Thermodynamics of Phosphate and Pyrophosphate Anions Binding by Polyammonium Receptors

Bazzicalupi, Carla; Bencini, Andrea; Bianchi, Antonio; Cecchi, Mirco; Escuder, Beatriu; Fusi, Vieri; Garcı́a-España, Enrique; Giorgi, Claudia; Luis, Santiago V.; Maccagni, Gianluca; Marcelino, Victor; Paoletti, Piero; Valtancoli, Barbara

doi:10.1021/ja983947y

Cited by 130 publications

(104 citation statements)

References 31 publications

(36 reference statements)

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“…This parameter is a simple evidence of the different sequestering ability of several polycations towards polyanions. Similar investigations were carried out by Bazzicalupi et al [9] on the interaction of phosphate and pyrophosphate with several polyammonium receptors. They observed that although the electrostatic attraction is the driving force in anion interactions with polyammonium receptors, the stability trends of such complexes are not strictly determined by electrostatic contributions, in contrast with the general trend of increasing stability with increasing charge of receptors and anions.…”

Section: Free Energy Contribution Per Bondsupporting

confidence: 71%

“…In the literature the interaction of polyammonium cations with carboxylic anions was widely reported, whilst a lesser number of data is reported for other ligands containing, for example, phosphate groups, despite their widespread involvement in biological systems. Few examples of phosphate complexation by synthetic polyammonium receptors in water were reported by GarciaEspaña et al [8]; other papers also report [9][10][11] the enthalpy and entropy changes, which are important to interpret the main contribution for the stability of anion complexes in water.…”

Section: Introductionmentioning

confidence: 99%

“…The interaction of polyammonium cations with inorganic and organic polyanions [7][8][9][10][11][12][13] was mainly studied for low molecular weight molecules. In our previous papers, we already studied the interaction of different polyphosphates [13][14][15][16] and nucleotides [17] with biogenic amines.…”

Section: Introductionmentioning

confidence: 99%

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Sequestering ability of phytate towards protonated BPEI and other polyammonium cations in aqueous solution

Crea

Stefano

Porcino

et al. 2008

Biophysical Chemistry

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Please cite this article as: Francesco Crea, Concetta De Stefano, Nunziatina Porcino, Silvio Sammartano, Sequestering ability of phytate towards protonated BPEI and other polyammonium cations in aqueous solution, Biophysical Chemistry (2008Chemistry ( ), doi: 10.1016Chemistry ( /j.bpc.2008 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT AbstractThe interaction between protonated branched poly(ethylenimine) [BPEI] and phytate (1,2,3,4,5,6 hexakis (di-hydrogen phosphate) myo-inositol) [Phy] was studied potentiometrically. The measurements were carried out at t = 25 °C and at low ionic strength values, without addition of supporting electrolyte, to avoid interferences with other anions and cations. In order to simplify the data treatment, BPEI was considered as a simple tetramine. Different species Phy(BPEI)H j , with j = 6,7,8, and Phy(BPEI) 2 H 7 were found, having quite high stability. The ability of phytate to sequester BPEI was quantified by considering the parameter pL 50 , namely the concentration (-log [Phy] tot ) necessary to bind 50% of polyammonium cation (as trace). In our experimental conditions, for the system phytate-BPEI-proton we have pL 50 = 7.01, at pH = 7.4 and I = 0.04 mol L -1 . As for other phytate-polyammonium cation systems, the stability of the phytate-BPEI species is strictly proportional to the charges involved in the formation reactions. Therefore, it was possible to calculate the free energy contribution per bond, 0 b G Δ = 4.4±0.4 kJ mol -1 . The dependence on temperature and ionic strength of the stability of phytate-low/high molecular weight polyammonium cations species, was studied using some semiempirical equations and enthalpy data for the protonation of both components. The dependence on temperature of the stability is quite low and the variation of pL 50 in the range 15 ≤ t/°C ≤ 37 is less than 0.5 log units. On the contrary, the effect of ionic strength is highly significant, with a lowering of pL 50 of ≈ 2 log units (I = 0 to 0.15 mol L -1 ).

