Solution Behavior of Glyco-Copoly(l-Glutamic Acid)s in Dilute Saline Solution.

A small series of copoly(α,l-glutamic acid/dl-allylglycine)s with the same chain length and allylglycine content (∼10 mol %) but different spatial distribution of allylglycine units was synthesized and subsequently glycosylated via thiol-ene chemistry. Dilute aqueous copolypeptide solutions (0.1 wt %, physiological saline) were analyzed by circular dichroism spectroscopy, dynamic light scattering, and cryogenic transmission electron microscopy. The copolypeptides adopted a random coil or α-helix conformation, depending on solution pH, and the glycosylated residues either distorted or enhanced the folding into an α-helix depending on their location and spatial distribution along the chain. However, regardless of their secondary structure and degree of charging, all partially glycosylated copolypeptides self-assembled into 3D spherical structures, supposedly driven by a hydrophilic effect promoting microphase separation into glucose-rich and glutamate-rich domains.

Ring-Opening Terpolymerisation of Elemental Sulfur Waste with Propylene Oxide and Carbon Disulfide via Lithium Catalysis.

Elemental sulfur, a waste product of the oil refinement process, represents a promising raw material for the synthesis of degradable polymers. We show that simple lithium alkoxides facilitate the polymerisation of elemental sulfur S8 with industrially relevant propylene oxide (PO) and CS2 (a base chemical sourced from waste S8 itself) to give poly(monothiocarbonate-alt-Sx) in which x can be controlled by the amount of supplied sulfur. The in situ generation of thiolate intermediates obtained by a rearrangement, which follows CS2 and PO incorporation, allows to combine S8 and epoxides into one polymer sequence that would otherwise not be possible. Mechanistic investigations reveal that alkyl oligosulfide intermediates from S8 ring opening and sulfur chain length equilibration represent the better nucleophiles for inserting the next PO if compared to the trithiocarbonates obtained from the competing CS2 addition, which causes the sequence selectivity. The polymers can be crosslinked in situ with multifunctional thiols to yield reprocessable and degradable networks. Our report demonstrates how mechanistic understanding allows to combine intrinsically incompatible building blocks for sulfur waste utilisation.

Sol-Gel-Derived Ordered Mesoporous High Entropy Spinel Ferrites and Assessment of Their Photoelectrochemical and Electrocatalytic Water Splitting Performance.

The novel material class of high entropy oxides with their unique and unexpected physicochemical properties is a candidate for energy applications. Herein, it is reported for the first time about the physico- and (photo-) electrochemical properties of ordered mesoporous (CoNiCuZnMg)Fe2 O4 thin films synthesized by a soft-templating and dip-coating approach. The A-site high entropy ferrites (HEF) are composed of periodically ordered mesopores building a highly accessible inorganic nanoarchitecture with large specific surface areas. The mesoporous spinel HEF thin films are found to be phase-pure and crack-free on the meso- and macroscale. The formation of the spinel structure hosting six distinct cations is verified by X-ray-based characterization techniques. Photoelectron spectroscopy gives insight into the chemical state of the implemented transition metals supporting the structural characterization data. Applied as photoanode for photoelectrochemical water splitting, the HEFs are photostable over several hours but show only low photoconductivity owing to fast surface recombination, as evidenced by intensity-modulated photocurrent spectroscopy. When applied as oxygen evolution reaction electrocatalyst, the HEF thin films possess overpotentials of 420 mV at 10 mA cm-2 in 1 m KOH. The results imply that the increase of the compositional disorder enhances the electronic transport properties, which are beneficial for both energy applications.

Mesoporous CuFe2 O4 Photoanodes for Solar Water Oxidation: Impact of Surface Morphology on the Photoelectrochemical Properties.

