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Preparation and improvement of dry jujube flavor through Maillard reaction
Jujube (Ziziphus jujube Mill.), also known as Chinese dates, have been consumed as a traditional food for thousands of years. Apart from its abundant nutritional ingredients and well-known functional effects, jujube also contributes to the unique flavor in human’s cuisines. Drying fresh jujube fruits could reduce water activity and elongate the shelf life for further use and storage, so most Chinese jujubes are consumed in the dried form. Besides, drying would concentrate flavor precursors within jujube fruits and potentially generate more aroma compounds. Maillard reaction is considered to happen during this thermal treatment and plays an important role in producing aromas with baking and roasting characters of dry jujube. In this thesis, we centered on the correlations between non-volatile flavor precursors and Maillard-type volatile compounds, and controlled the production of desirable flavors while unraveling the underlying chemical mechanisms inherent in reaction cascades.
Firstly, we determined the content of protein and free amino acids within the dry jujube fruits. Given that the limited amount of protein quantified, we chose to utilize flavourzyme to hydrolyze it to release more oligopeptides and free amino acids as the potential flavor precursors in Maillard reaction. In terms of the results of GC-MS, Maillard-type volatiles obtained with enzyme treatment showed significant difference to the untreated group, such as pyrazines and furaneol. The formation of furans, pyrrolizines and azepines were more influenced by thermal reaction than enzymatic hydrolysis. In which due to the abundance of pyrrolizines and azepines formed, we considered proline as an important flavor precursor for dry jujube. In addition, asparagine and proline were found as major amino acids of the dry jujube sample, both before and after enzyme treatment in free amino acid analysis, which suggested their promising potential to produce N-containing aroma heterocyclics in Maillard reaction, such as pyrazines, pyrrolizines and azepines.
Secondly, in order to further investigate the contribution of major amino acids to dry jujube flavor, we utilized model reactions as the primary methodology approach and compare the concentration of Maillard-type volatile compounds between jujube aqueous extracts and the model reaction of asparagine, proline with glucose. Concentration of pyrazines, furans and furaneol formed in the model reaction was equivalent to that of dry jujube, but pyrrolizines and azepines derived from proline were displayed as the predominant group of compounds among overall volatile products.
Moreover, to explore the gap between the formation of proline-specific compounds and other Maillard-type volatiles, we developed a series of model reactions involving asparagine, aspartic acid, proline with glucose to investigate the influence of deamidation, and further promote the generation of pyrazines by introducing lysine to the reaction system. Quantitative results of model reaction products demonstrated that pyrazines were not significantly increased in under deamidation while proline-specific compounds had a rapid enhancement at the same time. With excellent ability to form pyrazines, lysine did help to increase the formation of pyrazines, but still far fewer than pyrrolizines and azepines. It was assumed that proline would preferentially react with α-dicarbonyl compounds in Maillard reaction cascades with lower activation energies.
Lastly, to exploit the potential of asparagine as the flavor precursor for dry jujube, we studied amadori rearrangement products of asparagine with glucose (Asn-Glc-ARP) through its formation, characterization and stability. With the study on the effect of reaction temperature, pH values and reaction time, the ideal reaction condition for accumulation of Asn-Glc-ARP was determined at 100 ℃ for 40 min under pH 7. Asparagine was prone to degrade from Asn-Glc-ARP in alkaline pH values within lower temperature range while in acidic environment with high temperatures, deamidation of Asn-Glc-ARP to Asp-Glc-ARP (amadori rearrangement products of aspartic acid with glucose) displayed as the dominant pathway. The structure of Asn-Glc-ARP was proposed as 1-deoxy-1-L-asparagino-D-fructose after separation and purification. Also, the content of Asn-Glc-ARP within dry jujube fruit was quantitated at 8.1 ± 0.5 mg/g.Ph.D.Includes bibliographical reference
4-pyridinyl and 4-pyridylidene pincer iridium cations for alkane dehydrogenation
Alkane dehydrogenation is a cornerstone of the modern chemical industry, converting our most abundant organic, natural resources—petroleum and natural gas—to valuable chemical intermediates and building blocks. Light alkanes can be selectively converted to light olefins such as propylene and isobutylene. Longer-chain alkanes tend to aromatize to mixtures of aromatic compounds. Selectively dehydrogenating higher alkanes, particularly linear alkanes, to olefins remains a challenging reaction under typical conditions in commercial refining processes.
