Shining light on fluoride detection: a comprehensive study exploring the potential of coumarin precursors as selective turn-on fluorescent chemosensors.

In this study, we report a fluoride chemosensor based on the use of a non-fluorescent pre-coumarin, compound 1. This compound undergoes selective fluoride-triggered formation of coumarin 2, with a concomitant turn-on fluorescence signal. Although compound 1 exists as a mixture of alkene isomers (2 : 1 in favor of the E isomer), only the minor Z-isomer undergoes cyclization. Nonetheless, comprehensive computational and experimental studies provide evidence that in situ isomerization of E-1 to Z-1, followed by fluoride-triggered phenolate evolution and intramolecular cyclization, facilitates the generation of coumarin 2 in high yield. Moreover, this system is an effective turn-on fluorescence sensor for fluoride anions, which displays outstanding selectivity (limited response to other commonly occurring analytes), sensitivity (lowest reported limits of detection for this sensor class), and practicality (works in solution and on paper to generate both fluorometric and colorimetric responses). Ongoing efforts are focused on expanding this paradigm to other pre-coumarin scaffolds, which also undergo analyte-specific coumarin formation accompanied by turn-on fluorescence.

Paper-based manganese and ß-cyclodextrin sensors for colorimetric sulfur dioxide detection.

Reported herein is a novel detection method for sulfur dioxide in aqueous solutions, in which the presence of sulfur dioxide leads to color changes of filter paper modified with both ß-cyclodextrin and manganese. This detection method is rapid (less than 5 min required for complete color change), sensitive (limits of detection as low as 33 ppm), broadly applicable (tolerant of a range of pH values), and practical (color changes can be observed via naked eye detection and quantified via straightforward color analysis). Extensive optimization of each component provides insight into the unique stabilizing effect of cyclodextrin in preventing the filter paper from permanganate-induced degradation, and mechanistic analysis points to an oxidation-reduction reaction as responsible for the observed color changes. Overall, these results lay the groundwork for the development of practical sulfur dioxide sensors for use in the food and beverage industry, and provide precedent for the use of cyclodextrin as a stabilizing force in paper-based chemical sensors.

A dipodal bimane-ditriazole-diCu(II) complex serves as an ultrasensitive water sensor.

An ultrasensitive fluorescent water sensor based on a dipodal bimane-Cu(II) complex is reported here. This complex, which is non-fluorescent in the absence of water, demonstrates a remarkable turn-on fluorescence in the presence of extremely low (0.000786% v/v) concentrations of water, via highly selective water-induced displacement of copper and restoration of the innate bimane fluorescence.

Sonication-Induced, Solvent-Selective Gelation of a 1,8-Napthalimide-Conjugated Amide: Structural Insights and Pollutant Removal Applications.

Reported herein is the synthesis, characterization, and dye removal applications of a highly solvent-selective organogel-forming amide, compound 1, which contains a 1,8-naphthalmide moiety, flexible n-hexyl chain, and benzene ring. This compound displayed remarkable solvent selectivity, with gel formation occurring only in the presence of alkylated aromatic solvents. Detailed structural characterization of the gels, combined with notable theoretical insights, is invoked to explain the highly selective gelation properties of compound 1, as is a comparison to non-gel forming structural isomer 2, which contains the same structural elements in a different arrangement. Finally, the ability of the gel derived from compound 1 to act as a reusable material for the efficient removal of cationic organic dyes from contaminated aqueous environments is also reported, with up to 11 repeated uses of the gel still maintaining the ability to effectively remove Rhodamine B.

Ronald C.D. Breslow (1931-2017): A career in review.

Reviewed herein are key research accomplishments of Professor Ronald Charles D. Breslow (1931-2017) throughout his more than 60 year research career. These accomplishments span a wide range of topics, most notably physical organic chemistry, medicinal chemistry, and bioorganic chemistry. These topics are reviewed, as are topics of molecular electronics and origin of chirality, which combine to make up the bulk of this review. Also reviewed briefly are Breslow's contributions to the broader chemistry profession, including his work for the American Chemical Society and his work promoting gender equity. Throughout the article, efforts are made to put Breslow's accomplishments in the context of other work being done at the time, as well as to include subsequent iterations and elaborations of the research.

