Eric V. Anslyn

Artificial receptors for the recognition of phosphorylated molecules

Artificial Receptors for the Recognition of Phosphorylated Molecules Amanda E. Hargrove, Sonia Nieto, Tianzhi Zhang, Jonathan L. Sessler,* and Eric V. Anslyn* Department of Chemistry and Biochemistry, University of Texas at Austin, 1 University Station A5300, Austin, Texas 78712-0165, United States Universidad de Zaragoza, Zaragoza, Spain Henkel Corporation, Rocky Hill, Connecticut 06067 Department of Chemistry, Yonsei University, Seoul, 120-749 Korea

Differential receptor arrays and assays for solution-based molecular recognition.

Nature has inspired an emergent supramolecular field of synthetic receptor arrays and assays for the pattern-based recognition of various bioanalytes and metal species. The synthetic receptors are not necessarily selective for a particular analyte, but the combined signal response from the array is diagnostic for the analyte. This tutorial review describes recent work in the literature for this emerging supramolecular field and details basic array and assay design principles. We review the analytes targeted, signaling types used, and pattern recognition. Developing specific receptors for the solution-based analysis of complex analytes and mixtures is a daunting task. A solution to this difficult task has been inspired by natures use of arrays of receptors in the senses of taste and smell. An emerging field within supramolecular chemistry is the use of synthetic and readily available receptors in array formats for the detection of analytes in solution. Each receptor in a differential array does not necessarily have selectivity for a particular analyte, but the combined fingerprint response can be extracted as a diagnostic pattern visually, or using chemometric tools. This new genre of molecular recognition is advancing rapidly with several groups developing novel array platforms and receptors.

Abiotic guanidinium containing receptors for anionic species

Abstract In the field of molecular recognition, the guanidinium group has been established as a highly effective functional group in the binding of anionic guests. This moiety has been proven to form a strong interaction with anions through charge pairing and hydrogen bonding in competitive solvent systems. The group also features a high p K a value, allowing for its utility over an expansive pH range. As a result of these qualities, the guanidinium group has become ubiquitous in literature involving the design and synthesis of receptor molecules for small target anions. An overview of the inclusion of the guanidinium group within synthetic receptor molecules is presented in this review article.

Teaching Old Indicators New Tricks: A Colorimetric Chemosensing Ensemble for Tartrate/Malate in Beverages

The competition between tartrate and a common indicator (1) for a synthetic host (2) has been used to quantitate tartrate in beverages derived from grapes. The approach demonstrates a general method for the development of colorimetric assays in highly competitive media.

Anion recognition: synthetic receptors for anions and their application in sensors.

Important contributions to the field of anion sensing include electrochemical lipophilic uranyl salophene receptors incorporated into membranes that act as fluoride-selective potentiometric microsensors. A promising optical-based sensor, selective for cyclic AMP, involves a preorganized, molecularly imprinted polymer employing an intrinsic fluorophore. Competition methods using ensembles of recognition units and external indicators have been used to sense citrate in highly competitive media and micromolar concentrations of inositol(tris)phosphate in water. In addition, DNA dendrimers immobilized on a quartz-crystal microbalance acted as an elegant biosensor for Cryptosporidium DNA. These designs display the varied methods of anion detection currently being pursued.

A Chemosensor for Citrate in Beverages

Competitive binding like that in immunoassays is the principle behind the chemosensor based on receptor 1, which was used to measure the concentration of citrate (2) in a series of common beverages. Citrate displaces the fluorescent colorimetric probe 5-carboxylfluorescein (3) from 1, and the process can be monitored by UV or fluorescence spectroscopy.

A Highly Selective Low-Background Fluorescent Imaging Agent for Nitric Oxide

We introduce a novel sensing mechanism for nitric oxide (NO) detection with a particular easily synthesized embodiment (NO(550)), which displays a rapid and linear response to NO with a red-shifted 1500-fold turn-on signal from a dark background. Excellent selectivity was observed against other reactive oxygen/nitrogen species, pH, and various substances that interfere with existing probes. NO(550) crosses cell membranes but not nuclear membranes and is suitable for both intra- and extracellular NO quantifications. Good cytocompatibility was found during in vitro studies with two different cell lines. The high specificity, dark background, facile synthesis, and low pH dependence make NO(550) a superior probe for NO detection when used as an imaging agent.

Chromogenic/Fluorogenic Ensemble Chemosensing Systems.

Jiasheng Wu,† Bomi Kwon,‡ Weimin Liu,† Eric V. Anslyn, Pengfei Wang,*,† and Jong Seung Kim*,‡ †Key Laboratory of Photochemical Conversion and Optoelectronic Materials and CityU-CAS Joint Laboratory of Functional Materials and Devices, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China ‡Department of Chemistry, Korea University, Seoul 136-701, Korea Department of Chemistry, The University of Texas at Austin, 105 E. 24th, Street-Stop A5300, Austin, Texas 78712-1224, United States

Using Enantioselective Indicator Displacement Assays To Determine the Enantiomeric Excess of α-Amino Acids

Enantioselective indicator displacement assays (eIDAs) were used for the determination of enantiomeric excess (ee) of alpha-amino acids as an alternative to the labor-intensive technique of chromatography. In this study, eIDAs were implemented by the use of two chiral receptors [(Cu(II)(1)](2+), [Cu(II)(2)](2+)) in conjunction with the indicator chrome azurol S. The two receptors were able to enantioselectively discriminate 13 of the 17 analyzed alpha-amino acids. Enantiomeric excess calibration curves were made using both receptors and then used to analyze true test samples to check the systems ability to determine ee accurately. The proposed method uses a conventional UV-vis spectrophotometer to monitor the colorimetric signal, which allows for a potential high-throughput screening (HTS) method for determining ee. The techniques created consistently produced results accurate enough for rapid preliminary determination of ee.

The uses of supramolecular chemistry in synthetic methodology development: examples of anion and neutral molecular recognition

The principles of supramolecular chemistry have successfully permeated through a broad range of organic chemistry subdisciplines. One subdiscipline that is not routinely associated with supramolecular chemistry is that of organic synthetic methodology. Though sometimes indiscernible, non-bonded and bonding supramolecular interactions play a large role in chemical reactions and catalysis. Many synthetic methods hinge on the creation of anionic charge, albeit just partial, at some step during this process, and hence are prime targets for molecular recognition interactions. Examples are artificial enzymes, biomimetic catalysis, organocatalysis, and many of the catalysts that are derived from a combinatorial screen. Further, supramolecular chemistry is playing an increasingly large role in high-throughput analytical techniques. This tutorial review ties together supramolecular approaches to methodology creation, combinatorial screening, and analytical protocols. The goal is to show, and further predict, that supramolecular chemistry will continually increase its impact in organic synthetic methodology development.