Saccharide Sensing with Molecular Receptors Based on Boronic Acid

James, Tony D.; Sandanayake, K. R. A. Samankumara; Shinkai, Seiji

doi:10.1002/anie.199619101

Cited by 894 publications

(520 citation statements)

References 120 publications

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“…Repeated elemental analysis of 1 gave data within 0.7% of calculated values; boron-containing compounds often present analytical difficulties because of the formation of incombustible residues. 69 Synthesis of Helicate 1. To a 50-mL Schlenk flask were added (S)-(-)-1-amino-2,3-propanediol (64.7 mg, 0.710 mmol, 2 equiv), 2,9-diformyl-1,10-phenanthroline 40 (84.0 mg, 0.355 mmol, 1 equiv), and water (5 mL).…”

Section: Methodsmentioning

confidence: 99%

Self-Sorting Chiral Subcomponent Rearrangement During Crystallization

et al. 2007

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Abstract:The incorporation of enantiopure 1-amino-2,3-propanediol as a subcomponent into a dicopper double helicate resulted in perfect chiral induction of the helicate's twist. DFT calculations allowed the determination of the helicity of the complex in solution. The same helical induction, in which S amines induced a Λ helical twist, was observed in the solid state by X-ray crystallography. Electronic structure calculations also revealed that the unusual deep green color of this class of complexes was due to a metalto-ligand charge transfer excitation, in which the excited state possesses a valence delocalized Cu2 3+ core. The use of a racemic amine subcomponent resulted in the formation of a dynamic library of six diastereomeric pairs of enantiomers. Surprisingly, this library converted into a single pair of enantiomers during crystallization. We were able to observe this process reverse upon redissolution, as initial ligand exchange was followed by covalent imine metathesis.

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Section: Methodsmentioning

confidence: 99%

Self-Sorting Chiral Subcomponent Rearrangement During Crystallization

et al. 2007

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“…14−16 Boronate affinity adsorbents such as Affi-Gel 601 have been widely applied as promising materials for the specific capture of nucleosides because boronic acid groups can reversibly form five-or six-membered cyclic esters with cis-diol compounds when the pH of the solution is altered. 17 However, laborious manipulation and low loading capacity are significant limitations of these materials. 18−20 Recently, boronate-functionalized nanoadsorbents have attracted wide attention, 21−23 especially magnetic nanoparticles, 24−26 for their large surfaceto-area ratio, quick magnetic resonance, and controllable surface modification.…”

mentioning

confidence: 99%

Facile Synthesis of Boronate-Decorated Polyethyleneimine-Grafted Hybrid Magnetic Nanoparticles for the Highly Selective Enrichment of Modified Nucleosides and Ribosylated Metabolites

Shan

Qiao

et al. 2013

Anal. Chem.

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Ribosylated metabolites, especially modified nucleosides, have been extensively evaluated as cancer-related biomarkers. Boronate adsorbents are considered to be promising materials for extracting them from complex matrices. However, the enrichment of ribosylated metabolites in low abundance is still a challenge due to the limited capacity and selectivity of the existing boronate adsorbents. In this study, a novel type of magnetic nanoparticles named Fe 3 O 4 @ SiO 2 @PEI-FPBA was synthesized by grafting polyethyleneimine (PEI) onto the surface of Fe 3 O 4 @SiO 2 before modification by boronate groups. The high density of the amino groups on the PEI chains supplied a large number of binding sites for boronate groups. Thus, the adsorption capacity (1.34 ± 0.024 mg/g) of the nanoparticles, which is 6-to 7-fold higher than that of analogous materials, was greatly improved. The unreacted secondary amines and tertiary amines of the PEI enhanced the aqueous solubility of the nanoparticles, which could efficiently reduce nonspecific adsorption. The nanoparticles were able to capture 1,2 cis-diol nucleosides from 1000-fold interferences. Moreover, the flexible chains of PEI were favorable for effective enrichment and quick equilibration (<2 min). Finally, 60 ribose conjugates were enriched from human urine using the nanoparticles. Among them, 43 were identified to be nucleosides and other ribosylated metabolites. Nine low abundance modified nucleosides were detected for the first time. In conclusion, Fe 3 O 4 @SiO 2 @PEI-FPBA is an attractive candidate material for the highly selective enrichment of 1,2-cis-diol compounds.R ibonucleic acids (RNA) play crucial roles in many fundamental bioprocesses, and modifications in their bases or ribose are closely correlated with bioactivity. 1 Ribonucleosides as end products directly reflect the degradation rate of the RNA. Due to the lack of phosphorylases in cells, modified nucleosides cannot be reused as normal nucleosides for RNA synthesis and are thus excreted from the cell into the biofluids. 2 In tumor cells, the impaired tRNA metabolism usually leads to abnormal levels of modified nucleosides. 3 Therefore, modified nucleosides have been extensively studied in the search for cancer-related biomarkers. 4−6 Previous research has focused mainly on the detection of several common modified nucleosides in urine through chromatography or capillary electrophoresis coupled with mass spectrometry (MS) or UV detection. 7−11 Detection of potentially unknown modified nucleosides is significant for discovering new cancer biomarkers. However, the low concentrations and serious matrix interferences in the biological samples set great obstacles for their detection. Therefore, appropriate pretreatment approaches are necessary for the comprehensive analysis of nucleosides.Online solid phase extraction (SPE) purification by aprotic boronic acid chromatography (ApBAC) encounters an incompatibility issue between the loading solvents and the separation solvents. 12,13 For offline purif...