Fluorescence-Based Sensing of Pesticides Using Supramolecular Chemistry.

The detection of pesticides in real-world environments is a high priority for a broad range of applications, including in areas of public health, environmental remediation, and agricultural sustainability. While many methods for pesticide detection currently exist, the use of supramolecular fluorescence-based methods has significant practical advantages. Herein, we will review the use of fluorescence-based pesticide detection methods, with a particular focus on supramolecular chemistry-based methods. Illustrative examples that show how such methods have achieved success in real-world environments are also included, as are areas highlighted for future research and development.

Highly Sensitive Water Detection Through Reversible Fluorescence Changes in a syn-Bimane Based Boronic Acid Derivative.

Reported herein is a fluorometric and colorimetric sensor for the presence of trace amounts of water in organic solvents, using syn-bimane based boronate ester 1. This sensor responds to the presence of water with a highly sensitive turn-off fluorescence response, with detection limits as low as 0.018% water (v/v). Moreover, analogously high performance was observed when compound 1 was adsorbed on filter paper, with the paper-based sensor responding both to the presence of liquid water and to humid atmospheres. Reusability of the paper-based sensor up to 11 cycles was demonstrated, albeit with progressive decreases in the performance, and 1H NMR and mass spectrometry analyses were used to explain the observed, hydrolysis-based sensor response.

Highly sensitive detection of cobalt through fluorescence changes in ß-cyclodextrin-bimane complexes.

A supramolecular complex of syn-(methyl,methyl)bimane (1) and ß-cyclodextrin demonstrates a sensitive (limit of detection = 0.60 nM) and selective fluorescence turn-off response in the presence of cobalt in aqueous media, with calibration curves enabling quantitation in solution and using filter papers on which bimane and cyclodextrin were adsorbed. 1H NMR spectroscopy provides insight into interactions underlying the sensor performance.

Efficient Detection and Removal of Polycyclic Aromatic Hydrocarbons Using Cyclodextrin-Modified Cellulose.

Covalent functionalization of cellulose with ß-cyclodextrin by succinic acid-promoted cross-linking leads to a dual-function material that efficiently promotes proximity-induced energy transfer from polycyclic aromatic hydrocarbons (PAHs) to squaraine fluorophores with high quantum yields, and removes PAHs from aqueous solution through non-covalent binding. This material, which possesses a high functionalization density (0.17 µg/mm2 of cyclodextrin on cellulose), promotes energy transfer efficiencies as high as 58 % (for an anthracene donor in combination with a squaraine fluorophore acceptor), and leads to the removal of up to 91 % of a PAH (pyrene) from aqueous solution by mixing of the solution with the functionalized material. Overall, the high performance of this material in both proximity-induced energy transfer and the removal of PAHs from water means that such a method has significant potential impact in a variety of real-world environmental remediation scenarios.

Use of α-cyclodextrin to Promote Clean and Environmentally Friendly Disinfection of Phenolic Substrates via Chlorine Dioxide Treatment.

The use of chlorine dioxide to disinfect drinking water and ameliorate toxic components of wastewater has significant advantages in terms of providing safe water. Nonetheless, significant drawbacks toward such usage remain. These drawbacks include the fact that toxic byproducts of the disinfection agents are often formed, and the complete removal of such agents can be challenging. Reported herein is one approach to solving this problem: the use of α-cyclodextrin to affect the product distribution in chlorine dioxide-mediated decomposition of organic pollutants. The presence of α-cyclodextrin leads to markedly more oxidation and less aromatic chlorination, in a manner that is highly dependent on analyte structure and other reaction conditions. Mechanistic hypotheses are advanced to explain the cyclodextrin effect, and the potential for use of α-cyclodextrin for practical wastewater treatment is also discussed.

Enhanced Characterization of Pyrene Binding in Mixed Cyclodextrin Systems via Fluorescence Spectroscopy.

