Coke formation in the oxidative dehydrogenation of ethylbenzene to styrene by TEOM

A packed bed microbalance reactor setup (TEOM-GC) is used to investigate the formation of coke as a function of time-on-stream on γ-Al2O3 and 3P/SiO2 catalyst samples under different conditions for the ODH reaction of ethylbenzene to styrene. All samples show a linear correlation of the styrene selectivity and yield with the initial coverage of coke. The COX production increases with the coverage of coke. On the 3 wt% P/SiO2 sample, the initial coke build-up is slow and the coke deposition rate increases with time. On alumina-based catalyst samples, a fast initial coke build-up takes place, decreasing with time-on-stream, but the amount of coke does not stabilize. A higher O2 : EB feed ratio results in more coke, and a higher temperature results in less coke. This coking behaviour of Al2O3 can be described by existing "monolayer-multilayer" models. Further, the coverage of coke on the catalyst varies with the position in the bed. For maximal styrene selectivity, the optimal coverage of coke should be sufficient to convert all O2, but as low as possible to prevent selectivity loss by COX production. This is in favour of high temperature and low O2 : EB feed ratios. The optimal coke coverage depends in a complex way on all the parameters: temperature, the O2 : EB feed ratio, reactant concentrations, and the type of starting material. This journal is

Oxidative dehydrogenation of ethylbenzene to styrene over alumina:effect of calcination

Commercially available γ-Al2O3 was calcined at temperatures between 500 and 1200 °C and tested for its performance in the oxidative ethylbenzene dehydrogenation (ODH) over a wide range of industrially-relevant conditions. The original γ-Al2O 3, as well as η- and α-Al2O3, were tested. A calcination temperature around 1000/1050 °C turned out to be optimal for the ODH performance. Upon calcination the number of acid sites (from 637 to 436 μmol g-1) and surface area (from 272 to 119 m 2 g-1) decrease, whereas the acid site density increases (from 1.4 to 2.4 sites per nm2). Less coke, being the active catalyst, is formed during ODH on the Al-1000 sample compared to γ-Al 2O3 (30.8 wt% vs. 21.6 wt%), but the coke surface coverage increases. Compared with γ-Al2O3, the EB conversion increased from 36% to 42% and the ST selectivity increased from 83% to 87%. For an optimal ST selectivity the catalyst should contain enough coke to attain full conversion of the limiting reactant oxygen. The reactivity of the coke is changed due to the higher density and strength of the Lewis acid sites that are formed by the high temperature calcination. The Al-1000 sample and all other investigated catalysts lost ODH activity with time on stream. The loss of selectivity towards more COX formation is directly correlated with the amount of coke. © The Royal Society of Chemistry 2013.

Effective knowledge integration in emergency response organizations

Natural and man-made disasters have gained attention at all levels of policy-making in recent years. Emergency management tasks are inherently complex and unpredictable, and often require coordination among multiple organizations across different levels and locations. Effectively managing various knowledge areas and the organizations involved has become a critical emergency management success factor. However, there is a general lack of understanding about how to describe and assess the complex nature of emergency management tasks and how knowledge integration can help managers improve emergency management task performance. ^ The purpose of this exploratory research was first, to understand how emergency management operations are impacted by tasks that are complex and inter-organizational and second, to investigate how knowledge integration as a particular knowledge management strategy can improve the efficiency and effectiveness of the emergency tasks. Three types of specific knowledge were considered: context-specific, technology-specific, and context-and-technology-specific. ^ The research setting was the Miami-Dade Emergency Operations Center (EOC) and the study was based on the survey responses from the participants in past EOC activations related to their emergency tasks and knowledge areas. The data included task attributes related to complexity, knowledge area, knowledge integration, specificity of knowledge, and task performance. The data was analyzed using multiple linear regressions and path analyses, to (1) examine the relationships between task complexity, knowledge integration, and performance, (2) the moderating effects of each type of specific knowledge on the relationship between task complexity and performance, and (3) the mediating role of knowledge integration. ^ As per theory-based propositions, the results indicated that overall component complexity and interactive complexity tend to have a negative effect on task performance. But surprisingly, procedural rigidity tended to have a positive effect on performance in emergency management tasks. Also as per our expectation, knowledge integration had a positive relationship with task performance. Interestingly, the moderating effects of each type of specific knowledge on the relationship between task complexity and performance were varied and the extent of mediation of knowledge integration depended on the dimension of task complexity. ^

Graduate program culture and intention to persist: Working adults in cohort and non-cohort programs

