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This work presents two molecular fluorescent probes 1 and 2 for the selective determination of physiologically relevant K+ levels in water based on a highly K+/Na+ selective building block, the o-(2-methoxyethoxy)phenylaza-18-crown-6 lariat ether unit. Fluorescent probe 1 showed a high K+-induced fluorescence enhancement (FE) by a factor of 7.7 of the anthracenic emission and a dissociation constant (K-d) value of 38mm in water. Further, for 2+K+, we observed a dual emission behavior at 405 and 505nm. K+ increases the fluorescence intensity of 2 at 405nm by a factor of approximately 4.6 and K+ decreases the fluorescence intensity at 505nm by a factor of about 4.8. Fluorescent probe 2+K+ exhibited a K-d value of approximately 8mm in Na+-free solutions and in combined K+/Na+ solution a similar K-d value of about 9mm was found, reflecting the high K+/Na+ selectivity of 2 in water. Therefore, 2 is a promising fluorescent tool to measure ratiometrically and selectively physiologically relevant K+ levels.
We report a 1,2,3-triazol fluoroionophore for detecting Na+ that shows in vitro enhancement in the Na+-induced fluorescence intensity and decay time. The Na+-selective molecule 1 was incorporated into a hydrogel as a part of a fiber optical sensor. This sensor allows the direct determination of Na+ in the range of 1-10 mM by measuring reversible fluorescence decay time changes.
The new K+-selective fluorescent probes 1 and 2 were obtained by Cu-I-catalyzed 1,3-dipolar azide alkyne cycloaddition (CuAAC) reactions of an alkyne-substituted [1,3]dioxolo[4,5-f][1,3]benzodioxole (DBD) ester fluorophore with azido-functionalized N-phenylaza-18-crown-6 ether and N-(o-isopropoxy) phenylaza-18-crown-6 ether, respectively. Probes 1 and 2 allow the detection of K+ in the presence of Na+ in water by fluorescence enhancement (2.2 for 1 at 2000mm K+ and 2.5 for 2 at 160mm K+). Fluorescence lifetime measurements in the absence and presence of K+ revealed bi-exponential decay kinetics with similar lifetimes, however with different proportions changing the averaged fluorescence decay times ((f(av))). For 1 a decrease of (f(av)) from 12.4 to 9.3ns and for 2 an increase from 17.8 to 21.8ns was observed. Variation of the substituent in ortho position of the aniline unit of the N-phenylaza-18-crown-6 host permits the modulation of the K-d value for a certain K+ concentration. For example, substitution of H in 1 by the isopropoxy group (2) decreased the K-d value from >300mm to 10mm. 2 was chosen for studying the efflux of K+ from human red blood cells (RBC). Upon addition of the Ca2+ ionophor ionomycin to a RBC suspension in a buffer containing Ca2+, the fluorescence of 2 slightly rose within 10min, however, after 120min a significant increase was observed.
A desirable goal is to synthesize easily accessible and highly K+/Na+-selective fluoroionophores to monitor physiological K+ levels in vitro and in vivo. Therefore, highly K+/Na+-selective ionophores have to be developed. Herein, we obtained in a sequence of only four synthetic steps a set of K+-responsive fluorescent probes 4, 5 and 6. In a systematic study, we investigated the influence of the alkoxy substitution in ortho position of the aniline moiety in -conjugated aniline-1,2,3-triazole-coumarin-fluoroionophores 4, 5 and 6 [R=MeO (4), EtO (5) and iPrO (6)] towards the K+-complex stability and K+/Na+ selectivity. The highest K+-complex stability showed fluoroionophore 4 with a dissociation constant K-d of 19mm, but the K-d value increases to 31mm in combined K+/Na+ solutions, indicating a poor K+/Na+ selectivity. By contrast, 6 showed even in the presence of competitive Na+ ions equal K-d values (K-d(K+)=45mm and K-d(K+/Na+)=45mm) and equal K+-induced fluorescence enhancement factors (FEFs=2.3). Thus, the fluorescent probe 6 showed an outstanding K+/Na+ selectivity and is a suitable fluorescent tool to measure physiological K+ levels in the range of 10-80mm in vitro. Further, the isopropoxy-substituted N-phenylaza[18]crown-6 ionophore in 6 is a highly K+-selective building block with a feasible synthetic route.
