Ruthenium Complexation in an Aluminium Metal–Organic Framework and Its Application in Alcohol Oxidation Catalysis

A ruthenium trichloride complex has been loaded into an aluminium metal–organic framework (MOF), MOF‐253, by post‐synthetic modification to give MOF‐253‐Ru. MOF‐253 contains open bipyridine sites that are available to bind with the ruthenium complex. MOF‐253‐Ru was characterised by elemental analysis, N₂ sorption and X‐ray powder diffraction. This is the first time that a Ru complex has been coordinated to a MOF through post‐synthetic modification and used as a heterogeneous catalyst. MOF‐253‐Ru catalysed the oxidation of primary and secondary alcohols, including allylic alcohols, with PhI(OAc)₂ as the oxidant under very mild reaction conditions (ambient temperature to 40 °C). High conversions (up to >99 %) were achieved in short reaction times (1–3 h) by using low catalyst loadings (0.5 mol % Ru). In addition, high selectivities (>90 %) for aldehydes were obtained at room temperature. MOF‐253‐Ru can be recycled up to six times with only a moderate decrease in substrate conversion.     

Convergent procedure for the synthesis of trifluoromethyl-containing N-(pyridinyl-triazolyl)pyrimidin-2-amines

This study describes a simple and efficient procedure to synthesize a novel series of fourteen 4-substituted N-(5-pyridinyl-1H-1,2,4-triazol-3-yl)-6-(trifluoromethyl)pyrimidin-2-amines, where the 4-substituents are H, CH₃, C₆H₅, 4-FC₆H₄, 4-CH₃C₆H₄, 4-CH₃OC₆H₄ and 2-Furyl; from the cyclocondensation reaction of N-[5-(pyridinyl)-1H-1,2,4-triazol-3-yl]guanidines with 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trifluoroalk-3-en-2-ones. The reactions were carried out in ethanol under reflux for 18 h and led to 40-68% yields. N-(Pyridyl-triazolyl)guanidine precursors were further obtained from reactions of cyanoguanidine with nicotinic or isonicotinic acid hydrazides and the halogenated enones from trifluoroacetylation of enolethers or acetals.     

Rapid thermally assisted donor-acceptor catenation

Charged donor-acceptor [2]catenanes containing cyclobis(paraquat-p-phenylene) as the ring component can be synthesised in yields of up to 88% in under one hour by heating two precursors in the presence of macrocyclic polyether templates in N,N-dimethylformamide at 80 °C.     

Rules of engagement promote polarity in RNA trafficking

Many cell biological pathways exhibit overall polarity (net movement of molecules in one direction) even though individual molecular interactions in the pathway are freely reversible. The A2 RNA trafficking pathway exhibits polarity in moving specific RNA molecules from the nucleus to localization sites in the myelin compartment of oligodendrocytes or dendritic spines in neurons. The A2 pathway is mediated by a ubiquitously expressed trans-acting trafficking factor (hnRNP A2) that interacts with a specific 11 nucleotide cis-acting trafficking sequence termed the A2 response element (A2RE) found in several localized RNAs. Five different molecular partners for hnRNP A2 have been identified in the A2 pathway: hnRNP A2 itself, transportin, A2RE RNA, TOG (tumor overexpressed gene) and hnRNP E1, each playing a key role in one particular step of the A2 pathway. Sequential interactions of hnRNP A2 with different molecular partners at each step mediate directed movement of trafficking intermediates along the pathway. Specific "rules of engagement" (both and, either or, only if) govern sequential interactions of hnRNP A2 with each of its molecular partners. Rules of engagement are defined experimentally using three component binding assays to measure differential binding of hnRNP A2 to one partner in the presence of each of the other partners in the pathway. Here we describe rules of engagement for hnRNP A2 binding to each of its molecular partners and discuss how these rules of engagement promote polarity in the A2 RNA trafficking pathway. For molecules with multiple binding partners, specific rules of engagement govern different molecular interactions. Rules of engagement are ultimately determined by structural relationships between binding sites on individual molecules. In the A2 RNA trafficking pathway rules of engagement governing interactions of hnRNP A2 with different binding partners provide the basis for polarity of movement of intermediates along the pathway.     

Peer validation of a method to confirm chloramphenicol in honey by liquid chromatography-tandem mass spectrometry

Chloramphenicol (CAP) is extracted from an aqueous dilution of honey using ethyl acetate. The extracts are evaporated and redissolved in water. CAP is then extracted from the aqueous solutions using reversed-phase solid-phase extraction cartridges. CAP is eluted from the reversed-phase cartridges with acetonitrile-water and re-extracted into ethyl acetate. The ethyl acetate is evaporated, and the residue is reconstituted in an aqueous solution. Extracts are chromatographed using a reversed-phase column and analyzed by electrospray negative mode tandem mass spectrometry. Four product ions of precursors m/z 321 or 323 are monitored. The method meets confirmation criteria recommended by the U.S. Food and Drug Administration and 4-point identification criteria established by the European Union. With slight modifications to accommodate different equipment, the method was validated in 2 laboratories.