Assembling Multiporphyrin Stacks Inside the DNA Double Helix

Double stranded DNA hybrids containing up to four consecutive, face-to-face stacked porphyrins are described. Non-nucleosidic, 5,15-bisphenyl-substituted porphyrin building blocks were incorporated into complementary oligonucleotide strands. Upon hybridization multiple porphyrins are well accommodated inside the DNA scaffold without disturbing the overall B-DNA structure. The formation of double strands containing up to four free base porphyrins is enabled without compromising duplex stability. UV/vis, fluorescence, and CD spectroscopy demonstrate the formation of porphyrins H-aggregates inside the DNA double helix and provide evidence for the existence of strong excitonic coupling between interstrand stacked porphyrins. H-aggregation results in considerable fluorescence quenching. Most intense CD effects are observed in stacks containing four porphyrins. The findings demonstrate the value of DNA for the controlled formation of molecularly defined porphyrin aggregates.

A Bundle of Services Increased Ascertainment of Tuberculosis among HIV-Infected Individuals Enrolled in a HIV Cohort in Rural Sub-Saharan Africa.

OBJECTIVES To report on trends of tuberculosis ascertainment among HIV patients in a rural HIV cohort in Tanzania, and assessing the impact of a bundle of services implemented in December 2012, consisting of three components:(i)integration of HIV and tuberculosis services; (ii)GeneXpert for tuberculosis diagnosis; and (iii)electronic data collection. DESIGN Retrospective cohort study of patients enrolled in the Kilombero Ulanga Antiretroviral Cohort (KIULARCO), Tanzania.). METHODS HIV patients without prior history of tuberculosis enrolled in the KIULARCO cohort between 2005 and 2013 were included.Cox proportional hazard models were used to estimate rates and predictors of tuberculosis ascertainment. RESULTS Of 7114 HIV positive patients enrolled, 5123(72%) had no history of tuberculosis. Of these, 66% were female, median age was 38 years, median baseline CD4+ cell count was 243 cells/µl, and 43% had WHO clinical stage 3 or 4. During follow-up, 421 incident tuberculosis cases were notified with an estimated incidence of 3.6 per 100 person-years(p-y)[95% confidence interval(CI)3.26-3.97]. The incidence rate varied over time and increased significantly from 2.96 to 43.98 cases per 100 p-y after the introduction of the bundle of services in December 2012. Four independent predictors of tuberculosis ascertainment were identified:poor clinical condition at baseline (Hazard Ratio (HR) 3.89, 95% CI 2.87-5.28), WHO clinical stage 3 or 4 (HR 2.48, 95% CI 1.88-3.26), being antiretroviralnaïve (HR 2.97, 95% CI 2.25-3.94), and registration in 2013(HR 6.07, 95% CI 4.39-8.38). CONCLUSION The integration of tuberculosis and HIV services together with comprehensive electronic data collection and use of GeneXpert increased dramatically the ascertainment of tuberculosis in this rural African HIV cohort.

Triple-helix formation in the antiparallel binding motif of oligodeoxynucleotides containing N(9)- and N(7)-2-aminopurine deoxynucleosides

Triplex-forming oligodeoxynucleotide 15mers, designed to bind in the antiparallel triple-helical binding motif, containing single substitutions (Z) of the four isomeric alphaN(7)-, betaN(7)-, alphaN(9)- and betaN(9)-2-aminopurine (ap)-deoxyribonucleosides were prepared. Their association with double-stranded DNA targets containing all four natural base pairs (X-Y) opposite the aminopurine residues was determined by quantitative DNase I footprint titration in the absence of monovalent metal cations. The corresponding association constants were found to be in a rather narrow range between 1.0 x 10(6) and 1.3 x 10(8) M(-1). The following relative order in Z x X-Y base-triple stabilities was found: Z = alphaN(7)ap: T-A > A-T> C-G approximately G-C; Z = betaN(7)ap: A-T > C-G > G-C > T-A; Z = alphaN(9)ap: A-T = G-C > T-A > C-G; and Z = betaN(9)ap: G-C > A-T > C-G > T-A

A curved RNA helix incorporating an internal loop with G·A and A·A non-Watson–Crick base pairing

The crystal structure of the RNA dodecamer 5′-GGCC(GAAA)GGCC-3′ has been determined from x-ray diffraction data to 2.3-Å resolution. In the crystal, these oligomers form double helices around twofold symmetry axes. Four consecutive non-Watson–Crick base pairs make up an internal loop in the middle of the duplex, including sheared G·A pairs and novel asymmetric A·A pairs. This internal loop sequence produces a significant curvature and narrowing of the double helix. The helix is curved by 34° from end to end and the diameter is narrowed by 24% in the internal loop. A Mn2+ ion is bound directly to the N7 of the first guanine in the Watson–Crick region following the internal loop and the phosphate of the preceding residue. This Mn2+ location corresponds to a metal binding site observed in the hammerhead catalytic RNA.

