Catalytic transformation of aliphatic alcohols to corresponding esters in O2 under neutral conditions using visible-light irradiation

Selective oxidation of aliphatic alcohols under mild and base-free conditions is a challenging process for organic synthesis. Herein, we report a one-pot process for the direct oxidative esterification of aliphatic alcohols that is significantly enhanced by visible-light irradiation at ambient temperatures. The new methodology uses heterogenerous photocatalysts of gold–palladium alloy nanoparticles on a phosphate-modified hydrotalcite support and molecular oxygen as a benign oxidant. The alloy photocatalysts can absorb incident light, and the light-excited metal electrons on the surface of metal nanoparticles can activate the adsorbed reactant molecules. Tuning the light intensity and wavelength of the irradiation can remarkably change the reaction activity. Shorter wavelength light (<550 nm) drives the reaction more efficiently than light of longer wavelength (e.g., 620 nm), especially at low temperatures. The phosphate-exchanged hydrotalcite support provides sufficient basicity (and buffer) for the catalytic reactions; thus, the addition of base is not required. The photocatalysts are efficient and readily recyclable. The findings reveal the first example of using “green” oxidants and light energy to drive direct oxidative esterification of aliphatic alcohols under base-free, mild conditions.

Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr

In a previous paper, we described the room temperature rapid, selective, reversible, and near quantitative Cu-activated nitroxide radical coupling (NRC) technique to prepare 3-arm polystyrene stars. In this work, we evaluated the Cu-activation mechanism, either conventional atom transfer or single electron transfer (SET), through kinetic simulations. Simulation data showed that one can describe the system by either activation mechanism. We also found through simulations that bimolecular radical termination, regardless of activation mechanism, was extremely low and could be considered negligible in an NRC reaction. Experiments were carried out to form 2- and 3-arm PSTY stars using two ligands, PMDETA and Me6TREN, in a range of solvent conditions by varying the ratio of DMSO to toluene, and over a wide temperature range. The rate of 2- or 3-arm star formation was governed by the choice of solvent and ligand. The combination of Me6TREN and toluene/DMSO showed a relatively temperature independent rate, and remarkably reached near quantitative yields for 2-arm star formation after only 1 min at 25 °C.

Laboratories transformation

BACKGROUND OR CONTEXT Laboratories provide the physical spaces for engineering students to connect with theory and have a personal hands-on learning experience. Learning space design and development is well established in many universities however laboratories are often not part of that movement. While active, collaborative and group learning pedagogies are all key words in relation to these new spaces the concepts have always been central to laboratory based learning. The opportunity to build on and strengthen good practice in laboratories is immense. In the 2001 review “Universities in Crisis” many references are made to the decline of laboratories. One such comment in the review was made by Professor Ian Chubb (AVCC), who in 2013, as Chief Scientist for Australia, identifies the national concern about STEM education and presents a strategic plan to address the challenges ahead. What has been achieved and changed in engineering teaching and research laboratories in this time? PURPOSE OR GOAL A large number of universities in Australia and New Zealand own laboratory and other infrastructure designed well for the era they were built but now showing signs of their age, unable to meet the needs of today’s students, limiting the effectiveness of learning outcomes and presenting very low utilisation rates. This paper will present a model for new learning space design that improves student experience and engagement, supporting academic aims and significantly raising the space utilisation rate. APPROACH A new approach in laboratory teaching and research including new management has been adopted by the engineering disciplines at QUT. Flexibility is an underpinning principle along with the modularisation of fixed teaching and learning equipment, high utilisation of spaces and dynamic pedagogical approaches. The revitalised laboratories and workshop facilities are used primarily for the engineering disciplines and increasingly for integrated use across many disciplines in the STEM context. The new approach was built upon a base of an integrated faculty structure from 2005 and realised in 2010 as an associated development with the new Science and Engineering Centre (SEC). Evaluation through student feedback surveys for practical activities, utilisation rate statistics and uptake by academic and technical staff indicate a very positive outcome. DISCUSSION Resulting from this implementation has been increased satisfaction by students, creation of social learning and connecting space and an environment that meets the needs and challenges of active, collaborative and group learning pedagogies. Academic staff are supported, technical operations are efficient and laboratories are effectively utilised. RECOMMENDATIONS/IMPLICATIONS/CONCLUSION Future opportunities for continuous improvement are evident in using the student feedback to rectify faults and improve equipment, environment and process. The model is easily articulated and visible to other interested parties to contribute to sector wide development of learning spaces.