Organometallic pincer iridium complexes have emerged as the most active and selective catalysts for the conversion of alkanes to olefins, either by direct removal of hydrogen gas under non-equilibrium conditions or through (thermoneutral) transfer hydrogenation of a sacrificial olefin. Since the seminal reports on first-generation pincer iridium catalysts such as (tBu4PCP)Ir, (iPr4PCP)Ir, and (tBu4POCOP)Ir, continuing research has studied structural modifications to the ligand architecture (wingtip modifications, linker modifications, and entirely new frameworks) to improve catalytic turnover frequencies and turnover numbers.
Chapter 1 of this dissertation presents a summary of the structure-reactivity relationship of pincer iridium catalysts for alkane dehydrogenation as they are understood today. Section 1 discusses catalysts that operate through low-oxidation state iridium(I/III) cycles. Sections 2 and 3 summarizes recent progress in alkane dehydrogenation by high-oxidation state iridium(III) and iridium(III/V) catalytic cycles. Section 4 discusses on-going efforts to interface pincer iridium-catalyzed alkane dehydrogenation cycles with electrochemical cells. Section 5 presents a rationale for studying 4-pyridinyl and 4-pyridylidene pincer iridium complexes for alkane dehydrogenation.
Chapter 2 identifies a surprising (based on precedent) oxidatively-driven, intramolecular, sp3 C-H activation in the 4-pyridinyl complex (pN-tBu4PCP)IrHCl. Stoichiometric reactions are used to show that this cyclometallation can be performed through separated proton and electron transfer. An iridium(II) intermediate is identified through NMR monitoring and quenching with TEMPO-H. Through Density Funcitonal Theory (DFT) studies, the unexpected sensitivity of this complex is attributed to metal-ligand proton tautomerism, wherein a (4-pyridylidene-PCP)iridium(I) chloride is present in trace concentrations at equilibrium but has an oxidation potential over 1 V lower than the iridium(III) tautomer (pN-tBu4PCP)IrHCl. Importantly, calculations identify the key role of the (pN-tBu4PCP)IrCl+ cation in C-H activation. This work suggests that metal-ligand proton tautomerism can be used to sharply lower applied potentials in electrocatalysis; and also that a catalytic alkane (transfer) dehydrogenation cycle operating through cationic iridium(III) intermediates is available even to first-generation, phosphine and phosphinite-based pincer iridium catalysts.
In Chapter 3, synthetic progress toward a 4-pyridylidene PCP pincer iridium catalyst is discussed. Through DFT calculations, this is predicted to be a highly active catalyst for alkane transfer dehydrogenation. It is fundamentally interesting as a test of our ability to predict highly-active catalysts through theory. Initial experimental efforts toward such a complex encountered challenges due to unselective metalation of the pro-ligand 3,5-bis(di-tert-butylphosphinomethyl)pyridine with iridium. This led to a revision of the targeted pro-ligand. The new pro-ligand 3,5-bis(di-tert-butylphosphinomethyl)-2,6-dimethylpyridine successfully formed the complex (pN-tBu4PCP)IrHCl (presented in Chapter 2), but subsequent quaternization of the pyridyl nitrogen using alkylating or silylating reagents in the presence of iridium proved unviable. Methylating the pyridyl nitrogen at an earlier stage of ligand synthesis was successful, and the resulting N-methyl functionality was robust enough to carry through subsequent synthetic steps, metalation with iridium, and ancillary ligand exchanges on the iridium center. Studies of ancillary ligand exchanges and anion metathesis reactions have identified two potential pre-catalysts (leading to the same active catalyst) for use in catalytic alkane dehydrogenation studies: (pNMe-tBu4PCP)IrCl and (pNMe-tBu4PCP)IrH3 where pNMe-tBuPCP = 3,5-bis(di-tert-butylphosphinomethyl)-1,2,6-trimethylpyridinium.Ph.D.Includes bibliographical reference
Paternalism and resistance: the impact of global intervention on teacher training in Liberia
Educational development in Liberia has been reliant on the funding and technical support of international organizations. Liberia, like many countries in Sub-Saharan Africa, suffers the consequences of extractive colonialism and global capitalism. It has been plagued by political instability and civil war. The vulnerability of Liberia as a whole, and the Liberian education system in particular, makes the influence of international donors and agencies disproportionately powerful. My study aims to uncover the role of international organizations in educational development in Liberia and the implications of their involvement. To what extent has the involvement of international organizations fostered or suppressed Liberian voices in educational development in Liberia? The study provides