• 13C or Not 13C: selective synthesis of asymmetric carbon-13-labeled platinum(II) cis-acetylides.

      Archer, Stuart A.; Keane, Theo; Delor, Milan; Meijer, Anthony J. H. M.; Weinstein, Julia A.; University of Sheffield; Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom; Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom; Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom; Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom; et al. (American Chemical Society, 2016-08-09)
      Asymmetric isotopic labeling of parallel and identical electron- or energy-transfer pathways in symmetrical molecular assemblies is an extremely challenging task owing to the inherent lack of isotopic selectivity in conventional synthetic methods. Yet, it would be a highly valuable tool in the study and control of complex light-matter interactions in molecular systems by exclusively and nonintrusively labeling one of otherwise identical reaction pathways, potentially directing charge and energy transport along a chosen path. Here we describe the first selective synthetic route to asymmetrically labeled organometallic compounds, on the example of charge-transfer platinum(II) cis-acetylide complexes. We demonstrate the selective 13C labeling of one of two acetylide groups. We further show that such isotopic labeling successfully decouples the two ν(C≡C) in the mid-IR region, permitting independent spectroscopic monitoring of two otherwise identical electron-transfer pathways, along the 12C≡12C and 13C≡13C coordinates. Quantum-mechanical mixing leads to intriguing complex features in the vibrational spectra of such species, which we successfully model by full-dimensional anharmonically corrected DFT calculations, despite the large size of these systems. The synthetic route developed and demonstrated herein should lead to a great diversity of asymmetric organometallic complexes inaccessible otherwise, opening up a plethora of opportunities to advance the fundamental understanding and control of light-matter interactions in molecular systems.
    • Adoption of eco-advantage by SMEs: emerging opportunities and constraints

      Oxborrow, Lynn; Brindley, Clare; Nottingham Trent University (Emerald Group Publishing Limited, 2013)
      Purpose: Esty and Winston (2006) assert that businesses need to adopt 'eco-advantage'. This paper aims to explore the viability of SMEs achieving 'eco-advantage' by considering their understanding of sustainability issues, how they adopt and innovate in terms of sustainability and the benefits and obstacles they face. Methodology: The research approach is exploratory, comprised of 15 SME embedded cases based in the UK. The cases are participants in short interventions in sustainable product and process design as a part of a university knowledge transfer project, representing the overall case. Cases are based on interviews with company participants and collaborating academics, supplemented by documentary and observational evidence. Findings: The results build on the work on 'eco-advantage' (Esty and Winston, 2006), highlighting marketing, rather than compliance issues as a catalyst for change. The newly aware SME enters a development process which involves cumulative capabilities, gaining a nascent inner confidence, which includes espousing wider sustainable values and attempts at influencing internal and upstream practices in four dominant ways: use of alternative materials, enhancing recyclability (Sharma et al, 2010), local sourcing, and product to service shift (Maxwell and van der Vorst 2003), though few fully embrace strategic ecological and economic advantage. Obstacles include ephemerality of benefits (Shearlock et al, 2000) and practicalities of implementing internal and supply chain innovations.
    • Aligning the sustainable supply chain to green marketing needs: a case study

      Brindley, Clare; Oxborrow, Lynn; Nottingham Trent University (Elsevier, 2013-09-11)
      The research explores the challenges facing organisations in aligning sustainable procurement requirements and marketing needs and the attendant shifts in supply chain management practices. Whilst external influences are readily understood (e.g. regulation and customer demand), less is understood about the implications for suppliers trying to meet sustainable procurement requirements and the organisational challenges of aligning marketing with sustainable supply chain management. An exploratory case study of a UK University catering department has been undertaken, to explore the strategies, processes and relationships associated with synthesising sustainable supply chain and green marketing needs. The empirical findings illustrate the divergence between organisational perspectives on sustainability and procuring sustainable products with marketing demands. Thus, the findings extend the theoretical discussion on sustainable supply chains by providing empirical data based on real-life implementation and from this an emergent aligned supply chain model is proposed, which confirms two drivers for alignment, lean and resource efficient and local and seasonal contingent on market demand. The findings emphasise the benefits of a reverse information flow, the importance of intermediaries, and relationships in its fulfilment, while indicating the resurgence of a supply push of sustainable products into core markets. Future research directions are also posited.
    • All things being equal?: equality and diversity in Careers education, information, advice and guidance