Metal Clips Induce Folding of a Short Unstructured Peptide into an a-Helix via Turn Conformations in Water. Kinetic versus Thermodynamic Products

Short peptides corresponding to two to four a-helical turns of proteins are not thermodynamically stable helices in water. Unstructured octapeptide Ac-His1*-Ala2-Ala3-His4*-His5*-Glu6-Leu7-His8*-NH2 (1) reacts with two [Pd ((NH2)-N-15(CH2)(2) (NH2)-N-15)(NO3)(2)] in water to form a kinetically stable intermediate, [{Pden}(2)-{(1,4)(5,8)-peptide}](2), in which two 19-membered metallocyclic rings stabilize two peptide turns. Slow subsequent folding to a thermodynamically more stable two-turn a-helix drives the equilibrium to [{Pden}(2)-{(1,5)(4,8)-peptide}] (3), featuring two 22-membered rings. This transformation from unstructured peptide via turns to an a-helix suggests that metal clips might be useful probes for investigating peptide folding.

Distribuição de conteúdos em redes veiculares usando mecanismos de comunicação tolerantes ao atraso

The last couple of decades have been the stage for the introduction of new telecommunication networks. It is expected that in the future all types of vehicles, such as cars, buses and trucks have the ability to intercommunicate and form a vehicular network. Vehicular networks display particularities when compared to other networks due to their continuous node mobility and their wide geographical dispersion, leading to a permanent network fragmentation. Therefore, the main challenges that this type of network entails relate to the intermittent connectivity and the long and variable delay in information delivery. To address the problems related to the intermittent connectivity, a new concept was introduced – Delay Tolerant Network (DTN). This architecture is built on a Store-Carry-and-Forward (SCF) mechanism in order to assure the delivery of information when there is no end-to-end path defined. Vehicular networks support a multiplicity of services, including the transportation of non-urgent information. Therefore, it is possible to conclude that the use of a DTN for the dissemination of non-urgent information is able to surpass the aforementioned challenges. The work developed focused on the use of DTNs for the dissemination of non-urgent information. This information is originated in the network service provider and should be available on mobile network terminals during a limited period of time. In order to do so, four different strategies were deployed: Random, Least Number of Hops First (LNHF), Local Rarest Bundle First (LRBF) e Local Rarest Generation First (LRGF). All of these strategies have a common goal: to disseminate content into the network in the shortest period of time and minimizing network congestion. This work also contemplates the analysis and implementation of techniques that reduce network congestion. The design, implementation and validation of the proposed strategies was divided into three stages. The first stage focused on creating a Matlab emulator for the fast implementation and strategy validation. This stage resulted in the four strategies that were afterwards implemented in the DTNs software Helix – developed in a partnership between Instituto de Telecomunicac¸˜oes (IT) and Veniam R , which are responsible for the largest operating vehicular network worldwide that is located in Oporto city. The strategies were later evaluated on an emulator that was built for the largescale testing of DTN. Both emulators account for vehicular mobility based on information previously collected from the real platform. Finally, the strategy that presented the best overall performance was tested on a real platform – in a lab environment – for concept and operability demonstration. It is possible to conclude that two of the implemented strategies (LRBF and LRGF) can be deployed in the real network and guarantee a significant delivery rate. The LRBF strategy has the best performance in terms of delivery. However, it needs to add a significant overhead to the network in order to work. In the future, tests of scalability should be conducted in a real environment in order to confirm the emulator results. The real implementation of the strategies should be accompanied by the introduction of new types of services for content distribution.

