Molecular dynamics approach to the structural characterization and transport properties of poly(acrylonitrile)/N,N-dimethylformamide solutions

Poly(acrylonitrile) (PAN) in N,N-dimethylformamide (DMF) is a popular solution for producing large variety of polymer products. To precisely describe the behaviours of PAN and DMF in the synthesis processes, it is significant to call for more details about the structure, some thermodynamic and dynamical properties of PAN-DMF solutions. A PAN-DMF solution was simulated via molecular dynamics with an all-atom OPLS type potential in both the NPT and NVT ensembles. The simulation results were evaluated with quantum mechanical calculations (MP2/6-311 ++G(d,p) and counterpoise procedure) and were compared with available experimental results. The liquid structure was illustrated with pair correlation functions and transport and dynamics properties were calculated with the mean-square displacements MSD and the velocity autocorrelation functions. The strong H-bonds of C≡N « H-C=O, CH » O=C-H and CH2 O=C-H, with distances of 2.55 Å, 2.55 Å and 2.65 Å, respectively, were found. The largest interaction energy of - 7.157 kcal/mol between DMF molecules and PAN molecules was found at 4.9 Å center-of-mass distance. A potential profile of intermolecular interaction of DMF with PAN along the interaction distance was presented, clearly showing an increase of DMF vaporisation heat when it getting close to PAN molecules. This provided very useful information to analyse the vaporisation behaviours of DMF at the microscopic level, which is essential to comprehensively understand molecular rearrangements towards the design of synthetic processes. The impact of the presence of the PAN on the DMF solution properties were also benchmarked with pure DMF solution.

The several social constructions of James, Jenks, and Prout: A contribution to the sociological theorization of childhood

The article is intended to contribute to the ongoing debate over theorizations of childhood, especially in the terms articulated by Allison James, Chris Jenkins and Alan Prout. The article focuses on the notion of social construction as a theory of childhood. There are four valid approaches to theorizing childhood. The tribal approach treats childhood as a kind of exotic tribe with its own beliefs, practices and institutions. The social structural approach treats childhood as a structurally necessary stratum in any society. The minority group approach treats childhood as an oppressed minority group, able to some extent to represent themselves and exert quasi-political action. The socially constructed approach constitutes the sociological view of childhood. The key role played by the idea of social construction is made extremely clear in the earlier work, Constructing and Reconstructing Childhood by James and Prout. Social constructionism is said to be an interpretive approach, related historically to research on children's understanding of adult experimenters' intentions. The senses of social construction that emerge from critical psychology overlap a great deal with those articulated in the new sociology of childhood.

Modeling and analyses of the retirement of deteriorated structures

With the increasing stock of aging structures, the strategy to model and analyse the retirement of deteriorated structures is becoming a challenging research field. As the converse of construction of new projects, the retirement of constructed facilities puts forward some new management and economics themes as well as environmental issues or adds some new contents even though the same issues are faced in construction. This research aims to model and analyse the maintenance and demolition activities of constructed facilities from economic and environmental perspectives. Both cost and carbon dioxide of maintenance and demolition activities are formulated based on those of construction activities and applied to an empirical study on deteriorated bridges. Further modelling and analysis is investigated to elaborate the demolition stage of a structure. The developed modelling and analysis methodology may enable the decision maker to determine the retirement strategy for a deteriorated structure.

Study of the dimensions that relate to the effectiveness of training systems : a systems approach

The purpose of this thesis is to explore dimensions that relate to the training systems effectiveness in a number of industry categories. The training system is taken as part of the reproducer boundary subsystem within the organisation (Miller 1978). The research has been developed on the assumption that no single criterion is appropriate as a measure of effectiveness of a training system (Campbell et al 1970). An index of criteria based on the different organisational variables that interact within an organisation is employed in the development of the study. In this research the structural variables (independent variables) including industry category, size and formalisation factors of the sample organisations will be related to the effectiveness of training systems in their organisations. This research attempts to formulate hypotheses in the field of training system research to contribute to a theory of training system impact studies. The popular areas of research in the field of training have mainly tended to focus separately on the effectiveness of training programmes, the economics of training, the social impact of training and the dynamics of training. To my knowledge there is no research work that tests the relationship between structure and the effectiveness of training systems.

Structural characterization of novel ionic materials incorporating the bis(trifluoromethanesulfonyl)amide anion

A range of low melting salts of the bis(trifluoromethanesulfonyl)amide (TFSA) anion with hindered organic cations (N-methyl-1-methylpyrrolinium, N,N-dimethylpyrrolidinium, N,N,N,-trimethylammonium, and N,N,N,N-tetrakis(n-propyl)ammonium) have been crystallized. Single-crystal X-ray diffraction data show these materials to consist of discrete ions with only weak C−H···O (or for Me₃NH N−H···O) contacts between the constituent atoms of the cations and anions close to the limits of van der Waals separations. Consequently, the observed physical properties of these materials presumably result from the diffuse negative charge on the TFSA anion and inefficient packing of these large and irregularly shaped ions.

