Site-selective direct arylation of unprotected adenine nucleosides mediated by palladium and copper:insights into the reaction mechanism

Reaction conditions facilitating the site-selective direct aryl functionalisation at the C-8 position of adenine nucleosides have been identified. Many different aromatic components may be effectively cross-coupled to provide a diverse array of arylated adenine nucleoside products without the need for ribose or adenine protecting groups. The optimal palladium catalyst loading lies between 0.5 and 5 mol %. Addition of excess mercury to the reaction had a negligible affect on catalysis, suggesting the involvement of a homogeneous catalytic species. A study by transmission electron microscopy (TEM) shows that metal containing nanoparticles, ca. 3 nm with good uniformity, are formed during the latter stages of the reaction. Stabilised PVP palladium colloids (PVP=N-polyvinylpyrrolidone) are catalytically active in the direct arylation process, releasing homogenous palladium into solution. The effect of various substituted 2-pyridine ligand additives has been investigated. A mechanism for the site-selective arylation of adenosine is proposed. © 2008 Elsevier Ltd. All rights reserved.

Antimicrobial activity of a chlorhexidine intravascular catheter site gel dressing

Objectives: The antimicrobial efficacy of a chlorhexidine gluconate (CHG) intravascular catheter gel dressing was evaluated against methicillin-resistant Staphylococcus aureus (MRSA) and an extended-spectrum β-lactamase (ESBL)-producing Escherichia coli. Chlorhexidine deposition on the skin surface and release from the gel were determined. Methods: The antimicrobial efficacy was evaluated in in vitro studies following microbial inoculation of the dressing and application of the dressing on the inoculated surface of a silicone membrane and donor skin [with and without a catheter segment and/or 10% (v/v) serum] on diffusion cells. Antimicrobial activity was evaluated for up to 7 days. Chlorhexidine skin surface deposition and release were also determined. Results: MRSA and E. coli were not detectable within 5 min following direct inoculation onto the CHG gel dressing. On the silicone membrane, 3 log and 6 log inocula of MRSA were eradicated within 5 min and 1 h, respectively. Time to kill was prolonged in the presence of serum and a catheter segment. Following inoculation of donor skin with 6 log cfu of MRSA, none was detected after 24 h. Chlorhexidine was released from the gel after a lag time of 30 min and increasing amounts were detected on the donor skin surface over the 48 h test period. The CHG gel dressing retained its antimicrobial activity on the artificial skin for 7 days. Conclusions: The CHG intravascular catheter site gel dressing had detectable antimicrobial activity for up to 7 days, which should suppress bacterial growth on the skin at the catheter insertion site, thereby reducing the risk of infection. © The Author 2011. Published by Oxford University Press on behalf of the British Society for Antimicrobial Chemotherapy. All rights reserved.

It's not queer to be gay: Miami and the emergence of the gay rights movement, 1945–1995

This work chronicles how queer individuals politicized their same-sex desires from the post-World War II era to the mid-1990s. Using Miami as a site of exploration, this work demonstrates the shift from understanding homosexuality as a same-sex "desire" to a distinct form of "civil rights." It argues that by no means was it inevitable that queer issues entered the American political mainstream. This project pays particular attention to Miami's Cuban exile community, as it managed to garner great socio-political power in the city. Like others in the city's power structure, Miami's Cuban exiles were also fundamentally traditionalists. Together, these phenomena crystallized into a matrix of obstacles that stunted the growth of the gay rights movement. This work demonstrates the historical dynamics of sexuality and politics by contextualizing immigration, ethnicity, race, consumerism, and Cold War domestic and foreign policy.

Faithful Genres: Rhetorics of the Civil Rights Mass Meeting

“Faithful Genres” examines how African Americans adapted the genres of the black church during the civil rights movement. Civil rights mass meetings, as the movement’s so-called “energy machine” and “heartbeat,” serve as the project’s central site of inquiry for these meetings were themselves adaptations of the genre of the black church service. The mass meetings served as the space to draw people into the movement, encourage people toward further activism, and testify to anyone watching that the African American community was working toward desegregation, voting rights, and racial equality. In Martin Luther King, Jr.’s words, “Through these meetings we were able to generate the power and depth which finally galvanized the entire Negro community.” In these weekly or sometimes even nightly meetings, participants inhabited the familiar genres of the black church, song, prayer, and testimony. As they did, they remade these genres to respond directly to white supremacy and to enact the changes they sought to create. While scholars have studied the speeches men and women such as King, Ralph Abernathy, and Fannie Lou Hamer delivered at meetings (Wilson; Selby; Holmes; Brooks), scholars have yet to examine how civil rights mass meetings functioned through a range of genres and rhetors. My study addresses this absence and invigorates this discussion to demonstrate how the other meeting genres beyond the speech—song, prayer, and testimony—functioned to create energy, sustenance, and motivation for activists. Examining these collectively enacted genres, I show how rhetors adapted song, prayer, and testimony toward strategic interventions. I also examine how activists took these same genres up outside the meetings to circulate them in broader contexts for new audiences. By recovering and defining the mass meeting as a flexible repertoire of genres and then examining the redeployment of meeting genres outside the meeting, “Faithful Genres” contributes to histories of civil rights and African American rhetorics, genre studies, and histories of religious rhetorics.