We have synthesized a set of new unsaturated macrocyclic dithioethers with an increasing number of flexible methylene units 1-7 (Scheme 2) to investigate the correlation between the ring size of these ligands, the chelation effect and the consequences for an efficient PdCl2 coordination. The dithioethers 1-7 and the complex [PdCl2(4)]center dot CHCl3 were characterized by X-ray diffraction analysis. The crystal structures of 1-7 show that 2-7 are better preorganized chelating ligands for an exocyclic PdCl2 coordination than 1. The chelation effect of 1-7, the orientation of the sulfur atoms and the S center dot center dot center dot S donor distances, are influenced by the flexibility of the methylene units. In this series the unsaturated macrocyclic ligands 5 and 6 are the best chelating ligands for an efficient PdCl2 coordination. Comparative solvent extraction experiments with mn-12S(2)O(2) (mn = maleonitrile) reveal that the low interface activity of the new ligands reduces the extraction rate. However, a comparison with open-chain dithiomaleonitriles shows the impact of the macrocyclic effect of 4 and 5 on the extraction yield.
A highly K+-selective two-photon fluorescent probe for the in vitro monitoring of physiological K+ levels in the range of 1-100 mM is reported. The two-photon excited fluorescence (TPEF) probe shows a fluorescence enhancement (FE) by a factor of about three in the presence of 160 mM K+, independently of one-photon (OP, 430 nm) or two-photon (TP, 860 nm) excitation and comparable K+-induced FEs in the presence of competitive Na+ ions. The estimated dissociation constant (K-d) values in Na+-free solutions (K-d(OP)=(28 +/- 5) mM and K-d(TP)=(36 +/- 6) mM) and in combined K+/Na+ solutions (K-d(OP)=(38 +/- 8) mM and K-d(TP)=(46 +/- 25) mM) reflecting the high K+/Na+ selectivity of the fluorescent probe. The TP absorption cross-section (sigma(2PA)) of the TPEF probe+160 mMK(+) is 26 GM at 860 nm. Therefore, the TPEF probe is a suitable tool for the in vitro determination of K+.
Over the years, we developed highly selective fluorescent probes for K+ in water, which show K+-induced fluorescence intensity enhancements, lifetime changes, or a ratiometric behavior at two emission wavelengths (cf. Scheme 1, K1-K4). In this paper, we introduce selective fluorescent probes for Na+ in water, which also show Na+ induced signal changes, which are analyzed by diverse fluorescence techniques. Initially, we synthesized the fluorescent probes 2, 4, 5, 6 and 10 for a fluorescence analysis by intensity enhancements at one wavelength by varying the Na+ responsive ionophore unit and the fluorophore moiety to adjust different K-d values for an intra- or extracellular Na+ analysis. Thus, we found that 2, 4 and 5 are Na+ selective fluorescent tools, which are able to measure physiologically important Na+ levels at wavelengths higher than 500 nm. Secondly, we developed the fluorescent probes 7 and 8 to analyze precise Na+ levels by fluorescence lifetime changes. Herein, only 8 (K-d=106 mm) is a capable fluorescent tool to measure Na+ levels in blood samples by lifetime changes. Finally, the fluorescent probe 9 was designed to show a Na+ induced ratiometric fluorescence behavior at two emission wavelengths. As desired, 9 (K-d=78 mm) showed a ratiometric fluorescence response towards Na+ ions and is a suitable tool to measure physiologically relevant Na+ levels by the intensity change of two emission wavelengths at 404 nm and 492 nm.
In this paper, we report on the fluorescence behaviour of three regioisomers which consist of two 9-anthracenyl fluorophores and of differently substituted dithiodicyanoethene moieties. These isomeric fluorescent probes show different quantum yields (phi(f)). In these probes, an oxidative photoinduced electron transfer (PET) from the excited 9-anthracenyl fluorophore to the dithiodicyanoethene unit quenches the fluorescence. This quenching process is accelerated by an intramolecular charge transfer (ICT) of the push-pull pi-electron system of the dithiodicyanoethene group. The acceleration of the PET depends on the strength of the ICT unit. The higher the dipole moment of the ICT unit, the stronger the observed fluorescence quenching. To the best of our knowledge, this is the first report of a regioisomeric influence on an oxidative PET by an ICT.