Ring-Opening Metathesis Polymerization of Norbornene-Based Monomers Obtained via the Passerini Three Component Reaction.

Ring-opening metathesis polymerization is a robust method to synthesize a variety of polymers by using ring-strained molecules as monomers, e.g., norbornenes. However, the synthesis of monomers with multiple functional groups remains a challenge, albeit peptide functional norbornenes have previously been used. Here, the Passerini three component reaction is exploited to synthesize norbornenes with two variable functional groups varying in bulkiness and distance from the polymerizable alkene. The results indicate that the functional groups do not affect the kinetics of the polymerization, whereas the length of the linker has a minor effect. Furthermore, a diblock-type copolymer is synthesized in a one-pot fashion, also indicating good control of the polymerization process. The thermal properties of all polymers are evaluated, highlighting the effect of monomer composition. This synthetic approach can be transferred to a variety of compounds, thus promising highly diverse polymers with complex compositions and architectures.

Synthesis and Encapsulation of Uniform Star-Shaped Block-Macromolecules.

Linear uniform oligomers synthesized via a two-step iterative cycle are postmodified with uniform octaethylene glycol monomethyl ether and finally coupled via azide-alkyne cycloaddition to yield uniform star-shaped block macromolecules with a mass ranging from 10 to 14 kDa. Each of the molecules is carefully characterized by NMR, electrospray ionization mass spectrometry (ESI-MS), and size exclusion chromatography (SEC) to underline their purity as well as their uniformity. The obtained star-shaped macromolecules are investigated in their ability to encapsulate dye molecules by carrying out qualitative solid-liquid phase transfer experiments.

Cyan-Emitting Cu(I) Complexes and Their Luminescent Metallopolymers.

Copper complexes have shown great versatility and a wide application range across the natural and life sciences, with a particular promise as organic light-emitting diodes. In this work, four novel heteroleptic Cu(I) complexes were designed in order to allow their integration in advanced materials such as metallopolymers. We herein present the synthesis and the electrochemical and photophysical characterisation of these Cu(I) complexes, in combination with ab initio calculations. The complexes present a bright cyan emission (λem ~ 505 nm) in their solid state, both as powder and as blends in a polymer matrix. The successful synthesis of metallopolymers embedding two of the novel complexes is shown. These copolymers were also found to be luminescent and their photophysical properties were compared to those of their polymer blends. The chemical nature of the polymer backbone contributes significantly to the photoluminescence quantum yield, paving a route for the strategic design of novel luminescent Cu(I)-based polymeric materials.

Progress Toward Sustainable Reversible Deactivation Radical Polymerization.

The recent focus of media and governments on renewability, green chemistry, and circular economy has led to a surge in the synthesis of renewable monomers and polymers. In this review, focussing on renewable monomers for reversible deactivation radical polymerizations (RDRP), it is highlighted that for the majority of the monomers and polymers reported, the claim to renewability is not always accurate. By closely examining the sustainability of synthetic routes and the renewability of starting materials, fully renewable monomers are identified and discussed in terms of sustainability, polymerization behavior, and properties obtained after polymerization. The holistic discussion considering the overall preparation process of polymers, that is, monomer syntheses, origin of starting materials, solvents used, the type of RDRP technique utilized, and the purification method, allows to highlight certain topics which need to be addressed in order to progress toward not only (partially) renewable, but sustainable monomers and polymers using RDRPs.

Bioinspired Polymer Systems with Stimuli-Responsive Mechanical Properties.

Materials with switchable mechanical properties are widespread in living organisms and endow many species with traits that are essential for their survival. Many of the mechanically morphing materials systems found in nature are based on hierarchical structures, which are the basis for mechanical robustness and often also the key to responsive behavior. Many "operating principles" involve cascades of events that translate cues from the environment into changes of the overall structure and/or the connectivity of the constituting building blocks at various levels. These concepts permit dramatic property variations without significant compositional changes. Inspired by the function and the growing understanding of the operating principles at play in biological materials with the capability to change their mechanical properties, significant efforts have been made toward mimicking such architectures and functions in artificial materials. Research in this domain has rapidly grown in the last two decades and afforded many examples of bioinspired materials that are able to reversibly alter their stiffness, shape, porosity, density, or hardness upon remote stimulation. This review summarizes the state of research in this field.

Self-Assembly of Temperature-Responsive Protein-Polymer Bioconjugates.