Metal oxide-based photoelectrodes for solar water splitting often utilize nanostructures to increase the solid-liquid interface area. This reduces charge transport distances and increases the photocurrent for materials with short minority charge carrier diffusion lengths. While the merits of nanostructuring are well established, the effect of surface order on the photocurrent and carrier recombination has not yet received much attention in the literature. To evaluate the impact of pore ordering on the photoelectrochemical properties, mesoporous CuFe2 O4 (CFO) thin film photoanodes were prepared by dip-coating and soft-templating. Here, the pore order and geometry can be controlled by addition of copolymer surfactants poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic® F-127), polyisobutylene-block-poly(ethylene oxide) (PIB-PEO) and poly(ethylene-co-butylene)-block-poly(ethylene oxide) (Kraton liquid™-PEO, KLE). The non-ordered CFO showed the highest photocurrent density of 0.2 mA/cm2 at 1.3 V vs. RHE for sulfite oxidation, but the least photocurrent density for water oxidation. Conversely, the ordered CFO presented the best photoelectrochemical water oxidation performance. These differences can be understood on the basis of the high surface area, which promotes hole transfer to sulfite (a fast hole acceptor), but retards oxidation of water (a slow hole acceptor) due to electron-hole recombination at the defective surface. This interpretation is confirmed by intensity-modulated photocurrent (IMPS) and vibrating Kelvin probe surface photovoltage spectroscopy (VKP-SPS). The lowest surface recombination rate was observed for the ordered KLE-based mesoporous CFO, which retains spherical pore shapes at the surface resulting in fewer surface defects. Overall, this work shows that the photoelectrochemical energy conversion efficiency of copper ferrite thin films is not just controlled by the surface area, but also by surface order.

Reversible Dehydration-Hydration of Poly(ethylene glycol) in Langmuir Monolayers of a Diblock Copolymer Inferred from Changes in Filament Curvature.

We investigated changes in the hydration state of poly(ethylene glycol) (PEG) through morphological changes in Langmuir monolayers of a PEG-poly(l-lactide) (PlLA) (PEG-b-PlLA) diblock copolymer. When the PEG blocks were hydrated, we observed a remarkable morphology of bundles of ring-like filaments, arranged concentrically, yielding densely packed disk-like objects with a hollow center. We attribute the uniform curvature of these filaments to a strong mismatch between the molecular volumes occupied by PlLA blocks and hydrated PEG blocks. Under the constraint that each hydrated PEG block is attached to a hydrophobic PlLA block anchored to the air-water interface, this mismatch of molecular volumes caused strong repulsion within the PEG layer, in particular when the PlLA blocks packed tightly. Induced by a transition in the ordering of the PlLA blocks, the PEG blocks lost their hydration shell and packed into a dense polymer brush, accompanied by a reduction of the pressure within the PEG layer. During this packing process, the curvature of the filaments was eliminated and the ring-like filaments fractured into small linear pieces. Upon compression, the linear pieces coalesced and formed long filaments aligned in parallel. Importantly, upon expansion of the Langmuir film, these changes in morphology were reversible, and the PEG blocks could be rehydrated and bundles of concentrically arranged ring-like filaments were reformed. We conclude that the change in curvature of the filaments provides a means for distinguishing between the hydrated and dehydrated states of PEG.

Multivariate Imaging for Fast Evaluation of In Situ Dark Field Microscopy Hyperspectral Data.

Dark field scattering microscopy can create large hyperspectral data sets that contain a wealth of information on the properties and the molecular environment of noble metal nanoparticles. For a quick screening of samples of microscopic dimensions that contain many different types of plasmonic nanostructures, we propose a multivariate analysis of data sets of thousands to several hundreds of thousands of scattering spectra. By using non-negative matrix factorization for decomposing the spectra, components are identified that represent individual plasmon resonances and relative contributions of these resonances to particular microscopic focal volumes in the mapping data sets. Using data from silver and gold nanoparticles in the presence of different molecules, including gold nanoparticle-protein agglomerates or silver nanoparticles forming aggregates in the presence of acrylamide, plasmonic properties are observed that differ from those of the original nanoparticles. For the case of acrylamide, we show that the plasmon resonances of the silver nanoparticles are ideally suited to support surface enhanced Raman scattering (SERS) and the two-photon excited process of surface enhanced hyper Raman scattering (SEHRS). Both vibrational tools give complementary information on the in situ formed polyacrylamide and the molecular composition at the nanoparticle surface.

