Nitrone [2]rotaxanes: Simultaneous chemical protection and electrochemical activation of a functional group

We report on the use of the hydrogen bond accepting properties of neutral nitrone moieties to prepare benzylic-amide-macrocycle-containing [2]rotaxanes in yields as high as 70 %. X-Ray crystallography shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and the two nitrone groups of the thread. Dynamic 1H NMR studies of the rates of macrocycle pirouetting in nonpolar solutions indicate that amide-nitrone hydrogen bonds are particularly strong, ~1.3 and ~0.2 kcal mol-1 stronger than similar amide-ester and amide-amide interactions, respectively. In addition to polarizing the N-O bond through hydrogen bonding, the rotaxane structure affects the chemistry of the nitrone groups in two significant ways: The intercomponent hydrogen bonding activates the nitrone groups to electrochemical reduction, a one electron reduction of the rotaxane being stablized by a remarkable 400 mV (8.1 kcal mol-1) with respect to the same process in the thread; encapsulation, however, protects the same functional groups from chemical reduction with an external reagent (and slows down electron transfer to and from the electroactive groups in cyclicvoltammetry experiments). Mechanical interlocking with a hydrogen bonding molecular sheath thus provides a route to an encapsulated polarized functional group and radical anions of significant kinetic and thermodynamic stability.

Photoinduced conjugation of Dithioester- and Trithiocarbonate-Functional RAFT polymers with alkenes

We report the photoinduced conjugation of polymers synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization with a number of low molecular weight (functional) olefins. Upon irradiation of a solution of an aliphatic alkene and the benzyl dithioacetic acid ester (CPDA) or dodecyl trithiocarbonate (DoPAT) functional poly(alkyl acrylate) at the absorption wavelength of the thiocarbonyl group (315 nm), incorporation of the alkene at the polymer chain-end occurred. The most efficient systems identified with regard to the rate of reaction and yield were poly(butyl acrylate)/CPDA/ethyl vinyl ether (78% monoinsertion product after 1 h) and poly(butyl acrylate)/CPDA/1-pentene (73% insertion product after 7 h) at ambient temperature. An in-depth analysis of the reaction mechanism by 1H NMR and online size-exclusion chromatography-electrospray ionization tandem mass spectrometry (SEC/ESI−MSn) revealed that a possible [2 + 2] photoaddition mechanism of conjugation does not take place. Instead, fast β-cleavage of the photoexcited RAFT-end group with subsequent radical addition of an alkene was observed for all employed systems. The presented reaction thus provides a means of spatial and temporal control for the conjugation of alkenes to thiocarbonyl thio-capped macromolecules via the use of UV radiation.

Functional fixation : experimental evidence on the presentation of financial information through different digital formats

This study examines whether, in the presentation of financial information, digital formats address the concern over users’ functional fixation. The accounting literature indicates that the presentation of financial information either within the financial statements or in the notes to the financial statements often creates functional fixation where users of financial statements fail to adjust for differences in accounting policy. This leads users to judge what would otherwise be identical financial situations as being different due to the different accounting policies and methods adopted. It has been suggested that the use of digital formats in presenting financial reports may overcome functional fixation. Using an experimental design involving accountants in public practice, the results indicate that the use of digital formats to present financial reports does not fully overcome the issue of functional fixation in the processing of financial information. Although the participants were able to identify and extract relevant information, irrespective of whether or not the information was presented within the financial statements or in the notes to the accounts, the evidence indicates that functional fixation remained when the participants made final decisions based on available information. This suggests that functional fixation may not be caused by access to or extraction of information but by the level of perceived significance based on where the information is reported in the financial statements. In general, the results indicate that current technology may not be able to fully reduce functional fixation in the evaluation of financial information prepared in accordance with different accounting policies and methods.

The teacher as reflexive professional : making visible the excluded discourse in teacher standards

In the current climate of accountability, political manoeuvring, changing curriculum, increasingly diverse student cohorts and community expectations, teachers, more than ever, need to develop the skills and abilities to be reflective and reflexive practitioners. This study examines national teacher professional standards from Australia and the UK to identify the extent to which reflexivity is embedded in key policy documents that are intended to guide the work of teachers in those countries. Using Margaret Archer's theories of reflexivity and morphogenesis, and methods of critical discourse analysis, we argue that these blueprints for teachers’ work exclude reflexivity as an essential and overarching discourse of teacher professionalism.

“Modeling with tools is easier, believe me” : the effects of tool functionality on modeling grammar usage beliefs

Increasingly, studies are reported that examine how conceptual modeling is conducted in practice. Yet, typically the studies to date have examined in isolation how modeling grammars can be, or are, used to develop models of information systems or organizational processes, without considering that such modeling is typically done by means of a modeling tool that extends the modeling functionality offered by a grammar through complementary features. This paper extends the literature by examining how the use of seven different features of modeling tools affects usage beliefs users develop when using modeling grammars for process modeling. We show that five distinct tool features positively affect usefulness, ease of use and satisfaction beliefs of users. We offer a number of interpretations about the findings. We also describe how the results inform decisions of relevance to developers of modeling tools as well as managers in charge for making modeling-related investment decisions.

‘It's the end of the university as we know it (and I feel fine)’: the Generation Y student in higher education discourse

This paper examines discussions of Generation Y within higher education discourse, arguing the sector’s use of the term to describe students is misguided for three reasons. First, portraying students as belonging to Generation Y homogenises people undertaking higher education as young, middle-class and technologically literate. Second, speaking of Generation Y students allows constructivism to be reinvented as a ‘new’ learning and teaching philosophy. Third, the Generation Y university student has become a central figure in concerns about technology’s role in learning and teaching. While the notion of the ‘Generation Y student’ creates the illusion that higher education institutions understand their constituents, ultimately, it is of little value in explaining young adults’ educational experiences.

Social defence and international reconstructon : illustrating the governance of post-war criminological discourse

This article examines the technocratic priorities of criminological discourse following the Second World War. In doing so, it charts the role and influence of the United Nations and the doctrine of social defence, and traces those shifts and events that have forged a nexus between criminological endeavour and processes of governance. This article aims to illustrate that social defence and international reconstruction provide a useful framework for understanding the links between power/knowledge and the pragmatic orientations of criminological scholarship.

Early local functional changes in the human diabetic retina : a global flash multifocal electroretinogram study

Purpose: To investigate early functional changes of local retinal defects in type II diabetic patients using the global flash multifocal electroretinogram (MOFO mfERG). Methods: Thirty-eight diabetic patients and 14 age-matched controls were recruited. Nine of the diabetics were free from diabetic retinopathy (DR), while the remainder had mild to moderate non-proliferative diabetic retinopathy. The MOFO mfERG was performed at high (98%) and low (46%) contrast levels. MfERG responses were grouped into 35 regions for comparison with DR classification at those locations. Z-scores of the regional mfERG responses were compared across different types of DR defects. Results: The mfERG waveform consisted of the direct component (DC) and the induced component (IC). Local reduction in DC and IC amplitudes were found in diabetic patients with and without DR. With increasing severity of retinopathy, there was a further deterioration in amplitude of both components. Under MOFO mfERG paradigm, amplitude was a useful screening parameter. Conclusion: The MOFO mfERG can help in detecting early functional anomalies before the appearance of visible signs, and may assist in monitoring further functional deterioration in diabetic patients.