A series of ruthenium (II)

Porin A from Mycobacterium smegmatis (MspA) is a highly stable, octameric channel protein, which acts as the main transporter of electrolytes across the cell membrane. MspA features a narrow, negatively charged constriction zone, allowing stable binding of various analytes thereby blocking the channel. Investigation of channel blocking of mycobacterial porins is of significance in developing alternate treatment methods for tuberculosis. The concept that ruthenium(II)quaterpyridinium complexes have the capability to act as efficient channel blockers for MspA and related porins, emerged after very high binding constants were measured by high-performance liquid chromatography and steady-state luminescence studies. Consequently, the interactions between the ruthenium(II) complex RuC2 molecules and MspA, leading to RuC2@MspA assemblies, have been studied utilizing time-resolved absorption/emission, atomic force microscopy, dynamic light scattering, ζ potential measurements, and isothermal titration calorimetry. The results obtained provide evidence for the formation of clusters/large aggregates of RuC2 and MspA. The results are of interest with respect to utilizing prospective channel blockers in porins. The combination of results from conceptually different techniques shed some light onto the chemical nature of MspA-channel blocker interactions thus contributing to the development of a paradigm for channel blocking.

The work presented here aims at utilizing poly-N-isopropyl-acrylamide/acrylic acid copolymers to create nanostructured layers on mica surfaces by a simple spin-casting procedure. The average composition of the copolymers determined by elemental analysis correlates excellently with the feed composition indicating that the radical polymerization process is statistical. The resulting surfaces were characterized by Atomic Force Microscopy (magnetic AC-mode) at the copolymer/air interface. Postpolymerization modification of the acrylic acid functions with perfluoro-octyl-iodide decreased the tendency towards spontaneous formation of nanopores. Crosslinking of individual polymer chains permitted the generation of ultraflat layers, which hosted the mycobacterial channel protein MspA, without compromising its channel function. The comparison of copolymers of very similar chemical composition that have been prepared by living radical polymerization and classic radical polymerization indicated that differences in polydispersity played only a minor role when poly-N-isopropyl-acrylamide/acrylic acid copolymers were spincast, but a major role when copolymers featuring the strongly hydrophobic perfluoro-octyl-labels were used. The mean pore diameters were 23.8±4.4 nm for P[(NIPAM)95.5-co-(AA)4.5] (PDI (polydispersity index)=1.55) and 21.8±4.2 nm for P[(NIPAM)95.3-co-(AA)4.7] (PDI=1.25). The depth of the nanopores was approx. 4 nm. When depositing P[(NIPAM)95-co-(AA)2.8-AAC8F17 2.2] (PDI=1.29) on Mica, the resulting mean pore diameter was 35.8±7.1 nm, with a depth of only 2 nm.

We have studied a new type of heterogeneous composite electrode featuring a ruthenium(II)-quaterpyridinium complex (Ru3PHOS) bearing six phosphonate groups for strong chemisorption on TiO 2 . Ru3PHOS@TiO 2 has then been deposited on microscopy glass slides using Ag-doped epoxy glue. Nanomolar amounts of palladium have been electrodeposited onto the Ru3PHOS@TiO 2 . To our surprise, we have observed the deposition of carbon needles onto the composite material when (photo)electrochemically reducing bicarbonate from aqueous buffers.