973 resultados para First-principles calculation
Resumo:
The first direct voltammetric response from a molybdenum enzyme under non-turnover conditions is reported. Cyclic voltammetry of dimethylsulfoxide reductase from Rhodobacter capsulatus reveals a reversible Mo-VI/V response at + 161 mV followed by a reversible Mo-V/IV response at -102 mV versus NHE at pH 8. The higher potential couple exhibits a pH dependence consistent with protonation upon reduction to the Mo-V state and we have determined the pK(a) for this semi-reduced species to be 9.0. The lower potential couple is pH independent within the range 5 < pH < 10. The optical spectrum of the Mo chromophore has been investigated with spectroelectrochemistry. At high potential, in its resting state, the enzyme exhibits a spectrum characteristic of the Mo-VI form. This changes significantly following bulk electrolysis (-400 mV versus NHE) at an optically transparent, indium-doped tin oxide working electrode, where a single visible electronic maximum at 632 nm is observed, which is comparable with spectra reported previously for the dithionite-reduced enzyme. This two-electron process is chemically reversible by reoxidizing the enzyme at the electrode in the absence of mediators or promoters. The activity of the enzyme has been established by observation of a catalytic current in the presence of DMSO at pH 8, where a sigmoidal (steady state) voltammogram is seen. Electronic supplementary material to this paper (Fig. S 1) can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00775-002-0374-y.
Resumo:
Resonance phenomena associated with the unimolecular dissociation of H2S --> SH + H have been investigated quantum mechanically by the Lanczos homogeneous filter diagonalization method using a newly developed potential energy surface (J. Chem. Phys. 2001, 114, 320). Resonance energies, widths (rates), and product state distributions have been obtained. Both dissociation rates and product state distributions of SH show, strong fluctuations, indicating that the dissociation of H2S is essentially irregular. Statistical analysis of neighboring level spacing and width distributions also confirms this behavior. The dissociation rates and product state distributions are compared to the predictions of quantum phase space theory.
Resumo:
In this paper we establish a foundation for understanding the instrumentation needs of complex dynamic systems if ecological interface design (EID)-based interfaces are to be robust in the face of instrumentation failures. EID-based interfaces often include configural displays which reveal the higher-order properties of complex systems. However, concerns have been expressed that such displays might be misleading when instrumentation is unreliable or unavailable. Rasmussen's abstraction hierarchy (AH) formalism can be extended to include representations of sensors near the functions or properties about which they provide information, resulting in what we call a sensor-annotated abstraction hierarchy. Sensor-annotated AHs help the analyst determine the impact of different instrumentation engineering policies on higher-order system information by showing how the data provided from individual sensors propagates within and across levels of abstraction in the AH. The use of sensor-annotated AHs with a configural display is illustrated with a simple water reservoir example. We argue that if EID is to be effectively employed in the design of interfaces for complex systems, then the information needs of the human operator need to be considered at the earliest stages of system development while instrumentation requirements are being formulated. In this way, Rasmussen's AH promotes a formative approach to instrumentation engineering. (C) 2002 Elsevier Science Ltd. All rights reserved.
Resumo:
Motion study is an engineering technology that analyzes human body motions. During the past decade (1990-1999) a series of studies investigated the role of motion study in developmental disabilities. This article reviews the literature on the applications of motion study in the field. A historical and conceptual review of motion study leading to the current status of studies is presented followed by a review of the research literature. Two main eras of research focus were identified. The first era (1990-1995) of studies established the superior effectiveness and efficiency of tasks designed with motion study or motion study-related principles over traditional site-based task designs. The second era (1995-1999) of studies examined the interaction between motion study-based task designs and other variables such as choice, preference, and functionally equivalent and competing task designs and communicative alternatives. Our review found that applying motion study principles as an antecedent guide and practice to eliminating or reducing ineffective motions and simplifying effective motions resulted in positive task outcomes with most of the participants.
