Ferrocene-cyclam: a redox-active macrocycle for the complexation of transition metal ions and a study on the influence of the relative permittivity on the coulombic interaction between metal cations

The reaction of 1,1'-ferrocene-bis(methylenepyridinium) salt with 1,4,8,11-tetraazacyclotetradecane-5,12-dione, followed by LiAlH4 reduction results in the formation of FcCyclam. Metal complexes of FcCyclam with M2+ = Co2+, Ni2+, Cu2+, and Zn2+ were synthesized from FcCyclam and the respective metal triflates. The complexation of Cu2+ and FcCyclam in CH3CN is preceeded by a rapid electron transfer, followed by a slower complex formation reaction and a reverse electron transfer. The protonation constants of FcCyclam and the stability constants for the Cu2+ complex of FcCyclam (logK = 9.26(4) for the formation of the [Cu(FcCyclam)]2+ complex) were determined in 1,4-dioxane/water 70:30 v/v, 0.1 moldm(-3), KNO3, 25 degrees C. By using FcCyclam one can selectively sense the presence of Cu2+ ions in the presence of Ni2+, Zn2+, Cd2+, Hg2+, and Pb2+ with a very large deltaE approximately 200 mV, depending on pH. The X-ray crystal structures of FcCyclam and of complexes with Co2+, Ni2+, Cu2+, and Zn2+ were determined and Fe-M2+ distances obtained: Fe-Co2+ 395.9, Fe-Ni2+ 385.4, Fe-Cu2+ 377.7, and Fe-Zn2+ 369.0 pm. The redox potential of FcCyclam is influenced in a characteristic manner by the complexation of M2+. A linear correlation of 1/r approximately/= deltaE [r = distance Fe-M2+ from crystal data, deltaE=-E1/2([M(FcCyclam)]2+) - E1/2(FcCyclam)] was found; this is indicative of a mainly Coulomb type interaction between the two metal centers. The nature of the Fe...M2+ interaction was also investigated by determining deltaE in several solvents (mixtures) of different dielectric constants epsilon. The expected relation of deltaE approximately/= 1/epsilon was only found at very high values of epsilon. At epsilon < 40 increased ion-pairing appears to reduce the effective positive charge at M2+ leading to progessively smaller values of deltaE with lowered epsilon. The dependence of deltaE and epsilon can be calculated semiquantitatively by combining the Fuoss ion-pairing theory with the Coulomb model.     

Fluorescent chemosensors containing a Ru(tpy)2 2+ core and open-chain polyazaalkanes

4-[4-(Bromomethyl)phenyl]-2,2:6,2-terpyridine reacts with triethylenetetraamine or tetraethylenepentaamine in CH₂Cl₂ to yield the ligands L¹ and L², respectively. Reaction of L¹ and L² with Ru(mtpy)Cl₃ (mtpy = 4-methyl-2,2:6,2-terpyridine) in MeOH yielded, after column chromatography and precipitation with [NH₄][PF₆], the compounds [Ru(L¹)(mtpy)][PF₆]₂ and [Ru(L²)(mtpy)][PF₆]₂. These metallo-receptors contain triethylenetetraamine or tetraethylenepentaamine recognition sites and [Ru(tpy)₂]²⁺ cores as fluorescent signalling subunits. The fluorescent behaviour of [Ru(L¹)(mtpy)]²⁺ and [Ru(L²)(mtpy)]²⁺ in the presence of metal ions and anions has been studied in MeCN:H₂O (70:30 v/v) as a function of the pH.     

Vacuum Stripping of Ethanol during High Solids Fermentation of Corn

In corn-ethanol industry, yeast stress inducing glucose concentrations produced during liquefaction and subsequent high ethanol concentrations produced during fermentation restrict slurry solids to 32 % w/w. These limits were circumvented by combining two novel technologies: (1) granular starch hydrolyzing enzyme (GSHE) to break down starch simultaneously with fermentation and (2) vacuum stripping to remove ethanol. A vacuum stripping system was constructed and applied to fermentations at 30, 40, and 45 % solids. As solids increased from 30 to 40 %, ethanol yield decreased from 0.35 to 0.29 L/kg. Ethanol yield from 45 % solids was only 0.18 L/kg. An improvement was conducted by increasing enzyme dose from 0.25 to 0.75 g/g corn and reducing yeast inoculum by half. After improvement, ethanol yield from 40 % solids vacuum treatment increased to 0.36 L/kg, comparable to ethanol yield from 30 % solids (control).