A Colorimetric Boronic Acid Based Sensing Ensemble for Carboxy and Phospho Sugars

Zhang, Tianzhi; Anslyn, Eric V.

doi:10.1021/ol060279+

Cited by 60 publications

(33 citation statements)

References 30 publications

(11 reference statements)

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“…Several methods are used to form a tetrahedral boron centre. Wulff-type boronic acids (such as 5) make use of an intramolecular B-N dative bond, and boroxoles such as 6 are formed by an intramolecular five-membered ring, with a pK a of around 7.2 [84]; phenylboronic acid (as sensing ensemble) [41]; proteasome inhibitor [3,8] and oligosaccharides such as structural and storage polysaccharides and cyclodextrins. Such complexity means that the differentiation of polysaccharides by small molecules remains a challenge.…”

Section: Recognition Of Mono- Oligo-and Polysaccharides By Boronic Amentioning

confidence: 99%

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Molecular recognition with boronic acids—applications in chemical biology

2013

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Small molecules have long been used for the selective recognition of a wide range of analytes. The ability of these chemical receptors to recognise and bind to specific targets mimics certain biological processes (such as proteinsubstrate interactions) and has therefore attracted recent interest. Due to the abundance of biological molecules possessing polyhydroxy motifs, boronic acids-which form fivemembered boronate esters with diols-have become increasingly popular in the synthesis of small chemical receptors. Their targets include biological materials and natural products including phosphatidylinositol bisphosphate, saccharides and polysaccharides, nucleic acids, metal ions and the neurotransmitter dopamine. This review will focus on the many ways in which small chemical receptors based on boronic acids have been used as biochemical tools for various purposes, including sensing and detection of analytes, interference in signalling pathways, enzyme inhibition and cell delivery systems. The most recent developments in each area will be highlighted.

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Section: Recognition Of Mono- Oligo-and Polysaccharides By Boronic Amentioning

confidence: 99%

“…Sensing ensembles such as these have been developed for a wide range of analytes including chiral diols [68], the anticoagulant oligosaccharide heparin [86], phosphosugars [12], nucleotides [84] and more [41,54,56,83].…”

Section: Displacement Assays As a Measure Of Enzyme Activitymentioning

confidence: 99%

Molecular recognition with boronic acids—applications in chemical biology

2013

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“…Because the indicator and host are non-covalently bonded, chemosensing ensembles offer many advantages over traditional chemosensors, in which the receptor and reporter units are covalently linked. Using this chemosensing concept, new methods have been developed to detect analytes such as oxalate [6], amino acids [7][8][9], caffeine [10], cocaine [11], phosphate [12,13], chloride [14], carboxylated and phosphorylated sugars [15], glucose oxidase [16], and chiral carboxylic acids [17].…”

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confidence: 99%

2-(4-Pyridyl)imino nitroxide-tetraphenylporphyrin zinc(II): A chemosensing ensemble for nicotine

2012

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2-(4-Pyridyl)imino nitroxide and tetraphenylporphyrin zinc(II) formed a stable complex by noncovalent bonding in a nonpolar solution. Nicotine displaced 2-(4-pyridyl)imino nitroxide when it was added to a solution of 2-(4-pyridyl)imino nitroxide-tetraphenylporphyrin zinc(II). The fluorescence intensity of tetraphenylporphyrin zinc(II) was altered by sequentially addition of 2-(4-pyridyl)imino nitroxide and nicotine. This was used to develop a new method for detection of nicotine. tetraphenylporphyrin zinc(II), imino nitroxide, detect, nicotine Citation:Han H F, Zhang G X, Wang H M. 2-(4-Pyridyl)imino nitroxide-tetraphenylporphyrin zinc(II): A chemosensing ensemble for nicotine. Chin Sci Bull, 2012Bull, , 57: 16091611, doi: 10.1007 In recent years, many chemosensing ensembles [1][2][3][4][5] have been reported for the detection of various analytes. In a typical chemosensing ensemble, an indicator first weakly binds to a host through non-covalent and hydrogen bonds. Then, the analyte of interest is added to the system and displaces the indicator from the host, which in turn induces a change in the spectrum of the system. Because the indicator and host are non-covalently bonded, chemosensing ensembles offer many advantages over traditional chemosensors, in which the receptor and reporter units are covalently linked. Nicotine is present in tobacco leaves and cigarette smoke, and has been used in pharmaceutical and synthetic applications and as an insecticide. Detection of nicotine is of particular importance in the tobacco industry and in toxicology [18][19][20]. Common nicotine detection methods include gas chromatography [21], liquid chromatography [22], and capillary electrophoresis [23]. Herein, we report a new method for detection of nicotine based on 2-(4-pyridyl)imino nitroxide-tetraphenylporphyrin zinc(II).The design rationale for the chemosensing ensemble is illustrated in Scheme 1. Porphyrin zinc(II) is highly fluorescent [24], and can easily form complexes with pyridine derivatives. For example, Yamauchi and co-worker [25,26] described formation of a tetraphenylporphyrin zinc(II) complex with 2-(4-pyridyl)nitronyl nitroxide. However, they only studied the spin properties of the excited state of this complex. In an earlier report [27], we detailed the fluorescence quenching caused by nitronyl nitroxide and imino nitroxide. Binding of either nitronyl or imino nitroxide to prophyrin zinc(II) is expected to quench its fluorescence. The absorption spectrum of 2-(4-pyridyl)nitronyl nitroxide shows peaks between 320-400 nm, and overlaps with the fluorescence spectrum of tetraphenylporphyrin zinc(II) (TPPZn). Accordingly, energy transfer will also contribute to quenching of the fluorescence of tetraphenylporphyrin zinc(II). For this reason, 2-(4-pyridyl)imino nitroxide (4-PIN), rather than 2-(4-pyridyl)nitronyl nitroxide, was chosen for the ensemble with TPPZn. Addition of a pyridine derivative to a mixed solution of 4-PIN and TPPZn will

