One-step macroscopic alignment of conjugated polymer systems by epitaxial crystallization during spin-coating

The one-step preparation of highly anisotropic polymer semiconductor thin films directly from solution is demonstrated. The conjugated polymer poly(3-hexylthiophene) (P3HT) as well as P3HT:fullerene bulk-heterojunction blends can be spin-coated from a mixture of the crystallizable solvent 1,3,5-trichlorobenzene (TCB) and a second carrier solvent such as chlorobenzene. Solidification is initiated by growth of macroscopic TCB spherulites followed by epitaxial crystallization of P3HT on TCB crystals. Subsequent sublimation of TCB leaves behind a replica of the original TCB spherulites. Thus, highly ordered thin films are obtained, which feature square-centimeter-sized domains that are composed of one spherulite-like structure each. A combination of optical microscopy and polarized photoluminescence spectroscopy reveals radial alignment of the polymer backbone in case of P3HT, whereas P3HT:fullerene blends display a tangential orientation with respect to the center of spherulite-like structures. Moreover, grazing-incidence wide-angle X-ray scattering reveals an increased relative degree of crystallinity and predominantly flat-on conformation of P3HT crystallites in the blend. The use of other processing methods such as dip-coating is also feasible and offers uniaxial orientation of the macromolecule. Finally, the applicability of this method to a variety of other semi-crystalline conjugated polymer systems is established. Those include other poly(3-alkylthiophene)s, two polyfluorenes, the low band-gap polymer PCPDTBT, a diketopyrrolopyrrole (DPP) small molecule as well as a number of polymer:fullerene and polymer:polymer blends. Macroscopic spherulite-like structures of the conjugated polymer poly(3-hexylthiophene) (P3HT) grow directly during spin-coating. This is achieved by processing P3HT or P3HT:fullerene bulk heterojunction blends from a mixture of the crystallizable solvent 1,3,5-trichlorobenzene and a second carrier solvent such as chlorobenzene. Epitaxial growth of the polymer on solidified solvent crystals gives rise to circular-symmetric, spherulite-like structures that feature a high degree of anisotropy.

Iron(II) spin transition complexes with dendritic ligands, Part I

The ligands G1- and G2-oligo (benzyl ether) (PBE) dendrons and their iron(II) complexes [Fe(Gn-PBE)3]A2·xH2O (with n = 1, 2 and A = triflate, tosylate) were prepared. The magnetic properties of the complexes were investigated by a SQUID magnetometer. All complexes exhibit gradual spin transition below room temperature. At very low temperatures the magnetic behaviour reflects zero-field splitting (ZFS) effects. 57Fe-Mössbauer spectroscopy was performed to distinguish between ZFS of high spin species and spin state conversion into the low spin state. Further characterisation was carried out by thermogravimetric analysis (TGA) and FT-IR spectroscopy. Structural features have been determined by powder XRD measurements.

Iron(II) spin-transition complexes with dendritic ligands, part II

The dendritic triazole-based complexes \[Fe(G1-BOC)3](triflate) 2·xH2O (1; G1-BOC = tert-butyl {3-\[3-(3-tert- butoxycarbonylaminopropyl)-5-(\[1,2,4]triazol-4-ylcarbamoyl)-phenyl]propyl} carbamate, triflate = CF3SO3-), \[Fe(G1-BOC) 3]-(tosylate)2·xH2O(2;tosylate = p-CH3PhSO3-),\[Fe(G1-DPBE)3]-(triflate) 2·xH2O {3; G1-DPBE = 3,5-bis(3,5- didodecaoxybenzyloxy)-N-\[1,2,4]triazol-4-ylbenzamide}, \[Fe(G1-DPBE) 3]-(tosylate)2·xH2O (4) and \[Fe(G1-DPBE)3](BF4)2·xH2O (5) were designed and synthesized. Magnetic and thermal properties of these novel complexes were characterized by magnetic susceptibility measurements, 57Fe Mössbauer spectroscopy and thermogravimetric analysis or differential scanning calorimetry, respectively. All dendritic complexes under study show different spin-transition behaviour with respect to the nature of different dendritic ligands and counteranions. Complexes 1 and 2 have pronounced effects of a spin-state change during the first heating process and gradual spintransition properties for further temperature treatments, whereas 3 and 4 exhibited a very sharp spin-state change in the first heating procedures. Complex 5 showed a gradual spin-transition curve. In this paper, we report how the magnetic properties of these complexes are correlated with noncoordinated water molecules and their effects on spin states.

