Monodisperse Nanoparticles from Self-Assembling Amphiphilic Cyclodextrins: Modulable Tools for the Encapsulation and Controlled Release of Pharmaceuticals
Alejandro Méndez‐ArdoyMarta Gómez-Garcı́aAnnabelle GèzeJean‐Luc PutauxDenis WouessidjeweCarmen Ortiz MelletJ. DefayeJosé M. Garcı́a FernándezJuan M. Benito
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Selective chemical functionalization of cyclodextrins (CDs) is a readily amenable methodology to produce amphiphilic macromolecules endowed with modulable self-organizing capabilities. Herein, the synthesis of well-defined amphiphilic CD derivatives, with a "skirt-type" architecture, that incorporate long-chain fatty esters at the secondary hydroxyl rim and a variety of chemical functionalities (e. g. iodo, bromo, azido, cysteaminyl or isothiocyanato) at the primary hydroxyls rim is reported. Nanoprecipitation of the new CD facial amphiphiles, or binary mixtures of them, resulted in nanoparticles with average hydrodynamic diameters ranging from 100 to 240 nm that were stable in suspension for several months. The precise size, zeta potential and topology of the nanoparticles are intimately dependent on the functionalization pattern at the CD scaffold. Highly efficient molecular encapsulation capabilities of poorly bioavailable drugs such as diazepam (DZ) were demonstrated for certain derivatives, the drug release profile being dependent on the type of formulation (nanospheres or nanocapsules). The efficiency and versatility of the synthetic strategy, together with the possibility of exploiting the reactivity of the functional groups at the nanoparticle surface, offer excellent opportunities to further manipulate the carrier capabilities of this series of amphiphilic CDs from a bottom-up approach. Keywords: Cyclodextrins, controlled drug release, drug delivery, facial amphiphiles, nanoparticles, nanospheres, nanocapsules, self-assembly, Nanoprecipitation, amphiphilesKeywords:
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Monodisperse hydrophilic quantum dots (QDs) are promising labeling materials for biomedical applications. However, the controllable preparation of monodisperse hydrophilic QDs with amphiphilic polymers remains a challenge. Herein, the molecular structures of amphiphilic polymers assembled on different-sized QDs are investigated. Both the experimental results and the molecular dynamics (MD) calculation suggest that the grafting ratio of amphiphilic polymers assembled on QDs increases as the size of QDs increases. Thus, the controllable preparation of different-sized monodisperse hydrophilic QDs can be achieved by simply varying the grafting ratio of amphiphilic molecules and applied in the simultaneous labeling of three tumor biomarkers.
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Abstract An amphiphilic organic cage was synthesized and used as self‐assembly synthon for the fabrication of novel functional supramolecular structures in solution. The transmission electron microscopy (TEM) results showed that this amphiphilic cage self‐assembled in aqueous solution into unilamellar nanotubes with a diameter of 29±4 nm at a concentration of 0.05 mg mL −1 . Interestingly, the self‐assembly of this cage significantly enhanced the anion‐π interactions as indicated by a remarkable increasement of association constant ( K a ) between Cl − and this amphiphilic cage after self‐assembly. In specific, K a was increased from 223 M −1 for discrete cages in methanol to 6800 M −1 for aggregated cages after self‐assembly in water at the same concentration of 2.26×10 −5 M. A mechanism based on a synergistic effect was proposed in order to explain this self‐assembly process through enhanced anion‐π interactions.
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Molecular self-assembly is a process to obtain a well defined structure from suitable starting materials. The study of self-assembly provides a fundamental understanding of the driving forces and co-operative interaction behind these processes. Among the plenty of molecules, an amphiphilic molecule, containing both hydrophilic and hydrophobic counter parts is one of the interesting building blocks to study the self-assembly processes. In this short review, the hierarchical self-assembly of amphiphilic molecules into various supramolecular architectures such as vesicles, spheres, flowers, tubes and fibrillar networks of nano- to micrometer dimensions and gels have been discussed.
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Amphiphilic peptides with or without oligoethylene glycol (OEG) chains based on 3,4-bis(benzyloxy)benzoic-linked glutamide were designed and their self-assembly was investigated. It was found that the amphiphilic peptide 3 with OEG chains could not only form stable gels in a wide range of solvents, but also showed better solubility in solvents than those without OEG chains. Fibrillar and nanotube structures were found in the gels formed and the width of the fibres could be tuned with added water content. The UV-vis and XRD results suggested that the driving forces for the peptide self-assembly were mainly intermolecular π–π and hydrogen-bonding interactions. These results provide a deeper understanding of the self-assembly mechanism and size control of nanofibrils formed by an OEG-based amphiphilic peptide.
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Abstract The construction of highly ordered organizations through self‐assembly is one of the most popular phenomena both in natural and artificial environments. Amphiphilic molecules are the most commonly used building blocks for the self‐assembly, which are conventionally known as amphiphilic low molecular weight surfactants with polar heads and nonpolar tails, or amphiphilic block copolymers (BCPs) consisting of covalently bonded hydrophilic and hydrophobic block chains. Compared with single surfactant self‐assembly system, binary amphiphiles co‐assembly systems composing of both small mass surfactants and amphiphilic BCPs feature high flexibilities and versatilities in materials designing and structure regulation, ascribing to the vast possibilities of intermolecular interactions within the systems and facile component modulations during the assembly processes. The amphiphilic features of the two kinds of molecules endow them with similar self‐assembly behaviors, while the unique and distinct characters of each kind of amphiphiles lead to various complex but highly diversified co‐assembly systems. According to the roles of the surfactant played in the co‐assembly system, in this review, we summarize the binary co‐assembly systems from three distinct types: 1) the co‐micellization system in which the surfactants are added into the BCPs assemblies as a self‐assembly assistant; 2) the co‐emulsification system in which the surfactants work as an emulsion stabilizer to assist and confine the assembly of BCPs in 3D geometries; 3) the co‐templating system where the individual micelles of both surfactant and BCPs are hierarchically arranged and distributed to guide the formation of hierarchical nanomaterials. Following this, the major potential applications of the nanomaterials synthesized from the binary amphiphiles in biological field are described. Finally, we shortly discuss the current challenges and future perspectives of the binary amphiphiles self‐assembly systems.
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Dendritic poly(phenylazomethine)s with dodecyl end groups have been synthesized. These dendrimers showed a stepwise radial complexation with metals and unique self-assembled structures. In their Full Paper on page 800 ff., K. Yamamoto et al. describe the synthesis and characterization of these new metal-storage nanocapsules.
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In this paper, the recent development of the self-assembly of amphiphilic block copolymers in solutions were reviewed, with emphasis on new morphologyies of aggregates,such as rod, wormlike, vesicle,onion and solid onion etc. At the same time, the potential applications of the self-assembly of amphiphilic block copolymers in solutions, to light and e-lectricity ,the release of pharmacies,gene enginerring were introduced. The preparation methods of aggregates were also reviewed.
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