The combination of matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-ToF-MS) and size exclusion chromatography (SEC) combined with pulsed laser polymerization has been used to evaluate propagation rate coefficients (kp) in bulk free-radical polymerization for the systems methyl methacrylate and styrene. By varying laser frequencies, the relation between polymer chain length and observed propagation rate coefficient (k p obs ) has been investigated in detail. It has been found that deviations between MALDI-ToF-MS and SEC at higher molecular weights are the result of instrumental effects in SEC. Moreover, using a model and taking into account experimental studies on the propagation of oligomeric species, it has been inferred that the relationship between k p obs and polymer chain length is the result of chain-length-dependent behavior of the true kp in the oligomeric range, therewith excluding any chain-length-dependent behavior at higher molecular weights.

Summary: A series of poly(ethylene glycol)‐block‐poly(ε‐caprolactone) diblock copolymers was synthesized and fully characterized. In particular, MALDI‐TOF MS results revealed interesting new insights into their molecular architecture. Small and defined micelles could be prepared from these block copolymers. Utilizing a high‐throughput screening approach, it was observed that these micelles are able to encapsulate/solubilize different guest molecules (e.g. drugs) depending on the solubility of the guest in water. Furthermore, it could be proven that a guest is located within a micelle and that these micelles can be utilized as transport vehicles for the encapsulated guest molecules.PEO‐b‐PCL diblock copolymers can encapsulate small guest molecules in the core of the polymeric micelles.imagePEO‐b‐PCL diblock copolymers can encapsulate small guest molecules in the core of the polymeric micelles.

The use of poly(styrene-co-maleic acid) (SMA) for the solubilization of lipid membranes and membrane proteins is becoming more widespread, and with this, the need increases to better understand the chemical properties of the copolymer and how these translate into membrane solubilization properties. SMA comes in many different flavors that include the ratio of styrene to maleic acid, comonomer sequence distribution, average chain length, dispersity, and potential chemical modifications. In this work, the synthesis and membrane active properties are described for 2:1 (periodic) SMA copolymers with M w varying from ∼1.4 to 6 kDa. The copolymers were obtained via an iterative RAFTmediated radical polymerization. Characterization of these polymers showed that they represent a well-defined series in terms of chain length and overall composition (F MAnh ∼ 0.33), but that there is heterogeneity in comonomer sequence distribution (F MSS ∼ 0.50) and some dispersity in chain length (1.1 < Đ < 1.6), particularly for the larger copolymers. Investigation of the interaction of these polymers with phosphatidylcholine lipid self-assemblies showed that all copolymers inserted equally effectively into lipid monolayers, independent of the copolymer length. Nonetheless, smaller polymers were more effective at solubilizing lipid bilayers into nanodiscs, possibly because longer polymers are more prone to become intertwined with each other, thereby hampering their solubilization efficiency. Nanodisc sizes were independent of the copolymer length. However, nanodiscs formed with larger copolymers were found to undergo slower lipid exchange, indicating a higher stability. The results highlight the usefulness of having well-defined copolymers for systematic studies.

A bifunctional initiator was synthesized and used for a sequence of a nickel initiated polymerization of gamma-benzyl-L-glutamate-N-carboxy anhydride and atom transfer radical polymerization of methyl methacrylate yielding a rod-coil block copolymer.

New amphiphilic block copolymers consisting of N‐vinyl pyrrolidone and vinyl acetate were synthesized via controlled radical polymerization using a reversible addition/fragmentation chain transfer (RAFT)/macromolecular design via the interchange of xanthates (MADIX) system. The synthesis was carried out in 1,4‐dioxane as process solvent. In order to get conclusions on the mechanism of the polymerization the molecular structure of formed copolymers was analysed by means of different analytical techniques. 13C NMR spectroscopy was used for the determination of the monomer ratios. End groups were analysed by means of matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. This technique was also used to determine possible fragmentations of the RAFT end groups. By means of a combination of size exclusion chromatography, 13C NMR and static light scattering molar mass distributions and absolute molar masses could be analysed. The results clearly show a non‐ideal RAFT mechanism.