      Hutchinson, Jo; Rolfe, Heather; Moore, Nicki; Bysshe, Simon; Bentley, Kieran; University of Derby (Equality and Human Rights Commission, 2011)
      In its education chapter, the Commission’s first Triennial Review of evidence on inequality, How Fair is Britain? Equality, Human Rights and Good Relations in 2010, found that educational attainment has been transformed in recent years. Around half of young people are now getting good qualifications at 16 (5+ A*-C GCSEs or equivalent including English and Maths) and, in 2008/09, 2.4 million students enrolled in higher education in the UK – a considerable change from a time when educational opportunities were only available to a minority of young people. However, the evidence shows that educational attainment continues to be strongly associated with socio-economic background. Stereotypical information and guidance can limit young people’s options and aspirations at an early age. Careers advice often reinforces traditional choices and young people have limited information on the pay advantages of nontraditional routes. Nearly one in four young people say that they have not had enough information to make choices for their future. This rises to just under a quarter of disabled young people.
    • Barriers to women achieving their entrepreneurial potential: women and risk

      Brindley, Clare; Nottingham Trent University (Emerald Group Publishing Limited, 2005)
      Purpose This paper provides a comprehensive summary of the academic literature with regard to risk and its role in the entrepreneurial experience of women. Entrepreneurial risk has an under?developed conceptual basis and distilling gender?specific aspects is difficult. Various academic disciplines have contributed to the topic of risk, e.g. economics, and often decision making is used to contextualise the topic. Though the literature does not always prove an association between the different facets of risk and entrepreneurship, there is general agreement that a number of factors, e.g. personal, political and social inter?relate to influence risk and subsequent behaviour. Design/methodology/approach Uses a desk?based approach to data collection. An overview of the main issues concerning risk and entrepreneurship is given to contexualise the gender aspects to be discussed, drawing on the extant literature. Findings The paper posits that an understanding of the gender aspects of risk is required if policy measures are to be constructive and help women overcome barriers and achieve their entrepreneurial potential. The conclusions drawn from the literature provide the foundations for a discussion of the likely policy measures that are required to encourage women entrepreneurs. Research limitations/implications A summary is provided of the research and information gaps that remain in terms of women entrepreneurship and risk with the aim of encouraging further research in the area. Originality/value Provides a comprehensive summary of the literature with regard to risk and the entrepreneurial experience of women, and discusses the likely policy measures required to encourage women entrepreneurs.
    • Be/come closer to home: Narratives of contested lands in the visual practices of Katerina Attalidou and Alexandra Handal

      Photiou, Maria; University of Derby (Taylor & Francis, 2016-05-27)
      Women from Cyprus and Palestine are citizens of divided countries and have experienced conspiracies and invasions that have confiscated their homelands. This article investigates visual practices of women artists and the ways in which they are embedded in the space of each location. It aims to reflect on artists' experiences of borders, location and narrations of homeland. It focuses on the artistic practices of Greek-Cypriot artist Katerina Attalidou and Alexandra Handal, who engage in questioning and challenging issues on homeland, borders, history, citizenship, identity and exile. This article will enquire as to how the idea of homeland 'real or imagined' is represented in visual works and will investigate how the usage of images and narratives can challenge the concept of home. Through the discussion of images this article will consider how these practices serve as a reminder of exile and develop a critical understanding of contemporary events and our reaction to them.
    • Career ambitions of teenage mothers: customer insight research

      Hutchinson, Jo; Moore, Nicki; University of Derby, iCeGS (iCeGS - International Centre for Guidance Studies, University of Derby, 2012)
      Teenage pregnancy is more common in some areas and among some groups of young women. Rates of teenage pregnancy in socially deprived areas are higher than the national average. Because of its association with deprivation, in 1999 the Social Exclusion Unit set out targets to Local Authorities to reduce the numbers of conceptions and increase the participation of young mothers in education, training and employment. Progress towards reducing conceptions has been steady but slow as the figure below from Nottinghamshire shows. It remains concentrated in geographic ‘hot spots’ in both the City and the County. Similarly fewer than 30% of young mothers in the City or the County are in education, employment or training. This research sought to find out more about these young women. Through interviews and data analysis the research explored the motivations and factors that influence when or whether a young mother will return to the labour market.
    • Career learning journeys of Derby and Derbyshire NEETs

