Hobartine: a tetracyclic indole alkaloid extracted from Aristotelia chilensis (maqui)

The natural compound hobartine {systematic name: (1R)‐3‐[(1S,5S)‐(4,4,8‐trimethylbicyclo[3.3.1]non‐7‐en‐2‐yl)methyl]‐2,3‐dihydro‐1H‐indole}, C₂₀H₂₆N₂, (I), is an indole alkaloid isolated from Aristotelia chilensis as part of a study of secondary metabolites from Chilean flora. The colourless compound has a tetracyclic structure closely related to the strongly coloured polymorphic structures discussed in Paz et al. [Acta Cryst. (2013), C 69 , 1509–1512] and Watson et al. [Acta Cryst. (1989), C 45 , 1322–1324]. The main differences reside in the absence of a keto group in (I) compared with the previous structures, as well as an endo double bond in (I) contrasting with the exo double bond found in the previous structures. The supramolecular structure of (I) in strongly related to the twofold screw axis, around which isolated chains build up, internally linked by an N—H...N hydrogen bond which is the only significant intermolecular interaction present in the structure.     

Versatile Metalloporphyrin-Based Electrochemical Sensing Applications: From Small Gasotransmitters to Macromolecules

At the beginning of his youthful sixth decade, this work is dedicated to Prof. Dr. Fabio Doctorovich. He is distinctive in organometallic chemistry. During his successful career, he has been studying the reactivity and application of metalloporphyrins. Metalloporphyrins are organometallic complexes that exhibit, through synthetic modifications, the ability to tune their optical and electrochemical properties and their selectivity towards a particular molecule or ion. For this reason, they are systems extremely useful as electrochemical sensors to detect and quantify a wide variety of analytes with high selectivity, even in real samples such as food, water, biological fluids, or pharmaceutical compounds. This review presents an up-to-date list of reports in which metalloporphyrins are used as electrochemical sensors. In addition to compiling a comprehensive and up-to-date list of reported sensors that utilize metalloporphyrins, this work aims to provide an overview of currently available tools and techniques for the detection of various chemical species through similar approaches, which are constantly being developed.     

Determination of methyl ester contents in biodiesel blends by FTIR-ATR and FTNIR spectroscopies

Partial last square regression (PLS) and artificial neural network (ANN) combined to FTIR-ATR and FTNIR spectroscopies have been used to design calibration models for the determination of methyl ester content (%, w/w) in biodiesel blends (methyl ester + diesel). Methyl esters were obtained by the methanolysis of soybean, babassu, dende, and soybean fried oils. Two sets of samples have been used: Group I, binary mixtures (diesel + one kind of methyl ester), corresponding to 96 biodiesel blends (0–100%, w/w), and Group II, quaternary mixtures (diesel + three types of methyl esters), corresponding to 60 biodiesel blends (0–100%, w/w). The PLS results have shown that the FTNIR model for Group I is more precise and accurate (±0.02 and ±0.06%, w/w). In the case of Group II the PLS models (FTIR-ATR and FTNIR) have shown the same accuracies, while the ANN/FTNIR models has presented better performance than the ANN/FTIR-ATR models. The best accuracy was achieved by the ANN/FTNIR model for diesel determination (0.14%, w/w) while the worthiest was that of dende ANN/FTIR-ATR model (0.6%, w/w). Precisions in Group II analysis ranged from 0.06 to 0.53% (w/w) and coefficients of variation were better than 3% indicating that these models are suitable for the determination of diesel–biodiesel blends composed of methyl esters derived from different vegetable oils.     

Physico-chemical processes in imidazolium ionic liquids

Among the various properties exhibited by ionic liquids (ILs)--especially those based on the imidazolium cation-their inherent ionic patterns, very low vapour pressure and pronounced self-organization in the solid, liquid and even in the gas phase are particularly interesting since this allows the use of these fluids as alternative and complementary media to classical organic solvents and water in many applications. Hence, reaction paths that involve charge-separated intermediates or transition states are accelerated--by lowering the activation barrier-in the presence of ILs when compared with those performed in classical organic solvents. It is also possible, for example, to observe, by electrochemical methods, transient species (ionic and radical) that are otherwise undetectible in water or in molecular organic solvents and to investigate the interactions and behaviour of molecular, biological and macromolecular species in solution using physical and chemical methods which require special conditions such as high-vacuum, and which have been traditionally limited to solid state chemistry.     

Spectroscopic and theoretical study of 2-acetylphenyl-2-naphthoate

Mid-, far-infrared and Raman vibrational spectra of 2-acetylphenyl-2-naphthoate have been measured at room and low temperatures. The molecule was also analyzed by means of ab initio calculations. The conformational space has been scanned using molecular dynamics and complemented with functional density calculations that optimize the geometry of the lowest energy conformers 2-acetylphenyl-2-naphthoate as obtained in the simulations. The vibrational frequencies and the (1)H and (13)C NMR chemical shifts were assigned using functional density calculations. The theoretical chemical shift values were compared with the experimental ones. The molecular electrostatic potential maps were obtained and analyzed.     

Epitaxial Overgrowth of LiKSO4 on β–K2SO4 Single Crystals

Nucleation of LiKSO₄ (LKS) crystals from non-equimolar solutions may occur epitaxially on the surface of previously nucleated β-K₂SO₄ (KS) crystals. Both compounds evince a profound hexagonal substructure, and have common topological features and similar coordination schemes. Moreover, they may be related by quantitative similarities between their translation parameters and by correspondence between their bond chains along the directions of epitaxy. The planes of epitaxy are (001)_KS, and (0001)_LKS' and on these planes [010]_KS is always parallel to [010]_LKS' with a misfit of 12.19%. Another pair of directions, [11 0]_KS and [100]_LKS' showing a small angular misfit (0.18°), exhibit an even lower linear misfit (3.09%).