Australian Synchrotron User Meeting 2014

Synchrotron users and experts from Australia, New Zealand, and further afield congregated in November for the Australian Synchrotron User Meeting 2014. Around 200 members of the synchrotron community attended the highly anticipated meeting held, in conjunction with the New User Symposium, at the Australian Synchrotron's National Centre for Synchrotron Science. Early career researchers played a prominent role at the meeting. Their achievements highlighted the promising capabilities of the region's next generation of synchrotron scientists.     

Concise Synthesis of (+)-[13C4]-Anatoxin-a by Dynamic Kinetic Resolution of a Cyclic Iminium Ion

An asymmetric total synthesis of [¹³C₄]-anatoxin-a ([¹³C₄]- 1 ) has been developed from commercially available ethyl [¹³C₄]-acetoacetate ([¹³C₄]- 15 ). The unique requirements associated with isotope incorporation inspired a new, robust, and highly scalable route, providing access to 0.110 g of this internal standard for use in the detection and precise quantification of anatoxin-a in freshwater. A highlight of the synthesis is a method that leverages a cyclic iminium ion racemization to achieve dynamic kinetic resolution in an enantioselective Morita–Baylis–Hillman (MBH) cyclization.     

Issues Mapping: A problem structuring method for addressing science and technology conflicts

There are new opportunities for the application of problem structuring methods to address science and technology risk conflicts through stakeholder dialogue. Most previous approaches to addressing risk conflicts have been developed from a traditional risk communication perspective, which tends to construct engagement between stakeholders based on the assumption that scientists evaluate technologies using facts, and lay participants do so based on their values. ‘Understanding the facts’ is generally privileged, so the value framings of experts often remain unexposed, and the perspectives of lay participants are marginalized. When this happens, risk communication methodologies fail to achieve authentic dialogue and can exacerbate conflict. This paper introduces ‘Issues Mapping’, a problem structuring method that enables dialogue by using visual modelling techniques to clarify issues and develop mutual understanding between stakeholders. A case study of the first application of Issues Mapping is presented, which engaged science and community protagonists in the genetic engineering debate in New Zealand. Participant and researcher evaluations suggest that Issues Mapping helped to break down stereotypes of both scientists and environmental activists; increased mutual understanding; reduced conflict; identified common ground; started building trust; and supported the emergence of policy options that all stakeholders in the room could live with. The paper ends with some reflections and priorities for further research.     

Click Chemistry Mediated Functionalization of Vertical Nanowires for Biological Applications

Semiconductor nanowires (NWs) are gaining significant importance in various biological applications, such as biosensing and drug delivery. Efficient and controlled immobilization of biomolecules on the NW surface is crucial for many of these applications. Here, we present for the first time the use of the Cu^I‐catalyzed alkyne–azide cycloaddition and its strain‐promoted variant for the covalent functionalization of vertical NWs with peptides and proteins. The potential of the approach was demonstrated in two complementary applications of measuring enzyme activity and protein binding, which is of general interest for biological studies. The attachment of a peptide substrate provided NW arrays for the detection of protease activity. In addition, green fluorescent protein was immobilized in a site‐specific manner and recognized by antibody binding to demonstrate the proof‐of‐concept for the use of covalently modified NWs for diagnostic purposes using minute amounts of material.     

Explicit extraction of absorption peak positions,widths and heights using higher order derivatives of total shape spectra by nonparametric processing of time signals as complex damped multi-exponentials

Sole lineshape estimation of non-parametrically computed higher-order derivatives of spectral envelopes in different modes (complex, real, imaginary, magnitude) is investigated. The processed time signals are sums of complex attenuated exponentials (harmonics). The peak parameters of the derivative spectra are directly connected to those of the customary (non-derivative) absorption lineshapes. Crucially, this permits the reconstruction of the latter from the former parameters (the latter are sought since they are unknown, whereas the former are extractable from the derivative envelopes). The cross-checking relationships of the lineshapes for the magnitude modes with the real and imaginary parts of the complex-valued envelopes (total shape spectra) are established. The explicit procedure and the necessary analytical expressions are presented for reconstruction of the exact locations, widths and heights of all the retrieved physical resonances (spectral peaks). These facets are illuminated in the derivative fast Padé transform (dFPT) using its non-parametric version, i.e. without solving the quantification problem (no polynomial rooting, no tackling of eigen-value problems, etc.). Two kinds of illustrations for derivative spectra are reported. One deals with the general Breit-Wigner resonance formula and its first three derivatives. The other is concerned with the dFPT in clinical diagnostics of relevance to breast cancer detection by magnetic resonance spectroscopy. A systematic parallel between these two examples is drawn to highlight, in a stepwise manner, the role of paramount importance played by derivative lineshapes, especially for disentangling overlapping resonances that invariably plague all quantitative analyses of spectra.     

Template-directed excimer formation via specific non-covalent interactions between pyrene guanidinium derivatives and nucleic acids

Structurally distinct guanidinium derivatives were evaluated for their ability to interact non-covalently with various nucleic acid sequences. Among the evaluated derivatives, 4-[(pyrene-1-ylmethyl)amino]butyl] guanidinium (pbg) was found to demonstrate strong excimer emission upon nucleic acid addition and high levels of discrimination between ds- and ss-DNA. The intensity of excimer emission proved to be dependent on the length of the linker probe as well as the oligonucleotide length and sequence. In particular, G-quadruplex prone structures were found to induce the highest excimer emissions among all nucleic acids tested.