Improving the transparency, openness and efficiency of e-government in Qatar in the era of Open Government Data, and beyond

This thesis investigates how Open Government Data (OGD) concepts and practices might be implemented in the State of Qatar to achieve more transparent, effective and accountable government. The thesis concludes with recommendations as to how Qatar, as a developing country, might enhance the accessibility and usability of its OGD and implement successful and sustainable OGD systems and practices.

Spin polarized DFT calculations of metal borides

The metal borides, in particular the diborides and hexaborides, contain stoichiometric forms that include insulators, semiconductors and superconductors. In addition, their end-member structures have high symmetry and two atoms although, in general, substitution(s) of multi-valent ions into the metal site occurs consistent with Vegard’s law. These characteristics allow for fundamental comparison of important physical properties such as superconductivity and insulation within a relatively simple structure type. Our early work1,2 has demonstrated this for the hexaborides and this work compares similar attributes across a broader suite of boride structures. In all cases, theoretical calculations are referenced to structures determined via high resolution neutron or X-ray diffraction experiments.

DIY media architecture: Open and participatory approaches to community engagement

Media architecture’s combination of the digital and the physical can trigger, enhance, and amplify urban experiences. In this paper, we examine how to bring about and foster more open and participatory approaches to engage communities through media architecture by identifying novel ways to put some of the creative process into the hands of laypeople. We review technical, spatial, and social aspects of DIY phenomena with a view to better understand maker cultures, communities, and practices. We synthesise our findings and ask if and how media architects as a community of practice can encourage the ‘open-sourcing’ of information and tools allowing laypeople to not only participate but become active instigators of change in their own right. We argue that enabling true DIY practices in media architecture may increase citizen control. Seeking design strategies that foster DIY approaches, we propose five areas for further work and investigation. The paper begs many questions indicating ample room for further research into DIY Media Architecture.

Adaptive estimation of hidden semi-Markov chains with parameterised transition probabilities and exponential decaying states

This paper develops maximum likelihood (ML) estimation schemes for finite-state semi-Markov chains in white Gaussian noise. We assume that the semi-Markov chain is characterised by transition probabilities of known parametric from with unknown parameters. We reformulate this hidden semi-Markov model (HSM) problem in the scalar case as a two-vector homogeneous hidden Markov model (HMM) problem in which the state consist of the signal augmented by the time to last transition. With this reformulation we apply the expectation Maximumisation (EM ) algorithm to obtain ML estimates of the transition probabilities parameters, Markov state levels and noise variance. To demonstrate our proposed schemes, motivated by neuro-biological applications, we use a damped sinusoidal parameterised function for the transition probabilities.

Regulating supply chains to improve health and safety

The fragmentation of previously integrated systems of production and service delivery has been an important feature of organisational restructuring over the last three decades. This article highlights the adverse implications of this development for the health and safety of workers, examines the extent to which current British health and safety law provides an adequate framework for addressing these outcomes and explores whether its capacity to do so could be enhanced through the introduction of new statutory provisions on the regulation of supply chains. It concludes that, in terms of both structure and operation, the present framework of law is problematic. It further argues that recent international initiatives show that it is feasible to develop such statutory provisions and that existing evidence suggests that provisions of this type could usefully be introduced in respect of a number of areas of activity where the implications of the externalisation of production and service delivery seem particularly problematic.

Regulating supply-chains to address the occupational health and safety problems associated with precarious employment: The case of home-based clothing workers in Australia

Over the past 20 years the labour market, workforce and work organisation of most if not all industrialised countries have been significantly refashioned by the increased use of more flexible work arrangements, variously labelled as precarious employment or contingent work. There is now a substantial and growing body of international evidence that many of these arrangements are associated with a significant deterioration in occupational health and safety (OHS), using a range of measures such as injury rates, disease, hazard exposures and work-related stress. Moreover, there is an emerging body of evidence that these arrangements pose particular problems for conventional regulatory regimes. Recognition of these problems has aroused the concern of policy makers - especially in Europe, North America and Australia - and a number of responses have been adopted in terms of modifying legislation, producing new guidance material and codes of practice and revised enforcement practices. This article describes one such in itiative in Australia with regard to home-based clothing workers. The regulatory strategy developed in one Australian jurisdiction (and now being ‘exported’ into others) seeks to counter this process via contractual tracking mechanisms to follow the work, tie in liability and shift overarching legal responsibility to the top of the supply chain. The process also entails the integration of minimum standards relating to wages, hours and working conditions; OHS and access to workers’ compensation. While home-based clothing manufacture represents a very old type of ‘flexible’ work arrangement, it is one that regulators have found especially difficult to address. Further, the elaborate multi-tiered subcont racting and diffuse work locations found in this industry are also characteristic of newer forms of contingent work in other industries (such as some telework) and the regulatory challenges they pose (such as the tendency of elaborate supply chains to attenuate and fracture statutory responsibilities, at least in terms of the attitudes and behaviour of those involved).

