988 resultados para Computational chemistry


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The Guardian reportage of the United Kingdom Member of Parliament (MP) expenses scandal of 2009 used crowdsourcing and computational journalism techniques. Computational journalism can be broadly defined as the application of computer science techniques to the activities of journalism. Its foundation lies in computer assisted reporting techniques and its importance is increasing due to the: (a) increasing availability of large scale government datasets for scrutiny; (b) declining cost, increasing power and ease of use of data mining and filtering software; and Web 2.0; and (c) explosion of online public engagement and opinion.. This paper provides a case study of the Guardian MP expenses scandal reportage and reveals some key challenges and opportunities for digital journalism. It finds journalists may increasingly take an active role in understanding, interpreting, verifying and reporting clues or conclusions that arise from the interrogations of datasets (computational journalism). Secondly a distinction should be made between information reportage and computational journalism in the digital realm, just as a distinction might be made between citizen reporting and citizen journalism. Thirdly, an opportunity exists for online news providers to take a ‘curatorial’ role, selecting and making easily available the best data sources for readers to use (information reportage). These activities have always been fundamental to journalism, however the way in which they are undertaken may change. Findings from this paper may suggest opportunities and challenges for the implementation of computational journalism techniques in practice by digital Australian media providers, and further areas of research.

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We present an approach to automating computationally sound proofs of key exchange protocols based on public-key encryption. We show that satisfying the property called occultness in the Dolev-Yao model guarantees the security of a related key exchange protocol in a simple computational model. Security in this simpler model has been shown to imply security in a Bellare {Rogaway-like model. Furthermore, the occultness in the Dolev-Yao model can be searched automatically by a mechanisable procedure. Thus automated proofs for key exchange protocols in the computational model can be achieved. We illustrate the method using the well-known Lowe-Needham-Schroeder protocol.

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The α,ω-diyne 4,7,10-trithiatrideca-2,11-diyne reacts with [RuCl2(PPh3)3] and KPF6 to form the phosphonio-substituted metallatricyclic salt [RuCl(PPh3){κ4C,S,S′,S′′-S(C≡CMe)C2H4SC2H4SC(PPh3)CMe}]PF6 arising from the activation of one alkynyl group toward nucleophilic attack by extraneous phosphine.

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The Guardian reportage of the United Kingdom Member of Parliament (MP) expenses scandal of 2009 used crowdsourcing and computational journalism techniques. Computational journalism can be broadly defined as the application of computer science techniques to the activities of journalism. Its foundation lies in computer assisted reporting techniques and its importance is increasing due to the: (a) increasing availability of large scale government datasets for scrutiny; (b) declining cost, increasing power and ease of use of data mining and filtering software; and Web 2.0; and (c) explosion of online public engagement and opinion.. This paper provides a case study of the Guardian MP expenses scandal reportage and reveals some key challenges and opportunities for digital journalism. It finds journalists may increasingly take an active role in understanding, interpreting, verifying and reporting clues or conclusions that arise from the interrogations of datasets (computational journalism). Secondly a distinction should be made between information reportage and computational journalism in the digital realm, just as a distinction might be made between citizen reporting and citizen journalism. Thirdly, an opportunity exists for online news providers to take a ‘curatorial’ role, selecting and making easily available the best data sources for readers to use (information reportage). These activities have always been fundamental to journalism, however the way in which they are undertaken may change. Findings from this paper may suggest opportunities and challenges for the implementation of computational journalism techniques in practice by digital Australian media providers, and further areas of research.

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There are at least four key challenges in the online news environment that computational journalism may address. Firstly, news providers operate in a rapidly evolving environment and larger businesses are typically slower to adapt to market innovations. News consumption patterns have changed and news providers need to find new ways to capture and retain digital users. Meanwhile, declining financial performance has led to cost cuts in mass market newspapers. Finally investigative reporting is typically slow, high cost and may be tedious, and yet is valuable to the reputation of a news provider. Computational journalism involves the application of software and technologies to the activities of journalism, and it draws from the fields of computer science, social science and communications. New technologies may enhance the traditional aims of journalism, or may require “a new breed of people who are midway between technologists and journalists” (Irfan Essa in Mecklin 2009: 3). Historically referred to as ‘computer assisted reporting’, the use of software in online reportage is increasingly valuable due to three factors: larger datasets are becoming publicly available; software is becoming sophisticated and ubiquitous; and the developing Australian digital economy. This paper introduces key elements of computational journalism – it describes why it is needed; what it involves; benefits and challenges; and provides a case study and examples. Computational techniques can quickly provide a solid factual basis for original investigative journalism and may increase interaction with readers, when correctly used. It is a major opportunity to enhance the delivery of original investigative journalism, which ultimately may attract and retain readers online.

