Distinct conformational properties determined by implicit and explicit representation of protein-solvent interactions. An analytical and computer simulation study

In the protein folding problem, solvent-mediated forces are commonly represented by intra-chain pairwise contact energy. Although this approximation has proven to be useful in several circumstances, it is limited in some other aspects of the problem. Here we show that it is possible to achieve two models to represent the chain-solvent system. one of them with implicit and other with explicit solvent, such that both reproduce the same thermodynamic results. Firstly, lattice models treated by analytical methods, were used to show that the implicit and explicitly representation of solvent effects can be energetically equivalent only if local solvent properties are time and spatially invariant. Following, applying the same reasoning Used for the lattice models, two inter-consistent Monte Carlo off-lattice models for implicit and explicit solvent are constructed, being that now in the latter the solvent properties are allowed to fluctuate. Then, it is shown that the chain configurational evolution as well as the globule equilibrium conformation are significantly distinct for implicit and explicit solvent systems. Actually, strongly contrasting with the implicit solvent version, the explicit solvent model predicts: (i) a malleable globule, in agreement with the estimated large protein-volume fluctuations; (ii) thermal conformational stability, resembling the conformational hear resistance of globular proteins, in which radii of gyration are practically insensitive to thermal effects over a relatively wide range of temperatures; and (iii) smaller radii of gyration at higher temperatures, indicating that the chain conformational entropy in the unfolded state is significantly smaller than that estimated from random coil configurations. Finally, we comment on the meaning of these results with respect to the understanding of the folding process. (C) 2009 Elsevier B.V. All rights reserved.

Exploring weak interactions to assemble a nitrosyl-ruthenium compound able to release NO under visible light irradiation

This work reports oil a novel nitrosyl-ruthenium complex hearing the azanaphthalene ligand quinazoline (qui) ill its coordination sphere. The product crystallizes with ail additional quinazoline molecule, yielding the compound cis-[Ru(bpy)(2)(qui)NO](PF(6))(3).(qui). This feature leads to all absorption band at lambda(max) = 430 nm in CH(3)CN and lambda(max) = 420 nm in phosphate buffer, which promotes the photorelease of nitric oxide under visible light irradiation (lambda > 400 nm), in 1 ethanol: 1 water (v/v) mixture or under physiological pH. Both the intensity and energy of this transition are dependent on solvent and solution pH, suggesting that the transition has a charge transfer nature, and that the association of the second quinazoline molecule with the complex is driven by weak interactions, possibly of the pi-stacking type. (C) 2009 Elsevier Ltd. All rights reserved.

Budlein A from Viguiera robusta inhibits leukocyte-endothelial cell interactions, adhesion molecule expression and inflammatory mediators release

Budlein A has been reported to exert some analgesic and anti-inflammatory properties. In this study, we have evaluated its effect on LPS-induced leukocyte recruitment in vivo and the mechanisms involved in its anti-inflammatory activity. In vivo, intravital videomicroscopy was used to determine the effects of budlein A on LPS-induced leukocyte-endothelial cell interactions in the murine cremasteric microcirculation. In vitro, the effects of budlein A on LPS-induced cytokine, chemokine and nitrites release, T-cell proliferative response as well as cell adhesion molecule expression (CAM) were evaluated. In vivo, intraperitoneal administration of budlein A (2.6 mM/kg) caused a significant reduction of LPS-induced leukocyte rolling flux, adhesion and emigration by 84, 92 and 96% respectively. In vitro, T-cell proliferative response was also affected by budlein A. When murine J774 macrophages were incubated with the sesquiterpene lactone, LPS-induced IL-1 beta, tumor necrosis factor-alpha (TNF-alpha) and keratinocyte-derived chemokine (KC) release were concentration-dependently inhibited. In human umbilical vein endothelial cells (HUVECs), budlein A also reduced the production of TNF-alpha, monocyte chemoattractant protein-1 (MCP-1), IL-8, nitrites and CAM expression elicited by LPS. Budlein A is a potent inhibitor of LPS-induced leukocyte accumulation in vivo. This effect appears to be mediated through inhibition of cytokine and chemokine release and down-regulation of CAM expression. Thus, it has potential therapeutic interest for the control of leukocyte recruitment that occurs in different inflammatory disorders. (C) 2009 Elsevier GrnbH. All rights reserved.