Is Habermas on Twitter? Social Media and the Public Sphere

Jürgen Habermas’s concept of the public sphere remains a major building block for our understanding of public communication and deliberation. Yet ‘the’ public sphere is a construct of its time, and the mass media-dominated environment which it describes has given way to a considerably more fragmented and complex system of distinct and diverse, yet interconnected and overlapping publics that represent different themes, topics, and approaches to mediated communication. This chapter argues that moving beyond the orthodox model of the public sphere to a more dynamic and complex conceptual framework provides the opportunity to more clearly recognise the varying forms that public communication can take, especially online. Unpacking the traditional public sphere into a series of public sphericules and micro-publics, none of which are mutually exclusive but which co-exist, intersecting and overlapping in multiple forms, is crucial for understanding the ongoing structural transformation of ‘the’ public sphere.

Plasmatic Transformation

The session examines the role of the metaphysical and physical in art and animation and how this relates to natural spaces. Soviet Russian film director and theorist Sergei Eisenstein saw animation as possessing an ability called “plasmaticity”, the capacity for a being to assume any conceivable form dynamically. He saw each being as “primordial protoplasm, not yet possessing a ‘stable’ form, but capable of assuming any form” (Eisenstein 1989, 21). He was enamoured by the capacity of animation to transform and be liberated, of being able to escape from a fixed and static identity—to embody a "rejection of the once-­‐and-­‐forever allotted form" in which we are held (Eisenstein 1989, 21). Czech Surrealist animator Jan Švankmajer uses a metaphysical approach based on a belief in animism to art and animation. He believes that objects possess a conscious life or spirit, he says ‘Objects conceal within themselves the events they’ve witnessed. I don’t actually animate objects. I coerce their inner life out of them.’ (Švankmajer in Imre 2009, 214) In this animistic world there are no boundaries or rules, no physical or conceptual restrictions; anything is possible, with inanimate objects and places able to become animate and transact in a conscious relationship with humans and each other. This session invites artists, animators and theorists to discuss their conceptions and approaches to using visuals to promote and provoke transformation.

Firm transformation: Advancing a Darwinian perspective

Purpose of the paper: The paper advocates a Darwinian explanation of the process of firm transformation. Existing, but generally opposing views related to the selection-adaptation debates are united to consider the dialogic nature of both approaches. It is argued that a Darwinian approach, as opposed to a neo-Darwinian or Lamarckian approach provides the means to scale the sides of a debate that has for too long divided scholars interested in firm and industry transformation. Approach: The paper addresses three specific issues to develop its Darwinian argument. Firstly, the various work of Geoff Hodgson that have for many years advanced Darwin's evolutionary ideas are used to argue the nature and application of Darwinism in the socio-economic domain. Secondly, the nature of what constitutes the elements of firm-environment interaction is considered to establish basic areas of focus through which the process of firm transformation is more understandable. Lastly, the construct absorptive capacity is likened to a mechanism of transmission through which the learning processes associated with the acquisition of favoured variations can be reconciled with the generic evolutionary processes of variation, selection, and retention. Findings: To understand the process of firm learning, the role of habits and routines must be outlined in specific detail. They cannot be assumed to perform interacting and replicating roles simultaneously. To do so, undermines the fundamental qualities of an evolutionary theory. What is the original/value of paper: The preliminary framework advanced takes us beyond the Darwinian - Lamarckian debate and provides elements of focus from which a greater understanding of the process of firm/industry transformation is possible.

