Vibrational spectroscopic studies of wool

Fourier transfonn (FT) Raman, Raman microspectroscopy and Fourier transform infrared (FTIR) spectroscopy have been used for the structural analysis and characterisation of untreated and chemically treated wool fibres. For FT -Raman spectroscopy novel methods of sample presentation have been developed and optimised for the analysis of wool. No significant fluorescence was observed and the spectra could be obtained routinely. The stability of wool keratin to the laser source was investigated and the visual and spectroscopic signs of sample damage were established. Wool keratin was found to be extremely robust with no signs of sample degradation observed for laser powers of up to 600 m W and for exposure times of up to seven and half hours. Due to improvements in band resolution and signal-to-noise ratio, several previously unobserved spectral features have become apparent. The assignment of the Raman active vibrational modes of wool have been reviewed and updated to include these features. The infrared spectroscopic techniques of attenuated total reflectance (ATR) and photoacoustic (P A) have been used to examine shrinkproofed and mothproofed wool samples. Shrinkproofing is an oxidative chemical treatment used to selectively modifY the surface of a wool fibre. Mothproofing is a chemical treatment applied to wool for the prevention of insect attack. The ability of PAS and A TR to vary the penetration depth by varying certain instrumental parameters was used to obtain spectra of the near surface regions of these chemically treated samples. These spectra were compared with those taken with a greater penetration depth, which therefore represent more of the bulk wool sample. The PA and ATR spectra demonstrated that oxidation was restricted to the near-surface layer of wool. Extensive curve fitting of ATR spectra of untreated wool indicated that cuticle was composed of a mixed protein conformation, but was predominately that of an a.-helix. The cortex was proposed to be a mixture of both a.helical and ~-pleated sheet protein conformations. These findings were supported by PAS depth profiling results. Raman microspectroscopy was used in an extensive investigation of the molecular structure of the wool fibre. This included determining the orientation of certain functional groups within the wool fibre and the symmetry of particular vibrations. The orientation ofbonds within the wool fibre was investigated by orientating the wool fibre axis parallel and then perpendicular to the plane of polarisation of the electric vector of the incident radiation. It was experimentally determined that the majority of C=O and N-H bonds of the peptide bond of wool lie parallel to the fibre axis. Additionally, a number of the important vibrations associated with the a-helix were also found to lie parallel to the fibre axis. Further investigation into the molecular structure of wool involved determining what effect stretching the wool fibre had on bond orientation. Raman spectra of stretched and unstretched wool fibres indicated that extension altered the orientation ofthe aromatic rings, the CH2 and CH3 groups of the amino acids. Curve fitting results revealed that extension resulted in significant destruction of the a-helix structure a substantial increase in the P-pleated sheet structure. Finally, depolarisation ratios were calculated for Raman spectra. The vibrations associated with the aromatic rings of amino acids had very low ratios which indicated that the vibrations were highly symmetrical.

4-Carbamoylpiperidinium phenylacetate hemihydrate

In the structure of the title compound, C6H13N2O+ C8H7O2- . 0.5H2O, the asymmetric unit comprises two isonipecotamide cations, two phenylacetate anions and a water molecule of solvation. The hydrogen-bonding environments for both sets of ion pairs are essentially identical with the piperidinium and amide 'ends' of each cation involved in lateral heteromolecular hydrogen-bonded cyclic N---H...O associations [graph set R2/2(11)] which incorporate a single carboxyl O-atom acceptor. These cyclic motifs enclose larger R5/5(21) cyclic systems forming sheet substructures which lie parallel to (101) and are linked across b by the single water molecule via water O---H...O(carboxyl) associations to give a two-dimensional duplex-sheet structure

rac-Ammonium cis-2-carboxycyclohexane-1-carboxylate

In the structure of the title compound, cis NH4+ C8H11O4-, the carboxylic acid and carboxyl groups of the cation adopt C-C-C-O torsion angles of 174.9(2) and -145.4(2)deg. respecticely with the alicyclic ring. The ammonium H atoms of the cations give a total of five hydrogen-bonding associations with carboxyl O-atom acceptors of the anion which, together with a carboxylic acid O-H...O(carboxyl) interaction give two-dimensional sheet structures which lie in the (101) planes in the unit cell.

