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.     

The importance of chain length for the polyphosphate enhancement of acidic potassium permanganate chemiluminescence

Sodium polyphosphate is commonly used to enhance chemiluminescence reactions with acidic potassium permanganate through a dual enhancement mechanism, but commercially available polyphosphates vary greatly in composition. We have examined the influence of polyphosphate composition and concentration on both the dual enhancement mechanism of chemiluminescence intensity and the stability of the reagent under analytically useful conditions. The average chain length (n) provides a convenient characterisation, but materials with similar values can exhibit markedly different distributions of phosphate oligomers. There is a minimum polyphosphate chain length (∼6) required for a large enhancement of the emission intensity, but no further advantage was obtained using polyphosphate materials with much longer average chain lengths. Providing there is a sufficient average chain length, the optimum concentration of polyphosphate is dependent on the analyte and in some cases, may be lower than the quantities previously used in routine detection. However, the concentration of polyphosphate should not be lowered in permanganate reagents that have been partially reduced to form high concentrations of the key manganese(III) co-reactant, as this intermediate needs to be stabilised to prevent formation of insoluble manganese(IV).     

Determination of selected neurotransmitter metabolites using monolithic column chromatography coupled with chemiluminescence detection

The oxidation of selected clinically important neurotransmitter metabolites with acidic potassium permanganate in the presence of polyphosphates evokes chemiluminescence of sufficient intensity to enable the sensitive determination of these species. Limits of detection for 5-hydroxyindole-3-acetic acid (5-HIAA), vanilmandelic acid (VMA; α,4-dihydroxy-3-methoxybenzeneacetic acid), 4-hydroxy-3-methoxyphenylglycol (MHPG), homovanillic acid (HVA, 4-hydroxy-3-methoxyphenylacetic acid) and 3,4-dihydroxyphenylacetic acid (DOPAC) were between 5 × 10⁻⁹ and 4 × 10⁻⁸ M, using flow-injection analysis methodology. In addition, we demonstrate the rapid determination of homovanillic acid and 5-hydroxyindole-3-acetic acid in human urine - without the need for extraction procedures - using monolithic column chromatography with chemiluminescence detection.     

Search for a very light CP-odd Higgs boson in top quark decays from pp collisions at sqrt(s)]=1.96 TeV

We present the results of a search for a very light CP-odd Higgs boson a(1)(0) originating from top quark decays t → H(±)b → W(±(*)) a(1)(0)b, and subsequently decaying into τ+ τ-. Using a data sample corresponding to an integrated luminosity of 2.7 fb(-1) collected by the CDF II detector in pp collisions at 1.96 TeV, we perform a search for events containing a lepton, three or more jets, and an additional isolated track with transverse momentum in the range 3 to 20 GeV/c. Observed events are consistent with background sources, and 95% C.L. limits are set on the branching ratio of t → H(±)b for various masses of H(±) and a(1)(0).     

Observation of the baryonic flavor-changing neutral current decay Λb(0)→Λμ+μ-

We report the first observation of the baryonic flavor-changing neutral current decay Λ(b)(0)→Λμ(+)μ(-) with 24 signal events and a statistical significance of 5.8 Gaussian standard deviations. This measurement uses a pp collisions data sample corresponding to 6.8 fb(-1) at √s = 1.96 TeV collected by the CDF II detector at the Tevatron collider. The total and differential branching ratios for Λ(b)(0)→Λμ(+)μ(-) are measured. We find B(Λ(b)(0)→Λμ(+)μ(-))=[1.73 ± 0.42(stat) ± (syst)] × 10(-6). We also report the first measurement of the differential branching ratio of B(s)(0)→?μ(+)μ(-), using 49 signal events. In addition, we report branching ratios for B(+)→K(+)μ(+)μ(-), B(0)→K(0)μ(+)μ(-), and B→K(*)(892)μ(+)μ(-) decays.     

Invariant mass distribution of jet pairs produced in association with a W boson in pp collisions at sqrt[s]=1.96 TeV

We report a study of the invariant mass distribution of jet pairs produced in association with a W boson using data collected with the CDF detector which correspond to an integrated luminosity of 4.3 fb(-1). The observed distribution has an excess in the 120-160 GeV/c(2) mass range which is not described by current theoretical predictions within the statistical and systematic uncertainties. In this Letter, we report studies of the properties of this excess.     

Blackett Memorial Lecture Air safety: end of the golden age?

First-World aviation has become so safe that a passenger who takes a domestic jet flight every day would, on average, go 36?000 years before succumbing to a fatal crash. But certain aerial dangers that were practically absent from the First World in the 1990s might be poised for a resurgence. (Among these hazards are terrorism, mid-air collisions, and ground collisions.) We explore recent data about the mortality risk of air travel, and discuss the prospects for the years ahead.