Synthesis of Diels–Alder adducts of the quinolizidine alkaloids N-methylcytisine, (−)-leontidine,and (−)-thermopsine with N-phenylmaleimide

The Diels–Alder adducts of the quinolizidine alkaloids N-methylcytisine, (?)-leontidine, and (?)-thermopsine with N-phenylmaleimide have been synthesized. The structures and absolute configurations of the new asymmetric centers of the products were determined by NMR spectroscopy experiments, QC-calculations, and X-ray data.     

Organic Cage Dumbbells

Molecular dumbbells with organic cage capping units were synthesised via a multi-component imine condensation between a tri-topic amine and di- and tetra-topic aldehydes. This is an example of self-sorting, which can be rationalised by computational modelling.     

Widened derangements and generalized Laguerre polynomials

The Ramanujan Journal - Let $$D_h$$ , $$E_k$$ and $$F_{\alpha }$$ be sets of size $$h,k,\alpha $$ respectively, with $$k \le h$$ . We define a strongly widened derangement to be a permutation of...     

Optimization and validation of organochlorine compounds in adipose tissue by SPE‐gas chromatography

Scientific evidence has shown an association between organochlorine compounds (OCC) exposure and human health hazards. Concerning this, OCC detection in human adipose samples has to be considered a public health priority. This study evaluated the efficacy of various solid‐phase extraction (SPE) and cleanup methods for OCC determination in human adipose tissue. Octadecylsilyl endcapped (C₁₈‐E), benzenesulfonic acid modified silica cation exchanger (SA), poly(styrene‐divinylbenzene (EN) and EN/RP₁₈ SPE sorbents were evaluated. The relative sample cleanup provided by these SPE columns was evaluated using gas chromatography with electron capture detection (GC–ECD). The C₁₈‐E columns with strong homogenization were found to provide the most effective cleanup, removing the greatest amount of interfering substance, and simultaneously ensuring good analyte recoveries higher than 70%. Recoveries > 70% with standard deviations (SD) < 15% were obtained for all compounds under the selected conditions. Method detection limits were in the 0.003–0.009 mg/kg range. The positive samples were confirmed by gas chromatography coupled with tandem mass spectrometry (GC‐MS/MS). The highest percentage found of the OCC in real samples corresponded to HCB, o,p′‐DDT and methoxychlor, which were detected in 80 and 95% of samples analyzed respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

1H NMR Study on the Isomerization of 2,4,6-Triphenyl-4H-Seleno(Thio)Pyrans

It is shown using ¹H NMR spectroscopy that 2,4,6-triphenyl-4H-seleno(thio)pyrans can be isomerized into 2H-isomers by the action of lithium perchlorate or lithium chloride in DMF or only by DMF. The reaction time is found to depend on the Lewis acidity of used salt. It is supposed that isomerization in presence of Lewis acids proceeds as endocyclic 1,3-proton transfer or as a series of two 1,2-hydride shifts.     

Molecular Recognition of Carbonyl Compounds by Uranyl-salophen Based Neutral Receptors Driven by Van Der Waals Forces

The complexation of the salophen-uranyl metallocleft 2 and of its half-cleft analogue 3 with enones and other carbonyl compounds was assessed in chloroform by UV-Vis titration and, occasionally, by FT-IR measurements. Complexes with receptors 2 and 3 are in all cases more stable than those with the control unsubstituted uranyl-salophen 1 , showing that in addition to the primary binding force provided by coordination of the carbonyl oxygen to the uranium, a significant driving force for complexation, typically in the range of 2-3 kcal/mol, results from van der Waals interactions of the guest with the aromatic walls. Replacement of the phenyl group in 3 with larger aromatic residues to give 4 and 5 , led to enhanced complex stabilities, due to more extended contact surfaces between host and guest.