Self-assembling amphiphilic Janus dendrimers: mesomorphic properties and aggregation in water

Abstract

The self-assembly behaviour both in bulk and in water of amphiphilic dendrimeric derivatives based on bis-MPA is the central theme of this article. The designed molecules possess two parts with different polarity; this feature is the key factor that forces their self-assembly in water into supramolecular architectures, due to hydrophobic interactions between the lipophilic fractions of the molecules, and the appearance of mesomorphic order in bulk in response to a variation of temperature (thermotropic liquid 10 crystals). The effects provoked by the hydrophilic/lipophilic balance of the molecule were studied varying the generation of the corresponding dendrons and combining them via CuAAC click chemistry in order to obtain symmetrical and unsymmetrical final Janus dendrimers. The ability of the aggregates formed in water to encapsulate hydrophobic drugs has also been explored.

Nanoobjects formed by ionic PAMAM dendrimers: hydrophilic/lipophilic modulation and encapsulation properties

“…According to previous studies, 27,31 we chose an initial total concentration of 0.5 mM in water for both self-assembly and encapsulation experiments. The self-aggregation was studied through the oil-inwater method, 30 using dichloromethane as the volatile solvent (see the ESI, † part 3).…”

Multifunctional triazolylferrocenyl Janus dendron: Nanoparticle stabilizer, smart drug carrier and supramolecular nanoreactor

“…Normally, in the molecular structure of JDs, the hydrophilic dendron is composed of poly(ethylene glycol), amino, hydroxyl and carboxyl groups, while the hydrophobic part is often constructed of aliphatic chains with different length, poly(benzyl ether) and so on. However, there are few reports on the synthesis and functional applications of Janus metallodendrimers .…”

“…[6][7][8][9] Their asymmetric structures lead to new and efficient characteristic properties for the formation of complex self-assembled materials that are presently inconceivable for homogeneous or symmetric dendrimers, [10] and many applications have been investigated, especially in the fields of materials and biology, such as thermal actuators, [11] ionic liquids, [12] catalysis, [13] light harvesting systems, [14] bioimaging, [15] optoelectronics [16] and drug delivery. [17] Normally, in the molecular structure of JDs, the hydrophilic dendron is composed of poly(ethylene glycol), [18] amino, [19] hydroxyl [20] and carboxyl groups, [21] while the hydrophobic part is often constructed of aliphatic chains with different length, [18] poly(benzyl ether) [13] and so on. However, there are few reports on the synthesis and functional applications of Janus metallodendrimers.…”

Self-Assembly Behavior of Amphiphilic Janus Dendrimers in Water: A Combined Experimental and Coarse-Grained Molecular Dynamics Simulation Approach

“…Amphiphilic Janus dendrimers (JDs) are molecules composed of polar (hydrophilic) and non-polar (hydrophobic) dendritic blocks [ 1 ]. This characteristic is the key factor that favors the spontaneous self-assembly of JDs in water into complex supramolecular structures [ 2 ]. The variation in the chemical structure of JDs allows achieving a rich palette of morphologies in water, such as cubosomes, disks, tubular vesicles, helical ribbons and bilayered vesicles, termed as dendrimersomes [ 3 ].…”

“…In this work, experimental methods and CG-MD simulation were combined to evaluate the self-assembly behavior in water of a second-generation bis-MPA amphiphilic Janus dendrimer ( Figure 1 ). Bis-MPA dendrimers have already been studied [ 2 ], being perfectly suitable to build drug carriers, due to their low cytotoxicity and biodegradability. Nevertheless, this is the first report where the self-assembly phenomenon of this type of amphiphilic JD is molecularly explored using a CG-MD simulation.…”