SCHOOL DISTRICT GOVERNANCE AND KNOWLEDGE-FIT IN DECISION RIGHTS: HOW DISTRICTS RECRUIT AND HIRE SCHOOL LIBRARIANS

This study examines the organizational structures and decision-making processes used by school districts to recruit and hire school librarians. For students to acquire the information and technology literacy education they need, school libraries must be staffed with qualified individuals who can fulfill the librarian’s role as leader, teacher, instructional partner, information specialist, and program administrator. Principals are typically given decision rights for hiring staff, including school librarians. Research shows that principals have limited knowledge of the skills and abilities of the school librarian or the specific needs and functions of the library program. Research also indicates that those with specific knowledge of school library programs, namely school district library supervisors, are only consulted on recruiting and hiring about half the time. School districts entrust library supervisors with responsibilities such as professional development of school librarians only after they are hired. This study uses a theoretical lens from research on IT governance, which focuses on the use of knowledge-fit in applying decision rights in an organization. This framework is appropriate because of its incorporation of a specialist with a specific knowledge set in determining the placement of input and decision rights in the decision-making processes. The method used in this research was a multiple-case study design using five school districts as cases, varying by the involvement of the supervisors and other individuals in the hiring process. The data collected from each school district were interviews about the district’s recruiting and hiring practices with principals, an individual in HR, library supervisors, and recently hired school librarians. Data analysis was conducted through iterative coding from themes in the research questions, with continuous adjustments as new themes developed. Results from the study indicate that governance framework is applicable to evaluating the decision-making processes used in recruiting and hiring school librarians. However, a district’s use of governance did not consistently use knowledge-fit in the determination of input and decision rights. In the hiring process, governance was more likely to be based on placing decision rights at a certain level of the district hierarchy rather than the location of specific knowledge, most often resulting in site-based governance for decision rights at the school-building level. The governance of the recruiting process was most affected by the shortage or surplus of candidates available to the district to fill positions. Districts struggling with a shortage of candidates typically placed governance for the decision-making process on recruiting at the district level, giving the library supervisor more opportunity for input and collaboration with human resources. In districts that use site-based governance and that place all input and decision rights at the building level, some principals use their autonomy to eliminate the school library position in the allotment phase or hire librarians that, while certified through testing, do not have the same level of expertise as those who achieve certification through LIS programs. The principals in districts who use site-based governance for decision rights but call on the library supervisor for advisement stated how valuable they found the supervisor’s expertise in evaluating candidates for hire. In no district was a principal or school required to involve the library supervisor in the hiring of school librarians. With a better understanding of the tasks involved, the effect of district governance on decision-making, and the use of knowledge to assign input and decision rights, it is possible to look at how all of these factors affect the outcome in the quality of the hire. A next step is to look at the hiring process that school librarians went through and connect those with the measurable outcomes of hiring: school librarian success, retention, and attrition; the quality of school library program services, outreach, and involvement in a school; and the perceptions of the success of the school librarian and the library program as seen from students, teachers, administrators, parents, and other community stakeholders.

Employee workplace rights.

"OSHA 3021-08R."

