Phenol Fluorophores Research Articles

A General Strategy Toward pH‐Resistant Phenolic Fluorophores for High‐Fidelity Sensing and Bioimaging Applications

AbstractAryl alcohol‐type or phenolic fluorophores offer diverse opportunities for developing bioimaging agents and fluorescence probes. Due to the inherently acidic hydroxyl functionality, phenolic fluorophores provide pH‐dependent emission signals. Therefore, except for developing pH probes, the pH‐dependent nature of phenolic fluorophores should be considered in bioimaging applications but has been neglected. Here we show that a simple structural remedy converts conventional phenolic fluorophores into pH‐resistant derivatives, which also offer “medium‐resistant” emission properties. The structural modification involves a single‐step introduction of a hydrogen‐bonding acceptor such as morpholine nearby the phenolic hydroxyl group, which also leads to emission bathochromic shift, increased Stokes shift, enhanced photo‐stability and stronger emission for several dyes. The strategy greatly expands the current fluorophores’ repertoire for reliable bioimaging applications, as demonstrated here with ratiometric imaging of cells and tissues.

A General Strategy Toward pH-Resistant Phenolic Fluorophores for High-Fidelity Sensing and Bioimaging Applications.

Aryl alcohol-type or phenolic fluorophores offer diverse opportunities for developing bioimaging agents and fluorescence probes. Due to the inherently acidic hydroxyl functionality, phenolic fluorophores provide pH-dependent emission signals. Therefore, except for developing pH probes, the pH-dependent nature of phenolic fluorophores should be considered in bioimaging applications but has been neglected. Here we show that a simple structural remedy converts conventional phenolic fluorophores into pH-resistant derivatives, which also offer "medium-resistant" emission properties. The structural modification involves a single-step introduction of a hydrogen-bonding acceptor such as morpholine nearby the phenolic hydroxyl group, which also leads to emission bathochromic shift, increased Stokes shift, enhanced photo-stability and stronger emission for several dyes. The strategy greatly expands the current fluorophores' repertoire for reliable bioimaging applications, as demonstrated here with ratiometric imaging of cells and tissues.

Alizarin-based molecular probes for the detection of hydrogen peroxide and peroxynitrite.

Phenol fluorophores are a large family of fluorophores, which have attracted more and more attention in the design of probes. Using the self-assembly of aromatic boronic acid with Alizarin Red S (ARS) and Gallein (GAL), the novel chemosensors ARS-CBA and GAL-CBA were provided for hydrogen peroxide (H2O2), which demonstrated their ability to detect H2O2 with indicator displacement assay (IDA) by colorimetric and electrochemical measurements. After ARS-CBA and GAL-CBA reacted with H2O2, the systems displayed a red-shifted visible color change in aqueous media and off-on electrochemical signals showing generation of phenol. The chemosensor ARS-CBA also had good performance in fluorometric measurements and turn-off fluorescent response indicated removal of aromatic boronic acid. In addition, a designed near-infrared (NIR) dual-modal fluorescent probe alizarin blue S (ABS) was used for peroxynitrite (ONOO-) with a visible colorimetric change in dimethyl sulfoxide (DMSO) and "on-off" fluorescent response indicating the oxidation of hydroxyl. The flexible Phenol fluorophores are allowed to prepare multiple fluorescent probes towards H2O2 or ONOO- for environmental and physiological applications.

Comparison of the properties of standard soil and aquatic fulvic and humic acids based on the data of differential absorbance and fluorescence spectroscopy

This study compared effects of pH, ionic strength and complexation with Mg2+ on the chromophores and fluorophores of aquatic and terrestrial NOM exemplified by the standard isolates Suwannee River fulvic and humic acid (SRFA and SRHA) and Pahokee Peat fulvic and humic acids (PPFA and PPHA) provided by the International Humic Substance Society (IHSS). The intensity of the differential spectra of the NOM isolates increased monotonically with pH. These spectra comprised contributions of similar chromophore systems associated with the carboxylic and phenolic moieties. The intensity of SRFA and PPFA fluorescence changed non-monotonically vs. pH indicating that the deprotonation of the phenolic fluorophores decreased their emission yields. Examination of the effects of pH on the slopes of the log-transformed absorbance of NOM showed that the influence of deprotonation on the conformations of PPFA and PPHA molecules was less prominent than those for SRFA but not dissimilar to those of SRHA. Changes of the differential spectra and spectral slopes showed that Mg2+/PPFA and Mg2+/PPHA complexation was more effected by electrostatic interactions while the involvement of phenolic groups was notable for SRFA. The observed trends highlight similarities and differences in the properties of the chromophores and fluorophores in the standard isolates of soil and aquatic NOM. These results necessitate further systematic comparison of the properties of NOM isolates and those of unaltered NOM.