a “Southern perspective” and postcolonial critique of the experience of global intervention in educational development in Liberia that can also inform understanding of Northern involvement in the Global South more broadly. The study gives voice to, and makes visible the perspectives and experiences of Liberian educators at all levels. Results from the study can be used to inform teacher training and professional development that aims to promote critical awareness regarding the necessity of the local communities, and the capacity of Liberian educators for innovation. In conjunction with postcolonial perspectives, I framed my study using the Vertical Case Study approach (Barlett & Vavrus, 2014; Vavrus, & Bartlett, 2009; Sensing, 2011) which provides a robust framework for investigating questions relating to how extra-local forces shape educational policy and practice. Drawing on content analysis of global and national policy documents; quantitative analysis of financial and administrative data from national agencies; and in-depth interview data from global, national and local administrators and educators, I examined the extent to which educational policy, teaching and curriculum in Liberia are shaped by global forces and the extent to which there is evidence of Liberians resistance to global norms in shaping policy and practice to reflect the historical, political, cultural and social realities of the Liberian context.Ph.D.Includes bibliographical reference
Unlocking visual reasoning: exploring representations for enhanced problem-solving
The success of deep learning systems in various applications hinges on their ability to extract structured and invariant representations. However, visual reasoning remains challenging due to the complexity of high-dimensional sensory input and the necessity for high-level abstraction. In contrast, humans excel at this complex process by using simple design principles based on realizing low-level abstractions and their relations from the visual input. Hence, understanding why humans excel at this cognitive task while current computational models fall short of solving visual reasoning tasks in a human-like hierarchical manner is increasingly apparent. Current reasoning models require enormous training data, exhibit sensitivity to perturbations, and lack the capacity to generalize to new reason- ing tasks. In this dissertation, we aim to address these limitations of visual perception and visual reasoning.
The thesis comprises two main parts. The first part is devoted to Visual Reasoning via Disentangled Representations, delves into extracting high-quality disentangled representations and devising modules to tackle reasoning tasks using these representations. We begin with the pursuit of understanding and learning disentangled representations that encodes the salient (data-generative) factors of variation in the data independently. To achieve this, we present a novel VAE-based approach capable of disentangling latent representations in fully unsupervised manner. Our approach harnesses the total correlation (TC) within the latent space by introducing a relevance indicator variable. This variable pinpoints and emphasizes significant factors, characterized by substantial prior KL divergence, while filtering out noise-associated factors with minimal variation. Our method automatically identifies and assimilates genuine factors, even in scenarios where the count of such factors remains explicitly unknown. Furthermore, it outperforms existing methods both quantitatively and qualitatively. These disentangled latent factors, adept at independently mapping generative factors, prove invaluable in reasoning puzzles where visual attributes correspond to specific rules like constancy, progression or arithmetic. They enable the derivation of rules capable of solving various puzzles. Additionally, these representations exhibit sample efficiency and superior generalization, rendering them ideal for solving visual reasoning problems. Expanding on this concept, we propose a computational model that addresses visual reasoning tasks as an end-to-end joint representation-reasoning learning framework. This framework leverages the weak inductive bias present in reasoning datasets to accomplish these tasks concurrently. Specifically focusing on Raven’s Progressive Matrices (RPMs) as our reasoning task, we introduce a general generative graphical model (GM-RPM). Sub- sequently, we propose the “Disentangling-based Abstract Reasoning Network (DAReN)”, aligning with the principles of GM-RPM. Evaluating our model across disentanglement and reasoning benchmarks demonstrates consistent improvement over existing state-of-the-art models in both domains. Our results underscore the necessity of structured representations for solving visual reasoning tasks.