Determination of particle concentration in the breathing zone for four different types of office ventilation systems

Many factors affect the airflow patterns, thermal comfort, contaminant removal efficiency and indoor air quality at individual workstations in office buildings. In this study, four ventilation systems were used in a test chamber designed to represent an area of a typical office building floor and reproduce the real characteristics of a modern office space. Measurements of particle concentration and thermal parameters (temperature and velocity) were carried out for each of the following types of ventilation systems: a) conventional air distribution system with ceiling supply and return; b) conventional air distribution system with ceiling supply and return near the floor; c) underfloor air distribution system; and d) split system. The measurements aimed to analyse the particle removal efficiency in the breathing zone and the impact of particle concentration on an individual at the workstation. The efficiency of the ventilation system was analysed by measuring particle size and concentration, ventilation effectiveness and the Indoor/Outdoor ratio. Each ventilation system showed different airflow patterns and the efficiency of each ventilation system in the removal of the particles in the breathing zone showed no correlation with particle size and the various methods of analyses used.

Particle and gaseous emissions from compressed natural gas and ultralow sulphur diesel-fuelled buses at four steady engine loads

Exhaust emissions from thirteen compressed natural gas (CNG) and nine ultralow sulphur diesel in-service transport buses were monitored on a chassis dynamometer. Measurements were carried out at idle and at three steady engine loads of 25%, 50% and 100% of maximum power at a fixed speed of 60 kmph. Emission factors were estimated for particle mass and number, carbon dioxide and oxides of nitrogen for two types of CNG buses (Scania and MAN, compatible with Euro 2 and 3 emission standards, respectively) and two types of diesel buses (Volvo Pre-Euro/Euro1 and Mercedez OC500 Euro3). All emission factors increased with load. The median particle mass emission factor for the CNG buses was less than 1% of that from the diesel buses at all loads. However, the particle number emission factors did not show a statistically significant difference between buses operating on the two types of fuel. In this paper, for the very first time, particle number emission factors are presented at four steady state engine loads for CNG buses. Median values ranged from the order of 1012 particles min-1 at idle to 1015 particles km-1 at full power. Most of the particles observed in the CNG emissions were in the nanoparticle size range and likely to be composed of volatile organic compounds The CO2 emission factors were about 20% to 30% greater for the diesel buses over the CNG buses, while the oxides of nitrogen emission factors did not show any difference due to the large variation between buses.

The development of a new four-year Construction Technology and Management Stream at QUT

This paper focuses on the development and delivery of a core construction management (CM) unit, which forms the capstone of a four-unit CM stream in an undergraduate programme in the Faculty of Built Environment and Engineering at the Queensland University of Technology. UDB410 (Construction Management) is a final year unit that consolidates skills students have learned throughout their degree, hopefully graduating them as work-ready construction managers. It was developed in consultation with the Queensland Chapter of the Australian Institute of Building (AIB) and is a final year unit in the undergraduate Bachelor of Urban Development (CM) course. The unit uses various tools such as the OSIRIS business database (Bureau van Dijk Electronic Publishing, 2009), the AROUSAL (UK Version) construction business simulation (Lansley, 2009) and the Denison Organisational Culture Survey (Denison, 2000) to facilitate the development of skills in managing a construction company. The objectives of the paper are: • To track the rationale and development of the UDB410 unit sand describe the way in which this final year unit integrates learning from other parts of the course within which it is located as well as capping-off the CM stream of core units; • To highlight the difficulties of blending a balance of technology and management in a single unit; and • To explain how partnering with the construction industry benefited the learning quality of the unit.

Four years after graduation : occupational therapists' work destinations and perceptions of preparedness for practice

Objective: The present study sought to identify the work destinations of graduates and ascertain their perceived preparedness for practice from a regional occupational therapy program, which had been specifically developed to support the health requirements of northern Australians by having an emphasis on rural practice. ---------- Design: Self-report questionnaires and semistructured in-depth telephone interviews. ---------- Participants: Graduates (n = 15) from the first cohort of occupational therapists from James Cook University, Queensland. ---------- Main outcome measure: The study enabled comparisons to be made between rural and urban based occupational therapists, while the semistructured interviews provided a deeper understanding of participants' experiences regarding their preparation for practice. ---------- Results: Demographic differences were noted between occupational therapists working in rural and urban settings. Rural therapists were predominantly younger and had worked in slightly more positions than their urban counterparts. The study also offered some insights into the value that therapists placed on the subjects taught during their undergraduate occupational therapy training, and had highlighted the differences in perceptions between therapists with rural experience and those with urban experience regarding the subjects that best prepared them for practice. Generally, rural therapists reported that all subjects included in the curriculum had equipped them well for practice. ---------- Conclusions: Findings suggest the need to undertake further research to determine the actual nature of rural practice, the personal characteristics of rural graduates and the experiences of students while on rural clinical placements.