Cooperative organizations of small molecular surfactants and amphiphilic block copolymers: Roles of surfactants in the formation of binary co‐assemblies

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 coassembly 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 selfassembly systems.

New Water-Soluble Magnetic Field-Induced Drug Delivery System Obtained Via Preferential Molecular Marriage over Narcissistic Self-Sorting

“…This is because the SS-NC has a higher hydrophobic component than the NS-NC, and the cooperative effect of multiple hydrophobic chains may also help the SS-NC to form before the NS-NC. 59,60 In addition, the increasing weight ratio of mPEG−PLLA to 0.05−0.1 mg/mL (w/v) over IONP@PLLA (0.05 mg/mL) has resulted in increased formation of SS-NCs, while IONP@ PLLA has decreased, as observed in TEM images (Figure S15). The core−shell structure of SS-NCs can be seen clearly in the TEM image in Figure 3c.…”

“…Interestingly, the SS-NC has a lower IC than the NS-NC . This is because the SS-NC has a higher hydrophobic component than the NS-NC , and the cooperative effect of multiple hydrophobic chains may also help the SS-NC to form before the NS-NC . , …”

Surfactant and Block Copolymer Nanostructures: From Design and Development to Nanomedicine Preclinical Studies

“…The process of self-assembly of small molecular weight amphiphilic molecules (i.e., surfactants) has been thoroughly studied over the years, while a general classification has been made regarding the type of charge of the polar head group ( Figure 1 ). In short, the three main categories are those of cationic (CTAB, CTAC), anionic (C14Na), and zwitterionic (dodecyldimethylamine oxide), and finally, a fourth category is that of non–ionic molecules (Tween 80, Span 80) [ 19 ].…”

“…Amongst the advantages that the above chimeric systems have to offer is their ability to encapsulate active pharmaceutical ingredients to be transferred and absorbed via multiple administration routes [ 29 ]. A key point in the use of such components in a single nanoparticulate formulation is perhaps the fact that surfactants of low molecular weight and long chain block copolymers exhibit analogous self-assembly behaviors in solutions and at interfaces, allowing for co-assembly in thermodynamically stable nanostructures [ 19 , 61 ].…”

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“…[89,90] As a result, commonly used surfactants such as CTAB, P123, and F127 in the synthesis procedure could produce various types of pore, such as worm-like, hexagonal, and cubic pore structures. [91] Moreover, using a particular template via different routes of synthesis can also resulted in MBGs of different morphology and textures. [60] In this regard, using surfactants such as CTAB, F127, and P123 as structure-directing agents for MBG synthesis, in many studies has resulted in MBGs with diverse final mesopore size, volume, and surface area, ranging from 2 to 10 nm, 0.4 to 0.7 cm 3 , and 150 to 1000 m 2 g −1 , respectively.…”