volcanic ash beds. The lowermost paleosol is composed of smectite- rich red mudstone, with greenish gray drab haloes, and weather into hummocks. The sediments within this part of the section are the lithologic equivalent of the Peanut Peak member of Toadstool Park, NE and reflect a moist humid environment. Overlying these sediments is the lithologic equivalent of the Big Cottonwood Creek member. These sediments are comprised of smectite poor mudstones and yellow/beige sandstones, are indurated with calcium carbonate, and reflect a more arid environment. The transitional zone between the Peanut Peak and Big Cottonwood Creek lithologies corresponds with an increase in volcanism from the Great Basin, impact events, and building of ephemeral glaciers on Antarctica. The impact events and increase in volcanism, while synchronous with the transitional zone between the Peanut Peak and Big Cottonwood Creek lithologies, cannot explain the long term climatic perturbation, which persists within the White River Group. Instead, the climatic deterioration is likely explained by the building of ephemeral Antarctic ice sheets, which was compounded by the increase in volcanism and impacts. Regional variations in ä18O isotopes within the White River Group can likely explain the suggested variations in paleoclimate across the Eocene-Oligocene transition.
    • Late Helladic IIIC Pottery at Mycenae: Production Trends after the Collapse of Palatial Administration

      Betancourt, Philip P., 1936-; Evans, Jane DeRose, 1956-; Myer, George H.; Koehl, Robert B. (Temple University. Libraries, 2017)
      This dissertation examines trends in the production of pottery at Mycenae in the Late Helladic (LH) IIIC period (ca. 1200–1125 B.C.E) through the analysis of published ceramic material from the site. It includes my own study of select unpublished material from recent excavations on the Citadel (Building Kappa) and in the Lower Town. The LH IIIC period, considered the beginning of the Dark Ages in Greece, immediately followed the end of the Mycenaean palatial system, a phenomenon referred to as the Collapse. The Collapse is characterized by the complete destruction of many sites, possible loss of population, and a decrease in the number of occupied areas, and the subsequent LH IIIC period is associated with socioeconomic, demographic, and artistic decline. There are, however, notable indications of continued activity at many Greek mainland sites, a notable sign being the proliferation of elaborate vase painting. Through an examination of how certain pottery shapes and decorative styles were manufactured and utilized at LH IIIC Mycenae, key trends and developments can be discerned, and the changing preferences of the market for which these objects were produced can be understood. I conclude that these developments can be characterized as intentional responses of potters to the crisis that followed the demise of the palatial administration. Potters in LH IIIC were able to create and exploit a sustainable market, one that both reflected and influenced shifting political and social realities of communities now operating outside of a palace-dominated system; their advances would influence pottery production in Greece for centuries to come.