Hyperbranched polyethylenimines as versatile precursors for the preparation of different type of unimolecular micelles

Abstract Hyperbranched polyethylenimine (HPEI) was successfully employed as precursor for the preparation of unimolecular inverted and aqueous micelles. The unimolecular inverted micelles (UIMs) obtained by the amidation of HPEI with 1,1′-carbonyldiimidazole (CDI) activated palmitic acid exhibited high encapsulation efficiency for hydrophilic anionic dyes and the efficiency could be enhanced significantly by decreasing the degree of amidation or quaternizing the residual amines. The weight ratio of loaded guests to the amidated HPEIs was not dependent on the molecular weight of HPEI core when the degree of amidation was kept constant. Decreasing the length of the aliphatic chain from 16 to …

Thermoresponsive hyperbranched polyethylenimines with isobutyramide functional groups

Core–shell-type multiarm star polyethylenimine-block-poly(ɛ-caprolactone): Synthesis and guest encapsulation potential

Novel multiarm star copolymers with poly(e-caprolactone) (PCL) as the arms and hyperbranched polyethylenimine (HPEI) as the core have been successfully prepared by the tin(II) 2-ethylhexanoate catalyzed ring-opening polymerization of e-caprolactone (CL) with HPEI used directly as a macroinitiator. Not only primary but also secondary amine groups of HPEI participate in initiating the ring-opening polymerization of CL with almost 100% initiation efficiency. The average degree of polymerization of the PCL arms can be controlled by the feed ratio of the monomers to the initiating sites. Because of the polarity difference of the PCL arms and HPEI core, the obtained multiarm star polymers display…

Water-Soluble Fluorescent Ag Nanoclusters Obtained from Multiarm Star Poly(acrylic acid) as “Molecular Hydrogel” Templates

Synergistic assembly of hyperbranched polyethylenimine and fatty acids leading to unusual supramolecular nanocapsules

Self-assembly of hyperbranched polyethylenimine (PEI) and fatty acids leads to supramolecular inverted micellar structures that are able to irreversibly transfer water-soluble guest molecules into organic solvents. Perez Prieto, Julia, Julia.Perez@uv.es ; Stiriba, Salah Eddine, Salah.Stiriba@uv.es

Multi-Arm Star Polyglycerol-block-poly(tert-butyl acrylate) and the Respective Multi-Arm Poly(acrylic acid) Stars

Well-defined multi-arm star block copolymers, polyglycerol-block-poly(tert-butyl acrylate) (PG-b-PtBA), with average arm-numbers of 17, 27, 36, 66 and 90 arms, respectively, have been prepared by atom transfer radical polymerization (ATRP) of tBA in acetone, using a core-first strategy. After hydrolysis with excess concentrated HCl in refluxing dioxane, full hydrolysis of the tert-butyl ester groups was achieved, resulting in multi-arm star polyelectrolytes, polyglycerol-block-poly(acrylic acid) (PG-b-PAA). The hyperbranched macroinitiators employed were prepared on the basis of hyperbranched polyglycerols via esterification with 2-bromoisobutyryl bromide. Both CuBr/PMDETA and CuBr/Me 6 TRE…

Role of Topology and Amphiphilicity for Guest Encapsulation in Functionalized Hyperbranched Poly(ethylenimine)s

The promising potential of dendrimers in a variety of areas, such as catalysis, materials science and biomedicine is related to their globular shape, large number of modifiable surface functionalities and the presence of internal reservoirs.1 Their use in liquidliquid-phase transfer protocols, based on the encapsulation of guest molecules as drug delivery vehicles for pharmaceutical application, represents an important issue.2 Unfortunately, dendrimer synthesis is timeconsuming, which currently limits practical use to laboratory scale. For that reason, hyperbranched polymers prepared from ABm-type monomers in one-step processes have gained increasing interest.3 The development of the slow m…

Gold Nanoparticles Coated with a Thermosensitive Hyperbranched Polyelectrolyte: Towards Smart Temperature and pH Nanosensors

Multiarm star polyglycerol-block-poly(HEMA) as a versatile precursor for the preparation of micellar nanocapsules with different properties

Well-defined multiarm star polymer with hyperbranched polyglycerol as core and poly(2-hydroxyethyl methacrylate) (PHEMA) as arms were used as precursor for the preparation of inverted and aqueous micellar nanocapsules. The partial modification of the hydroxyl groups of PHEMA arms with aliphatic chains led to the formation of inverted micellar nanocapsules. The hydrophilic dye encapsulation capacity of the inverted micelles can be enhanced significantly by transforming the inner hydroxyl groups of PHEMA arms into quaternized amine groups. The modification of the outer and inner hydroxyl groups of PHEMA arms with polyethylene glycol acid chloride and pivaloyl chloride, respectively, resulted …

Supramolecular Thermotropic Liquid Crystalline Materials with Nematic Mesophase Based on Methylated Hyperbranched Polyethylenimine and Mesogenic Carboxylic Acid

Supramolecular interaction of fully methylated hyperbranched polyethylenimines (PEI) with a mesogen-based carboxylic acid, 5-(p-cyanobiphenoxy)pentanoic acid, results in the formation of supramolecular complexes exhibiting thermotropic liquid crystalline (LC) mesophases. In contrast to the common smectic mesophases of most dendritic LC polymers, nematic LC phase were observed. The complexation of PEI and the mesogen units is due to electrostatic interaction between the carboxylate groups and the ammonium end groups of PEI. LC properties were investigated by a combination of differential scanning calorimetry, polarizing light optical microscopy, and X-ray diffractometry.

Synthesis of multiarm star poly(glycerol)-block-poly(2-hydroxyethyl methacrylate).

Well-defined multiarm star block copolymers poly(glycerol)-b-poly(2-hydroxyethyl methacrylate) (PG-b-PHEMA) with an average of 56, 66, and 90 PHEMA arms, respectively, have been prepared by atom transfer radical polymerization (ATRP) of HEMA in methanol by a core-first strategy. The hyperbranched macroinitiators employed were prepared on the basis of well-defined hyperbranched polyglycerol by esterification with 2-bromoisobutyryl bromide. Polydispersites M(w)/M(n) of the new multiarm stars were in the range of 1.11-1.82. Unexpectedly, with the combination of CuCl/CuBr(2)/2,2'-bipyridyl as catalyst, the polymerization conversion can be driven to maximum values of 79%. The control of CuCl cat…

Unprecedented blue intrinsic photoluminescence from hyperbranched and linear polyethylenimines: Polymer architectures and pH-effects

The intrinsic photoluminescence properties of hyperbranched polyethylenimines (PEIs) and their linear counterpart (LPEIs) have been studied in absence of any classical fluorescent probes. The comparison of the inherent fluorescence emission between hyperbranched polyethylenimines and their linear analogues demonstrates that linear polyamines are capable of producing strong intrinsic photoluminescence species having long excited lifetimes without need of having a tridimensional-branched structure. The creation of inherently fluorescent polymeric centers from hyperbranched and linear polyethyleimines can be modulated by specific chemical modification and oxidation of amine groups as well as b…