Order and disorder in the structures of two crystal polymorphs of the adduct bis(quinolinium-2-carboxylate) DL-malic acid

The structures of two polymorphs of the anhydrous cocrystal adduct of bis(quinolinium-2-carboxylate) DL-malic acid, one triclinic the other monoclinic and disordered, have been determined at 200 K. Crystals of the triclinic polymorph 1 have space group P-1, with Z = 1 in a cell with dimensions a = 4.4854(4), b = 9.8914(7), c = 12.4670(8)Å, α = 79.671(5), β = 83.094(6), γ = 88.745(6)deg. Crystals of the monoclinic polymorph 2 have space group P21/c, with Z = 2 in a cell with dimensions a = 13.3640(4), b = 4.4237(12), c = 18.4182(5)Å, β = 100.782(3)deg. Both structures comprise centrosymmetric cyclic hydrogen-bonded quinolinic acid zwitterion dimers [graph set R2/2(10)] and 50% disordered malic acid molecules which lie across crystallographic inversion centres. However, the oxygen atoms of the malic acid carboxylic groups in 2 are 50% rotationally disordered whereas in 1 these are ordered. There are similar primary malic acid carboxyl O-H...quinaldic acid hydrogen-bonding chain interactions in each polymorph, extended into two-dimensional structures but in l this involves centrosymmetric cyclic head-to-head malic acid hydroxyl-carboxyl O-H...O interactions [graph set R2/2(10)] whereas in 2 the links are through single hydroxy-carboxyl hydrogen bonds.

Teenager loner in a chat room tangled up in guile and guilability : a review

ADAM Cass's I Love You, Bro is an engaging portrayal of just how far some young people can go in constructing fantasy worlds online. The play is, according to Cass, based on the case of two teenage boys in Britain in the early 2000s. Troubled teen Johnny lives at home with his mother and her new partner. Lurking in an online chat room one day, he strikes up a conversation with MarkyMark, a slightly older soccer-playing boy from the popular crowd in his own local town, who mistakes him for a girl. The plot unfolds from this one moment of mistaken identity. Johnny concocts an increasingly tenuous series of characters, plot twists and intrigues to try to maintain his relationship with MarkyMark and deal with the lie at the heart of his first love, eventually conspiring - as he tells us from the first moment - to cause his own murder.

New stress and velocity fields for highly frictional granular materials

The idealised theory for the quasi-static flow of granular materials which satisfy the Coulomb-Mohr hypothesis is considered. This theory arises in the limit that the angle of internal friction approaches $\pi/2$, and accordingly these materials may be referred to as being `highly frictional'. In this limit, the stress field for both two-dimensional and axially symmetric flows may be formulated in terms of a single nonlinear second order partial differential equation for the stress angle. To obtain an accompanying velocity field, a flow rule must be employed. Assuming the non-dilatant double-shearing flow rule, a further partial differential equation may be derived in each case, this time for the streamfunction. Using Lie symmetry methods, a complete set of group-invariant solutions is derived for both systems, and through this process new exact solutions are constructed. Only a limited number of exact solutions for gravity driven granular flows are known, so these results are potentially important in many practical applications. The problem of mass flow through a two-dimensional wedge hopper is examined as an illustration.

Environmental management and wildlife in Queensland : a review of Queensland mammal species designated as scarce

From 19 authoritative lists with 164 entries of ‘endangered’ Australian mammal species, 39 species have been reported as extinct. When examined in the light of field conditions, the 18 of these species thought to be from Queensland consist of (a) species described from fragmentary museum material collected in the earliest days of exploration, (b) populations inferred to exist in Queensland by extrapolation from distribution records in neighbouring States or countries, (c) inhabitants of remote and harsh locations where search effort is extraordinarily difficult (especially in circumstances of drought or flooding). and/or (d) individuals that are clearly transitory or peripheral in distribution. ‘Rediscovery’ of such scarce species - a not infrequent occurrence - is nowadays attracting increasing attention. Management in respect of any scarce wildlife in Queensland presently derives from such official lists. The analyses here indicate that this method of prioritizing action needs review. This is especially so because action then tends to be centred on species chosen out of the lists for populist reasons and that mostly addresses Crown lands. There is reason to believe that the preferred management may lie private lands where casual observation has provided for rediscovery and where management is most desirable and practicable.