We report a simple temperature-responsive bioconjugate system comprising superfolder green fluorescent protein (sfGFP) decorated with poly[(oligo ethylene glycol) methyl ether methacrylate] (PEGMA) polymers. We used amber suppression to site-specifically incorporate the non-canonical azide-functional amino acid p-azidophenylalanine (pAzF) into sfGFP at different positions. The azide moiety on modified sfGFP was then coupled using copper-catalyzed "click" chemistry with the alkyne terminus of a PEGMA synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. The protein in the resulting bioconjugate was found to remain functionally active (i.e., fluorescent) after conjugation. Turbidity measurements revealed that the point of attachment of the polymer onto the protein scaffold has an impact on the thermoresponsive behavior of the resultant bioconjugate. Furthermore, small-angle X-ray scattering analysis showed the wrapping of the polymer around the protein in a temperature-dependent fashion. Our work demonstrates that standard genetic manipulation combined with an expanded genetic code provides an easy way to construct functional hybrid biomaterials where the location of the conjugation site on the protein plays an important role in determining material properties. We anticipate that our approach could be generalized for the synthesis of complex functional materials with precisely defined domain orientation, connectivity, and composition.

Bio-inspired materials to control and minimise insect attachment.

More than three quarters of all animal species on Earth are insects, successfully inhabiting most ecosystems on the planet. Due to their opulence, insects provide the backbone of many biological processes, but also inflict adverse impacts on agricultural and stored products, buildings and human health. To countermeasure insect pests, the interactions of these animals with their surroundings have to be fully understood. This review focuses on the various forms of insect attachment, natural surfaces that have evolved to counter insect adhesion, and particularly features recently developed synthetic bio-inspired solutions. These bio-inspired solutions often enhance the variety of applicable mechanisms observed in nature and open paths for improved technological solutions that are needed in a changing global society.

Insect Antiadhesive Surfaces Using Electrosprayed Wrinkled Ethyl Cellulose Particles.

A range of plants developed leaves, the surfaces of which prevent or diminish insect adhesion due to their microscopic topography. Well known examples include the leaves of the lychee tree (Litchi chinensis). Here, we report a method to coat substrates with ethyl cellulose microparticles that exhibit wrinkled surfaces, resulting in surface morphologies that closely resemble those of insect repelling plants, i.e., Litchi chinensis. The microparticles were prepared by electrospraying, a method that allowed tuning of the particle size and surface morphology. By measuring the traction forces of Colorado potato beetles walking on these surfaces, the wrinkly microsphere parameters were optimized, resulting in biomimetic surfaces that surpass the antiadhesive properties of the biological role model. This study may pave the way to sustainable, nontoxic insecticide replacements.

Highly Cross-Linked, Physiologically Responsive, Mechanically Adaptive Polymer Networks Made by Photopolymerization.

Mechanically adaptive materials that soften upon exposure to physiological conditions are useful for biomedical applications, notably as substrates for implantable neural electrodes. So far, device fabrication efforts have largely relied on shaping such devices by laser cutting, but this process makes it difficult to produce complex electrode architectures and leads to ill-defined surface chemistries. Here, we report mechanically adaptive, physiologically responsive polymers that can be photopolymerized and thus patterned via soft lithography and photolithography. The adaptive polymer networks produced exhibit, in optimized compositions, a ca. 500-fold decrease of their storage modulus when exposed to simulated physiological conditions, for example, from 2.5 GPa to 5 MPa. This effect is caused by modest swelling (30% w/w), which in turn leads to plasticization so that the polymer network's glass transition temperature is reduced from 145 to 25 °C. The polymer networks can further be rendered pH-responsive by the incorporation of methacrylic acid. The dual stimuli-responsive materials thus made show promise as coatings or substrates for drug delivery devices.

Discussion on "Aperiodic Copolymers".

In a recent Viewpoint (ACS Macro Lett. 2014, 3, 1020), J.-F. Lutz brought to the community's attention the need for more informative nomenclature, especially with respect to macromolecules with prescribed but not repeating sequences of monomers. Lutz proposes the use of the term "aperiodic" for this situation. In this Viewpoint, we comment on the need for such nomenclature and offer some alternatives for consideration.

Recyclable l-Proline Functional Nanoreactors with Temperature-Tuned Activity Based on Core-Shell Nanogels.

Recyclable core-shell (CS) nanogels based on l-proline-containing hydrophobic cores with a thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) shell have been synthesized via a seeded precipitation polymerization process. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to verify the successful addition of the shell and investigate the thermoresponsive properties of the nanostructures. The catalytic activity of the nanogels was assessed in a model asymmetric aldol reaction, where an enhancement was observed with increasing temperature, attributed to the hydrophobic nature of the PNIPAM shell. However, when a nanogel was synthesized with core-shell morphology based on a gradient of cross-linking density in the corona (GS), a dramatic drop in activity was observed at elevated temperatures: the collapse of the outer, lightly cross-linked, "corona" polymer chains appears to block access to the catalytic core. High activity and enantioselectivity were maintained in a number of recovery and reuse cycles, highlighting the recycling potential of these catalytic nanostructures.