Search results for "Supramolecular"
showing 10 items of 830 documents
Self-Complementary Dimers of Oxalamide-Functionalized Resorcinarene Tetrabenzoxazines
2018
Self‐complementarity is a useful concept in supramolecular chemistry, molecular biology and polymeric systems. Two resorcinarene tetrabenzoxazines decorated with four oxalamide groups were synthesized and characterized. The oxalamide groups possessed self‐complementary hydrogen bonding sites between the carbonyls and amide groups. The self‐complementary nature of the oxalamide groups resulted in self‐included dimeric assemblies. The hydrogen bonding interactions within the tetrabenzoxazines gave rise to the formation of dimers, which were confirmed by single‐crystal X‐ray diffractions analysis and supported by NMR spectroscopy and mass spectrometry. The self‐included dimers were connected b…
Ion mobility-mass spectrometry of supramolecular complexes and assemblies
2019
Despite their structural and functional differences, synthetic supramolecular assemblies share many similarities with biological assemblies, especially enzymes. The assemblies can be on the same length scale, and their structures and guest binding are typically governed by non-covalent interactions. Thus, only relatively weak interactions define the shape of a synthetic supramolecule or the secondary and tertiary structure of a protein, such that the resulting dynamism makes structure elucidation challenging. For biomolecules such as peptides, proteins, glycans and lipids this has often been tackled using ion mobility–mass spectrometry (IM-MS), whereby analyte ions are separated according t…
Supramolecular Modification of ABC Triblock Terpolymers in Confinement Assembly
2018
The self-assembly of AB diblock copolymers in three-dimensional (3D) soft confinement of nanoemulsions has recently become an attractive bottom up route to prepare colloids with controlled inner morphologies. In that regard, ABC triblock terpolymers show a more complex morphological behavior and could thus give access to extensive libraries of multicompartment microparticles. However, knowledge about their self-assembly in confinement is very limited thus far. Here, we investigated the confinement assembly of polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P4VP-b-PT or SVT) triblock terpolymers in nanoemulsion droplets. Depending on the block weight fractio…
Binding abilities of polyaminocyclodextrins: polarimetric investigations and biological assays.
2017
Three polyaminocyclodextrin materials, obtained by direct reaction between heptakis(6-deoxy-6-iodo)-β-cyclodextrin and the proper linear polyamines, were investigated for their binding properties, in order to assess their potential applications in biological systems, such as vectors for simultaneous drug and gene cellular uptake or alternatively for the protection of macromolecules. In particular, we exploited polarimetry to test their interaction with some model p-nitroaniline derivatives, chosen as probe guests. The data obtained indicate that binding inside the host cavity is mainly affected by interplay between Coulomb interactions and conformational restraints. Moreover, simultaneous i…
Química supramolecular y aspectos biomédicos de azamacrociclos [1+1] de 1H-pirazol
2019
En este trabajo se presenta la síntesis y la caracterización de dos nuevas familias de ligandos azamacrocíclicos [1+1] constituidos por la unidad de 1H–pirazol y por una poliamina de distinta naturaleza. La primera familia está formada por cinco ligandos, los cuales se encuentran constituidos por la unidad de 1H–pirazol y por una poliamina de cadena abierta: L1–L5. La segunda familia está formada por tres ligandos de tipo escorpiando, los cuales se encuentran constituidos por la unidad de 1H–pirazol y por la poliamina tris(2–aminoetil)amina, que puede incorporar en su estructura la unidad de antraceno y la unidad de trifenilamina (TPA): L6–L8. El comportamiento ácido–base, así como la quími…
Feedback and Communication in Active Hydrogel Spheres with pH Fronts: Facile Approaches to Grow Soft Hydrogel Structures
2021
Abstract Compartmentalized reaction networks regulating signal processing, communication and pattern formation are central to living systems. Towards achieving life‐like materials, we compartmentalized urea‐urease and more complex urea‐urease/ester‐esterase pH‐feedback reaction networks into hydrogel spheres and investigate how fuel‐driven pH fronts can be sent out from these spheres and regulated by internal reaction networks. Membrane characteristics are installed by covering urease spheres with responsive hydrogel shells. We then encapsulate the two networks (urea‐urease and ester‐esterase) separately into different hydrogel spheres to devise communication, pattern formation and attracti…
Hexagonal Microparticles from Hierarchical Self-Organization of Chiral Trigonal Pd3L6 Macrotetracycles
2021
Construction of structurally complex architectures using inherently chiral, asymmetric, or multi-heterotopic ligands is a major challenge in metallosupramolecular chemistry. Moreover, the hierarchical self-organization of such complexes is unique. Here, we introduce a water-soluble, facially amphiphilic, amphoteric, chiral, asymmetric, and hetero-tritopic ligand derived from natural bile acid, ursodeoxycholic acid. We show that via the supramolecular transmetalation reaction, using nitrates of Cu(II) or Fe(III), and subsequently Pd(II), a superchiral Pd3L6 complex can be obtained. Even though several possible constitutional isomers of Pd3L6 could be formed, because of the ligand asymmetry a…
Supramolecular Assembly of Metal Complexes by (Aryl)I⋯dz2[PtII] Halogen Bond
2020
The theoretical data for the half‐lantern complexes [Pt(C^N)(μ‐S^N)] 2 ( 1 – 3 ; С^N is cyclometalated 2‐Ph‐benzothiazole; S^N is 2‐SH‐pyridine 1 , 2‐SH‐benzoxazole 2 , 2‐SH‐tetrafluorobenzothiazole 3 ) indicate that the Pt···Pt orbital interaction leads to an increment of the nucleophilicity of the outer d z 2 ‐orbitals to provide assembly with electrophilic species. 1 – 3 were co‐crystallized with bifunctional halogen bond (XB) donors to give adducts ( 1 – 3 ) 2 ∙(1,4‐diiodotetrafluorobenzene) and infinite polymeric [ 1 ·1,1’‐diiodoperfluorodiphenyl] n . X‐ray crystallography revealed that the supramolecular assembly is achieved via (Aryl)I∙∙∙ d z 2 [Pt II ] XB between iodine σ‐holes and …
Inside Cover: Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Mo…
2017
International audience; A hydrogen-bonded open framework with pores decorated by pyridyl groups was constructed by off-charge-stoichiometry assembly of protonated tetrakis(4-pyridyloxymethyl)methane and [Al(oxalate)(3)](3-), which are the H-bond donor and acceptor of ionic H-bond interactions, respectively. This supramolecular porous architecture (SPA-2) has 1nm-large pores interconnected in 3D with large solvent-accessible void (53%). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by means of various carboxylic acids including larger drug molecules. Competing sorption between acetic acid and its halogenated homologues evidenced good sel…
Multifacial Recognition in Binary and Ternary Cocrystals from 5-Halouracil and Aminoazine Derivatives
2018
A systematic analysis using single crystal X-ray diffraction was performed to explore the role exerted by potential intercomponent proton-transfer reactions in the supramolecular structures of A–B cocrystals formed by 5-haloderivatives of uracil (A), coupled with 2-aminoadenine simulants (aminoazines, B). Twelve new heterodimers were synthesized in different stoichiometries and cocrystallized by solvent cogrinding followed by solution crystallization. In the binary cocrystals, uracil or 1-methyluracil with halide modification at the 5 position (F, Cl, Br, I) was coupled with amino-aromatic N-heterocycles (melamine, 2,4,6-triaminopyrimidine, 2,6-diaminopyridine) as a multivalent site for pyr…