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“…An IDA both eliminates the need to incorporate the chromophore or fluorophore into the structure of the host, thus simplifying the synthesis of the host molecule, and allows one to tune the sensitivity of the assay because of the ability to change the identity and concentration of the indicator (8). Our research group and others have developed multicomponent optical sensors that function on the basis of an indicator displacement assay (9)(10)(11)(12).…”

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confidence: 99%

A general protocol for creating high-throughput screening assays for reaction yield and enantiomeric excess applied to hydrobenzoin

Shabbir

Regan

Anslyn

2009

Proc. Natl. Acad. Sci. U.S.A.

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A general approach to high-throughput screening of enantiomeric excess (ee) and concentration was developed by using indicator displacement assays (IDAs), and the protocol was then applied to the vicinal diol hydrobenzoin. The method involves the sequential utilization of what we define herein as screening, training, and analysis plates. Several enantioselective boronic acid-based receptors were screened by using 96-well plates, both for their ability to discriminate the enantiomers of hydrobenzoin and to find their optimal pairing with indicators resulting in the largest optical responses. The best receptor/indicator combination was then used to train an artificial neural network to determine concentration and ee. To prove the practicality of the developed protocol, analysis plates were created containing true unknown samples of hydrobenzoin generated by established Sharpless asymmetric dihydroxylation reactions, and the best ligand was correctly identified.artificial neural networks ͉ catalyst discovery ͉ enantioselective indicator displacement assay ͉ supramolecular chemistry T he unique role of chiral bioactive therapeutic substances is a source of inspiration for the design of efficient asymmetric catalytic processes (1). To this end, combinatorial synthesis and stockpiles of chiral ligands can afford large libraries of molecules as a potential source of new and improved catalysts (2, 3). Traditionally, the search for asymmetric catalysts has relied on iterative approaches wherein a single catalyst is designed, synthesized, tested, and optimized. This cycle is repeated until a catalytically active system is obtained with the desired level of enantioselectivity. In contrast, if a high-throughput screening (HTS) strategy for ee determination existed, it would enable one to rapidly identify effective asymmetric catalysts, thus allowing for a much broader range of catalyst candidates and experimental conditions to be evaluated (4, 5). However, most of these methods require prior derivatization of the analyte or require expensive instrumentation, and many are still quite slow. Herein, we report a colorimetric strategy based on indicator displacement assays (IDAs) for creating HTS protocols that can be used for the rapid determination of molecular chirality as well as the yield of a reaction.An indicator displacement assay relies on a colorimetric or fluorescent indicator that changes optical or electrochemical properties when bound to a host relative to being free in the bulk medium (6). The most commonly used indicators are pH indicators (7). The competition between an indicator and the guest of interest for the binding site of the host allows the determination of total guest (or analyte) concentration [G] t [Scheme 1 (Eq.1)]. An IDA both eliminates the need to incorporate the chromophore or fluorophore into the structure of the host, thus simplifying the synthesis of the host molecule, and allows one to tune the sensitivity of the assay because of the ability to change the identity and concentration of the ind...

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A Colorimetric Boronic Acid Based Sensing Ensemble for Carboxy and Phospho Sugars

Cited by 60 publications

References 30 publications

Molecular recognition with boronic acids—applications in chemical biology

Molecular recognition with boronic acids—applications in chemical biology

2-(4-Pyridyl)imino nitroxide-tetraphenylporphyrin zinc(II): A chemosensing ensemble for nicotine

A general protocol for creating high-throughput screening assays for reaction yield and enantiomeric excess applied to hydrobenzoin

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