Supramolecular Sensing with Phosphonate Cavitands

Melegari, Monica; Suman, Michele; Pirondini, Laura; Moiani, Davide; Massera, Chiara; Ugozzoli, Franco; Kalenius, Elina; Vainiotalo, Pirjo; Mulatier, Jean Christophe; Dutasta, J.-P.; Dalcanale, Enrico

doi:10.1002/chem.200800327

Cited by 76 publications

(71 citation statements)

References 46 publications

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“…2A). The affinity of this class of cavitand toward methanol has been previously reported (13), and also in this case the alcohol is stabilized within the cavity by a hydrogen bond with one P¼O group at the upper rim and by two CH-π interactions between two methyl hydrogens of the guest and two aromatic rings of the host (13). The results indicate that methanol is preferred by the cavitand over glycine methyl ester hydrochloride; the latter could be expected to interact through dipolar interactions between the P¼O groups and the positively charged nitrogen atom.…”

Section: Resultsmentioning

confidence: 77%

“…Among them, tetraphosphonate cavitands are outstanding: Their complexation ability spans from positively charged inorganic and organic species (9) to neutral molecules (10). This diverse complexation ability is the result of three interaction modes, which can be activated either individually or in combination by the host according to the guest requirements: (i) multiple ion-dipole interactions between the inward facing P¼O groups and the positively charged guests (11); (ii) single or dual H bonding involving the P¼O groups (11,12); and (iii) CH-π interactions between a methyl group present on the guest and the cavity of the host (13).…”

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confidence: 99%

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Exclusive recognition of sarcosine in water and urine by a cavitand-functionalized silicon surface

Biavardi

Tudisco²,

Maffei³

et al. 2012

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

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A supramolecular approach for the specific detection of sarcosine, recently linked to the occurrence of aggressive prostate cancer forms, has been developed. A hybrid active surface was prepared by the covalent anchoring on Si substrates of a tetraphosphonate cavitand as supramolecular receptor and it was proven able to recognize sarcosine from its nonmethylated precursor, glycine, in water and urine. The entire complexation process has been investigated in the solid state, in solution, and at the solid-liquid interface to determine and weight all the factors responsible of the observed specificity. The final outcome is a Si-based active surface capable of binding exclusively sarcosine. The complete selectivity of the cavitand-decorated surface under these stringent conditions represents a critical step forward in the use of these materials for the specific detection of sarcosine and related metabolites in biological fluids. molecular recognition | phosphonate cavitand

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Section: Resultsmentioning

confidence: 77%

mentioning

confidence: 99%

Exclusive recognition of sarcosine in water and urine by a cavitand-functionalized silicon surface

Biavardi

Tudisco²,

Maffei³

et al. 2012

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

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“…(2) To clarify the gas-phase properties of complexes formed by phosphonate cavitands, [9] since one of their applications is gas sensing [10]. The earlier reported results have shown that the phosphonate cavitands are capable of selectively forming complexes with alcohols [11][12][13][14] and ammonium ions [7,15,16], which has just recently led to application of phosphonate cavitands in supramolecular polymers [17], molecular recognition on silicon surfaces [18], and product protection in amine methylation reactions [19]. Number and positioning of the P ϭ O groups at the upper rim and their relative orientation with respect to the cavity are the key host parameters in defining the multiple H-bonding interactions involved in the recognition process [16].…”

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confidence: 99%

Hydrogen bonding in phosphonate cavitands: Investigation of host-guest complexes with ammonium salts

Kalenius

Neitola

Suman

et al. 2010

J. Am. Soc. Mass Spectrom.

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The H-bonding in alkylammonium complexes of phosphonate cavitands were studied by mass spectrometric methods and theoretical calculations. The alkylammonium ions included primary, secondary, and tertiary methyl-and ethylammonium ions. Their complexation with mono-, tetra-, and two di-phosphonate cavitands, which differ according to the number and position of H-bond acceptor P ϭ O groups, was evaluated by using different competition experiments, energy-resolved CID, gas-phase H/D-exchange, and ligand-exchange reactions, together with ab initio theoretical optimization of the complexes. The phosphonate cavitands with two or more adjacent P ϭ O groups were found to be selective towards secondary alkylammonium ions, due to simultaneous formation of two stable hydrogen bonds. In the ion-molecule reactions (both H/D-and ligand-exchange), the formation of two stable hydrogen bonds was observed either to slow down the reaction or to completely prevent it. This was, however, limited to situations where two hydrogen bonds are formed between the H-bond donor sites of the alkyl ammonium ion and the vicinal H-bond acceptor sites of the cavitand. (J Am Soc Mass Spectrom 2010, 21, 440 -450)

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“…Phosphonate cavitands are synthetic abiotic receptors (hosts) [39,40,43] with molecular recognition properties that have been exploited in gas sensing [44], supramolecular polymers [45,46], surface self-assembly [47], and product protection [48]. They are specifically designed to target small molecules bearing amino-functionalities via a synergistic combination of weak interactions such as H-bonding, dipole−dipole, and CH−π interactions.…”

Section: Breaking Good Probing Designer Drug Family With a Unique Sumentioning

confidence: 99%

Surface Nanomechanics of Biomolecules and Supramolecular Systems

Bergese¹,

Federici²

2017

Nanomechanics

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Surface nanomechanics of biomolecules and supramolecular systems is an interdisciplinary and vital area of current research, with implications/applications spanning from synthetic biology to regenerative medicine, from smart surfaces to molecular machines. Biomolecule surface transformations and nanomachinery arise upon "wiring" them onto surfaces and interfaces. Surface confinement of biomolecules is a common feature of biological systems (e.g., cell membranes) and often a mandatory step for translating their properties into real-world applications (e.g., biosensors). On surfaces biomolecules undergo peculiar transformations and interactions which they do not experience in solution. Such unedited effects open challenges in synthetic systems, for example, by altering or hindering the designed/expected property, but also disclose a wealth of opportunities and surprises. Based on our latest research, this chapter will bring fresh excerpts from the field. It will start with an accessible description of thermodynamics of surface nanomechanics of biomolecules and supramolecular systems and then will show how it can be implemented to gain understanding of grow factor cell signaling, to single out small ligands able to inhibit protein misfolding, to measure energetics of surface confined ferritin during iron loading, and to realize a universal probe for ammine-based designer drugs.

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Supramolecular Sensing with Phosphonate Cavitands

Cited by 76 publications

References 46 publications

Exclusive recognition of sarcosine in water and urine by a cavitand-functionalized silicon surface

Exclusive recognition of sarcosine in water and urine by a cavitand-functionalized silicon surface

Hydrogen bonding in phosphonate cavitands: Investigation of host-guest complexes with ammonium salts

Surface Nanomechanics of Biomolecules and Supramolecular Systems

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