Development of the student placement evaluation form: A tool for assessing student fieldwork performance

Evaluation of students undertaking fieldwork education placements is a critical process in the health professions. As training programs and practice evolve, systems for assessing students need to be reviewed and updated constantly. In 1995, staff of the occupational therapy training program at the University of Queensland, Australia decided to develop a new tool for assessing student fieldwork performance. Using an action research methodology, a team developed the Student Placement Evaluation Form, a flexible and comprehensive criterion-referenced evaluation tool. The present paper examines action research as an appropriate methodology for considering real-life organisational problems in a systematic and participatory manner. The action research cycles undertaken, including preliminary information gathering, tool development, trial stages and current use of the tool, are detailed in the report. Current and future development of the tool is also described.

A simple data logger for student-designed rocket experiments.

The final-year project for Mechanical & Space Engineering students at UQ often involves the design and flight testing of an experiment. This report describes the design and use of a simple data logger that should be suitable for collecting data from the students' flight experiments. The exercise here was taken as far as the construction of a prototype device that is suitable for ground-based testing, say, the static firing of a hybrid rocket motor.

Undergraduate student experiences and perceptions of group projects

This paper reports the experiences and perceptions of student group projects of three cohorts of undergraduates: a 3rd year capstone course in professional communication (N = 54), a 3rd year elective in chemical engineering (N = 29), and a core 2nd-year course in chemical engineering (N = 74).

The Rural Clinical Division: a student journey to rural medicine

Background: The University of Queensland has through an Australian Government initiative, established a Rural Clinical Division (RCD) at four regional sites in the southern and central Queensland. Over the fi rst four years of the existence of the RCD, an integrated package of innovative medical education has been developed. Method: The integrated aspects of the RCD program include: The Rural Medical Rotation: Every medical student undertakes an eight week rural rotation in Year 3. Year 3 and 4 MBBS - 100 students are currently spending one to two years in the rural school and demand is increasing. Interprofessional Education - Medical and Allied Health students attend lectures, seminars and workshops together and often share the same rural clinical placement. Rural health projects - allow students to undertake a project of benefi t to the rural community. Information Technology (IT) - the Clinical Discussion Board (CDB) and Personal Digital Assistants (PDA) demonstrate the importance of IT to medical students in the 21st century. Changing the Model of Medical Education - The Leichhardt Community Attachment Placement (LCAP), is a pilot study that resulted in the addition of three interns to the rural workforce. All aspects of the RCD are evaluated with surveys using both qualitative and quantitative free response questions, completed by all students regularly throughout the academic year. Results: Measures of impact include: Student satisfaction and quality of teaching surveys – 86-91% of students improved their clinical skills and understanding across all rotations. Academic results and progress – RCD students out-perform their urban colleagues. Intent to work in rural areas – 90% of students reported a greater interest in rural medicine. Intern numbers – rural / regional intern placements are increasing. Conclusions: The RCD proves to be a site for innovations all designed to help reach our primary goal of fostering increased recruitment of a rural medical workforce.

Suicide in urban New South Wales, Australia 1985-1994: Socio-economic and migrant interactions

Variation of suicide with socio-economic status (SES) in urban NSW (Australia) during 1985-1994, by sex and country or region of birth, was examined using Poisson regression analysis of vital statistics and population data (age greater than or similar to 15 yr). Quintiles of SES were defined by municipality of residence and comparisons of suicide by SES were adjusted for age and country (or region) of birth (COB), and examined by COB. Risk of suicide in females was 28% that of males for all adults and 21% for youth (age 15-24 yr). Suicide risk was lower in males from southern Europe, Middle East and Asia, and higher in northern and eastern European males, compared to the Australian-born. Risks for suicide increased significantly with decreasing SES in males, but not in females. The relationship of male suicide and SES was stronger when controlled for COB. For males, the relative risk of suicide, adjusted for age and COB, was 66% higher in the lowest SES quintile compared to the highest quintile, and 39% higher for youth (age 15-24 yr). For male suicide, the population attributable fraction for SES (less than the highest quintile) was 27%. Analysis of SES differentials in male suicide according to COB indicated a significant inverse suicide gradient in relation to SES for the Australian-born and those burn in New Zealand and the United Kingdom or fire. but not in non-English speaking COB groups, except for Asia. For Australian-born males, suicide risk was 71% higher in the lowest SES group (compared to the highest), adjusted for age. These findings indicate that SES plays an important role in male suicide rates among the Australian-born and migrants from English-speaking countries and Asia, and among youth; but not in female suicide, nor suicide in most non-English speaking migrant groups. Reduction in SES differentials through economic and social policies may reduce male suicide in lower SES groups and should be seen to be at least as important as individual level interventions. (C) 1998 Elsevier Science Ltd. All rights reserved.