The second part of my dissertation is devoted to learning tokenized spatial representations that grasp low-level visual concepts within each RPM image. We introduce “Spatially Attentive Transformers for Abstract Visual Reasoning (SARN)”, a novel computational model which integrates spatial semantics within visual elements, represented as spatio-visual tokens, capturing both intra-image and inter-image relationships within the puzzle. The reasoning module groups these tokens (by row or column) to capture the underlying rule binding the puzzle, thereby solving the visual reasoning task. Through extensive experiments on established RPM benchmarks, we demonstrate that our results surpass existing approaches. Furthermore, we validate that the learned rule representation exhibits increased robustness in novel tasks and better generalization to test-time domain shifts compared to current methods.
In a nutshell, this work underscores the necessity of acquiring structured representations to enhance visual reasoning performance. Thus, we address certain limitations in AI model design, as well as narrowing the gap between machine intelligence and human cognitive abilities.Ph.D.Includes bibliographical reference
Regalianus, Dryantilla, and the Carnuntum mint
An in-depth exploration into the corpus of Roman coinage produced in the brief reign of the usurper Regalianus in 260/261. Using both numismatics and prosopography, I argue that Regalianus' public persona can be discerned through careful analysis of his coins, mainly his attempts to promote a stable dynastic marriage, with a plethora of portraits propagandizing his wife Dryantilla. This research, broadly speaking, sheds light on the political complexities and social dynamics within Pannonia during the Crisis of the Third Century. This argument uses the following methodology for the first two chapters: it looks at two particular coins that have been found in recent catalogs, compares them with other dye types produced at this time, and then discusses prosopographic evidence of the pair. The thesis then concludes with a final chapter recontextualizing the character of Regalianus found in the Historia Augusta.M.A.Includes bibliographical reference
Chris and Jerel’s Initial Idea of Fairness in Ordinary Dice Games (Part 2 of 3)
This analytic is the second of three analytics that showcase the formulation of two students’ ideas of mathematical fairness. The analytics follow the argumentation of two students, Chris and Jerel, throughout two after-school sessions and one interview session as they investigate what makes a game involving rolling one or two dice fair. The first after-school session occurred on April 29, 2004. The second after-school session occurred on May 5, 2004, with the interview happening directly after the second session on the same day. The first analytic begins with Chris and Jerel discussing the fairness of a game involving a single die during the first session. By the end of the first session, Chris has designed his own game involving rolling two dice. The second analytic looks at Chris and Jerel’s work during the second after-school session and interview session where the pair explore a task investigating the fairness of a game involving rolling two dice. This game is different from the one Chris creates in the first analytic. The third analytic includes an investigation on the probability of rolling a sum of 7 versus a sum of 6 when rolling two dice that occurs during the interview.
In this, the second of the three analytics, sixth-grade students Chris and Jerel are solving a problem about fairness with a game using two fair dice. Gameplay involves rolling two dice and assigning points to either Player A or Player B based on the sum of the rolled dice. Player A gets one point (and Player B gets 0) for sums of 2, 3, 4, 10, 11 and 12. Player B gets one point (and Player A gets 0) for sums of 5, 6, 7, 8 and 9. The first player to accumulate ten points is the winner. The questions that students are asking about this game are: 1) Is this a fair game? Why or why not? 2) Play the game with a partner. Do the results of playing the game support your answer? 3) If you think the game is unfair, how could you change it so that it would be fair?
Chris and Jerel’s initial response to this game is to highlight that Player A has three “small” numbers (2, 3, and 4) and three “large” numbers (10, 11, and 12) while Player B has all “large” numbers (5, 6, 7, 8, and 9). This suggests that they are not relying on the number of outcomes assigned to each player (Player A having 6 assigned outcomes to Player B’s 5 assigned outcomes) as the measure of fairness for the game. They are considering the numbers assigned to each player (Player A’s 2, 3, 4, 10, 11, and 12 compared to Player B’s 5, 6, 7, 8, and 9) as important to the fairness of the game, demonstrating they are no longer exhibiting an equiprobability bias in the outcome of rolling two dice (as seen in Part 1). Instead, the pair begins to see that each outcome does not have the same probability of occurring.
