Production of anticancer polyenes through precursor-directed biosynthesis

The biosynthesis of the pyrrolyl moiety of the fungal metabolite rumbrin originates from pyrrole-2-carboxylic acid. In an effort to produce novel derivatives with enhanced biological activity a series of substituted pyrrole-2-carboxylates were synthesised and incubated with the producing organism, Auxarthron umbrinum. Several 4-halo-pyrrole-2-carboxylic acids were incorporated into the metabolite yielding three new derivatives: 3-fluoro-, 3-chloro- and 3-bromo-isorumbrin, which were generated in milligram quantities enabling cytotoxicity assays to be conducted. The 3-chloro- and 3-bromo-isorumbrins had improved activity against HeLa cells compared with rumbrin; 3-bromoisorumbrin also showed dramatically improved activity towards a lung cancer cell line (A549).     

F NMR applications in chemical biology

Although fluorine plays only a minor role in biology, its physicochemical properties have proven incredibly useful in the design of analogues of biologically important molecules. Analysis of organofluorine compounds by ¹⁹F NMR was largely confined to synthetic chemists but this technique is finding increasing applications in biological systems. The fluorine atom with its relative small size and 100% natural isotope abundance represents an attractive option for biological NMR studies. In this paper we review the recent literature highlighting the exploitation of ¹⁹F NMR in a range of research areas at the interface of chemistry and biology.     

Estimating Additive Character Sums for Fuchsian Groups

In the usual construction of non-holomorphic Eisenstein series, for a general Fuchsian group, a multiplicative character may be included. The properties of these series are well known. Here we instead include an additive character and develop the properties of the resulting series. We pay particular attention to additive characters that are non-cuspidal, i.e., that are not zero on some parabolic generators. These series may be used to estimate certain additive character sums. For example, asymptotics for a weighted sum over group elements that counts the number of appearances of a fixed generator of the Fuchsian group are obtained.     

The dynamic kinetic resolution of azlactones with thiol nucleophiles catalyzed by arylated, deoxygenated cinchona alkaloids

A significant improvement of the available organocatalytic methods (in terms of product substrate scope and product enantiomeric excess) for the generation of enantioenriched α-amino acid thioesters via the dynamic kinetic resolution of azlactones is reported. C-9 arylated cinchona alkaloid catalysts have been found to be considerably superior to other bifunctional alkaloid catalysts as the promoters of this asymmetric process.     

Epimorphic images of the [5,3,5] Coxeter group

We classify the normal subgroups of the Coxeter group $\varGamma =[5,3,5]$ , and of its even subgroup $\varGamma ^+$ , with quotient isomorphic to a finite simple group $L_2(q)$ . There are infinitely many such normal subgroups of $\varGamma ^+$ , each uniformising a compact orientable hyperbolic $3$ -manifold tessellated by dodecahedra; we determine the isometry groups of these manifolds and the symmetry groups of their tessellations. By contrast there is a single such normal subgroup of $\varGamma $ , uniformising a compact non-orientable $3$ -orbifold with isometry group $PGL_2(19)$ .     

Computational study-led organocatalyst design: a novel, highly active urea-based catalyst for addition reactions to epoxides

An in silico study examined the stabilities of hydrogen-bonded complexes between simple thiourea catalysts and three different electrophiles and identified a novel, highly active N-tosyl urea catalyst for the promotion of addition reactions to epoxide electrophiles. Synthesis and evaluation of 6 revealed it to be a powerful catalyst for the addition of 1,2-dimethylindole to styrene oxide under conditions in which simple N,N-bis-aryl ureas and thioureas (including 1) are inactive. Subsequent studies determined 6 to be compatible with a range of indole and epoxide substrates (including (E)-stilbene oxide) and found that relatively poor nucleophiles such as sterically and electronically deactivated anilines, thiophenol, and benzyl alcohol could be efficiently and regioselectively added to oxiranes under mild conditions.     

A Comparative Analysis of Conventional and Deep Eutectic Solvent (DES)-Mediated Strategies for the Extraction of Chitin from Marine Crustacean Shells

Chitin, the second most abundant biopolymer on earth, is utilised in a wide range of applications including wastewater treatment, drug delivery, wound healing, tissue engineering, and stem cell technology among others. This review compares the most prevalent strategies for the extraction of chitin from crustacean sources including chemical methods that involve the use of harsh solvents and emerging methods using deep eutectic solvents (DES). In recent years, a significant amount of research has been carried out to identify and develop environmentally friendly processes which might facilitate the replacement of problematic chemicals utilised in conventional chemical extraction strategies with DES. This article provides an overview of different experimental parameters used in the DES-mediated extraction of chitin while also comparing the purity and yields of associated extracts with conventional methods. As part of this review, we compare the relative proportions of chitin and extraneous materials in different marine crustaceans. We show the importance of the species of crustacean shell in relation to chitin purity and discuss the significance of varying process parameters associated with different extraction strategies. The review also describes some recent applications associated with chitin. Following on from this review, we suggest recommendations for further investigation into chitin extraction, especially for experimental research pertaining to the enhancement of the “environmentally friendly” nature of the process. It is hoped that this article will provide researchers with a platform to better understand the benefits and limitations of DES-mediated extractions thereby further promoting knowledge in this area.     

Hyperbolic Fourier coefficients of Poincaré series

The Ramanujan Journal - Poincaré (Ann Fac Sci Toulouse Sci Math Sci Phys 3:125–149, 1912) and Petersson (Acta Math 58(1):169–215, 1932) gave the now classical expression for the...