Highly Sensitive Switchable Sensors for Hydroxide on Glass Surfaces Based on Isoquinolinium-Quinolinium-substituted Acetylenes.

Bi-substituted acetylenes with a quinolinium and an isoquinolinium substituent are described, which reversibly form intensely colored adducts with O-nucleophiles and thus enable the detection of >0,5 ppm hydroxide on the surfaces of various glasses. Acids reconstitute the colorless bi-substituted acetylenes. The quinolinium and isoquinolinium rings are bound via their 2-, 3-, 4- and 1-, 3-, 4-positions to the triple bond, respectively. The choice of substitution sites of the hetarenium rings enables the design of mixed conjugated/cross-conjugated π-electron systems. Depending on the combination of binding sites, the frontier orbital profile, the triple bond polarization, the fluorescence behaviour, and the sensitivity to hydroxide differs.

Super-resolution Reflection Microscopy via Absorbance Modulation.

In recent years, fluorescence microscopy has been revolutionized. Reversible switching of fluorophores has enabled circumventing the limits imposed by diffraction. Thus, resolution down to the molecular scale became possible. However, to the best of our knowledge, the application of the principles underlying super-resolution fluorescence microscopy to reflection microscopy has not been experimentally demonstrated. Here, we present the first evidence that this is indeed possible. A layer of photochromic molecules referred to as the absorbance modulation layer (AML) is applied to a sample under investigation. The AML-coated sample is then sequentially illuminated with a one-dimensional (1D) focal intensity distribution (similar to the transverse laser mode TEM01) at wavelength λ1 = 325 nm to create a subwavelength aperture within the AML, followed by illumination with a Gaussian focal spot at λ2 = 633 nm for high-resolution imaging. Using this method, called absorbance modulation imaging (AMI) in reflection, we demonstrate a 2.4-fold resolution enhancement over the diffraction limit for a numerical aperture (NA) of 0.65 and wavelength (λ) of 633 nm.

Bis(thienyl)ethenes with α-methoxymethyl groups. Syntheses, spectroscopic Hammett plots, and stabilities in PMMA films.

A series of bis(thienyl)ethenes (BTEs) possessing perfluorocyclopentene backbones and methoxymethyl groups (MOM) in the 2/2'-positions of the thiophenes was prepared and examined. The substitution pattern of the 5/5'-positions was varied, covering the range from electron-donating to electron-withdrawing. The substituent effects of the absorption wavelengths of the ring-opened and the ring-closed isomers, which are interconverted by reversible 6π-electrocyclizations and cycloreversions, are studied by means of the spectroscopic Hammett equation and the Hammett-Brown equation. Excellent correlations of these linear free energy relationships were found, when the σp values of the Hammett equation, which summarize inductive, mesomeric and field effects, were replaced to the Hammett-Brown σp+ and σp- values which also take direct conjugation into account. We studied solvent effects on the spectroscopic properties and embedded the BTEs into polymethylmethacrylate (PMMA) coatings to examine their fatigue resistance. By our studies, the spectroscopic properties of BTEs can be adjusted by variation of the substitution pattern to a desired excitation wavelength for switching processes.