Although significant effort has been expended to analyze the binding of pyrene in ß-cyclodextrin and γ-cyclodextrin, little has been published on the binding of this guest in ß-cyclodextrin derivatives (methyl-ß-cyclodextrin and 2-hydroxypropyl-ß-cyclodextrin) or in mixtures of such derivatives, despite the fact that these derivatives are known to have different supramolecular properties that facilitate unique modes of complexation. Reported herein is a detailed spectroscopic investigation of the binding of pyrene in ß-cyclodextrin derivatives and in binary mixtures of cyclodextrins. Py values, defined as the ratio of representative vibronic bands in the fluorescence emission of pyrene, were used to measure changes in the pyrene microenvironment in the presence of the cyclodextrin hosts, and indicated that unmodified ß-cyclodextrin is unique in providing a fully hydrophobic environment for pyrene through the use of two cyclodextrins to bind a single pyrene guest. By comparison, both γ-cyclodextrin and modified ß-cyclodextrin analogues bind pyrene in a less hydrophobic environment through 1:1 binding stoichiometries that allow for continued interactions between the incompletely encapsulated pyrene guest and the aqueous solvent system. Binary mixtures of cyclodextrins were also explored and reinforce the unique properties of the unmodified ß-cyclodextrin host. Graphical Abstract The unique binding geometries of pyrene in beta-cyclodextrin and its derivatives leads to measurable fluorescence emission signals, whose information can be used to elucidate the highly structurally dependent binding geometries and stoichiometries.

A Paper-Based Device for Ultrasensitive, Colorimetric Phosphate Detection in Seawater.

High concentrations of certain nutrients, including phosphate, are known to lead to undesired algal growth and low dissolved oxygen levels, creating deadly conditions for organisms in marine ecosystems. The rapid and robust detection of these nutrients using a colorimetric, paper-based system that can be applied on-site is of high interest to individuals monitoring marine environments and others affected by marine ecosystem health. Several techniques for detecting phosphate have been reported previously, yet these techniques often suffer from high detection limits, reagent instability, and the need of the user to handle toxic reagents. In order to develop improved phosphate detection methods, the commonly used molybdenum blue reagents were incorporated into a paper-based, colorimetric detection system. This system benefited from improved stabilization of the molybdenum blue reagent as well as minimal user contact with toxic reagents. The colorimetric readout from the paper-based devices was analyzed and quantified using RGB analyses (via ImageJ), and resulted in the detection of phosphate at detection limits between 1.3 and 2.8 ppm in various aqueous media, including real seawater.

Ultrasensitive Detection of Nitrite through Implementation of N-(1-Naphthyl)ethylenediamine-Grafted Cellulose into a Paper-Based Device.

Reported herein is the immobilization of N-(1-naphthyl)ethylenediamine (NED) on cellulose via an epichlorohydrin (ECH)-based covalent attachment and the implementation of the functionalized cellulose into an ultrasensitive, paper-based device for nitrite detection. The reported functionalization procedure resulted in a 12.9-fold higher functionalization density than the density that results from the previously reported procedures, and the subsequent device allows for nitrite detection limits in synthetic freshwater and real seawater of 0.26 and 0.22 µM, respectively. The sensor is efficient in a wide range of temperature, humidity, turbidity, and salinity conditions and has been successfully applied for nitrite detection in real water samples.

Detection of anabolic steroids via cyclodextrin-promoted fluorescence modulation.

Reported herein is the detection of anabolic steroids through the use of cyclodextrin-promoted interactions between the analyte of interest and a high quantum yield fluorophore, which lead to measurable, analyte-specific changes in the fluorophore emission signal. By using a variety of ß-cyclodextrin derivatives (unmodified ß-cyclodextrin, methyl-ß-cyclodextrin, and 2-hydroxypropyl-ß-cyclodextrin) in combination with high quantum yield fluorophore rhodamine 6G, we detected five anabolic steroid analytes with 100% differentiation between structurally similar analytes and micromolar level limits of detection. Overall, these results show significant potential in the development of practical, fluorescence-based steroid detection devices.

Colorimetric Detection of Aliphatic Alcohols in ß-Cyclodextrin Solutions.

