Data bank: The PE Spectra of Paracyclophanes with Unsaturated Bridges and of Related Molecules

The PE spectroscopic data for a series of [2.2]paracyclophanes with olefinic and/or aromatic bridges, and of a few related molecules are reported, together with tentative assignments based on simple MO models.     

A sodium ion selective optode based on fluorescein octadecyl ether octadecyl ester and application in beverage and urine assay

A fast responsive sodium ion selective fluorescent optode membrane mounted on an optical fiber has been developed. The sensing membrane contained fluorescein octadecyl ether octadecyl ester (FODEE), potassium tetrakis(4-chlorophenyl) borate (KTpClPB) and a calix[4]arene tetraester in a plasticized poly(vinyl chloride) (PVC) matrix. It exhibited a reversible response to Na⁺ in 0.5 mol/l of HCl in the concentration range of 1.0×10⁻⁶ to 0.1 mol/l. The selectivity, response time, reproducibility and lifetime of the optode membrane were discussed. The practical use of this sensor was demonstrated by real sample analysis in complex sample solutions such as beverage and urine samples.     

Analysis of aluminum alloys by resonance-enhanced laser-induced breakdown spectroscopy: How the beam profile of the ablation laser and the energy of the dye laser affect analytical performance

In resonance-enhanced laser-induced breakdown spectroscopy, the sample was ablated by a laser pulse and the expanding plume was photoresonantly rekindled by a dye laser pulse. By sampling aluminum alloys for Mg, Pb, Si, and Cu, we showed that for the ablation step, Gaussian beams gave 2 to 3× better signal-to-noise ratio (SNR) than non-uniform beams. For the rekindling step, if no further sample destruction was allowed, dye laser pulses that intercepted the plume transversely gave 6 to 12× higher SNR than the longitudinal case. By combining Gaussian beams and transverse rekindling, the mass limit-of-detection for Mg was about 100 amol while non-resonant analysis was 10× more destructive. Sub-monolayer of oxides grown on laser-cleaned aluminum surfaces was detected by monitoring the AlO emissions of rekindled plumes; without resonant enhancements, they were not detectable no matter how destructive was the analysis. Time resolved studies showed that the Gaussian beam produced less dispersed plumes and that a stronger dye laser beam directed transversely heated up a bigger plume mass without over-heating the plume core. The analyte emissions were sustained while the continuum background remained low.     

Simple Biosensor with High Selectivity and Sensitivity: Thiol‐Specific Biomolecular Probing and Intracellular Imaging by AIE Fluorogen on a TLC Plate through a Thiol–Ene Click Mechanism

A handy, specific, sensitive bioprobe has been developed. Tetraphenylethene (TPE) was functionalized by a maleimide (MI) group, giving a TPE‐MI adduct that was nonemissive in both solution and the solid state. It was readily transformed into a fluorogen showing an aggregation‐induced emission (AIE) property by the click addition of thiol to its MI pendant. The click reaction and the AIE effect enabled TPE‐MI to function as a thiol‐specific bioprobe in the solid state. Thus, the spot of TPE‐MI on a TLC plate became emissive when it had been exposed to L ‐cysteine, an amino acid containing a thiol group, but remained nonemissive when exposed to other amino acids that lack free thiol units. The thiol‐activated emission was rapid and strong, readily detected by the naked eye at an analyte concentration as low as approximately 1 ppb, thanks to the “lighting up” nature of the bioprobing process. Similarly, the emission of TPE‐MI was turned on only by the proteins containing free thiol units, such as glutathione. Clear fluorescence images were taken when living cells were stained by using TPE‐MI as a visualization agent, affording a facile fluorescent maker for mapping the distribution of thiol species in cellular systems.     

Syntheses and Photophysical Properties of N‐Pyridylimidazol‐2‐ylidene Tetracyanoruthenates(II) and Photochromic Studies of Their Dithienylethene‐Containing Derivatives

A series of tetracyanoruthenate(II) with chelating pyridyl N‐heterocyclic carbene ligands (NHC‐py) was synthesized and characterized. Their photophysical and electrochemical properties as well as the photochromic behavior of their dithienylethene‐containing complexes were studied. Photocyclization was found to take place upon irradiation into the metal‐to‐ligand charge transfer (MLCT) absorption bands of these complexes, and evidence is provided to support the triplet‐sensitizing reaction pathway.