Cohort programs have been instituted at many universities to accommodate the growing number of mature adult graduate students who pursue degrees while maintaining multiple commitments such as work and family. While it is estimated that as many as 40–60% of students who begin graduate study fail to complete degrees, it is thought that attrition may be even higher for this population of students. Yet, little is known about the impact of cohorts on the learning environment and whether cohort programs affect graduate student retention. Retention theory stresses the importance of the academic department, quality of faculty-student relationships and student involvement in the life of the academic community as critical determinants in students' decisions to persist to degree completion. However, students who are employed full-time typically spend little time on campus engaged in the learning environment. Using academic and social integration theory, this study examined the experiences of working adult graduate students enrolled in cohort (CEP) and non-cohort (non-CEP) programs and the influence of these experiences on intention to persist. The Graduate Program Context Questionnaire was administered to graduate students (N = 310) to examine measures of academic and social integration and intention to persist. Sample t tests and ANOVAs were conducted to determine whether differences in perceptions could be identified between cohort and non-cohort students. Multiple linear regression was used to identify variables that predict students' intention to persist. While there were many similarities, significant differences were found between CEP and non-CEP student groups on two measures. CEP students rated peer-student relationships higher and scored higher on the intention to persist measure than non-CEP students. The psychological integration measure, however, was the strongest predictor of intention to persist for both the CEP and non-CEP groups. This study supports the research literature which suggests that CEP programs encourage the development of peer-student relationships and promote students' commitment to persistence.

Interactions of different arsenic species with thols: Chemical and biological implications

Arsenic has been classified as a group I carcinogen. It has been ranked number one in the CERCLA priority list of hazardous substances due to its frequency, toxicity and potential for human exposure. Paradoxically, arsenic has been employed as a successful chemotherapeutic agent for acute promyelocytic leukemia and has found some success in multiple myeloma. Since arsenic toxicity and efficacy is species dependent, a speciation method, based on the complementary use of reverse phase and cation exchange chromatography, was developed. Inductively coupled plasma mass spectrometer (ICP-MS), as an element specific detector, and electrospray ionization mass spectrometer (ESI-MS), as a molecule specific detector, were employed. Low detection limits in the µg. L−1 range on the ICP-MS and mg. L−1 range on the ESI-MS were obtained. The developed methods were validated against each other through the use of a Deming plot. With the developed speciation method, the effects of both pH on the stability of As species and reduced glutathione (GSH) concentration on the formation and stability of arsenic glutathione complexes were studied. To identify arsenicals in multiple myeloma (MM) cell lines post arsenic trioxide (ATO) and darinaparsin (DAR) incubation, an extraction method based on the use of ultrasonic probe was developed. Extraction tools and solvents were evaluated and the effect of GSH concentration on the quantitation of arsenic glutathione (As-GSH) complexes in MM cell extracts was studied. The developed method was employed for the identification of metabolites in DAR incubated cell lines where the effect of extraction pH, DAR incubation concentration and incubation time on the relative distribution of the As metabolites was assessed. A new arsenic species, dimethyarsinothioyl glutathione (DMMTA V-GS), a pentavalent thiolated arsenical, was identified in the cell extracts through the use of liquid chromatography tandem mass spectrometry. The formation of the new metabolite in the extracts was dependent on the decomposition of s-dimethylarsino glutathione (DMA(GS)). These results have major implications in both the medical and toxicological fields of As because they involve the metabolism of a chemotherapeutic agent and the role sulfur compounds play in this mechanism.

Scaffolding in Second Language Learning and Instruction

In a study of the triadic interaction among pairs of advanced second language learners engaged in a complex language task, it was found that the scaffolding provided by the researcher was determinant in keeping the participants on task and encouraging language production, thus facilitating both language development and comprehension.

Adiamento da aposentadoria e o significado do trabalho para servidores de uma universidade federal

This study investigated the intention of the older workers to continue working after state pension age/time. On this way, it explores the relation between this intention and factors related with the meanings of the work and retirement. Specifically, it was examined that factors related to work and non-work are predictors of the intention to continue working, and it was explored if meanings of retirement are linked to this decision. It is a crosssectional mixed methods study, using a survey conducted with 283 federal civil servants of a federal Northeastern University which were near retirement. It envolved an on-line questionnaire, with open-ended questions and the likert-type scale "Older Worker's Intention to Continue Working" (OWICW) of Shacklock and Brunneto (2011), which was validated to the Brazilian version. The quantitative data were analyzed using descriptive and multivariate statistics, specifically procedures for comparing means and coefficients of multiple logistic regression. The qualitative data were analyzed using the lexicographical technique Descending Hierarchical Classification. The findings indicate that most participants want to continue in paid work, and that perception of personal autonomy at work, interpersonal relationships at work, interests outside of work, and flexible working arrangements are significant predictors of intention to continue working. Furthermore, the perception of personal autonomy at work, flexible working arrangements, and the financial incentives are predictors of decision to postpone retirement and remain in the organization. The analysis revealed five patterns of meanings of retirement: "worker's right", "resting", "idle time at home", "new stage in the life course", and "enjoy the use of time”. The decision to postpone retirement is linked to idleness and lack of substitutionary activities work, and the decision to stop working linked to retirement as a life with more quality. The study provides information that can contribute with management policies before the process of retirement decision.