      Hutchinson, Jo; Korzeniewski, Richard; Moore, Nicki; University of Derby, iCeGS (iCeGS - International Centre for Guidance Studies, University of Derby, 2011-03)
      Young people (aged under 25 years) typically represent a third of all unemployed people across Derby and Derbyshire. The numbers of young people aged between 16 and 18 years old who are either not in education, employment or training (known as NEETs) in Derby and Derbyshire is a concern for local communities, businesses, support organisations, and families. In early 2010 changes to support services and structures were being undertaken, whilst at the same time the economic downturn was affecting opportunities for employment and training. The opportunity that arose at this time through the EMIEP project to undertake research both about, and with, the local NEET population was seized upon locally as a way to better understand the realities of being NEET through systematic analysis of the NCCIS database alongside qualitative analysis of interviews with 40 young people who were categorised as NEET. It finds that those young people with multiple disadvantage feel better supported by services than those whose NEET status derived from just one or two disadvantaging factors.
    • Career transitions in marketing: from corporate life to self-employment

      Brindley, Clare; Foster, Carley; Wheatley, Dan; Nottingham Trent University (Praeger, 2014)
    • Career-related learning and science education: the changing landscape

      Hutchinson, Jo; University of Derby, iCeGS (The Association for Science Education, 2012)
      Pupils ask STEM subject teachers about jobs and careers in science, but where else do they learn about work? This article outlines career-related learning within schools in England alongside other factors that influence pupils’ career decisions. The effect of the Education Act 2011 will be to change career learning in schools. The impact on science educators as advisers, facilitators, commissioners or managers of career-related learning is discussed, with a conclusion that, while science educators are not career educators, they nevertheless can support career-related learning in their delivery of the curriculum alongside enhancement and enrichment activities.
    • Challenging the concept of risk in relation to women's entrepreneurship

      Humbert, Anne Laure; Brindley, Clare; European Institute for Gender Equality; Nottingham Trent University (Emerald Group Publishing Limited, 2015)
      Purpose This paper aims to challenge the myth of risk-averseness among women entrepreneurs and analyses risk in the context of gender. It explores risk perceptions and examines the relationship between the concept of risk and women's socially attributed roles. Design/methodology/approach This paper adopts a qualitative approach, where ten Irish women business owners were interviewed, that encouraged them to talk about their entrepreneurial experiences. The research design aimed to elicit data concerning how gender and the socio-economic context influenced risk. Findings Risk is shown as a gendered concept which needs to be widened to suit the experiences of women entrepreneurs and the influences of the gendered expectations of care dictated by the socio-economic environment. Practical implications Risk as a concept needs to be expanded to go beyond financial risk. The different types of risk encountered by women should be addressed by policy to promote a further growth of women-led enterprises and support those considering self-employment. Originality/value The paper develops an understanding of risk among women entrepreneurs in their socio-economic context. It challenges the viewpoint of seeing women entrepreneurs as risk-averse and thus leading to low-growth prospects for their business ventures.
    • Criminal Lives 1780-1925: Punishing Old Bailey Convicts

      Allwork Larissa; Robert Shoemaker; Tim Hitchcock; AHRC Digital Panopticon (London Metropolitan Archives, 2017-12-11)
      Between 1700 and 1900 the British government stopped punishing the bodies of London’s convicts and increasingly sought to exile them and/or reform their minds. From hanging, branding and whipping the response to crime shifted to transportation and imprisonment. By the nineteenth century, judges chose between two contrasting forms of punishments: exile and forced labour in Australia, or incarceration in strictly controlled ‘reformatory’ prisons at home. This exhibition, based on material from London Metropolitan Archives and the AHRC funded Digital Panopticon research project, traces the impact of punishments on individual lives. It follows the men, women and children convicted in London from their crimes and trials through to their experiences of punishment and their subsequent lives.
    • Cultural determinants of competitiveness within SMEs

