Synthesis,crystal structure and conformational analysis of an unexpected [1,5]dithiocine product of aminopyridine and thiovanillin

The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C₂₁H₁₈N₂O₂S₂·0.463CH₃OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol^?1 between the two conformers.     

Azodicarboxylate-Mediated Peptide Cyclisation: Application to Disulfide Bond Formation in Solution and Solid Phase

Cyclic peptides are important molecules, playing key roles in protein architecture, as chemical probes, and increasingly as crucial structural elements of clinically-useful therapeutics. Herein we report methodology using azodicarboxylates as efficient reagents for the facile synthesis of cyclic peptides through a disulfide bridge. The utility of this approach in both solution and solid-phase, and compatibility with common amino acid side chain functionalities is demonstrated, resulting in cyclic peptides in good yield and purity. This approach has significant potential application for synthesis of molecules of biological or therapeutic significance.     

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.     

Making practice studyable

A common way to situate professional learning in practice is to use representations of teaching, such as videos of classroom instruction or samples of student work. Using representations of teaching, however, does not automatically lead to teacher learning. Learning in and from practice also requires supports that make such practice studyable. The authors introduce and explore the work of “making practice studyable” by analyzing a case of practice-based professional development in which the professional development designers deliberately tried to mediate participants’ learning in and from practice. From this analysis, the authors identified five categories of work that can help make practice studyable: (1) engaging the content, (2) providing insight into student thinking, (3) orienting to the instructional context, (4) providing lenses for viewing, and (5) developing a disposition of inquiry. These categories are then applied to the use of a representation of mathematics teaching in a course for preservice elementary teachers.     

Nanorod near-field radiative heat exchange analysis

A theoretical method for cylinder-to-cylinder radiative heat exchange is formulated. The method utilized was a modified version of a previously published numerical method for near-field sphere-to-sphere radiative exchange. Modifications were made to the numerical procedure to make it applicable to cylindrical geometry of nanorods. Nanorods investigated had length to diameter ratios of 3:1 and 7:1. The heat exchange of nanorods is plotted vs. gap to assess the impact of near-field radiative transfer as gap decreases. Graphical results of energy vs. nanorod radii are also presented. A nanorod-to-plane configuration is estimated utilizing a nanorod asymptotic method. The nanorod-to-nanorod method approximates a nanorod-to-plane geometric configuration when one nanorod radii is held constant, and the second nanorod radii is iteratively increased until the corresponding radiative exchange converges.     

Bioreduction of β-carboline imines to amines employing Saccharomyces bayanus

β-Carboline imine reductions mediated by Saccharomyces bayanus have been described achieving moderate to good enantiomeric excesses of the amine products. The enantiomeric excesses of the bioreduction showed a dependence on the imine substituents. Compounds presenting C₁–C₁₁ aliphatic substituent groups afforded amines with an (S)-configuration, whereas C₁₅ and higher aliphatic- and aromatic-substituted β-carboline imines achieved inversion of the configuration in the final (R)-2 amine products. Based on this data, a model for the Saccharomyces reduction is proposed.     

Quantification of Photosensitized Singlet Oxygen Production by a Fluorescent Protein

Fluorescent proteins are increasingly becoming actuators in a range of cell biology techniques. One of those techniques is chromophore‐assisted laser inactivation (CALI), which is employed to specifically inactivate the function of target proteins or organelles by producing photochemical damage. CALI is achieved by the irradiation of dyes that are able to produce reactive oxygen species (ROS). The combination of CALI and the labelling specificity that fluorescent proteins provide is useful to avoid uncontrolled photodamage, although the inactivation mechanisms by ROS are dependent on the fluorescent protein and are not fully understood. Herein, we present a quantitative study of the ability of the red fluorescent protein TagRFP to produce ROS, in particular singlet oxygen (¹O₂). TagRFP is able to photosensitize ¹O₂ with an estimated quantum yield of 0.004. This is the first estimation of a quantum yield of ¹O₂ production value for a GFP‐like protein. We also find that TagRFP has a short triplet lifetime compared to EGFP, which reflects relatively high oxygen accessibility to the chromophore. The insight into the structural and photophysical properties of TagRFP has implications in improving fluorescent proteins for fluorescence microscopy and CALI.     

Scaffold Effects on Osteogenic Differentiation of Equine Mesenchymal Stem Cells: An In Vitro Comparative Study

The in vitro viability, osteogenic differentiation, and mineralization of four different equine mesenchymal stem cells (MSCs) from bone marrow, periosteum, muscle, and adipose tissue are compared, when they are cultured with different collagen‐based scaffolds or with fibrin glue. The results indicate that bone marrow cells are the best source of MSCs for osteogenic differentiation, and that an electrochemically aggregated collagen gives the highest cell viability and best osteogenic differentiation among the four kinds of scaffolds studied.