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Section: Free Energy Contribution Per Bondsupporting

confidence: 71%

Section: Introductionmentioning

confidence: 99%

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Sequestering ability of phytate towards protonated BPEI and other polyammonium cations in aqueous solution

Crea

Stefano

Porcino

et al. 2008

Biophysical Chemistry

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“…The precipitate was collected by filtration, washed with diethyl ether and dried in vacuo, giving 3 as a white powder with 90 % of yield. 13 Compound 4: Compound 3 (1.5 g; 2 mmol) was added to a solution of bis-aminal 2 (1.2 g; 6.2 mmol) in 25 mL of dry DMF. The mixture was stirred at room temperature for 10 d. The precipitate was collected by filtration, washed with diethyl ether.…”

Section: Synthesis Of Lmentioning

confidence: 99%

“…The solid was dissolved in water; a subsequent addition of ethanol leads to a precipitate which is filtered and dried in vacuo, at 60°C, giving 4 as a white powder with 70 % of yield. 13 Compound L: A large excess of NaBH 4 (24 equiv.) was added in small portions over 1 h to a stirred solution of polyammonium salts 4 in absolute ethanol (1 g in 60 mL).…”

Section: Synthesis Of Lmentioning

confidence: 99%

A Tris‐Macrocycle with Proton Sponge Characteristics as Efficient Receptor for Inorganic Phosphate and Nucleotide Anions

Bencini¹,

Biagini²,

Giorgi³

et al. 2009

Eur J Org Chem

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International audienceSynthesis, characterisation and proton-sponge behaviour of a new linear constrained tris-macrocycle (L), containing three cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) reinforced macrocycles connected by two 2,6-pyridinediylbis(methylene) linkers, is reported. Protonated forms of L are efficient receptors for inorganic phosphate and nucleotide anions (ATP and ADP). The binding properties of L toward these substrates have been investigated in aqueous solution by means of potentiometric titrations, determining the stability constants of the adducts. The interaction mode was clarified by using 1H and 31P NMR measurements in aqueous solution and by means of molecular modelling calculations carried out on differently protonated species of L as well as on several nucleotide-receptor adducts. The stability of the adducts is mainly due to charge-charge and hydrogen bonding interactions between the polyphosphate chain of nucleotides and the ammonium groups of L.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009

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Complexation of Polyvalent Cyclodextrin Ions with Oppositely Charged Guests: Entropically Favorable Complexation Due to Dehydration

et al. 2000

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Thermodynamic parameters for complexation of polyvalent cyclodextrin (CD) cation and anion with oppositely charged guests have been determined in D2O containing 0.02 M NaCl by means of 1H-NMR spectroscopy. Protonated heptakis(6-amino-6-deoxy)-beta-CD (per-NH3+-beta-CD) forms stable inclusion complexes with monovalent guest anions. The enthalpy (deltaH) and entropy changes (deltaS) for complexation of per-NH3+-beta-CD with p-methylbenzoate anion (p-CH3-Ph-CO2-) are 3.8 +/- 0.7 kJ mol(-1) and 88.6 +/- 2.2 J mol(-1) K(-1), respectively. The deltaH and deltaS values for the native beta-CD-p-CH3-Ph-CO2- system are -8.6 +/- 0.1 kJ mol(-1) and 15.3 +/- 0.7 J mol(-1) K(-1), respectively. The thermodynamic parameters clearly indicate that dehydration from both the host and guest ions accounts for the entropic gain in inclusion process of p-CH3-Ph-CO2- into the per-NH3+-beta-CD cavity. The fact that the neutral guests such as 2,6-dihydroxynaphthalene and p-methylbenzyl alcohol hardly form the complexes with per-NH3+-beta-CD exhibits that van der Waals and/or hydrophobic interactions do not cause the complexation of the polyvalent CD cation with the monovalent anion. The acetate anion is not included into the per-NH3+-beta-CD cavity, while the butanoate and hexanoate anions form the inclusion complexes. The complexation of the alkanoate anions is entropically dominated. Judging from these results, it may be concluded that Coulomb interactions cooperated with inclusion are required for realizing the large entropic gain due to extended dehydration. Entropically favorable complexation was also observed for the anionic CD-cationic guest system. The present study might present a general mechanism for ion pairing in water.

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Thermodynamics of Phosphate and Pyrophosphate Anions Binding by Polyammonium Receptors

Cited by 130 publications

References 31 publications

Sequestering ability of phytate towards protonated BPEI and other polyammonium cations in aqueous solution

Sequestering ability of phytate towards protonated BPEI and other polyammonium cations in aqueous solution

A Tris‐Macrocycle with Proton Sponge Characteristics as Efficient Receptor for Inorganic Phosphate and Nucleotide Anions

Complexation of Polyvalent Cyclodextrin Ions with Oppositely Charged Guests: Entropically Favorable Complexation Due to Dehydration

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