Forensic Injustice: Human Rights, Archival Science and Racialized Feminicide in Guatemala

The call to access and preserve the state records that document crimes committed by the state during Guatemala’s civil war has become an archival imperative entangled with neoliberal human rights discourses of “truth, justice, and memory.” 200,000 people were killed and disappeared in Guatemala’s civil war including acts of genocide in which 85% of massacres involved sexual violence committed against Mayan women. This dissertation argues that in an attempt to tell the official story of the civil war, American Human Rights organizations and academic institutions have constructed a normative identity whose humanity is attached to a scientific and evidentiary value as well as an archival status representing the materiality and institutionality of the record. Consequently, Human Rights discourses grounded in Western knowledges, in particular archival science and law, which prioritize the appearance of truth erase the material and epistemological experience of indigenous women during wartimes. As a result, the subjectivity that has surfaced on the record as most legible has mostly pertained to non-indigenous, middle class, urban, leftist men who were victims of enforced disappearance not genocide. This dissertation investigates this conflicting narrative that remembers a non-indigenous revolutionary masculine hero and grants him justice in human rights courtrooms simply because of a document attesting to his death. A main research question addressed in this project is why the promise of "truth and justice" under the name of human rights becomes a contentious site for gendered indigenous bodies? I conduct a discursive and rhetorical analysis of documentary film, declassified Guatemalan police and military records such as Operation Sofia, a military log known for “documenting the genocide” during rural counterinsurgencies executed by the military. I interrogate the ways in which racialized feminicides or the hyper-sexualized racial violence that has historically dehumanized indigenous women falls outside of discourses of vision constructed by Western positivist knowledges to reinscribe the ideal human right subject. I argue for alternative epistemological frames that recognize genocide as sexualized and gendered structures that have simultaneously produced racialized feminicides in order to disrupt the colonial structures of capitalism, patriarchy and heterosexuality. Ironically, these structures of power remain untouched by the dominant human rights discourse and its academic, NGO, and state collaborators that seek "truth and justice" in post-conflict Guatemala.

Are the preference and selection patterns of hermit crabs for gastropod shells species- or site-specific?

Experimental analyses of hermit crabs and their preferences for shells are essential to understand the intrinsic relationship of the crabs' dependence on shells, and may be useful to explain their shell use pattern in nature. The aim of this study was to evaluate the effect of crab species and site on the pattern of shell use, selection, and preference in the south-western Atlantic hermit crabs Pagurus brevidactylus and Pagurus criniticornis, comparing sympatric and allopatric populations. Differently from the traditional approach to evaluate shell preference by simply determining the shell selection pattern (i.e., the number of shells of each type selected), preference was defined (according to [Liszka, D., Underwood, AJ., 1990. An experimental design to determine preferences for gastropod shells by a hermit-crab. J. Exp. Mar. Biol. Ecol., 137(1), 47-62]) by the comparison of the number of crabs changing for a particular shell type when three options were given (Cerithium atratum, Morula nodulosa, and Tegula viridula) with the number of crabs changing for this same type when only this type was offered. The effect of crab species was tested at Cabelo Gordo Beach, where P. brevidacrylus was found occupying shells of C. atratum, M. nodulosa, and T viridula in similar frequencies, whereas P. criniticornis occupied predominantly shells of C atratum. In laboratory experiments the selection patterns of the two hermit-crab species for these three gastropods were different, with P criniticornis selecting mainly shells of C atratum, and R brevidactylus selecting more shells of M. nodulosa. The shell preference was also dependent on crab species, with P. criniticornis showing a clear preference for shells of C atratum, whereas P. brevidactylus did not show a preference for any of the tested shells. The effect of site was tested for the two species comparing data from Cabelo Gordo to Preta (P brevidactylus) and Araca beaches (P. criniticornis). The pattern of shell use, selection, and preference was demonstrated to be dependent on site only for P. brevidactylus. The results also showed that the shell use pattern of P criniticornis can be explained by its preference at both sites, whereas for P. brevidactylus it occurred only at Cabelo Gordo, where the absence of preference was correlated with the similar use of the three gastropod species studied. Finally, the results showed that the shell selection pattern cannot be considered as a measure of shell preference, since it overestimates crab selectivity. (C) 2009 Elsevier B.V. All rights reserved.

Development of site-specific sediment quality guidelines for North and South Atlantic littoral zones: Comparison against national and international sediment quality benchmarks

