Investigation of photobleaching and saturation of single molecules by fluorophore recrossing events

A method for investigation of photobleaching and saturation of single molecules by fluorophore recrossing events in a laser beam is described. The diffraction-limited probe volumes encountered in single-molecule detection (SMD) produce high excitation irradiance, which can decrease available signal. The single molecules of several dyes were detected and the data was used to extract interpeak times above a defined threshold value. The interpeak times revealed the number of fluorophore recrossing events. The number of molecules detected that were within 2 ms of each other represented a molecular recrossing for this work. Calcein, fluorescein and R-phycoerythrin were analyzed and the saturation irradiance and photobleaching effects were determined as a function of irradiance. This approach is simple and it serves as a method of optimizing experimental conditions for single-molecule detection.     

The synthesis and characterisation of europium terpyridine-N-oxide complexes

Europium complexes of a series of terpyridine-N-oxide ligands have been prepared and structurally characterised by crystallographic studies. While the addition of three equivalents of terpyridine-1-oxide or terpyridine-1,1'-bisoxide results in complexes with nine co-ordinate tricapped trigonal prismatic or monocapped square antiprismatic geometries, respectively, three equivalents of the terpyridine-1,1',1'-trisoxide yields an unexpected 8 co-ordinate geometry. Luminescence studies of the three complexes in acetonitrile show a typical europium emission spectra, dominated by the (5)D(0)-(7)F(2) transition. While no simple trend in the relative quantum yields could be ascertained, the terpyridine-1-oxide complex was observed to have the most intense luminescence for this set of complexes.     

First CRDS-measurements of water vapour continuum in the 940 nm absorption band

Measurements of near-infrared water vapour continuum using continuous wave cavity ring down spectroscopy (cw-CRDS) have been performed at around 10611.6 and . The continuum absorption coefficients for N₂-broadening have been determined to be and at , and and at , respectively.These results represent the first near-IR continuum laboratory data determined within the complex spectral environment in the 940 nm water vapour band and are in reasonable agreement with simulations using the semiempirical CKD formulation.     

Effect of metal ion hydration on the interaction between sodium carboxylates and aluminum(III) or chromium(III) ions in aqueous solution

The interaction between sodium octanoate, decanoate, and dodecanoate and aluminum(III) and chromium(III) has been studied in water at natural pH values, starting well below the surfactant critical micelle concentration, using electrical conductivity, turbidity, and potentiometric measurements. With decanoate or dodecanoate, maximum interaction occurs at 3:1 stoichiometry, corresponding to charge neutralization. Although the solutions become turbid with both metal ions, indicating phase separation, differences are observed and attributed to the fact that aluminum(III) is relatively labile to substitution and rapidly replaces its water ligands, whereas chromium(III) is substitution inert. This shows up in well-defined floc formation with Al(3+), whereas Cr(3+) suspensions do not precipitate, probably because that replacement of coordinated water by carboxylate ligands is impeded. This can be overcome by increasing temperature, and differences in the thermal behavior with Al(3+) and Cr(3+) are suggested to be due to increased involvement of substitution reactions in the latter case. The effect of octanoate on the trivalent metal ions is less clear, and with Cr(3+) interaction only occurs when the carboxylate is in excess. Hydrophobic interactions between alkyl chains play a major role in driving phase separation. At high surfactant concentrations, the solid phases do not dissolve, in contrast to what is observed with the corresponding alkylsulfates. This has implications for use of these systems in metal separation through froth flotation. The concentration of metal ions in supernatant solution has been determined for sodium dodecanoate and sodium dodecylsulfate with Al(3+) and Cr(3+) over the whole surfactant concentration range by inductively coupled plasma-mass spectrometry (ICP-MS). From this, association constants have been determined and are found to be larger for the carboxylate than the alkylsulfate, in agreement with the greater Lewis basicity of the -CO(2)(-) group.     

Facile synthesis of metal-organic framework films via in situ seeding of nanoparticles

A facile in situ nanoparticle seeding method is reported to prepare MIL-101(Cr) films on alumina supports. The in situ seeding of MIL-101(Cr) nanoparticles was promoted by use of dimethylacetamide (DMA). The generality of this approach is further demonstrated for Cu(3)(btc)(2) films by using a (poly)acrylate promoter.     

Metal-organic frameworks post-synthetically modified with ferrocenyl groups: framework effects on redox processes and surface conduction

Metal-organic framework (MOF) materials based on zinc(II) and aluminium(III) dicarboxylate frameworks with covalently attached ferrocene functional redox groups were synthesised by post-synthetic modification and investigated by voltammetry in aqueous and non-aqueous media. In the voltammetry experiments, ferrocene oxidation occurs in all cases, but chemically reversible and stable ferrocene oxidation without decay of the voltammetric response requires a "mild" dichloroethane solvent environment. The voltammetric response in this case is identified as "surface-confined" with fast surface-hopping of electrons and without affecting the bulk of MOF microcrystals. In aqueous media a more complex pH-dependent multi-stage redox process is observed associated with chemically irreversible bulk oxidation and disintegration of the MOF framework. A characteristic 30 mV per pH unit dependence of redox potentials is observed attributed to a "framework effect": the hydroxide-driven MOF framework dissolution.     

Cascaded optical field enhancement in composite plasmonic nanostructures

We present composite plasmonic nanostructures designed to achieve cascaded enhancement of electromagnetic fields at optical frequencies. Our structures were made with the help of electron-beam lithography and comprise a set of metallic nanodisks placed one above another. The optical properties of reproducible arrays of these structures were studied by using scanning confocal Raman spectroscopy. We show that our composite nanostructures robustly demonstrate dramatic enhancement of the Raman signals when compared to those measured from constituent elements.     

Fe-site assignments in Y1Ba2Cu3O7 revisited

A new symmetric Fe³⁺ site (labelled E) (δ=0.28(2) mm/s and Δ=0.15 mm/s) is observed in the R₁Ba₂Cu₃O₇ family of superconductors for R=Y and Eu. The decay and growth of site E are established in two seemingly unrelated experiments, one as a function of room temperature aging for R=Y, and the other as a function of oxygen loading at elevated temperatures and pressures for R=Eu. In each experiment, the results show that site E is genetically related to the well documented chainsites A(Δ=1.9 mm/s), C(Δ=1.1 mm/s) and D(Δ=1.6 mm/s). We propose that site E represents a quasi-octahedral chain-site having pairs of O(1), O(4) and O(5) nearestneighbor oxygen sites. The two remaining doublets, B(Δ≈0.4 mm/s) and B′(Δ=0.78 mm/s) represent Fe³⁺ dopant sites present in the all-important CuO₂ planes, possessing coordination numbers of 6 and 5, respectively.