Atomic force microscopy of model lipid membranes

Supported lipid bilayers (SLBs) are biomimetic model systems that are now widely used to address the biophysical and biochemical properties of biological membranes. Two main methods are usually employed to form SLBs: the transfer of two successive monolayers by Langmuir–Blodgett or Langmuir–Schaefer techniques, and the fusion of preformed lipid vesicles. The transfer of lipid films on flat solid substrates offers the possibility to apply a wide range of surface analytical techniques that are very sensitive. Among them, atomic force microscopy (AFM) has opened new opportunities for determining the nanoscale organization of SLBs under physiological conditions. In this review, we first focus on the different protocols generally employed to prepare SLBs. Then, we describe AFM studies on the nanoscale lateral organization and mechanical properties of SLBs. Lastly, we survey recent developments in the AFM monitoring of bilayer alteration, remodeling, or digestion, by incubation with exogenous agents such as drugs, proteins, peptides, and nanoparticles.

Intracellular Delivery of Peptidyl Ligands by Reversible Cyclization: Discovery of a PDZ Domain Inhibitor that Rescues CFTR Activity

A general strategy was developed for the intracellular delivery of linear peptidyl ligands through fusion to a cell‐penetrating peptide and cyclization of the fusion peptides via a disulfide bond. The resulting cyclic peptides are cell permeable and have improved proteolytic stability. Once inside the cell, the disulfide bond is reduced to produce linear biologically active peptides. This strategy was applied to generate a cell‐permeable peptide substrate for real‐time detection of intracellular caspase activities during apoptosis and an inhibitor for the CFTR‐associated ligand (CAL) PDZ domain as a potential treatment for cystic fibrosis.     

Electrocatalytic Dihydrogen Production with a Robust Mesoionic Pyridylcarbene Cobalt Catalyst

A Co^III complex with a mesoionic pyridylcarbene ligand is presented. This complex is an efficient electrocatalyst for H₂ production at very low overpotential and high turnovers when using a (glassy carbon) GC electrode. The corresponding triazole complexes display no catalytic activity whatsoever under identical conditions. The remarkable robustness of the Co? C(carbene) bond towards acids is likely responsible for the high efficiency of this catalyst. The present results thus open new avenues for carbene‐based ligands for generating functional models for hydrogenases.     

Toeplitz determinants from compatibility conditions

In this paper we show, how a straightforward and natural application of a pair of fundamental identities valid for polynomials orthogonal over the unit circle, can be used to calculate the determinant of the finite Toeplitz matrix Δ _n , with the Fisher-Hartwig symbol. We use the same approach to compute a difference equation for expressions related to the determinants of symbols that have important application in the study of random permutations. E.L. Basor was supported in part by National Science Foundation grant DMS-0200167 and also in part by the EPSRC for a Visiting Fellowship.     

Distribution Functions for Random Variables for Ensembles of Positive Hermitian Matrices

Distribution functions for random variables that depend on a parameter are computed asymptotically for ensembles of positive Hermitian matrices. The inverse Fourier transform of the distribution is shown to be a Fredholm determinant of a certain operator that is an analogue of a Wiener-Hopf operator. The asymptotic formula shows that, up to the terms of order o(1), the distributions are Gaussian. Received: 5 November 1996 / Accepted: 8 January 1997     

A Note on Wiener-Hopf Determinants and the Borodin-Okounkov Identity

The continuous analogue of a Toeplitz determinant identity for Wiener-Hopf operators is proved. An example which arises from random matrix theory is studied and an error term for the asymptotics of the determinant is computed. Submitted: October 15, 2001? Revised: January 3, 2002.     

X-ray absorption study of light emitting silicon nanocrystals

X-ray absorption spectra obtained by total electron yield (TEY) at the Si absorption K-edge have been measured to have chemical and structural information about Si nanocrystals (Si-nc) produced by plasma-enhanced chemical vapour deposition (PECVD). The TEY technique has been employed to investigate the formation of Si-nc and the modification of the silica matrix as a function of annealing temperature (500–1250°C) and of silicon content in the film (35–46 at%). The amount of silicon present in the Si-nc has been evaluated by TEY. Thanks to Rutherford backscattering spectrometry measurements, the amount of Si atoms bonded to oxygen and to nitrogen, incorporated by PECVD, has been assessed. A compositional model that interprets the experimental findings is presented.     

Cooperative Metal Binding and Helical Folding in Model Peptides of Treble‐Clef Zinc Fingers

Synergy in zinc fingers : The comparison between peptide folding and metal binding properties of two model peptides of treble‐clef zinc fingers presenting high affinities for zinc and cobalt reveals a cooperative effect: the metal folds the peptide into a α‐helix, which in turn strengthens the metal core.