We aimed to develop site-specific sediment quality guidelines (SQGs) for two estuarine and port zones in Southeastern Brazil (Santos Estuarine System and Paranagua Estuarine System) and three in Southern Spain (Ria of Huelva, Bay of Cadiz, and Bay of Algeciras), and compare these values against national and traditionally used international benchmark values. Site-specific SQGs were derived based on sediment physical-chemical, toxicological, and benthic community data integrated through multivariate analysis. This technique allowed the identification of chemicals of concern and the establishment of effects range correlatively to individual concentrations of contaminants for each site of study. The results revealed that sediments from Santos channel, as well as inner portions of the SES, are considered highly polluted (exceeding SQGs-high) by metals, PAHs and PCBs. High pollution by PAHs and some metals was found in Sao Vicente channel. In PES, sediments from inner portions (proximities of the Ponta do Mix port's terminal and the Port of Paranagua) are highly polluted by metals and PAHs, including one zone inside the limits of an environmental protection area. In Gulf of Cadiz, SQGs exceedences were found in Ria of Huelva (all analysed metals and PAHs), in the surroundings of the Port of CAdiz (Bay of CAdiz) (metals), and in Bay of Algeciras (Ni and PAHs). The site-specific SQGs derived in this study are more restricted than national SQGs applied in Brazil and Spain, as well as international guidelines. This finding confirms the importance of the development of site-specific SQGs to support the characterisation of sediments and dredged material. The use of the same methodology to derive SQGs in Brazilian and Spanish port zones confirmed the applicability of this technique with an international scope and provided a harmonised methodology for site-specific SQGs derivation. (C) 2009 Elsevier B.V. All rights reserved.

Site fidelity and movements of gilthead sea bream (Sparus aurata) in a coastal lagoon (Ria Formosa, Portugal)

Short-time site fidelity and movements of gilthead sea bream (Sparus aurata) in a coastal lagoon were determined using passive acoustic telemetry. Nine fish, ranging from 20.1 to 32.5 cm total length, were surgically implanted with acoustic transmitters and monitored for up to 179 days. Minimum convex polygon areas ranged from 18,698.6 m(2) to 352,711.9 m(2). Home range sizes were small, with individuals using core areas on a daily basis. However, these core areas shifted within the study site over time towards the opening to the sea. Two different diel behaviors were recorded, with some individuals more active at night and others during day time. Some individuals also demonstrated homing abilities, returning to the capture site after being released more than 4 km away. (C) 2008 Elsevier Ltd. All rights reserved.

Molecular And Biochemical Characterization Of Caffeine Synthase And Purine Alkaloid Concentration In Guarana Fruit.

Guarana seeds have the highest caffeine concentration among plants accumulating purine alkaloids, but in contrast with coffee and tea, practically nothing is known about caffeine metabolism in this Amazonian plant. In this study, the levels of purine alkaloids in tissues of five guarana cultivars were determined. Theobromine was the main alkaloid that accumulated in leaves, stems, inflorescences and pericarps of fruit, while caffeine accumulated in the seeds and reached levels from 3.3% to 5.8%. In all tissues analysed, the alkaloid concentration, whether theobromine or caffeine, was higher in young/immature tissues, then decreasing with plant development/maturation. Caffeine synthase activity was highest in seeds of immature fruit. A nucleotide sequence (PcCS) was assembled with sequences retrieved from the EST database REALGENE using sequences of caffeine synthase from coffee and tea, whose expression was also highest in seeds from immature fruit. The PcCS has 1083bp and the protein sequence has greater similarity and identity with the caffeine synthase from cocoa (BTS1) and tea (TCS1). A recombinant PcCS allowed functional characterization of the enzyme as a bifunctional CS, able to catalyse the methylation of 7-methylxanthine to theobromine (3,7-dimethylxanthine), and theobromine to caffeine (1,3,7-trimethylxanthine), respectively. Among several substrates tested, PcCS showed higher affinity for theobromine, differing from all other caffeine synthases described so far, which have higher affinity for paraxanthine. When compared to previous knowledge on the protein structure of coffee caffeine synthase, the unique substrate affinity of PcCS is probably explained by the amino acid residues found in the active site of the predicted protein.

Synthesis And Antiproliferative Activity Of 8-hydroxyquinoline Derivatives Containing A 1,2,3-triazole Moiety.

Twelve novel 8-hydroxyquinoline derivatives were synthesized with good yields by performing copper-catalyzed Huisgen 1,3-dipolar cycloaddition (click reaction) between an 8-O-alkylated-quinoline containing a terminal alkyne and various aromatic or protected sugar azides. These compounds were evaluated in vitro for their antiproliferative activity on various cancer cell types. Protected sugar derivative 16 was the most active compound in the series, exhibiting potent antiproliferative activity and high selectivity toward ovarian cancer cells (OVCAR-03, GI50 < 0.25 μg mL(-1)); this derivative was more active than the reference drug doxorubicin (OVCAR-03, GI50 = 0.43 μg mL(-1)). In structure-activity relationship (SAR) studies, the physico-chemical parameters of the compounds were evaluated and docking calculations were performed for the α-glucosidase active site to predict the possible mechanism of action of this series of compounds.