Hydrogen bonding in the anhydrous 1:1 proton-transfer compounds of isonipecotamide with nitro-substituted benzoic acids: the salts of the three isomeric mononitrobenzoic acids and of 3,5-dinitrobenzoic acid

The structures of the anhydrous 1:1 proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with the three isomeric mononitro-substituted benzoic acids and 3,5-dinitrobenzoic acid, namely 4-carbamoylpiperidinium 2-nitrobenzoate (I), 4-carbamoylpiperidinium 3-nitrobenzoate (II), 4-carbamoylpiperidinium 4-nitrobenzoate (III), (C6H13N2O+ C7H4NO4-) and 4-carbamoylpiperidinium 3,5-dinitrobenzoate (IV) (C6H13N2O+ C7H5N2O6-)respectively, have been determined at 200 K. All salts form hydrogen-bonded structures: three-dimensional in (I), two-dimensional in (II) and (III) and one-dimensional in (IV). Featured in the hydrogen bonding of three of these [(I), (II) and (IV)] is the cyclic head-to-head amide--amide homodimer motif [graph set R2/2~(8)] through a duplex N---H...O association, the dimer then giving structure extension via either piperidinium or amide H-donors and carboxylate-O and in some examples [(II) and (IV)], nitro-O atom acceptors. In (I), the centrosymmetric amide-amide homodimers are expanded laterally through N-H...O hydrogen bonds via cyclic R2/4(8) interactions forming ribbons which extend along the c cell direction. These ribbons incorporate the 2-nitrobenzoate cations through centrosymmetric cyclic piperidine N-H...O(carboxyl) associations [graph set R4/4(12)], giving inter-connected sheets in the three-dimensional structure. In (II) in which no amide-amide homodimer is present, duplex piperidinium N-H...O(amide) hydrogen-bonding homomolecular associations [graph set R2/2(14)] give centrosymmetric head-to-tail dimers. Structure extension occurs through hydrogen-bonding associations between both the amide H-donors and carboxyl and nitro O-acceptors as well as a three-centre piperidinium N-H...O,O'(carboxyl) cyclic R2/1(4) association giving the two-dimensional network structure. In (III), the centrosymmetric amide-amide dimers are linked through the two carboxyl O-atom acceptors of the anions via bridging piperidinium and amide N-H...O,O'...H-N(amide) hydrogen bonds giving the two-dimensional sheet structure which features centrosymmetric cyclic R4/4(12) associations. In (IV), the amide-amide dimer is also centrosymmetric with the dimers linked to the anions through amide N-H...O(nitro) interactions. The piperidinium groups extend the structure into one-dimensional ribbons via N-H...O(carboxyl) hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation in molecular assembly and highlight the efficacy of the cyclic R2/2(8) amide-amide hydrogen-bonding homodimer motif in this process and provide an additional homodimer motif type in the head-to-tail R2/2(14) association.

Standards-driven reform years 1-10 : moderation an optional extra?

While externally moderated standards-based assessment has been practised in Queensland senior schooling for more than three decades, there has been no such practice in the middle years. With the introduction of standards at state and national levels in these years, teacher judgement as developed in moderation practices is now vital. This paper argues, that in this context of assessment reform, standards intended to inform teacher judgement and to build assessment capacity are necessary but not sufficient for maintaining teacher and public confidence in schooling. Teacher judgement is intrinsic to moderation, and to professional practice, and can no longer remain private. Moderation too is intrinsic to efforts by the profession to realise judgements that are defensible, dependable and open to scrutiny. Moderation can no longer be considered an optional extra and requires system-level support especially if, as intended, the standards are linked to system-wide efforts to improve student learning. In presenting this argument we draw on an Australian Research Council funded study with key industry partners (the Queensland Studies Authority and the National Council for Curriculum and Assessment of the Republic of Ireland). The data analysed included teacher interview data and additional teacher talk during moderation sessions. These were undertaken during the initial phase of policy development. The analysis identified those issues that emerge in moderation meetings that are designed to reach consistent, reliable judgements. Of interest are the different ways in which teachers talked through and interacted with one another to reach agreement about the quality of student work in the application of standards. There is evidence of differences in the way that teachers made compensations and trade-offs in their award of grades, dependent on the subject domain in which they teach. This article concludes with some empirically derived insights into moderation practices as policy and social events.