      Ritchie, Bob; Brindley, Clare; Nottingham Trent University (Emerald Group Publishing Limited, 2005)
      Purpose To develop a contingency framework that will assist in overcoming the concerns expressed about the ability to integrate and generalise findings from research studies into entrepreneurship and small? to medium?sized enterprises (SMEs). Design/methodology/approach A preliminary framework is developed as a contribution towards fulfilling the need for a means of connecting often, diverse studies into SMEs and entrepreneurship. The framework is evaluated initially in terms of previous studies in the field and subsequently employing results from the authors' own cross?national empirical studies involving ethnic, gender and cultural barriers to engaging in entrepreneurship. Findings The results from a series of empirical studies of experienced managers and aspiring managers are presented. The nature of the cultural differences and the implications for future research and policy making are evaluated. Issues such as the motivating and de?motivating factors associated with establishing and managing an SME are highlighted. Research limitations/implications The findings are used to initiate the development and formulation of a contingency framework of entrepreneurship, which identifies cultural factors and differences as significant contingency variables. Practical implications The importance of recognising the impact of cultural and gender differences on the development and application of policies and practices designed to stimulate and sustain entrepreneurship and enterprise is highlighted. This theoretical contribution should lead to more robust policy development. Originality/value The development of a contingency framework which addresses differences in the contextual circumstances in differing countries or regions in terms of culture, gender and ethnicity. Providing support for this framework based on the review of relevant literature and empirical evidence.
    • The D2N2 employability framework: Employers and schools supporting young people's routes to work

      Hutchinson, Jo; Dickinson, Berni; Vickers, Rob; Hooley, Tristram; University of Derby (D2N2, 2015)
      The D2N2 Employability Framework provides the methodology by which we can significantly improve the employability and life skills of our young people regardless of academic ability or which career pathway they chose to take. Collectively schools, colleges, training providers, wealth creating companies, social enterprises and the public sector have a duty to ensure that we give our young people the best chances in gaining employment and at the same time addressing the skills needs of employers within our area.
    • Defending a communicative theory of punishment: the relationship between hard treatment and amends

      Lee, Ambrose Y. K.; University of Oxford, Centre for Criminology (Oxford University Press, 2016-03-27)
      According to communicative theories of punishment, legal punishment is pro tanto justified because it communicates the censure that offenders deserve for their crimes. The aim of this article is to offer a modest defence for a particular version of a communicative theory. This version builds on the one that has been advanced by Antony Duff. According to him, legal punishment should be understood as a kind of (secular) penitential burden that is placed upon offenders to censure them for their crimes, with the aims that they will then come to repent, reform themselves and reconcile with those whom they have wronged. This article departs from Duff’s version, however, by arguing that the penitential burdens in question should be understood more specifically in terms of the amends that offenders ought to make to apologise for their criminal wrongdoings. The article then attempts to address three potential objections to this revised version of the communicative theory.
    • Delivering NEET policy packages? A decade of NEET policy in England

      Hutchinson, Jo; Beck, Vanessa; Hooley, Tristram; University of Derby; University of Leicester (Taylor and Francis, 2015)
      This article explores the way in which government policy shapes the lives of young people who are not in education, employment or training (NEET). In particular it examines how the concept of NEETs is set within a specific infrastructure and discourse for managing and supporting young people. The article provides a brief history of the NEET concept and NEET initiatives, before moving on to scrutinise the policies of the Coalition Government. A key distinction is made between those policies and practices that seek to prevent young people becoming NEET from those that seek to re-engage those who are NEET. It is argued that the Coalition has drawn on a similar active labour market toolkit to the previous Labour administration, but that this has been implemented with fewer resources and less co-ordination. It concludes that there is little reason to believe that Coalition policy will be any more successful than that of the previous government, and some reason to be concerned that it will lead to young people becoming more entrenched within NEET.
    • Developing business. developing careers: how and why employers are supporting the career development of their employees.

      Hutchinson, Jo; Devins, David; Hooley, Tristram; Kelsey, Sarah; University of Derby, iCeGS; Leeds Metropolitan University, Policy Research Institute (PRI) (UKCES, 2012)
    • A dinuclear ruthenium(II) phototherapeutic that targets duplex and quadruplex DNA