Resumo:
Clearing of native vegetation is a major threat to biodiversity in Australia. In Queensland, clearing has resulted in extensive ecosystem transformation, especially in the more fertile parts of the landscape. In this paper, we examine Queensland, Australian and some overseas evidence of the impact of clearing and related fragmentation effects on terrestrial biota. The geographic locus is the semi-arid regions. although we recognise that coastal regions have been extensively cleared. The evidence reviewed here suggests that the reduction of remnant vegetation to 30% will result in the loss of 25-35% of vertebrate fauna, with the full impact not realised for another 50-100 years, or even longer. Less mobile, habitat specialists and rare species appear to be particularly at risk. We propose three broad principles For effective biodiversity conservation in Queensland: (i) regional native vegetation retention thresholds of 50910: (ii) regional ecosystem thresholds of 30%: and (iii) landscape design and planning principles that protect large remnants, preferably > 2000 ha, as core habitats. Under these retention thresholds. no further clearing would be permitted in the extensively cleared biogeographic regions such as Brigalow Belt and New England Tablelands. Some elements of the biota. however, will require more detailed knowledge and targeted retention and management to ensure their security. The application of resource sustainability and economic criteria outlined elsewhere in this volume should be applied to ensure that the biogeographic regions in the north and west of Queensland that are largely intact continue to provide extensive wildlife habitat.
Resumo:
Back ground. Based on the well-described excess of schizophrenia births in winter and spring, we hypothesised that individuals with schizophrenia (a) would be more likely to be born during periods of decreased perinatal sunshine, and (b) those born during periods of less sunshine would have an earlier age of first registration. Methods. We undertook an ecological analysis of long-term trends in perinatal sunshine duration and schizophrenia birth rates based on two mental health registers (Queensland. Australia n = 6630; The Netherlands n = 24, 474). For each of the 480 months between 1931 and 1970, the agreement between slopes of the trends in psychosis and long-term sunshine duration series were assessed. Age at first registration was assessed by quartiles of long-term trends in perinatal sunshine duration, Males and females were assessed separately. Results. Both the Dutch and Australian data showed a statistically significant association between falling long-term trends in sunshine duration around the time of birth and rising schizophrenia birth rates for males only. In both the Dutch and Australian data there were significant associations between earlier age of first registration and reduced long-term trends in sunshine duration around the time of birth for both males and females, Conclusions. A measure of long-term trends in perinatal sunshine duration was associated with two epidemiological features of schizophrenia in two separate data sets. Exposures related to sunshine duration warrant further consideration in schizophrenia research. (C) 2002 Elsevier Science B.V. All rights reserved.
Resumo:
NMR spectroscopy and simulated annealing calculations have been used to determine the three-dimensional structure of NaD1, a novel antifungal and insecticidal protein isolated from the flowers of Nicotiana alata. NaD1 is a basic, cysteine-rich protein of 47 residues and is the first example of a plant defensin from flowers to be characterized structurally. Its three-dimensional structure consists of an a-helix and a triple-stranded anti-parallel beta-sheet that are stabilized by four intramolecular disulfide bonds. NaD1 features all the characteristics of the cysteine-stabilized up motif that has been described for a variety of proteins of differing functions ranging from antibacterial insect defensins and ion channel-perturbing scorpion toxins to an elicitor of the sweet taste response. The protein is biologically active against insect pests, which makes it a potential candidate for use in crop protection. NaD1 shares 31% sequence identity with alfAFP, an antifungal protein from alfalfa that confers resistance to a fungal pathogen in transgenic potatoes. The structure of NaD1 was used to obtain a homology model of alfAFP, since NaD1 has the highest level of sequence identity with alfAFP of any structurally characterized antifungal defensin. The structures of NaD1 and alfAFP were used in conjunction with structure - activity data for the radish defensin Rs-AFP2 to provide an insight into structure-function relationships. In particular, a putative effector site was identified in the structure of NaD1 and in the corresponding homology model of alfAFP. (C) 2002 Elsevier Science Ltd. All rights reserved.
Resumo:
Computer Science is a subject which has difficulty in marketing itself. Further, pinning down a standard curriculum is difficult-there are many preferences which are hard to accommodate. This paper argues the case that part of the problem is the fact that, unlike more established disciplines, the subject does not clearly distinguish the study of principles from the study of artifacts. This point was raised in Curriculum 2001 discussions, and debate needs to start in good time for the next curriculum standard. This paper provides a starting point for debate, by outlining a process by which principles and artifacts may be separated, and presents a sample curriculum to illustrate the possibilities. This sample curriculum has some positive points, though these positive points are incidental to the need to start debating the issue. Other models, with a less rigorous ordering of principles before artifacts, would still gain from making it clearer whether a specific concept was fundamental, or a property of a specific technology. (C) 2003 Elsevier Ltd. All rights reserved.
