title: Amphiphilic macrocycles bearing biofragment: molecular design as factor controlling self-assembly.
abstract: Two novel macrocyclic 6-methyluracilic amphiphiles (uracilophanes) with four (UP1) and two (UP2) uracil moieties and ammonium groups have been synthesized. Tetracationic multi-uracilophane is composed of two macrocyclic units bridged each other with an external methylene spacer, while in the cryptand-like dicationic uracilophane pyrimidinic moieties are connected with an internal methylene spacer. This internal spacer provided a conformational rigidity to the macrocycle. The self-assembly of the uracilophanes is studied and compared with a reference dicationic uracilophane (UP3) with no spacer fragment. Compounds UP1 and UP3 are capable of aggregating, which is characterized by the analogous critical micelle concentration of 1mM, although the former has four decyl tails versus two decyl tails in UP3 molecule. NMR self-diffusion, fluorimetry and DLS techniques revealed that bimodal size distribution occurs in the UP1 solution, with small (≤2nm) and large (ca. 30-50 nm) aggregates contributed. Unexpectedly, the cryptand-like uracilophane UP2 with the same hydrophobicity as UP3 does not form aggregates. The balance of the geometry and energetic factors was analyzed and compared with those contributing to the aggregation of the reference compound UP3. It was established that it is the geometry that controls the packing of the cryptand-like uracilophanes upon aggregation, while hydrophobic effect plays a minor role. In contrast, both factors control the aggregation of oligomeric macrocycle, with energetic factor prevailing. These findings are of importance for (i) the understanding the diverse structural behavior of bioamphiphiles that have very similar chemical structure, but different conformations; and (ii) the design of amphiphiles with controlled model of self-assembly. Supramolecular systems studied can be recommended for biotechnological applications.
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia. Electronic address: lucia@iopc.ru.
authors.forename: L Ya
authors.initials: LY
authors.lastname: Zakharova
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: V E
authors.initials: VE
authors.lastname: Semenov
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: V V
authors.initials: VV
authors.lastname: Syakaev
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: M A
authors.initials: MA
authors.lastname: Voronin
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: D R
authors.initials: DR
authors.lastname: Gabdrakhmanov
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: F G
authors.initials: FG
authors.lastname: Valeeva
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: A S
authors.initials: AS
authors.lastname: Mikhailov
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: A D
authors.initials: AD
authors.lastname: Voloshina
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: V S
authors.initials: VS
authors.lastname: Reznik
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: Sh K
authors.initials: ShK
authors.lastname: Latypov
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, 8, ul.Akad. Arbuzov, Kazan 420088, Russia.
authors.forename: A I
authors.initials: AI
authors.lastname: Konovalov
mesh_terms: D003217:Conductometry; D004058:Diffusion; D004553:Electric Conductivity; D006868:Hydrolysis; D008027:Light; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D009596:Nitrophenols / Q000737:chemistry; D010316:Particle Size; D012542:Scattering, Radiation; D012996:Solutions; D013050:Spectrometry, Fluorescence; D013500:Surface Tension; D013501:Surface-Active Agents / Q000138:chemical synthesis* / Q000737:chemistry*; D013696:Temperature; D014498:Uracil / Q000737:chemistry*
chemical_list: D047028:Macrocyclic Compounds; D009596:Nitrophenols; D012996:Solutions; D013501:Surface-Active Agents; D014498:Uracil; C024836:4-nitrophenol
keywords: Amphiphile; Geometry and energetic factors; Self-assembly; Uracilophane