Solid state solvation in amorphous organic thin films

The photoluminescence (PL) of the red laser dye DCM2, doped into blended thin films of polystyrene (PS) and the polar small molecule camphoric anhydride (CA), redshifts as the CA concentration increases. The DCM2 PL peaks at 2.20 eV (lambda=563 nm) for pure PS films and shifts to 2.05 eV (lambda=605 nm) for films with 24.5% CA (by mass). The capacitively measured electronic permittivity also increases from epsilon=2.4 to epsilon=5.6 with CA concentration. These results are consistent with the theory of solvatochromism developed for organic molecules in liquid solvents. To our knowledge, this work is the first application of a quantitative theory of solvation to organic molecules in amorphous thin films with continuously controllable permittivity, and demonstrates that "solid state solvation" can be used to predictably tune exciton energies in organic thin film structures.     

Ultrafine grain formation and coating mechanism arising from a blast coating process: A transmission electron microscopy analysis

This article examines the substrate/coating interface of a coating deposited onto mild steel and stainless steel substrates using an ambient temperature blast coating technique known as CoBlast. The process uses a coincident stream of an abrasive blast medium and coating medium particles to modify the substrate surface. The hypothesis for the high bond strength is that the abrasive medium roughens the surface while simultaneously disrupting the passivating oxide layer of the substrate, thereby exposing the reactive metal that then reacts with the coating medium. The aim of this study is to provide greater insight into the coating/substrate bonding mechanism by analysing the interface between a hydroxyapatite coating on both mild and stainless steel substrates. The coating adhesion was measured via a tensile test, and bond strengths of approximately 45 MPa were measured. The substrate/coating interface was examined using transmission electron microscopy and selected area diffraction. The analysis of the substrate/coating interface revealed the presence of ultrafine grains in both the coating and substrate at interface associated with deformation at the interface caused by particle impaction during deposition. The chemical reactivity resulting from the creation of these ultrafine grains is proposed to explain the high adhesive strength of CoBlast coatings.     

Highly stable ECL active films formed by the electrografting of a diazotized ruthenium complex generated in situ from the amine

The electrodeposition of the electrochemiluminescent (ECL) ruthenium complex, bis(2,2'-bipyridyl)(4'-(4-aminophenyl)-2,2'-bipyridyl)ruthenium(II), [Ru(bpy)(2)(apb)](2+), via the in situ formation of a diazonium species from aqueous media is reported. Surface characterization undertaken using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) determined that the layer is bound to the substrate via azo bonding. The layer displays good ECL activity and is stable over a long period of time. The excellent potential of this system for ECL sensing applications is demonstrated using the well-known ECL coreactant 2-(dibutylamino)ethanol (DBAE) as a model analyte, which can be detected to a level of 10 nM with a linear range between 10(-8) and 10(-4) M.     

Synthesis, electrochemistry and metal binding properties of monosubstituted ferrocenoyl peptides with thioether-containing sidechains

Ferrocenoyl peptides incorporating thioether functionality respond more strongly to mercury(II) than to other heavy metal ions in solution. Compounds reported previously in this context are all 1,1′-disubstituted, and all include two or more sulfur-containing amino acids. To test whether two thioether groups are required for effective mercury binding by these systems, we have prepared a series of singly-substituted ferrocenoyl peptides from ferrocenecarboxylic acid and l-methionine, S-methyl-l-cysteine or S-trityl-l-cysteine, and tested them as electrochemical probes for mercury(II). Nine ferrocenoyl peptides have been synthesised using a Boc-protecting group strategy and HBTU-mediated peptide coupling. The electrochemical properties of these compounds have been determined using cyclic voltammetry, and all show fully reversible one electron oxidation steps. Forward sweep half wave peaks (E_F), reverse sweep half wave peaks (E_R), peak separations (ΔE_P) and half wave potentials (E_1/2) are reported. Changes in the potential of the iron(II)/iron(III) redox couple of the ferrocene core have been used to quantify heavy metal-peptide interactions, revealing that these monotopic systems also respond more strongly to mercury(II) than to zinc(II), cadmium(II), silver(I) and lead(II). NMR experiments to characterise the peptide-mercury interaction implicate the thioether sulfur as the site of mercury binding and indicate 1:1 stoichiometry. The crystal structure of ferrocenoyl-S-methyl-l-cysteine methyl ester is also reported. The greater responsiveness of these systems to mercury(II) makes them interesting leads for the development of biologically inspired sensors for this toxic heavy metal.     

ESI-MS assay of M. tuberculosis cell wall antigen 85 enzymes permits substrate profiling and design of a mechanism-based inhibitor

Mycobacterium tuberculosis Antigen 85 enzymes are vital to the integrity of the highly impermeable cell envelope and are potential therapeutic targets. Kinetic analysis using a label-free assay revealed both mechanistic details and a substrate profile that allowed the design and construction of a selective in vitro mechanism-based inhibitor.     

Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2'-bipyridine)ruthenium(II) complexes

Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For example, the same factors that determine ΔG for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (Φ(ex)) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (Φ(p)) and the possibility of competing side reactions are found to be the main determinants of ECL intensity.     

TIRF microscopy as a screening method for non-specific binding on surfaces

We report a method for studying nanoparticle-biosensor surface interactions based on total internal reflection fluorescence (TIRF) microscopy. We demonstrate that this simple technique allows for high throughput screening of non-specific adsorption (NSA) of nanoparticles on surfaces of different chemical composition. Binding events between fluorescent nanoparticles and functionalized Zeonor? surfaces are observed in real-time, giving a measure of the attractive or repulsive properties of the surface and the kinetics of the interaction. Three types of coatings have been studied: one containing a polymerized aminosilane network with terminal -NH(2) groups, a second film with a high density of -COOH surface groups and the third with sterically restraining branched poly(ethylene)glycol (PEG) functionality. TIRF microscopy revealed that the NSA of nanoparticles with negative surface charge on such modified coatings decreased in the following order -NH(2)>-branched PEG>-COOH. The surface specificity of the technique also allows discrimination of the degree of NSA of the same surface at different pH.     

Probing the metal-to-ligand charge transfer first excited state in (η6-naphthalene)Cr(CO)3 and (η6-phenanthrene)Cr(CO)3 by resonance Raman spectroscopy and density functional theory calculations

The nature of the lowest energy optical transition for the complexes (η(6)-naphthalene)Cr(CO)(3) and (η(6)-phenanthrene)Cr(CO)(3) in the solid state has been investigated by Raman spectroscopy using a range of different excitation wavelengths progressively approaching the resonant condition. Examination of the resonantly enhanced Raman modes confirms that the first absorption is attributed predominantly to a metal-to-arene charge transfer transition for both complexes. A notable difference in the photochemistry of the two complexes was observed. In the case of the phenanthrene complex, population of the lowest energy excited state leads to a photochemical process which resulted in the loss of the arene ligand and formation of Cr(CO)(6).