Resumo:
This paper discusses the development of a new Bachelor of Education (Middle Years of Schooling) at The University of Queensland. The middle years of schooling have increasingly been the focus of education reform initiatives in Australia, but this has not been accompanied by significant increases in the number of teacher education institutions offering specialised middle schooling-level teacher preparation programmes. Considering the rapidly changing social and economic context and the emergent state of middle schooling in Australia, the programme represented a conceptual and practical opportunity and challenge for The University of Queensland team. Working collaboratively, the team sought to design a teacher education preservice programme that was both responsive and generative: that is, responsive to local school contexts and to current educational research and reform at national and international levels; and generative of cutting-edge theories and practices associated with middle schooling, teachers' work, and teacher education. This paper focuses on one component of the Middle Years of Schooling Teacher Education programme at The University of Queensland; namely, the practicum. We first present the underlying principles of the practicum programme and then examine "dilemmas" that emerged early in the practicum. These issues and tensions were associated with the ideals of "middle years" philosophy and the pragmatics of school reform associated with that new approach. In this paper, and within this context, we explore what it means to be both responsive and generative, and describe how we as teacher educators negotiated between the extremes these terms implied.
Resumo:
Background: In the presence of dNTPs, intact HIV-1 virions are capable of reverse transcribing at least part of their genome, a process known as natural endogenous reverse transcription (NERT). PCR analysis of virion DNA produced by NERT revealed that the first strand transfer reaction (1stST) was inefficient in intact virions, with minus strand (-) strong stop DNA (ssDNA) copy numbers up to 200 times higher than post-1stST products measured using primers in U3 and U5. This was in marked contrast to the efficiency of 1stST observed in single-round cell infection assays, in which (-) ssDNA and U3-U5 copy numbers were indistinguishable. Objectives: To investigate the reasons for the discrepancy in first strand transfer efficiency between intact cell-free virus and the infection process. Study design: Alterations of both NERT reactions and the conditions of cell infection were used to test whether uncoating and/or entry play a role in the discrepancy in first strand transfer efficiency. Results and Conclusions: The difference in 1stST efficiency could not be attributed simply to viral uncoating, since addition of very low concentrations of detergent to NERT reactions removed the viral envelope without disrupting the reverse transcription complex, and these conditions resulted in no improvement in 1stST efficiency. Virus pseudotyped with surface glycoproteins from either vesicular stomatitis virus or amphotrophic murine leukaemia virus also showed low levels of 1stST in low detergent NERT assays and equivalent levels of (-) ssDNA and 1stST in single-round infections of cells, demonstrating that the gp120-mediated infection process did not select for virions capable of carrying out 1stST. These data indicate that a post-entry event or factor may be involved in efficient HIV-1 reverse transcription in vivo. (C) 2002 Elsevier Science B.V. All rights reserved.
Resumo:
This report describes the road map we followed at our university to accommodate three main factors: financial pressure within the university system; desire to enhance the learning experience of undergraduates; and motivation to increase the prominence of the discipline of developmental biology in our university. We engineered a novel, multi-year undergraduate developmental biology program which was student-oriented, ensuring that students were continually exposed to the underlying principles and philosophy of this discipline throughout their undergraduate career. Among its key features are introductory lectures in core courses in the first year, which emphasize the relevance of developmental biology to tissue engineering, reproductive medicine, therapeutic approaches in medicine, agriculture and aquaculture. State-of-the-art animated computer graphics and images of high visual impact are also used. In addition, students are streamed into the developmental biology track in the second year, using courses like human embryology and courses shared with cell biology, which include practicals based on modern experimental approaches. Finally, fully dedicated third-year courses in developmental biology are undertaken in conjunction with stand-alone practical courses where students experience first-hand work in a research laboratory. Our philosophy is a cradle-to-grave approach to the education of undergraduates so as to prepare highly motivated, enthusiastic and well-educated developmental biologists for entry into graduate programs and ultimately post-doctoral research.