Student engagement with an ePortfolio : a case study of pre-service education students

The emergence of ePortfolios is relatively recent in the university sector as a way to engage students in their learning and assessment, and to produce records of their accomplishments. An ePortfolio is an online tool that students can utilise to record, catalogue, retrieve and present reflections and artefacts that support and demonstrate the development of graduate students’ capabilities and professional standards across university courses. The ePortfolio is therefore considered as both process and product. Although ePortfolios show promise as a useful tool and their uptake has grown, they are not yet a mainstream higher education technology. To date, the emphasis has been on investigating their potential to support the multiple purposes of learning, assessment and employability, but less is known about whether and how students engage with ePortfolios in the university setting. This thesis investigates student engagement with an ePortfolio in one university. As the educational designer for the ePortfolio project at the University, I was uniquely positioned as a researching professional to undertake an inquiry into whether students were engaging with the ePortfolio. The participants in this study were a cohort (defined by enrolment in a unit of study) of second and third year education students (n=105) enrolled in a four year Bachelor of Education degree. The students were introduced to the ePortfolio in an introductory lecture and a hands-on workshop in a computer laboratory. They were subsequently required to complete a compulsory assessment task – a critical reflection - using the ePortfolio. Following that, engagement with the ePortfolio was voluntary. A single case study approach arising from an interpretivist paradigm directed the methodological approach and research design for this study. The study investigated the participants’ own accounts of their experiences with the ePortfolio, including how and when they engaged with the ePortfolio and the factors that impacted on their engagement. Data collection methods consisted of an attitude survey, student interviews, document collection, a researcher reflective journal and researcher observations. The findings of the study show that, while the students were encouraged to use the ePortfolio as a learning and employability tool, most students ultimately chose to disengage after completing the assessment task. Only six of the forty-five students (13%) who completed the research survey had used the ePortfolio in a sustained manner. The data obtained from the students during this research has provided insight into reasons why they disengaged from the ePortfolio. The findings add to the understandings and descriptions of student engagement with technology, and more broadly, advance the understanding of ePortfolios. These findings also contribute to the interdisciplinary field of technology implementation. There are three key outcomes from this study, a model of student engagement with technology, a set of criteria for the design of an ePortfolio, and a set of recommendations for effective practice for those implementing ePortfolios. The first, the Model of Student Engagement with Technology (MSET) (Version 2) explored student engagement with technology by highlighting key engagement decision points for students The model was initially conceptualised by building on work of previous research (Version 1), however, following data analysis a new model emerged, MSET (Version 2). The engagement decision points were identified as: • Prior Knowledge and Experience, leading to imagined usefulness and imagined ease of use; • Initial Supported Engagement, leading to supported experience of usefulness and supported ease of use; • Initial Independent Engagement, leading to actual experience of independent usefulness and actual ease of use; and • Ongoing Independent Engagement, leading to ongoing experience of usefulness and ongoing ease of use. The Model of Student Engagement with Technology (MSET) goes beyond numerical figures of usage to demonstrate student engagement with an ePortfolio. The explanatory power of the model is based on the identification of the types of decisions that students make and when they make them during the engagement process. This model presents a greater depth of understanding student engagement than was previously available and has implications for the direction and timing of future implementation, and academic and student development activities. The second key outcome from this study is a set of criteria for the re-conceptualisation of the University ePortfolio. The knowledge gained from this research has resulted in a new set of design criteria that focus on the student actions of writing reflections and adding artefacts. The process of using the ePortfolio is reconceptualised in terms of privileging student learning over administrative compliance. The focus of the ePortfolio is that the writing of critical reflections is the key function, not the selection of capabilities. The third key outcome from this research consists of five recommendations for university practice that have arisen from this study. They are that, sustainable implementation is more often achieved through small steps building on one another; that a clear definition of the purpose of an ePortfolio is crucial for students and staff; that ePortfolio pedagogy should be the driving force not the technology; that the merit of the ePortfolio is fostered in students and staff; and finally, that supporting delayed task performance is crucial. Students do not adopt an ePortfolio just because it is provided. While students must accept responsibility for their own engagement with the ePortfolio, the institution has to accept responsibility for providing the environment, and technical and pedagogical support to foster engagement. Ultimately, an ePortfolio should be considered as a joint venture between student and institution where strong returns on investment can be realised by both. It is acknowledged that the current implementation strategies for the ePortfolio are just the beginning of a much longer process. The real rewards for students, academics and the university lie in the future.