Sinalização endógena do sistema Nociceptina/Orfanina FQ - receptor NOP: envolvimento na modulação da depressão experimental induzida por lipopolissacarídeo

During the last decades, it has been established that there is a relationship between major depression and activation of immune system. Nociceptin/orphanin FQ (N/OFQ) is the natural ligand of a Gi-protein coupled receptor named NOP, both compose the peptidergic system wich is involved in the regulation of mood states and inflammatory responses. Considering these actions, the present thesis aimed to investigate the consequences of blocking NOP signaling in lipopolysaccharide (LPS)-induced sickness and depressive-like behaviors in mice. Systemic administration of LPS doses, that do not cause sepsis in mice, induce changes in their behaviors related with activity of pro-inflammatory cytokines tumor necrosis factor-α (TNF-α) and interleukins 6 (IL-6) and 1β (IL-1 β). At the time points of 2 to 6 h and 24 h after intraperitoneal injection, mice treated with LPS displayed, respectively, sickness and depressive-like behaviors. In the present work the administration of LPS 0.8 mg/kg (ip) significantly induced sickness signs in Swiss and CD-1 mice, such as weight loss, transient reduction in rectal temperature and decrease of food and water intake. Moreover at 24 h after LPS injection these same mice strains displayed significantly increased immobility time on the tail suspension test (TST) when compared with control mice, this alteration was not related with possible locomotion impairments as verified on the open field test. Treatment with Nortriptyline 30 mg/kg (ip, 60 min prior the TST) reduced the immobility time of control and LPS-treated mice and was used as standard antidepressant. The NOP receptor antagonist SB-612111 (10 mg/kg, ip), 30 min prior LPS, did not modify LPS-induced sickness signs and depressive-like behavior. However, when injected 24 h after LPS treatment, SB-612111 (ip, 30 min prior the TST) as well as the peptidergic NOP receptor antagonist UFP-101 (10 nmol/2μL, icv, 5 min prior the TST) significantly reversed the toxin effects. The protocol of LPS-induced depressive-like states was also tested in NOP receptor knockout mice (NOP(-/-)) and their respective wild types (NOP(+/+)). LPS evoked transient rectal temperature reduction in NOP(-/-) mice and loss of body weight, food and water intake reduction in both NOP(+/+) and NOP(-/-) mice. The consumption of water was significantly different due to the genotype. LPS injection induced transient changes in pro-inflammatory cytokines. At 6 h after LPS injection, serum levels of TNF-α were significantly increased in NOP(+/+) and NOP(-/-) mice, as the IL-6 levels were significantly increased just in NOP(+/+) serum. At 24 h after LPS treatment the pro-inflammatory cytokines had returned to the baseline levels in both genotypes. LPS treatment elicited depressive-like effects in NOP(+/+) but not in NOP(-/-) mice. The data obtained during the execution of this doctoral thesis reveal that pharmacological and genetic blockade of NOP signaling does not affect LPS evoked sickness signs while reversing depressive-like behavior. In conclusion, these results highlight the involvement of the peptidergic system N/OFQ - NOP receptor in the modulation of behaviors related to mood and activation of the immune system.

Transplantes de córneas no estado do Rio Grande do Norte: aspectos epidemiológicos e clínicos