The nurse lecturer role in clinical practice conceptualized: helping clinical teachers provide optimal student learning

Despite the fairly wide reporting in the literature of the ma ny roles of clinical supervision by the nursing teacher, little attention has been given to conceptualizing the relative priorities these roles take during the process of supervising nursing students in clinical practice. The purpose of this paper is to consider the manifestations and implications of conflicting roles when nurse lecturers undertake clinical supervision. Previously published research will provide working examples of issues in a conceptual framework for clinical teaching.

Strategies of accommodation: Development of a coding system for conversational interaction

This study describes a coding system developed to operationalize the sociolinguistic strategies proposed by communication accommodation theory (CAT) in an academic context. Fifty interactions between two students (of Australian or Chinese ethnic background) or a student and faculty member were videotaped. A turn- and episode-based coding system was developed, focusing on verbal and nonverbal behavior. The development of this system is described in detail, before results are presented. Results indicated that status was the main influence on choice of strategies, particularly the extent and type of discourse management and interpersonal control. Participants' sew and ethnicity also played a role: Male participants made more use of interpretability (largely questions), whereas female participants used discourse management to develop a shared perspective. The results make clear that there is no automatic correspondence between behaviors and the strategies they constitute, and they point to the appropriateness of conceptualizing behavior and strategies separately in CAT.

Miscibility and specific interactions in blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate)

The properties of the hydrogen-bonded polymer blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate) are presented. Spectroscopic techniques such as C-13 solid-state NMR and FT-IR are used to probe specific interactions of the blends at various compositions. Spectral features from both techniques revealed that site-specific interactions are present, consistent with a significant degree of mixing of the blend components. Changes in chemical shift and line shape of the phenolic carbon and carbonyl resonances in the C-13 CPMAS spectra of the blends as a function of composition are interpreted as resulting from changes in the relative intensities of two closely overlapped signals. A quantitative measure of hydrogen-bonded carbonyl groups using C-13 NMR has been obtained which agreed well with the results from FT-IR analyses. It is also shown that C-13 NMR can be used to measure the fraction of hydroxyl groups associated with carbonyl groups, which was not possible previously using FT-IR due to extensive overlapping of bands in the hydroxyl stretching region. The results of measurements of H-1 T-1 and 1H T-1 rho indicate that PVPh and PEEMA are intimately mixed on a scale less than 2-3 nm.

Characterization of the sequential non-covalent and covalent interactions of the antitumour antibiotic hedamycin with double stranded DNA by NMR spectroscopy

Hedamycin, a member of the pluramycin class of antitumour antibiotics, consists of a planar anthrapyrantrione chromophore to which is attached two aminosugar rings at one end and a bisepoxide-containing sidechain at the other end, Binding to double-stranded DNA is known to involve both reversible and non-reversible modes of interaction. As a part of studies directed towards elucidating the structural basis for the observed 5'-pyGT-3' sequence selectivity of hedamycin, we conducted one-dimensional NMR titration experiments at low temperature using the hexadeoxyribonucleotide duplexes d(CACGTG)(2) and d(CGTACG)(2). Spectral changes which occurred during these titrations are consistent with hedamycin initially forming a reversible complex in slow exchange on the NMR timescale and binding through intercalation of the chromophore. Monitoring of this reversible complex over a period of hours revealed a second type of spectral change which corresponds with formation of a non-reversible complex. Copyright (C) 1999 John Wiley & Sons, Ltd.