Azacryptands as molecular cages for anions and metal ions

Amendola, Valeria; Bergamaschi, Greta; Miljkovic, Ana

doi:10.1080/10610278.2017.1339885

Cited by 39 publications

(17 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Cryptands are also versatile in terms of coordinating different metal ions. This results in tuning their selectivity and sensing to capture different types of molecules (e.g., halogens, carbonate, CN − ) [24,[37][38][39]. Thus, our HOPG-crypt was immersed in a 10 mM Co(ClO 4 ) 2 •6H 2 O aqueous solution (HOPG-crypt-Co, see materials and methods) and thoroughly washed with water.…”

Section: Resultsmentioning

confidence: 99%

Cryptand-Functionalized Highly Oriented Pyrolytic Graphite Electrodes

et al. 2021

View full text Add to dashboard Cite

Reproducible materials that have detection properties towards a certain molecule are very important for applications in the fabrication of devices. Among all the substrates that are used, highly oriented pyrolytic graphite allows to clearly image a monolayer. On the other hand, cryptand molecules are versatile because they can sense certain analytes with high selectivity. The highly oriented pyrolytic graphite electrode was first functionalized with an aryl bearing a bromine or an alkyne group to further attach cryptand molecules to its surface. The functionalization was performed through the electroreduction of aryl diazonium salts. While functionalization with an aryl-bromine produced a 20 nm-thick dendritic layer, functionalization of the surface with an aryl bearing a terminal alkyne produced a 9.7 nm-thick multilayer. However, if the diazonium salt is prepared in situ, a 0.9 nm monolayer with aryl–alkyne groups is formed. The alkyne functionalized electrode reacted with a bromo-cryptand through a Sonogashira C–C coupling reaction yielding electrodes functionalized with cryptands. These were immersed in a solution of a Co(II) salt resulting in Co(II)-cryptate modified electrodes, highlighting the ability of the cryptands’ modified electrode to sense metal ions. The electrode surface was analyzed by X-ray photoelectron spectroscopy after each modification step, which confirmed the successful functionalization of the substrate with both the cryptand and the cryptate. Cyclic voltammetry studies showed stable current response after approximately six cycles. Different reduction processes were detected for both cryptand (−1.40 V vs. SCE) and cryptate (−1.22 V vs. SCE) modified highly oriented pyrolytic graphite.

show abstract

Section: Resultsmentioning

confidence: 99%

Cryptand-Functionalized Highly Oriented Pyrolytic Graphite Electrodes

et al. 2021

View full text Add to dashboard Cite

show abstract

“…From another point of view, azacryptands are supramolecular metal complexes that are constituted by an organic core (azacryptand) with two coordinated metal ions [29] . Within these metal complexes, those formed by bistren cryptands (obtained by the reaction of two tris(2‐aminoethyl)amine and three dialdehyde linkers) and Cu II have been extensively used for the selective coordination of several dicarboxylates [30–32] . In particular, very recently, Amendola and co‐workers have demonstrated that t,t‐MA can coordinate effectively to a dicopper(II) bistren azacryptand and developed an indicator displacement assay for the fluorescence sensing of this benzene metabolite [33] …”

Section: Methodsmentioning

confidence: 99%

“…[29] Within these metal complexes, those formed by bistren cryptands (obtained by the reaction of two tris(2-aminoethyl)amine and three dialdehyde linkers) and Cu II have been extensively used for the selectivec oordination of several dicarboxylates. [30][31][32] In particular,v ery recently,A mendola and co-workers have demonstrated that t,t-MA can coordinate effectively to ad icopper(II) bistren azacryptanda nd developeda ni ndicator displacement assay for the fluorescences ensing of this benzene metabolite. [33] Based on the above, and following our interest in the development of hybrido rganic-inorganicm aterials for the design of chromo-fluorogenics ensing protocols as an alternative to molecular based probes, [34][35][36][37][38][39][40][41] we report herein the synthesis and characterization of ag ated nanodevice for the selectivea nd sensitiveq uantification of t,t-MA in urine.…”

mentioning

confidence: 99%

A Nanoprobe Based on Gated Mesoporous Silica Nanoparticles for The Selective and Sensitive Detection of Benzene Metabolite t,t‐Muconic Acid in Urine