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The health of tollbooth workers is seriously threatened by long-term exposure to polluted air from vehicle exhausts. Using traffic data collected at a toll plaza, vehicle movements were simulated by a system dynamics model with different traffic volumes and toll collection procedures. This allowed the average travel time of vehicles to be calculated. A three-dimension Computational Fluid Dynamics (CFD) model was used with a k–ε turbulence model to simulate pollutant dispersion at the toll plaza for different traffic volumes and toll collection procedures. It was shown that pollutant concentration around tollbooths increases as traffic volume increases. Whether traffic volume is low or high (1500 vehicles/h or 2500 vehicles/h), pollutant concentration decreases if electronic toll collection (ETC) is adopted. In addition, pollutant concentration around tollbooths decreases as the proportion of ETC-equipped vehicles increases. However, if the proportion of ETC-equipped vehicles is very low and the traffic volume is not heavy, then pollutant concentration increases as the number of ETC lanes increases.

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Recently, the numerical modelling and simulation for fractional partial differential equations (FPDE), which have been found with widely applications in modern engineering and sciences, are attracting increased attentions. The current dominant numerical method for modelling of FPDE is the explicit Finite Difference Method (FDM), which is based on a pre-defined grid leading to inherited issues or shortcomings. This paper aims to develop an implicit meshless approach based on the radial basis functions (RBF) for numerical simulation of time fractional diffusion equations. The discrete system of equations is obtained by using the RBF meshless shape functions and the strong-forms. The stability and convergence of this meshless approach are then discussed and theoretically proven. Several numerical examples with different problem domains are used to validate and investigate accuracy and efficiency of the newly developed meshless formulation. The results obtained by the meshless formations are also compared with those obtained by FDM in terms of their accuracy and efficiency. It is concluded that the present meshless formulation is very effective for the modelling and simulation for FPDE.

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A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

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Scoliosis is a spinal deformity that requires surgical correction in progressive cases. In order to optimize surgical outcomes, patient-specific finite element models are being developed by our group. In this paper, a single rod anterior correction procedure is simulated for a group of six scoliosis patients. For each patient, personalised model geometry was derived from low-dose CT scans, and clinically measured intra-operative corrective forces were applied. However, tissue material properties were not patient-specific, being derived from existing literature. Clinically, the patient group had a mean initial Cobb angle of 47.3 degrees, which was corrected to 17.5 degrees after surgery. The mean simulated post-operative Cobb angle for the group was 18.1 degrees. Although this represents good agreement between clinical and simulated corrections, the discrepancy between clinical and simulated Cobb angle for individual patients varied between -10.3 and +8.6 degrees, with only three of the six patients matching the clinical result to within accepted Cobb measurement error of +-5 degrees. The results of this study suggest that spinal tissue material properties play an important role in governing the correction obtained during surgery, and that patient-specific modelling approaches must address the question of how to prescribe patient-specific soft tissue properties for spine surgery simulation.

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The hydrodynamic behaviour of a novel flat plate photocatalytic reactor for water treatment is investigated using CFD code FLUENT. The reactor consists of a reactive section that features negligible pressure drop and uniform illumination of the photocatalyst to ensure enhanced photocatalytic efficiency. The numerical simulations allowed the identification of several design issues in the original reactor, which include extensive boundary layer separation near the photocatalyst support and regions of flow recirculation that render a significant portion of the reactive area. The simulations reveal that this issue could be addressed by selecting the appropriate inlet positions and configurations. This modification can cause minimal pressure drop across the reactive zone and achieves significant uniformization of the tested pollutant on the photocatalyst surface. The influence of roughness elements type has also been studied with a view to identify their role on the distribution of pollutant concentration on the photocatalyst surface. The results presented here indicate that the flow and pollutant concentration field strongly depend on the geometric parameters and flow conditions.

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The heterogeneous photocatalytic oxidation process offers a versatile promise in the detoxification and disinfection of wastewater containing hazardous organic compounds such as pesticides and phenolic compounds in storm and wastewater effluent. This process has gained wide attention due to its effectiveness in degrading and mineralizing the organic compounds into harmless and often useful components. To develop an efficient photocatalytic process, titanium dioxide has been actively studied in recent years due to its excellent performance as a photocatalyst under UV light irradiation. This paper aims at critically evaluating and highlighting the recent developments of the heterogeneous photocatalytic systems with a special focus on storm and wastewater treatment applications.