During gameplay, Shay (2008) explains that researchers had encouraged students to record the outcome of each roll of the dice. This naturally led to students beginning to list out the sample space for the game. We see in the second event, Chris and Jerel begin writing a list of sums for each outcome (i.e. 5=4+1, 5=2+3). During the interview, Chris and Jerel state they started writing out their sample space to figure out why Player B was winning. It is important to note that Chris and Jerel have a sample space of 21 outcomes rather than 36. Shay (2008) attributes this to students not considering symmetric pairs as separate events (for example, rolling a 3 and 4 versus rolling a 4 and 3). In the complete sample space of 36 outcomes, Player A has a 12/36 (approximately 0.333) chance of winning a single event, while Player B has a 24/36 (approximately 0.667) chance of winning a single event. With their sample space of 21 outcomes, Chris and Jerel conclude that Player B has 13 possible outcomes while Player A has 8 possible outcomes. This would mean Player B has a 13/21 (approximately 0.619) chance of winning a single event while Player A has an 8/21 (approximately 0.381) chance of winning a single event. This explains why the game is unfair in favor of Player B.
Throughout the discussion of the sample space for the game, Chris and Jerel mention that 7 came up the most when they were playing. Researcher Powell asks the pair why 7 comes up more than 6 when Chris and Jerel’s sample space shows an equal number of possibilities for rolling a sum of 6, 7, or 8. Chris suggests that a sum of 7 is rolled more frequently than 6 because 7 is comprised of sums of what he calls “big numbers.” These “big numbers” refers to rolling a 4, 5, or 6 on an individual die, while “small numbers” refers to rolling a 1, 2, or 3 on an individual die. This big and small number theory is explored in Part 3.
Problem Task:
Dice game 2:
Roll two dice. If their sum is 2, 3, 4, 10, 11, or 12, player A gets one point (and player B gets 0). If their sum is 5, 6, 7, 8, or 9, player B gets one point (and player A gets 0). Continue rolling the dice. The first person to get ten points is the winner. (1) Is this a fair game? Why or why not? (2) Play the game with a partner. Do the results of playing the game support your answer? Explain. (3) If you think the game is unfair, how could you change it so that it could be fair?
[Note: The game favors Player B with a ⅔ probability of winning a point and a probability of approximately .935 of winning a game.]
Videos Referenced:
Title: B89, Probability strand: Dice games with two players (Student View), grade 6, May 05, 2004, raw footage.
Raw footage link: https://rucore.libraries.rutgers.edu/rutgers-lib/70974/
Title: B90, 46a, Probability problems: Dice games for two players (Student view), Grade 6, May 5, 2004, raw footage
Raw footage link: https://rucore.libraries.rutgers.edu/rutgers-lib/70978/
Title: B91, 46b, Probability problems: Dice games for two players (Work view), Grade 6, May 5, 2004, raw footage
Raw footage link: https://rucore.libraries.rutgers.edu/rutgers-lib/70979/
References:
Shay, K. (2008). Tracing Middle School Students’ Understanding of Probability: A Longitudinal Study. Rutgers University
Transdiagnostic group behavioral activation therapy (gbat) with individual boosters: adaptations for autistic adults
Autistic adults experience high rates of co-occurring mental health conditions. Most adults have multiple mental health diagnoses at one time, painting a complex picture of symptom presentation and support needs. Despite the necessity of interventions that can address co-occurring diagnoses, research is limited in describing services that are accessible, evidence-based, and adapted for the needs of autistic adults. Behavioral activation is one treatment that may be well-suited to address these gaps and provide a transdiagnostic focus equipped to match the needs of this population. The present study investigated the feasibility, accessibility, and acceptability of a group-based, telehealth intervention rooted in behavioral activation. This study incorporated results from the pilot of the group, GBAT (Group Behavioral Activation Therapy), which was acceptable to autistic adults. Feedback from original GBAT members and group leaders were used to create adaptations, with the aim of increasing applicability of group content to autistic adults. The largest structural change was the inclusion of four individual booster sessions as a supplement to the ten group sessions, which aimed to increase personalization of treatment. Three participants completed the adapted group. Results suggest that group members found the group to be an acceptable treatment, and that each participant reported a reduction in the severity of at least one of their self-reported goals. Additionally, both participants and clinicians reported that the individual sessions allowed for unique, individualized conversations that aided in the understanding of psychoeducation and planning for home-based exposures.Psy.D.Includes bibliographical reference
The impact of meaningful smartphone alerts on attention: an examination of auditory distractions during the arrow-flanker task
