Polyether-Based Lipids Synthesized with an Epoxide Construction Kit: Multivalent Architectures for Functional Liposomes

Poly(isoglycerol methacrylate)-b-poly(d or l-lactide) Copolymers: A Novel Hydrophilic Methacrylate as Building Block for Supramolecular Aggregates

On the basis of a new acetal-protected glycerol monomethacrylate monomer (cis-1,3-benzylidene glycerol methacrylate/BGMA) a series of potentially biocompatible and partially biodegradable homo- and block copolymers were synthesized. ATRP polymerization of BGMA yielded well-defined polyacrylates with pendant benzylidene acetal groups and high glass transition temperatures (115−130 °C). This hydrophobic poly(cis-1,3-benzylidene glycerol methacrylate) could be readily transformed into the hydrophilic and water-soluble poly(1,3-dihydroxypropyl methacrylate), referred to as poly(isoglycerol methacrylate) (PIGMA). It exclusively contains primary hydroxyl groups and therefore differs significantly…

Rapid Access to Polyfunctional Lipids with Complex Architecture via Oxyanionic Ring-Opening Polymerization

Polymer-coated liposomes, particularly poly(ethylene glycol) (PEG)-substituted liposomes, have emerged as long-circulating carrier systems for drug delivery and diagnostic purposes. A rapid synthesis of three different types of multifunctional lipids with structurally diverse hydrophilic, polyether-based architectures via one- or two-pot approaches is described. Architectural variation is achieved by the combination of different oxyanionic polymerization strategies and various glycidyl ether building units. Branched polyglycerol lipids have been prepared via cholesterol- or 1,2-bis-n-alkyl glyceryl ether-initiated, oxyanionic ring-opening polymerization (ROP) of protected glycidyl ethers an…

Click modification of multifunctional liposomes bearing hyperbranched polyether chains.

Aiming at controlled modification of liposomal surface structures, we describe a postpreparational approach for surface derivatization of a new type of multifunctional, sterically stabilized liposomes. Application of dual centrifugation (DC) resulted in high encapsulation efficiencies above 50% at very small batch sizes with a total volume of 150 μL, which were conductive to fast and efficient optimization of variegated surface modification reactions. Cholesterol-polymer amphiphiles, including complex hyperbranched polyether structures bearing 1-4 terminal alkynes, were used in DC formulations to provide steric stabilization. The alkyne moieties were explored as anchors for the conjugation …

Hyperbranched Polyglycerol-Based Lipids via Oxyanionic Polymerization: Toward Multifunctional Stealth Liposomes

We describe the synthesis of linear-hyperbranched lipids for liposome preparation based on linear poly(ethylene glycol) (PEG) and hyperbranched polyglycerol (PG). Molecular weights were adjusted to values around 3000 g/mol with varying degrees of polymerization of the linear and the branched segments in analogy to PEG-based stealth lipids; polydispersities were generally low and below 1.3. The hydrophobic anchors were introduced into the lipid structures as initiators for the anionic polymerization of ethylene oxide and are either based on cholesterol or on different aliphatic glyceryl ethers. Complete incorporation of the apolar initiators was evidenced by MALDI-ToF analysis at all stages …

α ,ω n -Heterotelechelic Hyperbranched Polyethers Solubilize Carbon Nanotubes

The synthesis of novel linear-hyperbranched (linhb) polyether block copolymers based on poly(ethylene oxide) and branched poly(glycerol), bearing a single pyrene or myristyl moiety at the α-position of the linear chain is described. The polymers exhibit low polydispersity (M w /M n < 1.3) and controlled molecular weights (M n = 5 000 g·mol -1 ). The mainly hydrophilic block copolymers with multiple hydroxyl end groups readily dissolve multiwalled carbon nanotubes (MWCNTs) in water by mixing and subsequent sonification, resulting in noncovalent attachment of the linhb hybrid structure to the carbon nanotubes (CNTs). Transmission electron microscopy (TEM) was employed to visualize the solubil…

Langmuir and Langmuir-Blodgett films of multifunctional, amphiphilic polyethers with cholesterol moieties.

Langmuir films of multifunctional, hydrophilic polyethers containing a hydrophobic cholesterol group (Ch) were studied by surface pressure-mean molecular area (π-mmA) measurements and Brewster angle microscopy (BAM). The polyethers were either homopolymers or diblock copolymers of linear poly(glycerol) (lPG), linear poly(glyceryl glycidyl ether) (lPGG), linear poly(ethylene glycol) (lPEG), or hyperbranched poly(glycerol) (hbPG). Surface pressure measurements revealed that the homopolymers lPG and hbPG did not stay at the water surface after spreading and solvent evaporation, in contrast to lPEG. Because of the incorporation of the Ch group in the polymer structure, stable Langmuir films wer…

Mesogen-Initiated Linear Polyglycerol Isomers: The Ordering Effect of a Single Cholesterol Unit on “Sticky” Isotropic Chains

Synthesis, thermal properties, and the liquid crystalline (LC) order of polymers consisting of a single mesogenic cholesterol unit and flexible, linear polyglycerol (PG) or poly(glyceryl glycerol) (PGG) chains have been investigated. Incorporation of the single mesogen has been achieved by using cholesterol directly as an initiator for the oxyanionic ring-opening polymerization (ROP) of ethoxyethyl glycidyl ether (EEGE) or isopropylidene glyceryl glycidyl ether (IGG). The controlled polymerization allowed the synthesis of a series of peculiar rod–coil type polyethers with molecular weights of 600–2300 g/mol, representing a degree of polymerization (DPn) of 4–30 for both PG and PGG with the …