Implicit and explicit interactions in video mediated collaboration

In this paper we report the results of a study comparing implicit-only and explicit-only interactions in a collaborative, video-mediated task with shared content. Expanding on earlier work which has typically only evaluated how implicit interaction can augment primarily explicit systems, we report issues surrounding control, anxiousness and negotiation in the context of video mediated collaboration. We conclude that implicit interaction has the potential to improve collaborative work, but that there are a multitude of issues that must first be negotiated.

Chemotherapy pretreatment sensitizes solid tumor-derived cell lines to Vα24+ NKT cell-mediated cytotoxicity

There is an increasing awareness of the therapeutic potential for combining immune-based therapies with chemotherapy in the treatment of malignant diseases, but few published studies evaluate possible cytotoxic synergies between chemotherapy and cytotoxic immune cells. Human Vα24 +/Vβ11+ NKT cells are being evaluated for use in cell-based immunotherapy of malignancy because of their immune regulatory functions and potent cytotoxic potential. In this study, we evaluated the cytotoxicity of combinations of chemotherapy and NKT cells to determine whether there is a potential to combine these treatment modalities for human cancer therapy. The cytotoxicity of NKT cells was tested against solid-tumor derived cell lines NCI-H358, DLD-1, HT-29, DU-145, TSU-Pr1 and MDA-MB231, with or without prior treatment of these target cells, with a range of chemotherapy agents. Low concentrations of chemotherapeutic agents led to sensitization of cell lines to NKT-mediated cytotoxicity, with the greatest effect being observed for prostate cancer cells. Synergistic cytotoxicity occurred in an NKT cell in a dose-dependent manner. Chemotherapy agents induced upregulation of cell surface TRAIL-R2 (DR5) and Fas (CD95) expression, increasing the capacity for NKT cells to recognize and kill via TRAIL- and FasL-mediated pathways. We conclude that administration of cytotoxic immune cells after chemotherapy may increase antitumor activities in comparison with the use of either treatment alone.

Surface-mediated selective photocatalytic aerobic oxidation reactions on TiO2 nanofibres

N-doped TiO2 nanofibres were observed to possess lower aerobic oxidation activity than undoped TiO2 nanofibres in the selective photocatalytic aerobic oxidation of enzylamine and 4-methoxybenzyl alcohol. This was attributed to the reduction free energy of O2 adsorption in the vicinity of nitrogen dopant sites, as indicated by density functional theory (DFT) calculations when three-coordinated oxygen atoms are substituted by nitrogen atoms. It was found that the activity recovered following a controlled calcination of the N-doped NFs in air. The dependence of the conversion of benzylamine and 4-methoxybenzyl alcohol on the intensity of light irradiation confirmed that these reactions were driven by light. Action spectra showed that the two oxidation reactions are responsive to light from the UV region through to the visible light irradiation range. The extended light absorption wavelength range in these systems compared to pure TiO2 materials was found to result from the formation of surface complex species following adsorption of reactants onto the catalysts' surface, evidenced by the in situ IR experiment. Both catalytic and in situ IR results reveal that benzaldehyde is the intermediate in the aerobic oxidation of benzylamine to N-benzylidenebenzylamine process.

Amorphization by dislocation accumulation in shear bands

Microcrystalline γ-Y2Si2O7 was indented at room temperature and the deformation microstructure was investigated by transmission electron microscopy in the vicinity of the indent. The volume directly beneath the indent comprises nanometer-sized grains delimited by an amorphous phase while dislocations dominate in the periphery either as dense slip bands in the border of the indent or, further away, as individual dislocations. The amorphous layers and the slip bands are a few nanometers thick. They lie along well-defined crystallographic planes. The microstructural organization is consistent with a stress-induced amorphization process whereby, under severe mechanical conditions, the crystal to amorphous transformation is mediated by slip bands containing a high density of dislocations. It is suggested that the damage tolerance of γ-Y2Si2O7, which is exceptional for a ceramic material, benefits from this transformation.