This study aimed to expand on previous smartphone-based research on attention by investigating the influence of personally significant smartphone notifications on college students’ attention. Participants engaged in an arrow-flanker task encompassing three auditory alert trials: meaningful, scrambled, and no-distraction alerts drawn from text messages, ringtones, and social media platforms. We utilized median reaction time (RT) and mean accuracy rates for our performance metrics, while the familiarity ratings were used to gauge the personal significance of alerts. Participants then completed the Nomophobia Questionnaire (NMP-Q) to assess smartphone dependency and categorize them into low and high NMP-Q scorers, followed by the Smartphone Use Questionnaire to examine their smartphone use habits and emotional attachment to smartphones. To support our hypotheses, participants had to exhibit poorer median RT and accuracy mean performance for high NMP-Q scorers compared to low NMP-Q scorers, meaningful alerts versus scrambled and no-distraction alerts, and incongruent trials relative to congruent trials.Contrary to our expectations, the differences between high and low NMP-Q scorers for median RTs and mean accuracy rates proved insignificant, and the no-distraction alert trials exhibited significantly longer median RTs than meaningful and scrambled alerts. There were also insignificant differences between the three alerts for accuracy and the interaction between meaningful and scrambled alerts for median RTs. Moreover, our findings demonstrated significantly slower median RTs and decreased mean accuracy rates for incongruent flankers than congruent flankers, validating our third hypothesis. The familiarity rating analysis revealed a significant interaction for distraction types, with meaningful alerts rated significantly higher than scrambled alerts but no significant differences based on NMP-Q scores, which indicates that the meaningful alerts were personally significant. Additionally, low NMP-Q scorers silenced their smartphones significantly more often than high NMP-Q scorers, which indicates that high NMP-Q scores may be more exposed and distracted by smartphone notifications than low NMP-Q scorers. These insights highlight the complex interplay between personally significant smartphone alerts, individual characteristics, and cognitive performance among college students. Overall, our findings contribute to a deeper understanding of the implications of smartphone notifications on cognitive functioning and underscore the importance of considering individual differences in addressing smartphone-related distractions.M.A.Includes bibliographical reference
Dissociation in a historical context
Dissociation is both a clinical response to a traumatic experience and a cultural phenomenon reflected in conversation and literature. To understand how the cultural salience of dissociation has changed in the United States over time, we identified linguistic markers of dissociation. Study 1 uses Google Books data to trace the relative frequency of phrases suggestive of dissociative experiences in books published between 1900 and 2019, and tests whether the September 11, 2001, terrorist attacks affect the trajectories of these phrases. We found that phrases suggestive of dissociative experience increased over time. After 2001, there was initially a statistically significant decrease in phrases suggestive of amnesia and derealization, component experiences of dissociation. In the following years the salience of these phrases increased beyond what was predicted in the absence of 9/11. These trends were similar for language suggestive of identity fragmentation, absorption, depersonalization, and daydreaming, also facets of dissociative experience, however they did not reach significance. To evaluate if the increases in references to dissociative experiences found in books was mirrored by increases in the scientific study of dissociation, Study 2 examined the number of articles abstracted in PubMed between 1990 and 2022 with the keywords “dissociation” and “depersonalization.” The frequency of these terms, relative to the frequency of words related to other common psychiatric syndromes, accelerated post-2001. We discuss the implications of these findings.M.A.Includes bibliographical reference
Emotional and emotivational expression in hip-hop/r&b vs. country music: a comparative analysis
Lyrics for contemporary music can provide a window into the preferences and concerns of those who listen to it. However, there is a notable lack of research on the emotional and emotivational content of popular music. Furthermore, this gap in knowledge has thwarted our ability to thoroughly explain listeners’ personal alignment with certain genres that echo their emotional and social states by mentioning culturally significant themes. In this study, I compare the lyrics in two types of music, Country and Hip-Hop/R&B, to illuminate the concerns and preferences of two populations, young rural Whites and young urban Blacks. Hip-Hop lyrics, in comparison to those of Country, were hypothesized to contain more language suggestive of power, ambition, and money. Lyrics for all top fifty songs for each week for each genre were compiled, and then analyzed using the Language Inquiry Word Count (LIWC) program. Results were consistent with hypotheses, as Hip-Hop, in comparison to Country, was found to have a higher percentage of words suggestive of power, ambition, and money. These findings provide insights into the concerns and interests of two populations of young people and may be useful in alerting therapists to cultural differences.M.A.Includes bibliographical reference