This study aimed to characterize in a clinical and epidemiological way the patients who are on a waiting list for transplantation and the patients transplanted with corneal tissue in a corneal transplants reference service in the state of Rio Grande do Norte. It is an epidemiological study of a quantitative approach, with cross-sectional, descriptive and analytical cut including all patients on the waiting list for transplantation (population A) and the patients already transplanted with a corneal tissue (population B) in a reference service. In population A, there was a census conducted of patients on the waiting list for corneal transplantation (n=62 patients). In population B, the sample was non-probabilistic and corresponded to all corneal transplants performed in the service in the period from 2010 to 2014 (n=258). This study is approved by the Research Ethics Committee of the Federal University of Rio Grande do Norte, in Opinion 876 177 and CAAE 37533014.8.0000.5537. Data were collected in full in the period from January to April 2015, by two instruments built to systematize the necessary data collection. After being coded and tabulated, data were analyzed using the Statistical Package for Social Sciences software, version 20.0. The definition of variables and their distribution patterns were presented as frequencies and measures of central tendency while, for multivariate analysis, the effect of magnitude measures were applied (prevalence ratio) and measures of association (chi-square test or Fisher's exact test) for a 0.05 significance level. The results are shown in two scientific articles coming from the field survey data. It was found that the epidemiological profile of patients on the waiting list (n=62) showed a prevalence of individuals aged over 50 years old, female (54.84%) and residents of the middle region of East Rio Grande do Norte (66.13%). The clinical profile of patients with corneal transplantation (n=258) was characterized by being male (51.16%) with an average age of 49.33 years old and 57.75% were coming from East Rio Grande do Norte. The average time on the waiting list was 172.63 days in elective transplants and 9.03 days in urgent transplants. Keratoconus was the main indicator condition to perform the transplant. For patients on the waiting list, the variable “type of disorder of the cornea” showed statistically significant association with gender and age. For patients with corneal transplants, the variable "type of disorder of the cornea" was associated with the variables gender, age, previous surgery, failure of previous graft, classification of the eye and glaucoma. By characterizing the clinical and epidemiological profile of corneal transplants, it is possible to question the reality, pointing about the care that should be offered and develop targeted interventions to collective and individual needs intrinsic to patients who need this surgery as a treatment option.

Avaliação das Funções Executivas em Dependentes Químicos

The aim of this study was to investigate possible alterations in attentive functions and mental flexibility in individuals diagnosed with Addiction. The sample (n=40) was located for convenience, and included 20 individuals with addiction behaviors (G1), and 20 individuals who do not use harmfully psychoactive substances (G2). Assessment instruments used were: Experimental and Computerized Test of Continuous Performance, and the Wisconsin Card Sorting Test. It was concluded that individuals in the G1 group had a poorer performance in all categories analyzed on the Wisconsin Card Sorting Test and in reaction time on the Experimental and Computerized Test (p<0,05), showing a deficit in mental flexibility and attentive functions, which may have direct implications on addictive behaviors and treatment.

Mathematical Modeling of Perifusion Cell Culture Experiments

In perifusion cell cultures, the culture medium flows continuously through a chamber containing immobilized cells and the effluent is collected at the end. In our main applications, gonadotropin releasing hormone (GnRH) or oxytocin is introduced into the chamber as the input. They stimulate the cells to secrete luteinizing hormone (LH), which is collected in the effluent. To relate the effluent LH concentration to the cellular processes producing it, we develop and analyze a mathematical model consisting of coupled partial differential equations describing the intracellular signaling and the movement of substances in the cell chamber. We analyze three different data sets and give cellular mechanisms that explain the data. Our model indicates that two negative feedback loops, one fast and one slow, are needed to explain the data and we give their biological bases. We demonstrate that different LH outcomes in oxytocin and GnRH stimulations might originate from different receptor dynamics. We analyze the model to understand the influence of parameters, like the rate of the medium flow or the fraction collection time, on the experimental outcomes. We investigate how the rate of binding and dissociation of the input hormone to and from its receptor influence its movement down the chamber. Finally, we formulate and analyze simpler models that allow us to predict the distortion of a square pulse due to hormone-receptor interactions and to estimate parameters using perifusion data. We show that in the limit of high binding and dissociation the square pulse moves as a diffusing Gaussian and in this limit the biological parameters can be estimated.

From project ontologies to communities of virtue

Projects, as an organizing principle, can provide exciting contexts for innovative work. Thus far, project management discourse has tended to privilege the vital need to deliver projects ‘on time, on budget, and to specification’. In common with the call for papers for this workshop we suggest that perhaps the “instrumental rationality” underpinning this language of characterising project activity may create more problems than it solves. In this paper we suggest that such questions (and language) frame project contexts in a partial way. We argue that such concerns stem from a particular worldview or ontology, which we identify as a ‘being’ ontology. Here we contrast being and becoming project ontologies, to explore the questions, methods and interventions that each foregrounds. In an attempt to move this dialogue further than simply another contrast of modern and postmodernist accounts of project organising, we go on to consider some possible ethical concomitants of valuing being and becoming ontologies in project contexts.