Book Review: "The Interface: IBM and the Transformation of Corporate Design, 1945-1975", John Harwood, Minneapolis: University of Minnesota Press, 2011

Within the history of twentieth-century design, there are a number of well-known objects and stories that are invoked time and time again to capture a pivotal moment or summarize a much broader historical transition. For example, Marcel Breuer’s Model B3 chair is frequently used as a stand-in for the radical investigations of form and new industrial materials occurring at the Bauhaus in the mid-1920s. Similarly, Raymond Loewy’s streamlined pencil sharpener has become historical shorthand for the emergence of modern industrial design in the 1930s. And any discussion of the development of American postwar “organic design” seems incomplete without reference to Charles and Ray Eames’s molded plywood leg splint of 1942. Such objects and narratives are dear to historians of modern design. They are tangible, photogenic subjects that slot nicely into exhibitions, historical surveys, and coffee-table best sellers...

VEGF-mediated cell survival in non-small-cell lung cancer: implications for epigenetic targeting of VEGF receptors as a therapeutic approach

Aims: To evaluate the potential therapeutic utility of histone deacetylase inhibitors (HDACi) in targeting VEGF receptors in non-small-cell lung cancer. Materials & methods: Non-small-cell lung cancer cells were screened for the VEGF receptors at the mRNA and protein levels, while cellular responses to various HDACi were examined. Results: Significant effects on the regulation of the VEGF receptors were observed in response to HDACi. These were associated with decreased secretion of VEGF, decreased cellular proliferation and increased apoptosis which could not be rescued by addition of exogenous recombinant VEGF. Direct remodeling of the VEGFR1 and VEGFR2 promoters was observed. In contrast, HDACi treatments resulted in significant downregulation of the Neuropilin receptors. Conclusion: Epigenetic targeting of the Neuropilin receptors may offer an effective treatment for lung cancer patients in the clinical setting.

Orienting to emotion in computer-mediated Cognitive Behavioural Therapy

Exploring emotions is a defining feature of psychotherapy. This study explores how therapists explore emotions when they cannot see or hear their clients. In analysing 1,279 sessions of online text-based Cognitive Behavioural Therapy (CBT) we focused on therapists’ commiserations (e.g., “I’m sorry to hear that”) and their affective inferences (e.g., “that sounds very scary for you”). Both practices routinely prefaced moves to pursue a range of therapeutic activities, many of which did not prioritise sustained focus on the emotion that had just been oriented to. By separating message composition from message transmission, the modality used for these therapy sessions enabled therapists to combine orientations to emotion with attempts to shift the focus of discussion. Our analysis finds that although physically co-present and computer-mediated psychotherapy share a common focus on emotional experience, the modality used for therapy can be relevant in the design and use of these orientations. Data are in British English.

Leading Digital Transformation: Building Technology and Information Governance Capability in Boards of Directors and the C-Suite

Information and technology and its use in organisation transformation presents unprecedented opportunities and risks. Increasingly, the Governance of Enterprise Information and Technology (GEIT) competency in the board room and executive is needed. Whether your organization is small or large, public, private or not for profit or whether your industry is not considered high-tech, IT is impacting your sector – no exceptions. But there is a skill shortage in boards: GEIT capability is concerningly low. This capability is urgently needed across the board, including those directors who come from finance, legal, marketing, operations and HR backgrounds. Digital disruption also affects all occupations. Putting in place a vision will help ensure emergency responses will meet technology-related duty of care responsibilities. When GEIT-related forward thinking and planning is carried out at the same time that you put your business strategy and plan in place, your organization has a significantly increased chance of not only surviving, but thriving into the future. Those organizations that don’t build GEIT capability risk joining the growing list of once-leading firms left behind in the digital ‘cloud of smoke’. Those organizations that do will be better placed to reap the benefits and hedge against the risks of a digital world. This chapter provides actionable, research-based considerations and processes for boards to use, to build awareness, knowledge and skills in governing technology-related organization strategy, risk and value creation.