Domínguez

Blandez

Lozano‐Torres

et al. 2020

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Benzene is ah ighly toxic aromatic hydrocarbon. Inhalingb enzene can cause dizziness,v ertigo, headaches, aplasia,m utations and, in the moste xtreme cases, cancer. Trans,trans-muconic acid (t,t-MA) is one of the metabolization products of benzene. Although different analytical methods have been reported for the determination of t,t-MA, these are often expensive, requiret rainedp ersonnel, are not suitable foro n-site measurements, and use hazardous organics olvents. For theser easons, the development of reliable, selective and sensitivem ethodsf or rapid and in situ detection of t,t-MA are of importance. Addressing this challenge, an anodevice for the selectivea nd sensitive quantification of t,t-MA in urine is reported. The nanodevice used is achieved using mesoporous silica nanoparticles loaded with ad ye reporter and capped with ad icopper(II) azacryptand. Pore openinga nd payload release is induced rapidly (10min) and selectively with t,t-MA in urine, using as imple fluorimeter without sample pretreatment.

show abstract

“…Molecular receptors are appreciated as powerful tools for the selective recognition of either neutral or ionic guests in competing media. 1 , 3 − 6 In the context of anion recognition, research has led to the development of a plethora of anion sensors, anion-responsive materials, and organocatalytic processes involving anion complexation. 7 − 9 Compared to the macrocyclic parents, the preorganization and the well-defined cavity in macrobicycles give an important contribution to the selectivity of these systems for anionic guests.…”

Section: Introductionmentioning

confidence: 99%

“…Bistren-like azacryptands, in particular, have emerged among cage-like anion receptors. 1 , 3 , 4 , 6 In these systems, when the recognition of bidentate anionic guests is concerned, selectivity can be maximized by properly choosing the spacers between the tren subunits on the azacryptand skeleton. 1 Anion binding properties can be further improved by including two transition metal ions in the receptor cavity.…”

Section: Introductionmentioning

confidence: 99%

Sensing and Liquid–Liquid Extraction of Dicarboxylates Using Dicopper Cryptates

et al. 2020

Self Cite

View full text Add to dashboard Cite

We report the investigation of dicopper(II) bistren cryptate, containing naphthyl spacers between the tren subunits, as a receptor for polycarboxylates in neutral aqueous solution. An indicator displacement assay for dicarboxylates was also developed by mixing the azacryptate with the fluorescent indicator 5-carboxyfluorescein in a 50:1 molar ratio. Fluorimetric studies showed a significant restoration of fluorophore emission upon addition of fumarate anions followed by succinate and isophthalate. The introduction of hexyl chains on the naphthalene groups created a novel hydrophobic cage; the corresponding dicopper complex was investigated as an extractant for dicarboxylates from neutral water into dichloromethane. The liquid–liquid extraction of succinate—as a model anion—was successfully achieved by exploiting the high affinity of this anionic guest for the azacryptate cavity. Extraction was monitored through the changes in the UV–visible spectrum of the dicopper complex in dichloromethane and by measuring the residual concentration of succinate in the aqueous phase by HPLC-UV. The successful extraction was also confirmed by 1 H-NMR spectroscopy. Considering the relevance of polycarboxylates in biochemistry and in the environmental field, e.g., as waste products of industrial processes, our results open new perspectives for research in all contexts where recognition, sensing, or extraction of polycarboxylates is required.

show abstract

Azacryptands as molecular cages for anions and metal ions

Cited by 39 publications

References 45 publications

Cryptand-Functionalized Highly Oriented Pyrolytic Graphite Electrodes

Cryptand-Functionalized Highly Oriented Pyrolytic Graphite Electrodes

A Nanoprobe Based on Gated Mesoporous Silica Nanoparticles for The Selective and Sensitive Detection of Benzene Metabolite t,t‐Muconic Acid in Urine

Sensing and Liquid–Liquid Extraction of Dicarboxylates Using Dicopper Cryptates

Contact Info

Product

Resources

About