Contrasting impacts of pH on the abiotic transformation of hydrochar-derived dissolved organic matter mediated by δ-MnO2

Hydrochar produced from hydrothermal carbonization of agricultural waste becomes a promising soil conditioner, and especially, its labile fraction, dissolved organic matter (DOM) may play an important role in improving soil fertility and quality. However, little is known about the interaction and transformation of hydrochar-derived DOM with soil reactive components after its amendment into soil. The abiotic transformation of hydrochar-derived DOM by a common soil metal oxide, δ-MnO2 at environmentally relevant pHs (4, 6 and 8) was investigated by using a combination of batch experiments and advanced spectroscopic techniques. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and fluorescence spectroscopy revealed that lignins and carboxyl-rich alicyclic molecules were predominant in hydrochar-derived DOM and phenolic fluorophores were the dominant fluorescent composition. In the presence of δ-MnO2, hydrochar-derived DOM was rapidly transformed via both decomposition and polycondensation, resulting in significant structure changes of hydrochar-derived DOM with increasing humic-like fraction similar to soil organic matter (SOM). The transformation process of hydrochar-derived DOM molecules was highly pH-dependent, with polycondensation occurring preferentially at pH 8 and more rapid oxidation at pH 4. Meanwhile, δ-MnO2 was reduced to Mn(II) and Mn(III) during the reaction, and the accumulation of Mn(III) in the solid phase of δ-MnO2 reached a maximum at pH 4. Collectively, the results characterized the transformation mechanism of DOM by δ-MnO2 at molecular level, which provided a new perspective for better understanding of the biogeochemical processes of biochar for its application in soil quality improvement and remediation.

Multicolour fluorescent memory based on the interaction of hydroxy terphenyls with fluoride anions.

Memory operations based on variation of a molecule's properties are important because they may lead to device miniaturization to the molecular scale or increasingly complex information processing protocols beyond the binary level. Molecular memory also introduces possibilities related to information-storage security where chemical information (or reagents) might be used as an encryption key, in this case, acidic/basic reagents. Chemical memory that possesses both volatile and non-volatile functionality requires reversible conversion between at least two chemically different stable or quasi-stable states. Here we have developed the phenol-phenoxide equilibrium of phenol fluorophores as a data storage element, which can be used to write or modulate data using chemical reagents. The properties of this system allow data to be stored and erased either in non-volatile or volatile modes. We also demonstrate non-binary switching of states made possible by preparation of a composite containing the molecular memory elements.

Synthesis and utility of fluorogenic acetoxymethyl ethers.

Phenolic fluorophores such as fluorescein, Tokyo Green, resorufin, and their derivatives are workhorses of biological science. Acylating the phenolic hydroxyl group(s) in these fluorophores masks their fluorescence. The ensuing ester is a substrate for cellular esterases, which can restore fluorescence. These esters are, however, notoriously unstable to hydrolysis, severely compromising their utility. The acetoxymethyl (AM) group is an esterase-sensitive motif that can mask polar functionalities in small molecules. Here, we report on the use of AM ether groups to mask phenolic fluorophores. The resulting profluorophores have a desirable combination of low background fluorescence, high chemical stability, and high enzymatic reactivity, both in vitro and in cellulo. These simple phenyl ether-based profluorophores could supplement or supplant the use of phenyl esters for imaging biochemical and biological systems.

Phenol-containing bis(oxazolines): synthesis and fluorescence sensing of amines

The fluorescence sensing of primary amines as their neutral forms has been studied with bis(oxazolinyl)phenols (Me-BOP, Ph-BOP), which are efficiently synthesized starting from mesitylene in six steps and in overall 12–22% yields. The BOP sensors showed fluorescence enhancement toward butylamine and several arylethylamines, whereas they showed fluorescence quenching toward secondary and branched amines. The opposite fluorescence behavior is explained by an increased conformational restriction at the excited state, at which a proton transfer complex between the host and guest forms that is stabilized in a tripodal hydrogen bonding mode. This is the first example in which fluorescence enhancement is observed in amine sensing with phenolic fluorophores. Enantiomeric α-chiral organoamines were also sensed with different fluorescent intensity changes by Ph-BOP, complementing the previous tris(oxazolines) that sense enantiomeric α-chiral organoammonium ions.