The current gold standard to reduce non-specific cellular uptake of drug delivery vehicles is by covalent attachment of poly(ethylene glycol) (PEG). It is thought that PEG can reduce protein adsorption and thereby confer a stealth effect. Here, we show that polystyrene nanocarriers that have been modified with PEG or poly(ethyl ethylene phosphate) (PEEP) and exposed to plasma proteins exhibit a low cellular uptake, whereas those not exposed to plasma proteins show high non-specific uptake. Mass spectrometric analysis revealed that exposed nanocarriers formed a protein corona that contains an abundance of clusterin proteins (also known as apolipoprotein J). When the polymer-modified nanocarriers were incubated with clusterin, non-specific cellular uptake could be reduced. Our results show that in addition to reducing protein adsorption, PEG, and now PEEPs, can affect the composition of the protein corona that forms around nanocarriers, and the presence of distinct proteins is necessary to prevent non-specific cellular uptake.

Cells are integral to all forms of life due to their compartmentalization by the plasma membrane. However, living organisms are immensely complex. Thus there is a need for simplified and controllable models of life for a deeper understanding of fundamental biological processes and man-made applications. This is where the bottom-up approach of synthetic biology comes from: a stepwise assembly of biomimetic functionalities ultimately into a protocell. A fundamental feature of such an endeavor is the generation and control of model membranes such as liposomes and polymersomes. We compare and contrast liposomes and polymersomes for a better a priori choice and design of vesicles and try to understand the advantages and shortcomings associated with using one or the other in many different aspects (properties, synthesis, self-assembly, applications) and which aspects have been studied and developed with each type and update the current development in the field.

In recent years the littering of plastics and the problems related to their persistence in the environment have become a major focus in both research and the news. Biodegradable polymers like poly(lactic acid) are seen as a suitable alternative to commodity plastics. However, poly(lactic acid) is basically non-degradable in seawater. Similarly, the degradation rate of other biodegradable polymers also crucially depends on the environments they end up in, such as soil or marine water, or when used in biomedical devices. In this Minireview, we show that biodegradation tests carried out in artificial environments lack transferability to real conditions and, therefore, highlight the necessity of environmentally authentic and relevant field-testing conditions. In addition, we focus on ecotoxicological implications of biodegradable polymers. We also consider the social aspects and ask how biodegradable polymers influence consumer behavior and municipal waste management. Taken together, this study is intended as a contribution towards evaluating the potential of biodegradable polymers as alternative materials to commodity plastics.

The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazene bases. In addition, the commercially relevant double-metal cyanide (DMC) catalyst systems are discussed. Besides the synthetic progress, new types of multifunctional linear PEG (mf-PEG) and PPO structures accessible by copolymerization of EO or PO with functional epoxide comonomers are presented as well as complex branched, hyperbranched, and dendrimer like polyethers. Amphiphilic block copolymers based on PEO and PPO (Poloxamers and Pluronics) and advances in the area of PEGylation as the most important bioconjugation strategy are also summarized. With the ever growing toolbox for epoxide polymerization, a "polyether universe" may be envisaged that in its structural diversity parallels the immense variety of structural options available for polymers based on vinyl monomers with a purely carbon-based backbone.

The ubiquity of polymeric materials in daily life comes with an increased fire risk, and sustained research into efficient flame retardants is key to ensuring the safety of the populace and material goods from accidental fires. Phosphorus, a versatile and effective element for use in flame retardants, has the potential to supersede the halogenated variants that are still widely used today: current formulations employ a variety of modes of action and methods of implementation, as additives or as reactants, to solve the task of developing flame‐retarding polymeric materials. Phosphorus‐based flame retardants can act in both the gas and condensed phase during a fire. This Review investigates how current phosphorus chemistry helps in reducing the flammability of polymers, and addresses the future of sustainable, efficient, and safe phosphorus‐based flame‐retardants from renewable sources.

In the rapidly evolving multidisciplinary field of polymer therapeutics, tailored polymer structures represent the key constituent to explore and harvest the potential of bioactive macromolecular hybrid structures. In light of the recent developments for anticancer drug conjugates, multifunctional polymers are becoming ever more relevant as drug carriers. However, the potentially best suited polymer, poly(ethylene glycol) (PEG), is unfavorable owing to its limited functionality. Therefore, multifunctional linear copolymers (mf-PEGs) based on ethylene oxide (EO) and appropriate epoxide comonomers are attracting increased attention. Precisely engineered via living anionic polymerization and defined with state-of-the-art characterization techniques-for example real-time (1)H NMR spectroscopy monitoring of the EO polymerization kinetics-this emerging class of polymers embodies a powerful platform for bio- and drug conjugation.

Reactions and polymerizations at the interface of two immiscible liquids are reviewed. The confinement of two reactants at the interface to form a new product can be advantageous in terms of improved reaction kinetics, higher yields, and selectivity. The presence of the liquid-liquid interface can accelerate the reaction, or a phase-transfer catalyst is employed to draw the reaction in one phase of choice. Furthermore, the use of immiscible systems, e.g., in emulsions, offers an easy means of efficient product separation and heat dissipation. A general overview on low molecular weight organic chemistry is given, and the applications of heterophase polymerization, occurring at or in proximity of the interface, (mostly) in emulsions are presented. This strategy can be used for the efficient production of nano- and microcarriers for various applications.

The synthesis of poly(ethylene glycol) (PEG) copolymers with multiple amino functionalities within the chain is described, relying on an epoxide comonomer bearing a protected amino group. N,Ndibenzyl amino glycidol (DBAG) and ethylene oxide (EO) were copolymerized via anionic polymerization, leading to well-defined polymers with varied comonomer content and low polydispersities (M w /M n in the range of 1.1 to 1.2). Subsequent hydrogenolysis with Pearlman's catalyst afforded poly(ethylene glycol-coamino glycerol)s (PEG-co-PAG) with a precisely adjusted number of randomly incorporated amino groups in the range of 2-15%. For the first time, the kinetics of an EO copolymerizations have has been directly monitored by 1 H NMR spectroscopy in real time. Monomer consumption and compositional drift in monomer feed have been studied for various reaction temperatures, revealing a slightly tapered yet random DBAG distribution in the copolymers. The random structure of the copolymers was confirmed by detailed 13 C NMR characterization of EO-and DBAG-centered triad sequence distribution and DSC measurements.