Palladium (II) - Catalyzed C3-Selective Friedel-Crafts Reaction of Indoles with Aziridines

The [PdCl2(MeCN)2]-catalyzed C3-selective Friedel-Crafts reaction of 2,2-disubstituted and 2-aryl-N-tosylaziridines with indoles is reported. For the 2,2-disubstituted substrates, [PdCl2(MeCN)2] alone, without any ancillary ligands, is an efficient catalyst for the ring-opening reaction. The presence of 1,4-benzoquinone as an additive was found to enhance the ring-opening reaction of the less-reactive 2-arylaziridines. This reaction displayed a broad substrate scope with respect to the indole substrate and is operationally simple. Finally, when 1,3-dimethylindole was employed as a substrate, the de-aromatized pyrroloindoline product was obtained in high yield and good diastereoselectivity

metaSHARK: a WWW platform for interactive exploration of metabolic networks

The metaSHARK (metabolic search and reconstruction kit) web server offers users an intuitive, fully interactive way to explore the KEGG metabolic network via a WWW browser. Metabolic reconstruction information for specific organisms, produced by our automated SHARKhunt tool or from other programs or genome annotations, may be uploaded to the website and overlaid on the generic network. Additional data from gene expression experiments can also be incorporated, allowing the visualization of differential gene expression in the context of the predicted metabolic network. metaSHARK is available at

Advanced organic chemistry laboratory curricula in Australian universities: Investigating the major topics and approaches to learning

A key goal of tertiary education is to prepare graduates with the training, skills, and knowledge necessary to thrive in the workforce. In chemistry, 50% of undergraduate students from Australia, New Zealand and the UK plan to pursue a career that uses chemistry (Ogunde et al., 2017). However, it has also been noted that there is a mismatch in the skills desired by industry when compared with what is taught to undergraduates (Martin et al., 2011; Yasin & Yueying, 2017). Laboratory work is an essential part of undergraduate programs with the objective of developing practical and interpersonal skills with ‘real world’ engagement in chemistry. It is therefore concerning to note the perception among industry stakeholders that the laboratory skills of high-achieving chemistry graduates do not meet the desired standard (Kirton et al., 2014). To extend our understanding regarding the importance and value of undergraduate laboratory skills, techniques, and equipment usage; semi-structured interviews were conducted with key external stakeholders, academics, and post-graduate teaching staff. This presentation will discuss the key findings from our perspectives analysis interviews with various organic chemistry experts across the country from both industry and academia. Key findings include the belief: the purpose of second-year laboratory courses is to teach and developing competency with laboratory skills, whilst third-year laboratory courses should build on this with student application of learned skills whether through lab project design or problem-solving tasks/challenges. REFERENCES Kirton, S. B., Al-Ahmad, A., & Fergus, S. (2014). Using Structured Chemistry Examinations (SChemEs) As an Assessment Method To Improve Undergraduate Students’ Generic, Practical, and Laboratory-Based Skills. Journal of Chemical Education, 91(5), 648-654. Martin, C. B., Schmidt, M., & Soniat, M. (2011). A Survey of the Practices, Procedures, and Techniques in Undergraduate Organic Chemistry Teaching Laboratories. Journal of Chemical Education, 88(12), 1630-1638. Ogunde, J. C., Overton, T. L., Thompson, C. D., Mewis, R., & Boniface, S. (2017). Beyond graduation: motivations and career aspirations of undergraduate chemistry students [10.1039/C6RP00248J]. Chemistry Education Research and Practice, 18(3), 457-471. Yasin, N. Y. B. M., & Yueying, O. (2017). Evaluating the Relevance of the Chemistry Curriculum to the Workplace: Keeping Tertiary Education Relevant. Journal of Chemical Education, 94(10), 1443-1449

Gold- and Silver-Catalysed Cyclisation Reactions of β-Amino Allenes

Herein we report the formation of pyrrolines and tetrahydropyridines from the cyclisation reactions of β-amino allenes by both AuI and AgI catalysts in yields ranging from 5 to 70 %. AuI catalysts favour a 5-endo-dig cyclisation before rapid rearrangement to the 5-exo-dig product, while AgI favours a 6-endo-trig cyclisation. We also report the first known Ag2O catalysed cyclisation reaction of an allene which occurred in good yield (61 %)

Divergent gold-catalysed reactions of cyclopropenylmethyl sulfonamides with tethered heteroaromatics

Cyclopropenylmethyl sulfonamides with tethered heteroaromatics have been demonstrated to undergo divergent gold-catalysed cyclisation reactions. A formal dearomative (4+3) cycloaddition takes place with furan-tethered substrates, yielding densely functionalised 5,7-fused heterocycles related to the bioactive curcusone natural products. Indole-tethered substrates display divergent reactivity giving biologically important tetrahydro-β-carbolines via a Friedel-Crafts mechanism

Engaging students in explaining and representing pharmacology by creating blended media