Deliberation and journalism

The first chapter in 'International Journalism and Democracy' re-examines current ideas about the role of journalism in promoting democracy, introducing the concept of "deliberative journalism". 'Deliberation and Journalism' lists the ways in which journalists can assist deliberation and politics in communities around the world. The chapter defines deliberation as a specific form of conversation that precedes and promotes decision-making and action by members of a community. The author recognises the difficulty of engaging in deliberation in communities that are divided by different interests, identities, backgrounds, resources and needs. She provides examples of strategies that journalists can use to encourage inclusive and productive deliberation in the face of community diversity. The chapter introduces examples of types of deliberative journalism that have emerged around the globe. These include strategies that have been sometimes been labeled as public journalism, civic journalism, peace journalism, development journalism, citizen journalism, the street press, community journalism, environmental journalism, and social entrepreneurism. The chapter also includes models of journalism that have not yet been given any particular name. Although the book identifies problems surrounding the theory and practice of these forms of journalism, the author notes that this is to be expected. Most models of deliberative journalism are relatively new, with none being more than a few decades old. The author concludes that resolution of these problems will only occur incrementally.

Listening to voices of self : digital journaling among gifted young adolescents

The lives of gifted young adolescents are often subject to adult-generated and expert narratives that can impact a developing sense of self. However, opportunities for gifted young adolescents to represent themselves as informants can emerge through digital forms of qualitative research. This paper reports on the value of digital writing of journal entries, delivered by email to a researcher over several months, as an alternative to face-to-face interviews. Journaling methods combined with techniques of 'listening for voices' can support young adolescents in generating their own multi-vocal narratives of self. This method capturing self-narratives in email form has the potential to produce rich understandings of individual young adolescents' self-constructions.

Civic engagement and associationalism : the impact of group membership scope versus intensity of participation

The relationship between participation in civic and political activities and membership of voluntary associations is now well established. What is less clear is the relative impacts of how much time people spend on group activities (associational intensity), and the number and type of groups that individuals are involved with (associational scope). Does it matter in terms of civic engagement, for example, whether one is a member of a quilting-circle or trade union? Does it matter whether association ‘membership’ is simply an annual payment or a major commitment of time and energy? In this article, we use a large survey to explore these questions empirically by focusing on the membership patterns and civic engagement practices of 4,001 citizens drawn from eight suburbs across Greater Melbourne, Australia. Our findings indicate that, while associational intensity is positively related to civic engagement, associational scope (the number of group memberships per person), is a more influential determinant of the level of civic and political participation. The results also suggest that while all forms of associationalism are important in terms of fostering greater levels of civic activity, not all forms have the same impact.

Organometallic macrocyclic chemistry. 8.(1) : an unusual metallacycle derived from phosphine−alkynyl thioether coupling

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.

Governing depression in law students and the shaping of legal personae

Since a recent Australian study found that university law students experience higher rates of depression than medical students and legal professionals (Kelk et al. 2009), the mental health of law students has increasingly become a target of government. To date, however, there has been no attempt to analyse these practices as an activity of government in advanced liberal societies. This paper addresses this imbalance by providing an initial analytics of the government of depression in law schools. It demonstrates how students are responsibilised to manage the risks and uncertainties of legal education by constructing resilient forms of personal and professional personae. It highlights that, in order to avoid depression, students are encouraged to shape not just their minds and bodies according to psychological and biomedical discourses, but are also to govern their ethical dispositions and become virtuous persons. This paper also argues that these forms of government are tied to advanced liberal forms of rule, as they position the law student as the locus of responsibility for depression, imply that depression is caused by an individual failing, and entrench students within responsibilising and entrepreneurial forms of subjectivity.