Reframing Chinese animation: from classicism to postmodernism in post-1949 non-commercial Chinese animated films

This thesis focuses on Chinese non-commercial animated films produced from 1949 to date, with the aim of remapping and reframing Chinese animation in the light of existing theories, critiques, and frameworks drawn from studies in animation, film, and screen media. I suggest that Chinese animation has experienced three aesthetic transformations since 1949, primarily influenced by traditional Chinese culture, by Western modernist art and literature and, most recently, by postmodernism, respectively. Thus, the research traces and thoroughly investigates these three distinctive phases of Chinese animation in chronological order, from the classical period (1950s– 1980s) to modernism (1980s–2000s) and postmodernism (after 2000s). More in detail, I first rethink and re-evaluate the success of classical Chinese animation and the Chinese school of animation and, at the same time, I explore the influence of the political situation of the time on Chinese animation. Through careful analysis of A Da (1934–87) and other Chinese animators’ practices and theory, then, I argue that a remarkable modernist transformation took place in Chinese animation between the 1980s and 2000s, mainly driven by Western modernism and the Chinese “cultural fever” movement. Finally, through a discussion of the latest non-commercial animations produced after 2005, and especially those of Bu Hua (1973– ), for the first time I classify and theorize contemporary Chinese animations within a postmodern framework. By reframing existing views and broadening the scope of the analysis to encompass new areas and frameworks, this thesis aims to provide the reader with a comprehensive and systematic understanding of post-1949 Chinese animation and to offer an original contribute to scholarship, also working as a starting point for further research in this area.

Effective Knowledge Integration in Emergency Response Organizations

Natural and man-made disasters have gained attention at all levels of policy-making in recent years. Emergency management tasks are inherently complex and unpredictable, and often require coordination among multiple organizations across different levels and locations. Effectively managing various knowledge areas and the organizations involved has become a critical emergency management success factor. However, there is a general lack of understanding about how to describe and assess the complex nature of emergency management tasks and how knowledge integration can help managers improve emergency management task performance. The purpose of this exploratory research was first, to understand how emergency management operations are impacted by tasks that are complex and inter-organizational and second, to investigate how knowledge integration as a particular knowledge management strategy can improve the efficiency and effectiveness of the emergency tasks. Three types of specific knowledge were considered: context-specific, technology-specific, and context-and-technology-specific. The research setting was the Miami-Dade Emergency Operations Center (EOC) and the study was based on the survey responses from the participants in past EOC activations related to their emergency tasks and knowledge areas. The data included task attributes related to complexity, knowledge area, knowledge integration, specificity of knowledge, and task performance. The data was analyzed using multiple linear regressions and path analyses, to (1) examine the relationships between task complexity, knowledge integration, and performance, (2) the moderating effects of each type of specific knowledge on the relationship between task complexity and performance, and (3) the mediating role of knowledge integration. As per theory-based propositions, the results indicated that overall component complexity and interactive complexity tend to have a negative effect on task performance. But surprisingly, procedural rigidity tended to have a positive effect on performance in emergency management tasks. Also as per our expectation, knowledge integration had a positive relationship with task performance. Interestingly, the moderating effects of each type of specific knowledge on the relationship between task complexity and performance were varied and the extent of mediation of knowledge integration depended on the dimension of task complexity.

(Table 2, page 10) Bulk spectroscopic, X-ray fluorescence and colorimetric analyses of samples from the San Pablo ferro-manganese pavement

The Bedford Institute of Oceanography provided ship time on the C.S.S. Hudson during the B.I.0. 1967 Metrology and IODAL Cruise for surveying two separate bottom features in the North Atlantic; the Flemish Cap and the San Pablo Seamount one of the Kelvin Seamounts (also known as the New England Seamounts) about 400 miles SSE of Halifax, Nova Scotia. Underwater photography, dredging, and drilling showed San Pablo seamount to have a very considerable covering of manganese deposit, which may be recoverable by mining. San Pablo Seamount was surveyed and sampled; good hauls were made both on the top and on the slopes, at various depths from 500-1000 fathoms; in all cases samples of an unusual stratified manganese-iron ore were recovered. In the hope of gaining additional information in the immediate sample area, one of the dredges had been previously modified to accommodate underwater photographic equipment. X-ray chemical analyses indicate that the ore contains 20 to 25 per cent MnO2, with similar amounts of Fe2O3. Since bottom photographs indicate that these deposits form a continuous cover 1 foot to 3 feet thick over most of the seamount, it is estimated that there are ore reserves in the order of 10 to 30 M tons above 1,000 fathoms.