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Heterobifunctional poly(ethylene glycol)s (PEGs) are key structures for bioconjugation in the context of the “PEGylation” strategy to enhance blood circulation times of, for example, peptide drugs or “stealth” liposomes. The formation of heterobifunctional PEGs from symmetric PEG diols is challenging because of limited yields of the targeted monofunctional product and difficulties associated with separation steps. On the basis of a detailed comparison of reaction conditions, we have investigated a “polymer desymmetrization” strategy to maximize the yields of monofunctional PEG tosylate. The tosylation reaction in the presence of the heterogeneous catalyst silver oxide and potassium iodide in a specific stoichiometric ratio proved to be highly efficient, resulting in 71–76% yield of monofunctional PEG depending on molecular weight, exceeding the expected value of 50% in a statistical reaction without addition of a catalyst. For characterization as well as for the preparative separation of monotosylated PEG...

In the last decades, the number of allergic patients has increased dramatically. Allergen-specific immunotherapy (SIT) is the only available cause-oriented therapy so far. SIT reduces the allergic symptoms, but also exhibits some disadvantages; that is, it is a long-lasting procedure and severe side effects like anaphylactic shock can occur. In this work, we introduce a method to encapsulate allergens into nanoparticles to avoid severe side effects during SIT. Degradable nanocarriers combine the advantage of providing a physical barrier between the encapsulated cargo and the biological environment as well as responding to certain local stimuli (like pH) to release their cargo. This work introduces a facile strategy for the synthesis of acid-labile poly(ethylene glycol) (PEG)-macromonomers that degrade at pH 5 (physiological pH inside the endolysosome) and can be used for nanocarrier synthesis. The difunctional, water-soluble PEG dimethacrylate (PEG-acetal-DMA) macromonomers with cleavable acetal units were analyzed with 1H NMR, SEC, and MALDI-ToF-MS. Both the allergen and the macromonomers were entrapped inside liposomes as templates, which were produced by dual centrifugation (DAC). Radical polymerization of the methacrylate units inside the liposomes generated allergen-loaded PEG nanocarriers. In vitro studies demonstrated that dendritic cells (DCs) internalize the protein-loaded, nontoxic PEG-nanocarriers. Furthermore, we demonstrate by cellular antigen stimulation tests that the nanocarriers effectively shield the allergen cargo from detection by immunoglobulins on the surface of basophilic leucocytes. Uptake of nanocarriers into DCs does not lead to cell maturation; however, the internalized allergen was capable to induce T cell immune responses.