Sustainable urban infrastructure management : integration of urban computer modelling

Purpose - This paper seeks to examine the complex relationships between urban planning, infrastructure management, sustainable urban development, and to illustrate why there is an urgent need for local governments to develop a robust planning support system which integrates with advance urban computer modelling tools to facilitate better infrastructure management and improve knowledge sharing between the community, urban planners, engineers and decision makers. Design/methodology/approach - The methods used in this paper includes literature review and practical project case observations. Originality/value - This paper provides an insight of how the Brisbane's planning support system established by Brisbane City Council has significantly improved the effectiveness of urban planning, infrastructure management and community engagement through better knowledge management processes. Practical implications - This paper presents a practical framework for setting up a functional planning support system within local government. The integration of the Brisbane Urban Growth model, Virtual Brisbane and the Brisbane Economic Activity Monitoring (BEAM) database have proven initially successful to provide a dynamic platform to assist elected officials, planners and engineers to understand the limitations of the local environment, its urban systems and the planning implications on a city. With the Brisbane's planning support system, planners and decision makers are able to provide better planning outcomes, policy and infrastructure that adequately address the local needs and achieve sustainable spatial forms.

Dynamics of pattern writing and erasure in photorefractive lithium niobate for data storage applications

The present rate of technological advance continues to place significant demands on data storage devices. The sheer amount of digital data being generated each year along with consumer expectations, fuels these demands. At present, most digital data is stored magnetically, in the form of hard disk drives or on magnetic tape. The increase in areal density (AD) of magnetic hard disk drives over the past 50 years has been of the order of 100 million times, and current devices are storing data at ADs of the order of hundreds of gigabits per square inch. However, it has been known for some time that the progress in this form of data storage is approaching fundamental limits. The main limitation relates to the lower size limit that an individual bit can have for stable storage. Various techniques for overcoming these fundamental limits are currently the focus of considerable research effort. Most attempt to improve current data storage methods, or modify these slightly for higher density storage. Alternatively, three dimensional optical data storage is a promising field for the information storage needs of the future, offering very high density, high speed memory. There are two ways in which data may be recorded in a three dimensional optical medium; either bit-by-bit (similar in principle to an optical disc medium such as CD or DVD) or by using pages of bit data. Bit-by-bit techniques for three dimensional storage offer high density but are inherently slow due to the serial nature of data access. Page-based techniques, where a two-dimensional page of data bits is written in one write operation, can offer significantly higher data rates, due to their parallel nature. Holographic Data Storage (HDS) is one such page-oriented optical memory technique. This field of research has been active for several decades, but with few commercial products presently available. Another page-oriented optical memory technique involves recording pages of data as phase masks in a photorefractive medium. A photorefractive material is one by which the refractive index can be modified by light of the appropriate wavelength and intensity, and this property can be used to store information in these materials. In phase mask storage, two dimensional pages of data are recorded into a photorefractive crystal, as refractive index changes in the medium. A low-intensity readout beam propagating through the medium will have its intensity profile modified by these refractive index changes and a CCD camera can be used to monitor the readout beam, and thus read the stored data. The main aim of this research was to investigate data storage using phase masks in the photorefractive crystal, lithium niobate (LiNbO3). Firstly the experimental methods for storing the two dimensional pages of data (a set of vertical stripes of varying lengths) in the medium are presented. The laser beam used for writing, whose intensity profile is modified by an amplitudemask which contains a pattern of the information to be stored, illuminates the lithium niobate crystal and the photorefractive effect causes the patterns to be stored as refractive index changes in the medium. These patterns are read out non-destructively using a low intensity probe beam and a CCD camera. A common complication of information storage in photorefractive crystals is the issue of destructive readout. This is a problem particularly for holographic data storage, where the readout beam should be at the same wavelength as the beam used for writing. Since the charge carriers in the medium are still sensitive to the read light field, the readout beam erases the stored information. A method to avoid this is by using thermal fixing. Here the photorefractive medium is heated to temperatures above 150�C; this process forms an ionic grating in the medium. This ionic grating is insensitive to the readout beam and therefore the information is not erased during readout. A non-contact method for determining temperature change in a lithium niobate crystal is presented in this thesis. The temperature-dependent birefringent properties of the medium cause intensity oscillations to be observed for a beam propagating through the medium during a change in temperature. It is shown that each oscillation corresponds to a particular temperature change, and by counting the number of oscillations observed, the temperature change of the medium can be deduced. The presented technique for measuring temperature change could easily be applied to a situation where thermal fixing of data in a photorefractive medium is required. Furthermore, by using an expanded beam and monitoring the intensity oscillations over a wide region, it is shown that the temperature in various locations of the crystal can be monitored simultaneously. This technique could be used to deduce temperature gradients in the medium. It is shown that the three dimensional nature of the recording medium causes interesting degradation effects to occur when the patterns are written for a longer-than-optimal time. This degradation results in the splitting of the vertical stripes in the data pattern, and for long writing exposure times this process can result in the complete deterioration of the information in the medium. It is shown in that simply by using incoherent illumination, the original pattern can be recovered from the degraded state. The reason for the recovery is that the refractive index changes causing the degradation are of a smaller magnitude since they are induced by the write field components scattered from the written structures. During incoherent erasure, the lower magnitude refractive index changes are neutralised first, allowing the original pattern to be recovered. The degradation process is shown to be reversed during the recovery process, and a simple relationship is found relating the time at which particular features appear during degradation and recovery. A further outcome of this work is that the minimum stripe width of 30 ìm is required for accurate storage and recovery of the information in the medium, any size smaller than this results in incomplete recovery. The degradation and recovery process could be applied to an application in image scrambling or cryptography for optical information storage. A two dimensional numerical model based on the finite-difference beam propagation method (FD-BPM) is presented and used to gain insight into the pattern storage process. The model shows that the degradation of the patterns is due to the complicated path taken by the write beam as it propagates through the crystal, and in particular the scattering of this beam from the induced refractive index structures in the medium. The model indicates that the highest quality pattern storage would be achieved with a thin 0.5 mm medium; however this type of medium would also remove the degradation property of the patterns and the subsequent recovery process. To overcome the simplistic treatment of the refractive index change in the FD-BPM model, a fully three dimensional photorefractive model developed by Devaux is presented. This model shows significant insight into the pattern storage, particularly for the degradation and recovery process, and confirms the theory that the recovery of the degraded patterns is possible since the refractive index changes responsible for the degradation are of a smaller magnitude. Finally, detailed analysis of the pattern formation and degradation dynamics for periodic patterns of various periodicities is presented. It is shown that stripe widths in the write beam of greater than 150 ìm result in the formation of different types of refractive index changes, compared with the stripes of smaller widths. As a result, it is shown that the pattern storage method discussed in this thesis has an upper feature size limit of 150 ìm, for accurate and reliable pattern storage.

