Strong hydrogen bond-mediated complexation of H2PO4− by neutral bis-thiourea hosts

Bühlmann, Philippe; Nishizawa, Seiichi; Xiao, Kang; Umezawa, Yoshio

doi:10.1016/s0040-4020(96)01094-0

Cited by 230 publications

(136 citation statements)

References 28 publications

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“…Our choice fell on the thiourea function which is known for its strong hydrogen donor ability [14]. Moreover, bis-thiourea moieties selectively bind to dihydrogenphosphate via multitopic hydrogen bonding [15], giving stronger complexes with H 2 PO 4 -than any synthetic neutral receptor known so far.…”

Section: Introductionmentioning

confidence: 99%

Iminothiol/thiourea tautomeric equilibrium in thiourea lipids impacts DNA compaction by inducing a cationic nucleation for complex assembly

Breton¹,

Bessodes²,

Bouaziz³

et al. 2009

Biophysical Chemistry

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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 A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT2 Abstract: Our research on lipidic vectors for transfection led us to develop thiourea lipids able to interact with DNA. Hence, we developed a series of lipopolythioureas based on the strong hydrogen bond donor ability of thiourea. More recently we have reported a branched hydroxylated bis-thiourea derivative with interesting transfecting properties. The last step of the syntheses involved a strong acidic condition, leading to an unstable product upon storage.Therefore we designed a new synthesis in mild acidic conditions. Though they exhibit the same mass, the lipids obtained in the two different conditions differ by their interaction with DNA. We therefore explored the physicochemical properties of these two lipids by different means that we describe in this article. In order to insure easier and reliable 13 C-NMR studies of the thiourea group we have designed the synthesis of the corresponding 13 C-labelled thiourea lipids. We have thus shown that when the lipid was submitted to mildly acidic medium; only the thiourea group was observed; while a thiourea/charged and/or uncharged iminothiol tautomeric equilibrium formed when the last step of the synthesis was submitted to low pH. NMR experiments showed that this tautomeric equilibrium could not form in polar solvents. However, UV experiments on the liposomal form of the lipopolythiourea showed the presence of the tautomers. Lipid/DNA interaction consequently differed according to the acidic treatment applied. Eventually, these results revealed that on this particular thiourea lipid, electrostatic interactions due to cationic thioureas are likely to be responsible for DNA compaction and that this tautomeric form of the thiourea could be stabilised by hydrogen bonds in a supramolecular assembly. Nevertheless, this does not reflect a general thiourea lipid/DNA interaction as other thiourea lipids that are able to compact DNA do not undergo an acidic treatment during the final stage of their synthesis.

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Section: Introductionmentioning

confidence: 99%

Iminothiol/thiourea tautomeric equilibrium in thiourea lipids impacts DNA compaction by inducing a cationic nucleation for complex assembly

Breton¹,

Bessodes²,

Bouaziz³

et al. 2009

Biophysical Chemistry

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“…An interpretation for DNA's quenching effect could be a multitopic hydrogen bonding interaction between the hydrophobic thiourea and the DNA fragment. Bisthiourea moieties selectively bind to dihydrogenphosphate via multitopic hydrogen bonding, giving stronger complexes with H 2 PO 4 - [24]. Naphthyl or groups bounded to polymer interact in aqueous media tend to form a sandwich-like dimeric conformation (excimer) regularly [25].…”

Section: Interactions With Dnamentioning

confidence: 99%

Novel fluorescent amphiphilic block copolymers: photophysics behavior and interactions with DNA

Lu¹,

Meng²,

Zhong³

2007

Express Polym. Lett.

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Abstract. In this study, novel amphiphilic fluorescent copolymers poly(N-vinylpyrrolidone)-b-poly(N-methacryloyl-N'-(α-naphthyl)thiourea) (PVP-b-PNT) were synthesized via ATRP with poly(N-vinylpyrrolidone)-Cl as macroinitiator and N-methacryloyl-N'-α-naphthylthiourea (NT) as hydrophobic segment. PVP-b-PNT copolymers were characterized by 1 H NMR, GPC-MALLS and fluorescence measurements. The aggregation behavior of PVP-b-PNT in water was investigated by transmission electron microscope (TEM) and dynamic light scattering (DLS) measurement. The photophysics behavior of PVP-b-PNT showed that block copolymer formed strong excimer. The interaction of DNA with the block copolymer made the excimer of block copolymer quench. The cytotoxicity result of PVP-b-PNT in cell culture in vitro indicated that this copolymer PVP-b-PNT had good biocompatibility.

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“…8 Bisthiourea-based receptors and modified thiourea-based receptors have been developed to enhance binding affinity and regulate binding selectivity. [9][10][11][12] Thiourea-based receptors rely on the structure and strength of hydrogen bonds between the thiourea group and an anion (see Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Thermodynamics of Complexation between Thiourea-based Receptor and Acetate in Water/Acetonitrile Mixture

et al. 2016

Self Cite

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A thiourea-based receptor has been extensively studied for selective anion recognition for reasons of its strong hydrogen bond donor ability. In the present study, the thermodynamics of complexation between a thiourea-based receptor and acetate was examined in a water/acetonitrile mixture. The receptor used in this study was N,N′-bis(p-nitrophenyl)thiourea (BNPTU). UV/vis spectroscopic titration and isothermal titration calorimetry (ITC) experiments clearly revealed endothermic and entropy-driven complexation of BNPTU with acetate in water/acetonitrile mixtures. Since the endothermic peaks found in water/acetonitrile mixtures were about three times greater than those in acetonitrile, it appears that preferential hydration of both receptor and acetate was responsible for the endothermic and entropy-driven complexation reaction. The thermodynamic properties found in this study have the potential to contribute to the design of a thiourea-based anion receptor. Keywords

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Strong hydrogen bond-mediated complexation of H2PO4− by neutral bis-thiourea hosts

Cited by 230 publications

References 28 publications

Iminothiol/thiourea tautomeric equilibrium in thiourea lipids impacts DNA compaction by inducing a cationic nucleation for complex assembly

Iminothiol/thiourea tautomeric equilibrium in thiourea lipids impacts DNA compaction by inducing a cationic nucleation for complex assembly

Novel fluorescent amphiphilic block copolymers: photophysics behavior and interactions with DNA

Thermodynamics of Complexation between Thiourea-based Receptor and Acetate in Water/Acetonitrile Mixture

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