Recruitment of class I hydrophobins to the air : water interface initiates a multi-step process of functional amyloid formation

Class I fungal hydrophobins form amphipathic monolayers composed of amyloid rodlets. This is a remarkable case of functional amyloid formation in that a hydrophobic:hydrophilic interface is required to trigger the self-assembly of the proteins. The mechanism of rodlet formation and the role of the interface in this process have not been well understood. Here, we have studied the effect of a range of additives, including ionic liquids, alcohols, and detergents, on rodlet formation by two class I hydrophobins, EAS and DewA. Although the conformation of the hydrophobins in these different solutions is not altered, we observe that the rate of rodlet formation is slowed as the surface tension of the solution is decreased, regardless of the nature of the additive. These results suggest that interface properties are of critical importance for the recruitment, alignment, and structural rearrangement of the amphipathic hydrophobin monomers. This work gives insight into the forces that drive macromolecular assembly of this unique family of proteins and allows us to propose a three-stage model for the interface-driven formation of rodlets.

Boom and bust in Australian screen policy: 10BA, the Film Finance Corporation, and Hollywood's 'race to the bottom'.

In recent years, a narrative has emerged in the Australian popular media about the box office 'unpopularity' of Australian feature films and the 'failure' of the domestic screen industry. This article explores the recent history of Australian screen policy with particular reference to the '10BA' tax incentive of the 1980s; the Film Finance Corporation of Australia (FFC), a government screen agency established in 1988 to bring investment bank-style portfolio management to Australia's screen industry; and local production incentive policies pursed by Australian state governments in a chase for Hollywood's runaway production.

We argue the 10BA incentive catalysed an unsustainable bubble in Australian production, while its policy successor, the FFC, fundamentally failed in its stated mission of 'commercial' screen financing (over its 20-year lifespan, the FFC invested 1.345 billion Australian dollars for 274.2 million Australian dollars recouped - a cumulative return of negative 80 percent). For their part, private investors in Australian films discovered that the screen production process involved high levels of risk.

Foreign-financed production also proved highly volatile, due to the vagaries of trade exposure, currency fluctuations and tax arbitrage. The result of these macro and micro-economic factors often structural and cross-border in nature was that Australia's screen industry failed to develop the local investment infrastructure required to finance a sustainable, non-subsidised local sector.

Allosteric Modulation of the HIV-1 gp120-gp41 Association Site by Adjacent gp120 Variable Region 1 (V1) N-Glycans Linked to Neutralization Sensitivity

The HIV-1 gp120-gp41 complex, which mediates viral fusion and cellular entry, undergoes rapid evolution within its external glycan shield to enable escape from neutralizing antibody (NAb). Understanding how conserved protein determinants retain functionality in the context of such evolution is important for their evaluation and exploitation as potential drug and/ or vaccine targets. In this study, we examined how the conserved gp120-gp41 association site, formed by the N- and Cterminal segments of gp120 and the disulfide-bonded region (DSR) of gp41, adapts to glycan changes that are linked to neutralization sensitivity. To this end, a DSR mutant virus (K601D) with defective gp120-association was sequentially passaged in peripheral blood mononuclear cells to select suppressor mutations. We reasoned that the locations of suppressors point to structural elements that are functionally linked to the gp120-gp41 association site. In culture 1, gp120 association and viral replication was restored by loss of the conserved glycan at Asn136 in V1 (T138N mutation) in
conjunction with the L494I substitution in C5 within the association site. In culture 2, replication was restored with deletion of the N139INN sequence, which ablates the overlapping Asn141-Asn142-Ser-Ser potential N-linked glycosylation sequons in
V1, in conjunction with D601N in the DSR. The 136 and 142 glycan mutations appeared to exert their suppressive effects by altering the dependence of gp120-gp41 interactions on the DSR residues, Leu593, Trp596 and Lys601. The 136 and/or 142
glycan mutations increased the sensitivity of HIV-1 pseudovirions to the glycan-dependent NAbs 2G12 and PG16, and also pooled IgG obtained from HIV-1-infected individuals. Thus adjacent V1 glycans allosterically modulate the distal gp120-
gp41 association site. We propose that this represents a mechanism for functional adaptation of the gp120-gp41 association site to an evolving glycan shield in a setting of NAb selection.

Numerical investigation of influence of the Martensite Volume Fraction on dp steels fracture behavior on the basis of digital material representation model

Development of the methodology for creating reliable digital material representation (DMR) models of dual-phase steels and investigation of influence of the martensite volume fraction on fracture behavior under tensile load are the main goals of the paper. First, an approach based on image processing algorithms for creating a DMR is described. Then, obtained digital microstructures are used as input for the numerical model of deformation, which takes into account mechanisms of ductile fracture. Ferrite and martensite material model parameters are evaluated on the basis of micropillar compression tests. Finally, the model is used to investigate the impact of the martensite volume fraction on the DP steel behavior under plastic deformation. Results of calculations are presented and discussed in the paper.