Microscopic modelling of freeway operations

Freeways are divided roadways designed to facilitate the uninterrupted movement of motor vehicles. However, many freeways now experience demand flows in excess of capacity, leading to recurrent congestion. The Highway Capacity Manual (TRB, 1994) uses empirical macroscopic relationships between speed, flow and density to quantify freeway operations and performance. Capacity may be predicted as the maximum uncongested flow achievable. Although they are effective tools for design and analysis, macroscopic models lack an understanding of the nature of processes taking place in the system. Szwed and Smith (1972, 1974) and Makigami and Matsuo (1990) have shown that microscopic modelling is also applicable to freeway operations. Such models facilitate an understanding of the processes whilst providing for the assessment of performance, through measures of capacity and delay. However, these models are limited to only a few circumstances. The aim of this study was to produce more comprehensive and practical microscopic models. These models were required to accurately portray the mechanisms of freeway operations at the specific locations under consideration. The models needed to be able to be calibrated using data acquired at these locations. The output of the models needed to be able to be validated with data acquired at these sites. Therefore, the outputs should be truly descriptive of the performance of the facility. A theoretical basis needed to underlie the form of these models, rather than empiricism, which is the case for the macroscopic models currently used. And the models needed to be adaptable to variable operating conditions, so that they may be applied, where possible, to other similar systems and facilities. It was not possible to produce a stand-alone model which is applicable to all facilities and locations, in this single study, however the scene has been set for the application of the models to a much broader range of operating conditions. Opportunities for further development of the models were identified, and procedures provided for the calibration and validation of the models to a wide range of conditions. The models developed, do however, have limitations in their applicability. Only uncongested operations were studied and represented. Driver behaviour in Brisbane was applied to the models. Different mechanisms are likely in other locations due to variability in road rules and driving cultures. Not all manoeuvres evident were modelled. Some unusual manoeuvres were considered unwarranted to model. However the models developed contain the principal processes of freeway operations, merging and lane changing. Gap acceptance theory was applied to these critical operations to assess freeway performance. Gap acceptance theory was found to be applicable to merging, however the major stream, the kerb lane traffic, exercises only a limited priority over the minor stream, the on-ramp traffic. Theory was established to account for this activity. Kerb lane drivers were also found to change to the median lane where possible, to assist coincident mergers. The net limited priority model accounts for this by predicting a reduced major stream flow rate, which excludes lane changers. Cowan's M3 model as calibrated for both streams. On-ramp and total upstream flow are required as input. Relationships between proportion of headways greater than 1 s and flow differed for on-ramps where traffic leaves signalised intersections and unsignalised intersections. Constant departure onramp metering was also modelled. Minimum follow-on times of 1 to 1.2 s were calibrated. Critical gaps were shown to lie between the minimum follow-on time, and the sum of the minimum follow-on time and the 1 s minimum headway. Limited priority capacity and other boundary relationships were established by Troutbeck (1995). The minimum average minor stream delay and corresponding proportion of drivers delayed were quantified theoretically in this study. A simulation model was constructed to predict intermediate minor and major stream delays across all minor and major stream flows. Pseudo-empirical relationships were established to predict average delays. Major stream average delays are limited to 0.5 s, insignificant compared with minor stream delay, which reach infinity at capacity. Minor stream delays were shown to be less when unsignalised intersections are located upstream of on-ramps than signalised intersections, and less still when ramp metering is installed. Smaller delays correspond to improved merge area performance. A more tangible performance measure, the distribution of distances required to merge, was established by including design speeds. This distribution can be measured to validate the model. Merging probabilities can be predicted for given taper lengths, a most useful performance measure. This model was also shown to be applicable to lane changing. Tolerable limits to merging probabilities require calibration. From these, practical capacities can be estimated. Further calibration is required of traffic inputs, critical gap and minimum follow-on time, for both merging and lane changing. A general relationship to predict proportion of drivers delayed requires development. These models can then be used to complement existing macroscopic models to assess performance, and provide further insight into the nature of operations.

Challenges in the supervisory boardroom : an exploratory study in the Netherlands

As a consequence of recent corporate governance reforms, the work of supervisory board members in the Dutch two-tier system has become more complex. The objectives of this study are to gain more insight in the current challenges that supervisory board members face and assess whether they are well-equipped to manage them. Based on a combination of an analysis of self-assessment reports, a web-based survey and semi-structured interviews, we conclude that the major challenges of supervisory board members lie in the field of interaction and collaboration with executives. Distinct ‘challenge areas’ were relatively often perceived as problematic as well as important, highlighting the need to improve the current functioning of boards. With regard to the skills that are present on supervisory boards, we find that individual qualities, like integrity, professionalism and knowledge, are better recognized than collective qualities for the supervisory board as a whole. In particular, openness and honesty are seen as important, but often lacking. The paper highlights several implications for scholars and practitioners.

Hexaaquamagnesium bis(3-carboxy-4-hydroxybenzenesulfonate) dihydrate

In the structure of the title compound, [Mg(H2O)6]2+ 2(C7H5O6S-). 2(H2O), the octahedral complex cations lie on crystallographic inversion centres and are hydrogen-bonded through the coordinated waters to the substituted benzenesulfonate monoanions and the water molecules of solvation, and together with a carboxylic acid O-H...O(sulfonate) association, give a three-dimensional structure.