The sensitive, selective, and practical detection of aliphatic alcohols is a continuing technical challenge with significant impact in public health research and environmental remediation efforts. Reported herein is the use of a ß-cyclodextrin derivative to promote proximity-induced interactions between aliphatic alcohol analytes and a brightly colored organic dye, which resulted in highly analyte-specific color changes that enabled accurate alcohol identification. Linear discriminant analysis of the color changes enabled 100% differentiation of the colorimetric signals obtained from methanol, ethanol, and isopropanol in combination with BODIPY and Rhodamine dyes. The resulting solution-state detection system has significant broad-based applicability because it uses only easily available materials to achieve such detection with moderate limits of detection obtained. Future research with this sensor system will focus on decreasing limits of detection as well as on optimizing the system for quantitative detection applications.

Identification of 15 Phthalate Esters in Commercial Cheese Powder via Cyclodextrin-Promoted Fluorescence Detection.

A challenge for detecting phthalates in commercial products such as cheese powders is that the composition of the products is highly complex, and current methods for detection rely on gas chromatography-mass spectrometry, which is not portable and cannot be used by individual consumers at a time and place of their choosing. Herein, we report the development of a new method for phthalate detection in cheese powder using cyclodextrin-promoted fluorescence detection, in which the presence of the phthalate analytes leads to highly analyte-specific changes in the fluorescence emission signal of a fluorophore bound in a cyclodextrin cavity. This method relies on subtle changes in the analyte affinity for the fluorophore and the cyclodextrin cavity and provides for markedly more straightforward sample preparation procedures and an extremely rapid read-out signal, with potential for the development of portable fluorescence sensors. Using this method, we were able to detect 15 phthalate esters with highly analyte-specific responses and at concentrations as low as 0.12 µM, which is well below regulatory levels of concern. Computational investigations strongly support the observed experimental trends.

Effects of Structural Variation in Conjugated Side Chains on the Photophysics of Conjugated Polymers in Nanoparticles.

Conjugated polymers (CPs) are widely used for a variety of applications as a result of their high quantum yields, strong extinction coefficients, and good stability to a variety of experimental conditions. In many cases, the use of conjugated polymer nanoparticles (CPNs) provides additional practical advantages. The ability to understand how the structure of the CP affects its photophysical properties has the potential to significantly accelerate research in this area. In this work we examine 3 CPs, including two novel polymer architectures, and evaluate how the structures of the conjugated side chains affect the photophysical properties of the free polymer chains as well as the properties of aggregated CPNs. Both the linker identity and the terminal aromatic rings of the side chains were found to affect the photophysical properties of the CPs, with the terminal groups leading to the most substantial changes in photophysical properties in all of the polymeric forms (well-solubilized in organic solvent and aggregated in nanoparticles).

Supramolecular Luminescent Sensors.

There is great need for stand-alone luminescence-based chemosensors that exemplify selectivity, sensitivity, and applicability and that overcome the challenges that arise from complex, real-world media. Discussed herein are recent developments toward these goals in the field of supramolecular luminescent chemosensors, including macrocycles, polymers, and nanomaterials. Specific focus is placed on the development of new macrocycle hosts since 2010, coupled with considerations of the underlying principles of supramolecular chemistry as well as analytes of interest and common luminophores. State-of-the-art developments in the fields of polymer and nanomaterial sensors are also examined, and some remaining unsolved challenges in the area of chemosensors are discussed.

Cyclodextrin-Promoted Fluorescence Detection of Aromatic Toxicants and Toxicant Metabolites in Commercial Milk Products.

The detection of polycyclic aromatic hydrocarbons (PAHs) and their metabolites in food and in agricultural sources is an important research objective due to the PAHs' known persistence, carcinogenicity, and toxicity. PAHs have been found in the milk of lactating cows, and in the leaves and stems of plants grown in PAH-contaminated areas, thereby making their way into both cow milk and plant milk alternatives. Reported herein is the rapid, sensitive, and selective detection of 10 PAHs and PAH metabolites in a variety of cow milks and plant milk alternatives using fluorescence energy transfer from the PAH to a high quantum yield fluorophore, combined with subsequent array-based statistical analyses of the fluorescence emission signals. This system operates with high sensitivity (low micromolar detection limits), selectivity (100% differentiation even between structurally similar analytes), and general applicability (for both unmodified lipophilic PAHs and highly polar oxidized PAH metabolites, as well as for different cow and plant milk samples). These promising results show significant potential to be translated into solid-state devices for the rapid, sensitive, and selective detection of PAHs and their metabolites in complex, commercial food products.