New nickel(II) and iron(II) helicates and tetrahedra derived from expanded quaterpyridines

As an extension of prior studies involving the linear quaterpyridine ligand, 5,5'''-dimethyl-2,2':5',5'':2'',2'''-quaterpyridine 1, the synthesis of the related expanded quaterpyridine derivatives 2 and 3 incorporating dimethoxy-substituted 1,4-phenylene and tetramethoxy-substituted 4,4'-biphenylene bridges between pairs of 2,2'-bipyridyl groups has been carried out via double-Suzuki coupling reactions between 5-bromo-5'-methyl-2'-bipyridine and the appropriate di-pinacol-diboronic esters using microwave heating. Reaction of 2 and 3 with selected Fe(II) or Ni(II) salts yields a mixture of both [M2L3]4+ triple helicates and [M4L6]8+ tetrahedra, in particular cases the ratio of the products formed was shown to be dependent on the reaction conditions; the respective products are all sufficiently inert to allow their chromatographic separation and isolation. Longer reaction times and higher concentrations were found to favour tetrahedron formation. The X-ray structures of solvated [Ni2(2)3](PF6)4, [(PF6) ⊂ Fe4(2)6](PF6)7, [Fe4(3)6](PF6)8 and [Ni4(3)6](PF6)8 have been determined, while the structure of the parent Fe(II) cage in the series, [(PF6) ⊂ Fe4(1)6](PF6)7, was reported previously. The internal volumes of the Fe(II) tetrahedral cages have been calculated and increase from 102 Å3 for [Fe4(1)6]8+ to 227 Å3 for [Fe4(2)6]8+ to 417 Å3 for [Fe4(3)6]8+ and to an impressive 839 Å3 for [Ni4(3)6]8+. The corresponding void volume in the triple helicate [Ni2(2)3]4+ is 29 Å3

5,5′-Bis[(trimethyl­silyl)meth­yl]-2,2′-bipyridine

The mol­ecule of the title compound, C18H28N2Si2, occupies a special position on an inversion centre. The Si—CH2—C(ipso) plane is approximately orthogonal to the plane of the pyridine rings, the corresponding dihedral angle being 82.0 (2)°

Ulvan: A systematic review of extraction, composition and function

Species of green macroalgae (Chlorophyta) of the genus Ulva are edible seaweeds with a range of health promoting bioactive components. Ulva is high in dietary fibre which promotes gastrointestinal health and is linked to a reduction in the incidence of chronic diseases. The fundamental active constituent of Ulva is the soluble fibre ulvan, a gelling sulfated polysaccharide with biological activities including immunomodulating, antiviral, antioxidant, antihyperlipidemic and anticancer. Ulvan also has the capacity to modulate cellular signalling processes in both plant and animal systems leading to beneficial effects on productivity and health. Consequently, ulvan is of significant interest as a constituent in human health, agricultural, and biomaterial products. This comprehensive systematic review investigates and recommends acid extraction, ultrafiltration, sugar constituent and molecular weight analysis for the extraction, purification, and characterisation of ulvan, respectively. The biological activities of ulvans are then critically reviewed

Nickel(II) and iron(II) triple helicates assembled from expanded quaterpyridines incorporating flexible linkages

In the present study the interaction of Fe(II) and Ni(II) with the related expanded quaterpyridines, 1,2-, 1,3- and 1,4-bis-(5'-methyl-[2,2']bipyridinyl-5-ylmethoxy)benzene ligands (4–6 respectively), incorporating flexible, bis-aryl/methylene ether linkages in the bridges between the dipyridyl domains, was shown to predominantly result in the assembly of [M2L3]4+ complexes; although with 4 and 6 there was also evidence for the (minor) formation of the corresponding [M4L6]8+ species. Overall, this result contrasts with the behaviour of the essentially rigid 'parent' quaterpyridine 1 for which only tetrahedral [M4L6]8+ cage species were observed when reacted with various Fe(II) salts. It also contrasts with that observed for 2 and 3 incorporating essentially rigid substituted phenylene and biphenylene bridges between the dipyridyl domains where reaction with Fe(II) and Ni(II) yielded both [M2L3]4+ and [M4L6]8+ complex types, but in this case it was the latter species that was assigned as the thermodynamically favoured product type. The X-ray structures of the triple helicate complexes [H2O⊂Ni2(4)3](PF6)4·THF·.2H2O, [Ni2(6)3](PF6)4·195MeCN·1.THF·1.82O, and the very unusual triple helicate PF6− inclusion complex, [(PF6)⊂Ni2(5)3](PF6)3·1.75eCN·5.25TF·0.25H2O are reported

Brown seaweed Sargassum siliquosum as an intervention for diet-induced obesity in male Wistar rats

The therapeutic potential of Sargassum siliquosum grown in Australian tropical waters was tested in a rat model of metabolic syndrome. Forty-eight male Wistar rats were divided into four groups of 12 rats and each group was fed a different diet for 16 weeks: corn starch diet (C); high-carbohydrate, high-fat diet (H) containing fructose, sucrose, saturated and trans fats; and C or H diets with 5% S. siliquosum mixed into the food from weeks 9 to 16 (CS and HS). Obesity, hypertension, dyslipidaemia, impaired glucose tolerance, fatty liver and left ventricular fibrosis developed in H rats. In HS rats, S. siliquosum decreased body weight (H, 547 ± 14; HS, 490 ± 16 g), fat mass (H, 248 ± 27; HS, 193 ± 19 g), abdominal fat deposition and liver fat vacuole size but did not reverse cardiovascular and liver effects. H rats showed marked changes in gut microbiota compared to C rats, while S. siliquosum supplementation increased gut microbiota belonging to the family Muribaculaceae. This selective increase in gut microbiota likely complements the prebiotic actions of the alginates. Thus, S. siliquosum may be a useful dietary additive to decrease abdominal and liver fat deposition

Metal template synthesis of a tripodal tris(bipyridyl) receptor that encapsulates a proton and an iron(II) centre in a pseudo cage

The Fe(ii) template synthesis of the first member of a new category of tripodal tris-bipyridine ligands incorporating a nitrogen bridgehead is reported. The X-ray structure of the reaction product shows that the ligand adopts a pseudo cage-like structure that encapsulates both a proton and an Fe(ii) ion in its cavity. The complex shows an extended helical arrangement that is effectively 'capped' at its open end by a hydrogen bonded PF6– counter ion that is symmetrically aligned with the 3-fold axis of the helix. A 1H NMR study demonstrated that the encapsulated proton can be reversibly exchanged under acid/base conditions in CD3CN

A new Fe-II quaterpyridyl M4L6 tetrahedron exhibiting selective anion binding

A rigid linear bis-bidentate quaterpyridine undergoes metal directed self-assembly with iron(II) salts yielding M4L6 host–guest complexes; selective anion binding for PF6− over BF4− is observed

Microwave synthesis of a rare [Ru2L3]4+ triple helicate and its interaction with DNA

A rare ruthenium(II) triple helicate of the type [Ru2L3]4+ (L=5,5'''-dimethyl-2,2':5',5'':2'',2'''-quaterpyridine) was synthesized in an unusually high yield by using microwave heating in ethylene glycol (see scheme). Efficient separation of the [Ru2L3]4+ helicate into its P and M isomers by DNA affinity chromatography indicated selective binding of P-[Ru2L3]4+ with various DNA sequences