A combined mechanistic and computational study of the gold(I)-catalyzed formation of substituted indenes

Substituted indenes can be prepared after a sequence [1,3] O-acyl shift-hydroarylation-[1,3] O-acyl shift. Each step is catalyzed by a cationic NHC-Gold(I) species generated in situ after reaction between [(IPr)AuOH] and HBF(4)·OEt(2). This interesting silver-free way is fully supported by a computational study justifying the formation of each intermediate.     

Compositional studies of human RPE lipofuscin: mechanisms of molecular modifications

The accumulation of lipofuscin has previously been implicated in several retinal diseases including Best's macular dystrophy, Stargardt's disease and age-related macular degeneration (AMD). Previously one of the major fluorophores of lipofuscin was identified as a bis-retinoid pyridinium salt called A2E, which is known to photochemically cause damage. In addition to A2E, there are numerous components in RPE lipofuscin that are unidentified. These compounds were determined to be structurally related to A2E by their fragmentation pattern with losses of 106, 190, 174 and/or 150 amu from the parent ion and the formation of fragments of ca 592 amu. The vast majority consists of relatively hydrophobic components corresponding to derivatized A2E with molecular weights in discrete groups of 800-900, 970-1080 and > 1200 m/z regions. In order to determine the mechanism of these modifications, A2E was chemically modified by; (1) the formation of specific esters, (2) reaction with specific aldehydes and (3) spontaneous auto-oxidation. The contribution of ester formation to the naturally occurring components of lipofuscin was discounted since their fragmentation patterns were different to those found in vivo. Alternatively, reactions with specific aldehydes result in nearly identical products as those found in vivo. Artificial aging of RPE lipofuscin gives a complex mixture of structurally related components. This results from the auto- and/or photooxidation of A2E to form aldehydes, which then back react with A2E giving a series of higher molecular weight products. The majority of these modifications result in compounds that are much more hydrophobic than A2E. These higher molecular weight materials have increased values of log P compared to A2E. This increase in hydrophobicity most likely aids in the sequestering of A2E into granules with the concomitant diminution of its reactivity. Therefore, these processes may serve as protective mechanisms for the RPE.     

{Au(IPr)}2(μ-OH)]X complexes: synthetic, structural and catalytic studies

The synthesis of a series of dinuclear gold hydroxide complexes has been achieved. These complexes of type [{Au(IPr)}₂(μ‐OH)]X (X=BF₄, NTf₂, OTf, FABA, SbF₆; IPr=2,6‐bis(disopropylphenyl)imidazol‐2‐ylidene; NTf₂=bis(trifluoromethanesulfonyl)imidate; OTf=trifluoromethanesulfonate; FABA=tetrakis(pentafluorophenyl)borate) are easily formed in the presence of water and prove highly efficient in the catalytic hydration of nitriles. Their facile formation in aqueous media suggests they are of relevance in gold‐catalyzed reactions involving water. Additionally, a series of [Au(IPr)(NCR)][BF₄] (R=alkyl, aryl) complexes was synthesized as they possibly occur as intermediates in the catalytic reaction mechanism. ¹H and ¹³C NMR data as well as key bond lengths obtained by X‐ray diffraction studies are compared and reveal an interesting structure–activity relationship. The collected data indicate a negligible effect of the nature of the nitrile on the reactivity of [Au(L)(NCR)][X] complexes in catalysis.     

Microdeformation in Heterogeneous Polymers,Revealed by Electron Microscopy

Recent investigations of the tensile fracture behaviour of representative glassy and semicrystalline impact-resistant polymers are reviewed, with emphasis on the microdeformation behaviour as revealed by electron microscopy of sections from bulk specimens, where the crack-tip damage zone has been embedded and/or stained under load, and on thin films deformed in situ. The insight that such techniques have provided into the toughening mechanisms is discussed.