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“…C arbohydrate recognition is an active area of supramolecular chemistry, motivated by the biological importance of saccharides and also by the unusual challenge represented by these complex substrates (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13). On the one hand, carbohydrates must be recognized and processed during metabolism, whereas saccharide motifs are known to mediate cell-cell recognition, the infection of cells by pathogens, and many aspects of the immune response (14)(15)(16)(17).…”

mentioning

confidence: 99%

“…In the presence of liquid water, the problem becomes yet more difficult. Recognition by means of boronate formation has been relatively successful (2,(7)(8)(9)(10), but there are few effective systems for binding saccharides from water by using noncovalent bonds (1,(11)(12)(13).…”

mentioning

confidence: 99%

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Ryan

Lecollinet²,

Velasco³

et al. 2002

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

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We have previously shown that macrotricyclic host 1a is a powerful receptor for glucopyranosyl units in the nonpolar medium of chloroform. However, the solubility properties of 1a did not permit studies of the extraction of carbohydrates from aqueous solution. This paper describes the synthesis of the new variant 1b, furnished with a highly lipophilic exterior array of 12 benzyloxy substituents. In homogeneous solution, 1b behaves much as 1a, binding n-octyl ␤-D-glucoside with Ka ‫؍‬ 720 M ؊1 in CD3OH͞CDCl3 (8:92). In twophase experiments, the improved solubility of 1b allows carbohydrate extraction to be observed. Three hexoses (glucose, galactose, and mannose), two pentoses (ribose and xylose), and the two methyl glucosides are all extracted substantially into chloroform from 1 M aqueous solutions. Among the hexoses, 1b shows notable affinity and selectivity for glucose, extracting detectable amounts even from 0.1 M aqueous solutions. C arbohydrate recognition is an active area of supramolecular chemistry, motivated by the biological importance of saccharides and also by the unusual challenge represented by these complex substrates (1-13). On the one hand, carbohydrates must be recognized and processed during metabolism, whereas saccharide motifs are known to mediate cell-cell recognition, the infection of cells by pathogens, and many aspects of the immune response (14-17). On the other, carbohydrates possess structures that are fairly large, irregular, and multivalent, while being quite similar to clusters of water molecules. Even in nonpolar solvents, selective carbohydrate receptors require extended, sophisticated architectures (1, 3-6). In the presence of liquid water, the problem becomes yet more difficult. Recognition by means of boronate formation has been relatively successful (2, 7-10), but there are few effective systems for binding saccharides from water by using noncovalent bonds (1, 11-13).A receptor can be shown to discriminate between saccharide and water in one of two ways. Firstly (and most obviously), it can be studied in homogeneous aqueous solution. Secondly, it can be designed for solubility in nonpolar media and studied in a two-phase system, demonstrating the ability to extract or transport the carbohydrate (18)(19)(20)(21)(22)(23)(24). This latter approach is directly relevant to the transport of carbohydrates across biological membranes. Boron-based systems have again proved quite effective (22-24). However, for those receptors operating through noncovalent interactions, success has been limited thus far. Positive results have been obtained with the less hydrophilic saccharides at high aqueous concentrations (18, 20), but not in general with the more hydrophilic substrates such as glucose. § Recently we described the tricyclic tetraester 1a (Fig. 1), a novel receptor that showed an exceptional affinity for n-octyl ␤-D-glucoside, remarkable ␤ vs. ␣ selectivity, and the unusual ability to dissolve solid glucose in CHCl 3 (25). Although we hoped to demonstrate the extraction of glucose ...

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Saccharide Sensing with Molecular Receptors Based on Boronic Acid

Cited by 894 publications

References 120 publications

Self-Sorting Chiral Subcomponent Rearrangement During Crystallization

Self-Sorting Chiral Subcomponent Rearrangement During Crystallization

Facile Synthesis of Boronate-Decorated Polyethyleneimine-Grafted Hybrid Magnetic Nanoparticles for the Highly Selective Enrichment of Modified Nucleosides and Ribosylated Metabolites

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

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