An exploration of NGO and media efforts to influence workplace practices and associated accountability within global supply chains

This paper investigates how social and environmental non-government organisations (NGOs) use the news media in an endeavour to create changes in the social performance and associated accountabilities of multinational buying companies’ (MBCs’) supply chains located in the developing country of Bangladesh. In this research, we explicitly seek the views of senior officers from global and local NGOs operating in Bangladesh, as well as the views of journalists from major global and local news media organisations. Our results show that social and environmental NGOs strategically use the news media in an effort to effect changes in corporate labour practices and related disclosure practices. More particularly, both the NGOs and the news media representatives stated that NGOs would be relatively powerless to create change in corporate without media coverage. This is the first known study to specifically address the joint and complementary role of NGOs and the news media in potentially creating changes in the social and environmental operating and disclosure practices of supply chains emanating from a developing country.

Implementation and evaluation of open source unified communications for SMBs

Unified Communication (UC) is the integration of two or more real time communication systems into one platform. Integrating core communication systems into one overall enterprise level system delivers more than just cost saving. These real-time interactive communication services and applications over Internet Protocol (IP) have become critical in boosting employee accessibility and efficiency, improving customer support and fostering business agility. However, some small and medium-sized businesses (SMBs) are far from implementing this solution due to the high cost of initial deployment and ongoing support. In this paper, we will discuss and demonstrate an open source UC solution, viz. “Asterisk” for use by SMBs, and report on some performance tests using SIPp. The contribution from this research is the provision of technical advice to SMBs in deploying UC, which is manageable in terms of cost, ease of deployment and support.

Integrated approach to optimize open-pit mine block sequencing

Critical stage in open-pit mining is to determine the optimal extraction sequence of blocks, which has significant impacts on mining profitability. In this paper, a more comprehensive block sequencing optimisation model is developed for the open-pit mines. In the model, material characteristics of blocks, grade control, excavator and block sequencing are investigated and integrated to maximise the short-term benefit of mining. Several case studies are modeled and solved by CPLEX MIP and CP engines. Numerical investigations are presented to illustrate and validate the proposed methodology.

A non-fullerene electron acceptor based on fluorene and diketopyrrolopyrrole building blocks for solution-processable organic solar cells with an impressive open-circuit voltage

A novel solution-processable non-fullerene electron acceptor 6,6′-(5,5′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DPP1) based on fluorene and diketopyrrolopyrrole conjugated moieties was designed, synthesized and fully characterized. DPP1 exhibited excellent solubility and high thermal stability which are essential for easy processing. Upon using DPP1 as an acceptor with the classical electron donor poly(3-hexylthiophene), solution processable bulk-heterojunction solar cells afforded a power conversion efficiency of 1.2% with a high open-circuit voltage (1.1 V). As per our knowledge, this value of open circuit voltage is one of the highest values reported so far for a bulk-heterojunction device using DPP1 as a non-fullerene acceptor.

Resolving the conflicts of sustainable world heritage landscapes in cities : fully open or limited access for visitors?

World Heritage Landscapes (WHLs) are receiving increased attention from researchers, urban planners, managers, and policy makers and many heritage values and resources are becoming irreversibly lost. This phenomenon is especially prominent for WHLs located in cities, where greater development opportunities are involved. Decision making for sustainable urban landscape planning, conservation and management of WHLs often takes place from an economic perspective, especially in developing countries. This, together with the uncertain source of funding to cover WHL operating and maintenance costs, has resulted in many urban managers seeking private sector funding either in the form of visitor access fees or leasing part of the site for high-rental facilities such as five star hotels, clubs and expensive restaurants. For the former, this can result in low-income urban citizens being unable to afford the access fees and hence contradicting the principle of equal access for all; while, for the latter, the principle of open access for all is equally violated. To resolve this conflict, a game model is developed to determine how urban managers should allocate WHL spaces to maximize the combination of economic, social and ecological benefits and cultural values. A case study is provided of the Hangzhou's West Lake Scenic Area, a WHL located at the centre of Hangzhou city, in which several high-rental facilities have recently been closed down by the local authorities due to charges of elitism and misuse of public funds by government officials. The result shows that the best solution is to lease a small space with high rents and leave the remainder of the site to the public. This solution is likely to be applicable only in cities with a strong economy.