Pharmacology is a challenging subject in a science degree that requires students to engage with complicated chemical reactions. Typical assessment tasks involve exams, lab reports and presentations. The aim of this study was to trial a new form of assessment task by getting students to analyse a journal article on a disease related to Pharmacology and then to explain key aspects of the article in a 4-5 minute digital media product that they create. The students had a choice of narrated media forms to represent their journal article — podcasts, digital story, video, slowmation (slow animation) or blended media. This presentation focuses on examples of blended media, which is a form that encourages students to integrate any combination of media such as video with animation and static images that students create and combine with expert-generated media from YouTube or Google Images to complement a narration to explain the science. There were 24 students enrolled in the subject Chem350 Principles of Pharmacology and each one was allocated a different journal article to summarise by making a media product. A one hour lecture was provided to students to explain how to make the different media forms supported by instructional resources on a website www.digiexplanations.com. The students then used their own technology such as mobile phones, digital still cameras and free movie making software on their own computers to create the blended media. The aim of this pilot study was to ascertain the students’ perceptions of making a blended media and how their allocated disease was represented. Data collected included observation of the students’ presentations, the blended media artifact and an interview with each student after the subject was completed. Results showed that all 24 students successfully made a 3-5 minute media product in their own time with minimal technological concerns. A wide variety of media to explain the disease in their allocated journal article were submitted including one podcast, five digital stories, 10 videos, three animations and 5 blended media. Three of the students who volunteered to be interviewed about the process of making their blended media product stated that the process was highly engaging and helped them to learn science in a new way and it was the first time they had made a narrated media product in their degree. Whilst this pilot study indicated that the students were engaged in re-representing the science content by creating a digital media product, further studies will need to be conducted to research the quality of science learning claimed by students. Blended media is a new form of student-generated media, which enables students to use their own technology to construct a narrated media product integrating many different media forms and is a multimodal representation to explain a science concept

Proton supplier role of binuclear gold complexes in promoting hydrofunctionalisation of nonactivated alkenes

Density functional theory (DFT) was used to investigate PR 3 AuOTf-catalyzed hydrofunctionalisation of nonactivated alkenes using acetic acid and phenol where OTf = triflate (CF 3 SO 3- ). The gold(i) complex itself is found to be unlikely to operate as the π-activator due to its relatively low electrophilicity. Instead, the concurrent coordination of two gold(i) complexes to a nucleophile (PhOH or AcOH) enhances the acidity of the latter\u27s proton and causes the ensuing binuclear complex to serve as a strong proton supplier for activating the alkene π-bonds. Alternatively, the binuclear complex is also susceptible to produce a hidden HOTf. This hidden acid is accessible for hydrofunctionalization to occur but it is not in sufficient concentration to decompose the final product

Inexact Solves in Interpolatory Model Reduction

We investigate the use of inexact solves for interpolatory model reduction and consider associated perturbation effects on the underlying model reduction problem. We give bounds on system perturbations induced by inexact solves and relate this to termination criteria for iterative solution methods. We show that when a Petrov-Galerkin framework is employed for the inexact solves, the associated reduced order model is an exact interpolatory model for a nearby full-order system; thus demonstrating backward stability. We also give evidence that for \h2-optimal interpolation points, interpolatory model reduction is robust with respect to perturbations due to inexact solves. Finally, we demonstrate the effecitveness of direct use of inexact solves in optimal ${\mathcal H}_2$ approximation. The result is an effective model reduction strategy that is applicable in realistically large-scale settings.Comment: 42 pages, 5 figure

MALT-45: A 7mm survey of the southern Galaxy - II. ATCA follow-up observations of 44GHz class I methanol masers

We detail interferometric observations of 44 GHz class I methanol masers detected by MALT-45 (a 7 mm unbiased auto-correlated spectral-line Galactic-plane survey) using the Australia Telescope Compact Array. We detect 238 maser spots across 77 maser sites. Using high-resolution positions, we compare the class I CH3OH masers to other star formation maser species, including CS (1–0), SiO v = 0 and the H53 α radio-recombination line. Comparison between the cross- and auto-correlated data has allowed us to also identify quasi-thermal emission in the 44 GHz class I methanol maser line. We find that the majority of class I methanol masers have small spatial and velocity ranges (<0.5 pc and <5 km s−1), and closely trace the systemic velocities of associated clouds. Using 870 μm dust continuum emission from the ATLASGAL survey, we determine clump masses associated with class I masers, and find that they are generally associated with clumps between 1000 and 3000 M⊙. For each class I methanol maser site, we use the presence of OH masers and radio recombination lines to identify relatively evolved regions of high-mass star formation; we find that maser sites without these associations have lower luminosities and preferentially appear towards dark infrared regions

The Category of Node-and-Choice Forms, with Subcategories for Choice-Sequence Forms and Choice-Set Forms

The literature specifies extensive-form games in many styles, and eventually I hope to formally translate games across those styles. Toward that end, this paper defines $\mathbf{NCF}$, the category of node-and-choice forms. The category's objects are extensive forms in essentially any style, and the category's isomorphisms are made to accord with the literature's small handful of ad hoc style equivalences. Further, this paper develops two full subcategories: $\mathbf{CsqF}$ for forms whose nodes are choice-sequences, and $\mathbf{CsetF}$ for forms whose nodes are choice-sets. I show that $\mathbf{NCF}$ is "isomorphically enclosed" in $\mathbf{CsqF}$ in the sense that each $\mathbf{NCF}$ form is isomorphic to a $\mathbf{CsqF}$ form. Similarly, I show that $\mathbf{CsqF_{\tilde a}}$ is isomorphically enclosed in $\mathbf{CsetF}$ in the sense that each $\mathbf{CsqF}$ form with no-absentmindedness is isomorphic to a $\mathbf{CsetF}$ form. The converses are found to be almost immediate, and the resulting equivalences unify and simplify two ad hoc style equivalences in Kline and Luckraz 2016 and Streufert 2019. Aside from the larger agenda, this paper already makes three practical contributions. Style equivalences are made easier to derive by [1] a natural concept of isomorphic invariance and [2] the composability of isomorphic enclosures. In addition, [3] some new consequences of equivalence are systematically deduced.Comment: 43 pages, 9 figure