Microarray expression profiling in melanoma reveals a BRAF mutation signature

We have used microarray gene expression profiling and machine learning to predict the presence of BRAF mutations in a panel of 61 melanoma cell lines. The BRAF gene was found to be mutated in 42 samples (69%) and intragenic mutations of the NRAS gene were detected in seven samples (11%). No cell line carried mutations of both genes. Using support vector machines, we have built a classifier that differentiates between melanoma cell lines based on BRAF mutation status. As few as 83 genes are able to discriminate between BRAF mutant and BRAF wild-type samples with clear separation observed using hierarchical clustering. Multidimensional scaling was used to visualize the relationship between a BRAF mutation signature and that of a generalized mitogen-activated protein kinase (MAPK) activation (either BRAF or NRAS mutation) in the context of the discriminating gene list. We observed that samples carrying NRAS mutations lie somewhere between those with or without BRAF mutations. These observations suggest that there are gene-specific mutation signals in addition to a common MAPK activation that result from the pleiotropic effects of either BRAF or NRAS on other signaling pathways, leading to measurably different transcriptional changes.

Managing the project learning paradox : a set-theoretic approach toward project knowledge transfer

Managing project-based learning is becoming an increasingly important part of project management. This article presents a comparative case study of 12 cases of knowledge transfer between temporary inter-organizational projects and permanent parent organizations. Our set-theoretic analysis of these data yields two major findings. First, a high level of absorptive capacity of the project owner is a necessary condition for successful project knowledge transfer, which implies that the responsibility for knowledge transfer seems to in the first place lie with the project parent organization, not with the project manager. Second, none of the factors are sufficient by themselves. This implies that successful project knowledge transfer is a complex process always involving configurations of multiple factors. We link these implications with the view of projects as complex temporary organizational forms in which successful project managers need to cope with complexity by simultaneously paying attention to both relational and organizational processes.

It's only temporary: Time frame and the dynamics of creative project teams

The success of many knowledge-intensive industries depends on creative projects that lie at the heart of their logic of production. The temporality of such projects, however, is an issue that is insufficiently understood. To address this, we study the perceived time frame of teams that work on creative projects and its effects on project dynamics. An experiment with 267 managers assigned to creative project teams with varying time frames demonstrates that compared to creative project teams with a relatively longer time frame, project teams with a shorter time frame focus more on the immediate present, are less immersed in their task, and utilize a more heuristic mode of information processing. Furthermore, we find that time frame moderates the negative effect of team conflict on team cohesion. These results are consistent with our theory that the temporary nature of creative projects shapes different time frames among project participants, and that it is this time frame that is an important predictor of task and team processes.

The molar effect on citizenship and nomad immigration: Reading, readingthe world and self

This presentation explores molarization and overcoding of social machines and relationality within an assemblage consisting of empirical data of immigrant families in Australia. Immigration is key to sustainable development of Western societies like Australia and Canada. Newly arrived immigrants enter a country and are literally taken over by the Ministry of Immigration regarding housing, health, education and accessing job possibilities. If the immigrants do not know the official language(s) of the country, they enroll in language classes for new immigrants. Language classes do more than simply teach language. Language is presented in local contexts (celebrating the national day, what to do to get a job) and in control societies, language classes foreground values of a nation state in order for immigrants to integrate. In the current project, policy documents from Australia reveal that while immigration is the domain of government, the subject/immigrant is nevertheless at the core of policy. While support is provided, it is the subject/immigrant transcendent view that prevails. The onus remains on the immigrant to “succeed”. My perspective lies within transcendental empiricism and deploys Deleuzian ontology, how one might live in order to examine how segmetary lines of power (pouvoir) reflected in policy documents and operationalized in language classes rupture into lines of flight of nomad immigrants. The theoretical framework is Multiple Literacies Theory (MLT); reading is intensive and immanent. The participants are one Korean and one Sudanese family and their children who have recently immigrated to Australia. Observations in classrooms were obtained and followed by interviews based on the observations. Families also borrowed small video cameras and they filmed places, people and things relevant to them in terms of becoming citizen and immigrating to and living in a different country. Interviews followed. Rhizoanalysis informs the process of reading data. Rhizoanalysis is a research event and performed with an assemblage (MLT, data/vignettes, researcher, etc.). It is a way to work with transgressive data. Based on the concept of the rhizome, a bloc of data has no beginning, no ending. A researcher enters in the middle and exists somewhere in the middle, an intermezzo suggesting that the challenges to molar immigration lie in experimenting and creating molecular processes of becoming citizen.