Nonionic surfactant-capped gold nanoparticles as postcolumn reagents for high-performance liquid chromatography assay of low-molecular-mass biothiols

Gold nanoparticles (GNPs) have been stabilized with nonionic surfactant ligands, i.e., Brij 35, and their aggregation could be induced rapidly and selectively by biologically active low-molecular-mass thiols including sulphydryl-containing amino acids (cysteine and homocysteine) and small peptides (glutathione, cysteinylglycine, and glutamylcysteine). A new postcolumn detection method has been developed for high-performance liquid chromatography (HPLC) assay of these small biothiols based on the analyte-induced aggregation of the GNPs. Compared with conventional thiol-reactive probes, the GNP colloids are easier to prepare, much more stable in aqueous solution over a wide pH range and at ambient temperature, and exhibit relatively high selectivity toward small biothiols. The analysis of human urine samples demonstrated that the proposed method is promising in HPLC assay of the small thiol molecules in biological fluids.     

High precision delta(17)O isotope measurements of oxygen from silicates and other oxides: method and applications

The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 μm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.5-2 mg of silicates or other oxide mineral grains. Respective precisions (1) of typically 0.08 and 0.04 per thousand are obtained for the complete analytical procedure. Departures from the mass-dependent oxygen isotope fractionation line are quantified by Delta(17)O; our precision (1) of such measurements on individual samples is shown to be +/-0.024 per thousand. In turn, this permits the offset between parallel, mass-dependent fractionation lines to be characterised to substantially greater precision than has been possible hitherto. Application of this system to investigate the (17)O versus (18)O relationship for numerous terrestrial whole-rock and mineral samples, of diverse geological origins and age, indicates that the complete data set may be described by a single, mass-dependent fractionation line of slope 0.5244+/- 0.00038 (standard error). Copyright 1999 John Wiley & Sons, Ltd.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.     

Synthesis of Unsymmetric Bipyridine–PtII–Alkynyl Complexes through Post‐Click Reaction with Emission Enhancement Characteristics and Their Applications as Phosphorescent Organic Light‐Emitting Diodes

Two unsymmetric bipyridine–platinum(II)–alkynyl complexes have been synthesised by a post‐click reaction. These metal complexes are found to exhibit emission enhancement properties. The photoluminescence quantum yield can be significantly increased from 0.03 in solution to 0.72 in solid‐state thin films. Efficient solution‐processable organic light‐emitting diodes have been fabricated by utilizing these complexes as phosphorescent dopants. A high external quantum efficiency of up to 5.8 % has been achieved.     

Measurement of multi-exponential optical decay processes by?phase-shift cavity ring-down

Multi-exponential decay waveforms are common occurrences in cavity ring-down spectroscopy and the respective ring-down times are typically obtained by fitting the ring-down waveform to the sum of exponential decay functions. In phase-shift cavity ring-down (CRD) spectroscopy the measurement of a single phase angle will not provide sufficient information and needs to be complemented by either intensity measurements or phase angle measurements at different modulation frequencies. Here, a formalism analogous to that developed for fluorescence lifetime spectroscopy is adapted to the phase-shift CRD technique and is tested for two types of waveguide CRD systems: (1) a single-mode fiber cavity in which light is confined by two identical Fiber Bragg Gratings and (2) a multimode fiber loop. By measuring the phase angle at different modulation frequencies, lifetimes for up to three different decay processes were obtained.     

Synthesis, characterization, spectroscopic, and electrochemiluminescence properties of a solvatochromic azacrown-containing cyanoruthenate(II): potential applications in separation and indirect photometric detection of cations and amino acids in HPLC

A new anionic ruthenium(II) complex, (Et4N)[Ru(tpyA18C6)(CN)3] (tpyA18C6=N-[4'-(2,2':6',2'-terpyridyl)]-1,4,7,10,13-pentaoxa-16-azacyclohexadodecane), has been synthesized and characterized. The complex was found to show pronounced solvatochromic behavior and, when dissolved in solution, changed its color from purple to yellow when the solvent system was varied from pure acetonitrile to pure water. Its absorption and emission energies in various solvents showed a linear dependence of the Gutman's acceptor number. The characteristic photoluminescence and electrochemiluminescence (ECL) of the complex were also found to be progressively quenched as the proportion of water in a water/acetonitrile mixture increased. Large changes in the chemical shifts of the 1H NMR and 13C NMR signals of [Ru(tpyA18C6)(CN)3]- in different solvents were observed. The complex has also been demonstrated to serve as a mobile-phase additive in high-performance liquid chromatography for separation of metal cations and amino acids. Comparison studies with the crown-free analogue, (Et4N)[Ru(tpy)(CN)3] (tpy = 2,2':6',2'-terpyridine), showed that other than the ion-pair effect, the allosteric host-guest interaction provided by the presence of the pendant crown was essential to the separation performance of the complex. Indirect detection of nonabsorbing analytes has been achieved by monitoring the absorbance changes of the eluent at the metal-to-ligand charge-transfer (MLCT) absorption band maximum of the complex at 445 nm. The effects of pH, ionic strength, and polarity of the mobile phase as well as the complex concentration on the selectivity and resolution have also been studied.     

Sensitive single-layered oxygen-sensing systems: polypyridyl ruthenium(II) complexes covalently attached or deposited as langmuir-blodgett monolayer on glass surfaces

Oxygen-sensing elements containing single-layered structures of luminescent indicators of ruthenium(II) bipyridyl complexes on glass surfaces prepared by covalent attachment and LB deposition are described. They are capable of detecting gaseous oxygen concentration by luminescence quenching of the indicator with reproducible and large quenching efficiencies that are comparable to the best quenching efficiencies obtained by other ruthenium(II) polypyridine based complexes immobilized in matrixes. The large quenching efficiencies for both films imply that the probe complexes are effectively quenched by oxygen, which is probably due to the thin single-layered structures with large surface-to-area ratio and short distance between the probe complexes and oxygen.     

Photochromic thienylpyridine-bis(alkynyl)borane complexes: toward readily tunable fluorescence dyes and photoswitchable materials

A series of diarylethene-containing N^C chelated thienylpyridine-bis(alkynyl)borane complexes has been designed and synthesized. Their photophysical and photochromic properties have been investigated and presented. The characteristic low-energy absorption band of their closed forms could be readily tuned from the visible range to the near-infrared region.     

New ruthenium(II) complexes functionalized with coumarin derivatives: synthesis, energy-transfer-based sensing of esterase, cytotoxicity, and imaging studies

Two new bichromophoric ruthenium(II) complexes, [Ru(bpy)(2)(bpy-CM)](PF(6))(2) and [Ru(bpy)(2)(bpy-CM343)](PF(6))(2) (bpy=2,2'-bipyridine, CM=coumarin) with appended coumarin ligands have been designed and synthesized. The energy-transfer-based sensing of esterase by the complexes has been studied by using UV/Vis and luminescence spectroscopic methods. The cytotoxicity and the cellular uptake of one of the complexes have also been investigated.