Modeling and analysis on the propagation dynamics of modern email malware

Due to the critical security threats imposed by email-based malware in recent years, modeling the propagation dynamics of email malware becomes a fundamental technique for predicting its potential damages and developing effective countermeasures. Compared to earlier versions of email malware, modern email malware exhibits two new features, reinfection and self-start. Reinfection refers to the malware behavior that modern email malware sends out malware copies whenever any healthy or infected recipients open the malicious attachment. Self-start refers to the behavior that malware starts to spread whenever compromised computers restart or certain files are visited. In the literature, several models are proposed for email malware propagation, but they did not take into account the above two features and cannot accurately model the propagation dynamics of modern email malware. To address this problem, we derive a novel difference equation based analytical model by introducing a new concept of virtual infected user. The proposed model can precisely present the repetitious spreading process caused by reinfection and self-start and effectively overcome the associated computational challenges. We perform comprehensive empirical and theoretical study to validate the proposed analytical model. The results show our model greatly outperforms previous models in terms of estimation accuracy. © 2013 IEEE.

Microstructure modeling and prediction of the mechanical properties of advanced high strength steels

Dual phase (DP) steels were modeled using 2D and 3D representative volume elements (RVE). Both the 2D and 3D models were generated using the Monte-Carlo-Potts method to represent the realistic microstructural details. In the 2D model, a balance between computational efficiency and required accuracy in truly representing heterogeneous microstructure was achieved. In the 3D model, a stochastic template was used to generate a model with high spatial fidelity. The 2D model proved to be efficient for characterization of the mechanical properties of a DP steel where the effect of phase distribution, morphology and strain partitioning was studied. In contrast, the current 3D modeling technique was inefficient and impractical due to significant time cost. It is shown that the newly proposed 2D model generation technique is versatile and sufficiently accurate to capture mechanical properties of steels with heterogeneous microstructure.

Distinct kinetics of molecular gelation in a confined space and its relation to the structure and property of thin gel films

Thin films of molecular gels formed in a confined space have potential applications in transdermal delivery, artificial skin, molecular electronics, etc. The microstructures and properties of thin gel films can be significantly different from those of their bulk counterparts. However, so far a comprehensive understanding of the effects of spatial confinement on the molecular gelation kinetics, fiber network structure and related mechanical properties is still lacking. In this work, using rheological techniques, we investigated the effect of one-dimensional confinement on the formation kinetics of fiber networks in the molecular gelation process. Fractal analyses of the kinetic information in terms of an extended Dickinson model enabled us to describe quantitatively the distinct kinetic signature of molecular gelation. The structural features derived from gelation kinetics support well the fractal patterns of the fiber networks acquired by optical and electron microscopy. With the kinetics-structure correlation, we can gain an in-depth understanding of the confinement-induced differences in the structure and consequently the mechanical properties of a model molecular gelling system. Particularly, the confinement induced structural transition, from a three-dimensional, dense and compact spherulitic network composed of highly branched fibers to a quasi-two-dimensional sparse spherulitic network composed of less branched fibers and entangled fibrils at the boundary areas, renders a gel film to become less stiff but more ductile. Our study suggests here a new strategy of engineering the fiber network microstructure to achieve functional gel films with unusual but useful properties.

Structural health monitoring: a practical approach to achieving in-situ and site-specific warning of pipeline corrosion and coating failure

An approach to achieving the ambitious goal of cost effectively extending the safe operation life of energy pipelines to, for instance, 100 years is the application of structural health monitoring and life prediction tools that are able to provide long-term remnant pipeline life prediction and in-situ pipeline condition monitoring. A critical step in pipeline structural health monitoring is the enhancement of technological capabilities that are required for quantifying the effects of key factors influencing buried pipeline corrosion and environmentally assisted materials degradation, and the development of condition monitoring technologies that are able to provide in-situ monitoring and site-specific warning of pipeline damage. This paper provides an overview of our current research aimed at developing new sensors for monitoring, categorising and quantifying the level and nature of external pipeline and coating damages under the combined effects of various inter-related variables and processes such as localised corrosion, coating damage and disbondment, cathodic shielding. The concept of in-situ monitoring and site-specific warning of pipeline corrosion is illustrated by a case of monitoring localised corrosion under disbonded coatings using a new corrosion monitoring probe. A basic principle that underpins the use of sensors to monitor localised corrosion has been presented: Localised corrosion and coating failure are not an accidental occurrence, it occurs as the result of fundamental thermodynamic instability of a metal exposed to a specific environment. Therefore corrosion and coating disbondment occurring on a pipeline will also occur on a sensor made of the same material and exposed to the same pipeline condition. Although the exact location of localised corrosion or coating disbondment could be difficult to pinpoint along the length of a buried pipeline, the ‘worst-case scenario’ and high risk pipeline sections and sites are predictable. Sensors can be embedded at these strategic sites to collect data that contain ‘predictor features’ signifying the occurrence of localised corrosion, CP failure, coating disbondment and degradation. Information from these sensors will enable pipeline owners to prioritise site survey and inspection operations, and to develop maintenance strategy to manage aged pipelines, rather than replace them.