      Archer, Stuart; Raza, Ahtasham; Dröge, Fabian; Robertson, Craig C.; Auty, Alexander J; Chekulaev, Dimitri M; Weinstein, Julia; Keane, Theo; Meijer, Anthony J. H. M.; Haycock, John; et al. (Royal Society of Chemistry, 2019-02-18)
      With the aim of developing a sensitizer for photodynamic therapy, a previously reported luminescent dinuclear complex that functions as a DNA probe in live cells was modified to produce a new isostructural derivative containing RuII(TAP)2 fragments (TAP = 1,4,5,8- tetraazaphenanthrene). The structure of the new complex has been confirmed by a variety of techniques including single crystal X-ray analysis. Unlike its parent, the new complex displays RuL-based 3MLCT emission in both MeCN and water. Results from electrochemical studies and emission quenching experiments involving guanosine monophosphate are consistent with an excited state located on a TAP moiety. This hypothesis is further supported by detailed DFT calculations, which take into account solvent effects on excited state dynamics. Cell-free steady-state and time-resolved optical studies on the interaction of the new complex with duplex and quadruplex DNA show that the complex binds with high affinity to both structures and indicate that its photoexcited state is also quenched by DNA, a process that is accompanied by the generation of the guanine radical cation sites as photo-oxidization products. Like the parent complex, this new compound is taken up by live cells where it primarily localizes within the nucleus and displays low cytotoxicity in the absence of light. However, in complete contrast to [{RuII(phen)2}2(tpphz)]4+, the new complex is therapeutically activated by light to become highly phototoxic toward malignant human melanoma cell line showing that it is a promising lead for the treatment of this recalcitrant cancer.
    • Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation.

      Delor, Milan; Archer, Stuart A.; Keane, Theo; Meijer, Anthony J. H. M.; Sazanovich, Igor V.; Greetham, Gregory M.; Towrie, Michael; Weinstein, Julia A.; University of Sheffield; Research Complex at Harwell (Springer, 2017-06-19)
      Ultrafast electron transfer in condensed-phase molecular systems is often strongly coupled to intramolecular vibrations that can promote, suppress and direct electronic processes. Recent experiments exploring this phenomenon proved that light-induced electron transfer can be strongly modulated by vibrational excitation, suggesting a new avenue for active control over molecular function. Here, we achieve the first example of such explicit vibrational control through judicious design of a Pt(II)-acetylide charge-transfer Donor-Bridge-Acceptor-Bridge-Donor “fork” system: asymmetric 13C isotopic labelling of one of the two -C≡C-bridges makes the two parallel and otherwise identical Donor→Acceptor electron-transfer pathways structurally distinct, enabling independent vibrational perturbation of either. Applying an ultrafast UVpump(excitation)-IRpump(perturbation)-IRprobe(monitoring) pulse sequence, we show that the pathway that is vibrationally perturbed during UV-induced electron-transfer is dramatically slowed down compared to its unperturbed counterpart. One can thus choose the dominant electron transfer pathway. The findings deliver a new opportunity for precise perturbative control of electronic energy propagation in molecular devices.
    • Directly coupled versus spectator linkers on diimine ptii acetylides—change the structure, keep the function

      Archer, Stuart A.; Keane, Theo; Delor, Milan; Bevon, Elizabeth; Auty, Alexander J.; Chekulaev, Dimitri; Sazanovich, Igor V.; Towrie, Michael; Meijer, Anthony J. H. M.; Weinstein, Julia A.; et al. (Wiley, 2017-12-27)
      Modification of light‐harvesting units with anchoring groups for surface attachment often compromises light‐harnessing properties. Herein, a series of [donor–acceptor–anchor] platinum(II) diimine (bis‐)acetylides was developed in order to systematically compare the effect of conjugated versus electronically decoupled modes of attachment of protected anchoring groups on the photophysical properties of light‐harvesting units. The first examples of “decoupled” phosphonate diimine PtII complexes are reported, and their properties are compared and contrasted to those of carboxylate analogues studied by a diversity of methods. Ultrafast time‐resolved IR and transient absorption spectroscopy revealed that all complexes have a charge‐transfer (CT) lowest excited state with lifetimes between 2 and 14 ns. Vibrational signatures and dynamics of CT states were identified; the assignment of electronic states and their vibrational origin was aided by TDDFT calculations. Ultrafast energy redistribution accompanied by structural changes was directly captured in the CT states. A significant difference between the structures of the electronic ground and CT excited states, as well as differences in the structural reorganisation in the complexes bearing directly attached or electronically decoupled anchoring groups, was discovered. This work demonstrates that decoupling of the anchoring group from the light‐harvesting core by a saturated spacer is an easy approach to combine surface attachment with high reduction potential and ten times longer lifetime of the CT excited state of the light‐absorbing unit, and retain electron‐transfer photoreactivity essential for light‐harvesting applications.