A Modular Synthesis of Teraryl-Based α-Helix Mimetics, Part†3: Iodophenyltriflate Core Fragments Featuring Side Chains of Proteinogenic Amino Acids.

Teraryl-based α-helix mimetics have proven to be useful compounds for the inhibition of protein-protein interactions (PPI). We have developed a modular and flexible approach for the synthesis of teraryl-based α-helix mimetics using a benzene core unit featuring two leaving groups of differentiated reactivity in the Pd-catalyzed cross-coupling used for teraryl assembly. In previous publications we have introduced the methodology of 4-iodophenyltriflates decorated with the side chains of some of the proteinogenic amino acids. We herein report the core fragments corresponding to the previously missing amino acids Arg, Asn, Asp, Met, Trp and Tyr. Therefore, our set now encompasses all relevant amino acid analogues with the exception of His. In order to be compatible with the triflate moiety, some of the nucleophilic side chains had to be provided in a protected form to serve as stable building blocks. Additionally, cross-coupling procedures for the assembly of teraryls were investigated.

Optical Sensing and Imaging of pH Values: Spectroscopies, Materials, and Applications.

This is the first comprehensive review on methods and materials for use in optical sensing of pH values and on applications of such sensors. The Review starts with an introduction that contains subsections on the definition of the pH value, a brief look back on optical methods for sensing of pH, on the effects of ionic strength on pH values and pKa values, on the selectivity, sensitivity, precision, dynamic ranges, and temperature dependence of such sensors. Commonly used optical sensing schemes are covered in a next main chapter, with subsections on methods based on absorptiometry, reflectometry, luminescence, refractive index, surface plasmon resonance, photonic crystals, turbidity, mechanical displacement, interferometry, and solvatochromism. This is followed by sections on absorptiometric and luminescent molecular probes for use pH in sensors. Further large sections cover polymeric hosts and supports, and methods for immobilization of indicator dyes. Further and more specific sections summarize the state of the art in materials with dual functionality (indicator and host), nanomaterials, sensors based on upconversion and 2-photon absorption, multiparameter sensors, imaging, and sensors for extreme pH values. A chapter on the many sensing formats has subsections on planar, fiber optic, evanescent wave, refractive index, surface plasmon resonance and holography based sensor designs, and on distributed sensing. Another section summarizes selected applications in areas, such as medicine, biology, oceanography, bioprocess monitoring, corrosion studies, on the use of pH sensors as transducers in biosensors and chemical sensors, and their integration into flow-injection analyzers, microfluidic devices, and lab-on-a-chip systems. An extra section is devoted to current challenges, with subsections on challenges of general nature and those of specific nature. A concluding section gives an outlook on potential future trends and perspectives.

Zn(II) Schiff Bases: Bright TADF Emitters for Self-referenced Decay Time-Based Optical Temperature Sensing.

Thermally activated delayed fluorescence (TADF) is a highly temperature-dependent process and can be used in optical thermometry. TADF-based optical thermometers reported so far show fairly high-temperature sensitivity but have poor brightness and significant oxygen cross-talk. A new class of TADF emitters, Zn(II) Schiff base complexes, possess excellent brightness and high temperature sensitivity of the decay time at ambient temperature (4.1%/K change of TADF lifetime at 25 °C), enabling a resolution better than 0.03 °C. Oxygen cross-sensitivity is eliminated by covering the sensing layer (luminophore in polystyrene) with an off-stoichiometry thiol-ene polymer as an oxygen-consuming layer, and a poly(vinylidene chloride-co-acrylonitrile) layer as an oxygen barrier. The material is stable after more than 2 months of storage at ambient air, which enables long-term temperature monitoring.

TADF-Emitting Zn(II)-Benzoporphyrin: An Indicator for Simultaneous Sensing of Oxygen and Temperature.

A new luminescent indicator is presented that enables simultaneous measurement of oxygen and temperature at a single wavelength. The indicator, an alkylsulfone-substituted Zn(II)-meso-tetraphenyltetrabenzoporphyrin, emits prompt and thermally activated delayed fluorescence (TADF). TADF is sensitive toward oxygen and temperature and is referenced against prompt fluorescence (PF) that is not affected by oxygen. The information on both parameters is accessed from the decay time of TADF and the temperature-dependent ratio of TADF and PF. Sensor foils, made from poly(styrene-co-acrylonitrile) and the indicator dye, enable temperature-compensated trace oxygen sensing (0.002-6 hPa pO2) at ambient conditions. Compared to the previously reported dual sensors based on two emitters, the new sensor significantly simplifies the experimental setup and eliminates risks of different leaching or photobleaching rates by utilizing only one indicator dye and operating at a single wavelength.

Spectroscopic Investigation of DCCH and FTSC as a potential pair for Förster Resonance Energy Transfer in different solvents.

Two molecules, 7-(diethylamino)coumarin-3-carbohydrazide (DCCH) and fluorescein-5-thiosemicarbazide (FTSC) were investigated in different solvents, under varying pH conditions regarding their spectroscopic properties for the usage as a Förster Resonance Energy Transfer (FRET) pair to study the molecular interaction between cellulosic surfaces. All the relevant spectroscopic properties to determine the Förster distance were measured and the performance as a FRET system was checked. From the results, it is clear that the environmental conditions need to be accurately controlled as both, but especially the FTSC dyes are sensitive to changes. For high enough concentrations positive FRET systems were observed in DMF, DMSO, H2O, THF and alkaline DMF. However due to the low quantum yield of the unmodified DCCH throughout the investigated parameter range and the strong environmental dependency of FTSC, both dyes are not preferable for being used in a FRET system for studying interaction between cellulosic surfaces.