Glycosaminoglycans (GAGs) as one major part of the glycocalyx are involved in many essential biological cell processes, as well as in many courses of diseases. Because of the potential therapeutic application of GAG polymers, fragments, and also derivatives toward different diseases (e.g., heparin derivatives against Alzheimer's disease), there is a continual growing demand for new chemical syntheses, which suffice the high claim to stereoselectivity and chemoselectivity. This Review summarizes the progress of chemical syntheses of GAGs over the last 10 years. For each class of the glycosaminoglycans-hyaluronan (HA), heparan sulfate/heparin (HS/HP), chondroitin/dermatan sulfate (CS/DS), and keratan sulfate (KS)-mainly novel glycosylation strategies, elongation sequences, and protecting group patterns are discussed, but also (semi)automated syntheses, enzymatic approaches, and functionalizations of synthesized or isolated GAGs are considered.

We present a baculovirus-based protein engineering method that enables site-specific introduction of unique functionalities in a eukaryotic protein complex recombinantly produced in insect cells. We demonstrate the versatility of this efficient and robust protein production platform, 'MultiBacTAG', (i) for the fluorescent labeling of target proteins and biologics using click chemistries, (ii) for glycoengineering of antibodies, and (iii) for structure-function studies of novel eukaryotic complexes using single-molecule Förster resonance energy transfer as well as site-specific crosslinking strategies.

Bioinspiration has emerged as an important design principle in the rapidly growing field of materials science and especially its subarea, soft matter science. For example, biological cells form hierarchically organized tissues that not only are optimized and designed for durability, but also have to adapt to their external environment, undergo self‐repair, and perform many highly complex functions. Being able to create artificial soft materials that mimic those highly complex functions will enable future materials applications. Herein, soft matter technologies that are used to realize bioinspired material structures are described, and potential pathways to integrate these into a comprehensive soft matter research environment are addressed. Solutions become available because soft matter technologies are benefitting from the synergies between organic synthesis, polymer chemistry, and materials science.

Chemically produced, accurately linkable oligosaccharides are of importance for the synthesis of neo‐glycoproteins. On the route to high‐mannose type N‐glycans, we present a convenient synthesis of several glycans bearing an azide moiety at the reducing end. An azido‐glycan core structure as valuable precursor was modified into the protected N‐glycan pentasaccharide core structure and the possibility of modular attachment of different antenna was demonstrated through synthesis of a pentamannose donor and glycosylation with the core structure. The azido function allows for chemical ligation with recombinantly modified proteins featuring noncanonical cyclooctyne amino acids, providing access to customized glycopatterns of glycoproteins, e.g., of antibodies that are of high interest for biopharmaceutical applications.

In the past decade, the phosphorescence of metal-free confined polymer structures has generated interest in optoelectronics due to their sustainability, low toxicity, and deployment in sensing applications. Herein, a free-standing array of laterally organized nanofibers was prepared via templated chemical vapor deposition polymerization into a liquid crystalline (LC) phase, and their optical properties were compared to compositionally identical films. The fibers converge into laterally aligned membranes that maintain a high internal order despite the surfaces of the membranes remaining uniform and closed. The membranes consisted of hourglass-shaped nanofibers with features in the micro- and nanometer regime. Free-standing nanofiber membranes differ from polymer films of equivalent chemical composition in several key features: (1) Anisotropic growth of polymer nanofibers with constraint and compliance to an LC template, (2) a high surface-to-volume ratio, and (3) the occurrence of a long-lived emission in the blue region, which persists for multiple seconds after excitation. This study constitutes the first report of long-lived emission from solid-state poly(p-xylylenes) nanofibers. Prospective applications of morphologically controlled polymer arrays with structural luminescence include organic sensors and optoelectronic devices.