A Journey from Thermally Tunable Synthesis to Spectroscopy of Phenylmethanimine in Gas Phase and Solution

Phenylmethanimine is an aromatic imine with a twofold relevance in chemistry: organic synthesis and astrochemistry. To tackle both aspects, a multidisciplinary strategy has been exploited and a new, easily accessible synthetic approach to generate stable imine-intermediates in the gas phase and in solution has been introduced. The combination of this formation pathway, based on the thermal decomposition of hydrobenzamide, with a state-of-the-art computational characterization of phenylmethanimine laid the foundation for its first laboratory observation by means of rotational electric resonance spectroscopy. Both E and Z isomers have been accurately characterized, thus providing a reliable basis to guide future astronomical observations. A further characterization has been carried out by nuclear magnetic resonance spectroscopy, showing the feasibility of this synthetic approach in solution. The temperature dependence as well as possible mechanisms of the thermolysis process have been examined.     

Minimizing Side Product Formation in Alkyne Functionalization of Ruthenium Complexes by Introduction of Protecting Groups

The synthesis of alkyne functionalized bipyridine ruthenium complexes are reported. The improved synthetic approach through application of stable protecting groups prevents formation of possible side products while facilitating purification. By applying copper-catalysed azide-alkyne cycloaddition reactions (CuAAC) pyrene units with flexible alkyl linkers are introduced at the periphery of the complex, opening up various applications including surface immobilization and DNA intercalation. All complexes are characterized structurally as well as photophysically, especially regarding the influence of the introduced alkyne and triazolyl substituents on their photophysical behavior.     

Materials,Furnaces, and Texts: How to Write About Making Glass Colours in the Seventeenth Century

Johann Kunckel's Ars Vitraria Experimentalis (1679) is arguably the most important text on seventeenth-century glassmaking. As an augmented German translation of Italian (1612) and English (1662) editions, Kunckel presented a complex and layered text that contained a plethora of recipes, elaborate commentaries and annotations, and various appendices dealing with glass-related technologies and arts. We reworked four recipes for rosichiero glass (a transparent red glass) in Kunckel's book to discover what strategies Kunckel employed to help readers engage with the recipes and to make the recipes work in the specificity of their own workshop. We learned that Kunckel regularly neglected to test the Italian recipes, and that not all of his corrections are improvements, thereby specifying our understanding of the “codification of error” as a strategy to write down colour-making knowledge. Instead, Kunckel made the choice to educate his readers on the very mechanisms of glass colouring to allow them to intervene to influence the colour of the glass and to gain further control over the making process. He argued that the colour of glass is sensitive to the manner in which ingredients are sourced and processed, and emphasised the importance of furnace management in optimising the colour of glass.     

A Convenient Synthesis 7,8-Dihydroisoquinolin-5(6H)-One

A new high-yield two step synthesis of 7,8-dihydroisoquinolin-5(6H)-one (3) from 5,6,7,8-tetrahydroisoquinoline (1) is described.     

A novel method for serum lipoprotein profiling using high performance capillary isotachophoresis

A new capillary isotachophoresis (cITP) method for lipoprotein profiling with superior lipoprotein coverage compared to previous methods has been developed, resolving twice as many lipoprotein species (18 peaks/fractions) in serum or plasma in less than 9.5 min. For this, a novel mixture of 24 spacers, including amino acids, dipeptides and sulfonic acids, was developed and fine-tuned, using predictive software (PeakMaster) and testing of spiked serum samples. Lipoprotein peaks were identified by serum-spiking with reference lipoproteins. Compatibility with common lipophilic stains for selective lipoprotein detection with either UV/Vis or laser-induced fluorescence was demonstrated. A special new capillary with a neutral coating (combining water-compatible OV1701-OH deactivation and methylation) was used for the first time for electrodriven separations, allowing very stable separations in a pH 8.8–9.4 gradient system, being functional for more than 100 injections. Excellent reproducibility was achieved, with coefficients of variation lower than 2.6% for absolute migration times. Comparison was performed with human plasma samples analyzed by NMR, leading to similar results with cITP after multivariate statistics, regarding group-clustering and lipoprotein species correlation. The new cITP method was applied to the analysis of serum samples from a LDL receptor knock-out mice model fed either a normal diet or a western-type diet. Differences in the lipoprotein levels and in the sublipoprotein types were detected, showing a shift to more atherogenic particles due to the high cholesterol diet. In summary, this novel method will allow more detailed and informative profiling of lipoprotein particle subtypes for cardiovascular disease research.     

Evolution of synthetic routes towards homochiral Tapentadol

Analysis of the literature shows that the development of synthetic approaches to Tapentadol, an agonist of the μ-opioid receptor and norepinephrine reuptake inhibitor, has followed four, partially overlapping, phases. The most advanced approaches, based on stereoselective syntheses, appeared only after 2010. The majority of the chemistry examples presented in this review come from patent applications and as such have not been subjected to rigorous peer review, but may serve well as an inspiration to organic chemists for solving analogous synthetic problems.