Powered two wheelers in a changing world : challenges and opportunities

Powered two wheelers (PTWs) come in diverse forms and are used for a range of purposes in very different parts of the world. In many parts of the world, the forms and uses of PTWs are changing, influenced by social, economic and demographic changes. Most of the challenges associated with PTWs relate to safety, while the majority of the opportunities relate to mobility. The challenges for improving safety relate to the PTW user, other road users, the road environment, the vehicle, data and research, and socio-political dimensions. The relative importance of particular challenges varies between developed and developing countries, and among developing countries according to whether PTWs are largely used for recreation or for transport. PTWs present a range of psychological, transport, economic and environmental opportunities to individuals and societies. The fun and excitement of riding PTWs is a major motivator for their purchase and use for recreational purposes, both off-road and on-road. The transport and economic advantages to the individual also need to be considered. At a societal level, research has examined the potential for increasing PTW volumes to reduce fossil fuel use and traffic congestion in busy cities. The future of PTWs may differ greatly between countries and environmental and technological changes are leading to an evolution in the form of PTWs to encompass new modes of personal transportation.

From reader to writer : citizen journalism as news produsage

Today, participatory or citizen journalism – journalism which enables readers to become writers – exists online and offline in a variety of forms and formats, operates under a number of editorial schemes, and focusses on a wide range of topics from the specialist to the generic, and the micro-local to the global. Key models in this phenomenon include veteran sites Slashdot and Indymedia, as well as news-related Weblogs; more recent additions into the mix have been the South Korean OhmyNews, which in 2003 was “the most influential online news site in that country, attracting an estimated 2 million readers a day” (Gillmor, 2003a, p. 7), with its new Japanese and international offshoots, as well as the Wikipedia with its highly up-to-date news and current events section and its more recent offshoot Wikinews, and even citizen-produced video news as it is found in sites such as YouTube and Current.tv.