Modular Toolkit of Multifunctional Block Copoly(2-oxazoline)s for the Synthesis of Nanoparticles.

Post-polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor-made materials with superior properties. This concept was adapted to well-defined block copolymers of the poly(2-oxazoline) family and demonstrated the large potential of these macromolecules as universal toolkit for numerous applications. Triblock copolymers with separated water-soluble, alkyne- and alkene-containing segments were synthesized and orthogonally modified with various low-molecular weight functional molecules by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and thiol-ene (TE) click reactions, respectively. Representative toolkit polymers were used for the synthesis of gold, iron oxide and silica nanoparticles.

New (and Old) Monomers from Biorefineries to Make Polymer Chemistry More Sustainable.

This opinion article describes recent approaches to use the "biorefinery" concept to lower the carbon footprint of typical mass polymers, by replacing parts of the fossil monomers with similar or even the same monomer made from regrowing dendritic biomass. Herein, the new and green catalytic synthetic routes are for lactic acid (LA), isosorbide (IS), 2,5-furandicarboxylic acid (FDCA), and p-xylene (pXL). Furthermore, the synthesis of two unconventional lignocellulosic biomass derivable monomers, i.e., α-methylene-γ-valerolactone (MeGVL) and levoglucosenol (LG), are presented. All those have the potential to enter in a cost-effective way, also the mass market and thereby recover lost areas for polymer materials. The differences of catalytic unit operations of the biorefinery are also discussed and the challenges that must be addressed along the synthesis path of each monomers.

Exploring Pathways to Equilibrate Langmuir Polymer Films.

Focusing on the phase-coexistence region in Langmuir films of poly(l-lactide), we investigated changes in nonequilibrated morphologies and the corresponding features of the isotherms induced by different experimental pathways of lateral compression and expansion. In this coexistence region, the surface pressure Π was larger than the expected equilibrium value and was found to increase upon compression, i.e., exhibited a nonhorizontal plateau. As shown earlier by using microscopic techniques [Langmuir 2019, 35, 6129-6136], in this plateau region, well-ordered mesoscopic clusters coexisted with a surrounding matrix phase. We succeeded in reducing Π either by slowing down the rate of compression or through increasing the waiting time after stopping the movement of the barriers, which allowed for relaxations in the coexistence region. Intriguingly, the most significant pressure reduction was observed when recompressing a film that had already been compressed and expanded, if the recompression was started from an area value smaller than the one anticipated for the onset of the coexistence region. This observation suggests a "self-seeding" behavior, i.e., pre-existing nuclei allowed to circumvent the nucleation step. The decrease in Π was accompanied by a transformation of the initially formed metastable mesoscopic clusters into a thermodynamically favored filamentary morphology. Our results demonstrate that it is practically impossible to obtain fully equilibrated coexisting phases in a Langmuir polymer film, neither under conditions of extremely slow continuous compression nor for long waiting times at a constant area in the coexistence region which allow for reorganization.

Poly(2-oxazoline)s Based on Phenolic Acids.

A series of phenolic-acid-based 2-oxazoline monomers with methoxy-substituted phenyl and cinnamyl side chains is synthesized and polymerized in a microwave reactor at 140 °C using methyl tosylate as the initiator. The obtained poly(2-oxazoline)s are characterized by NMR spectroscopy, MALDI-TOF mass spectrometry, and size-exclusion chromatography (SEC). Kinetic studies reveal that the microwave-assisted polymerization is fast and completed within less than ≈10 min for low monomer-to-initiator ratios of ≤25. Polymers with number-average molar masses of up to 6500 g mol-1 and low dispersity (1.2-1.3) are produced. The aryl methyl ethers are successfully cleaved with aluminum triiodide/N,N'-diisopropylcarbodiimide to give a poly(2-oxazoline) with pendent catechol groups.

Controlling Nucleation in Quasi-Two-Dimensional Langmuir Poly(l-lactide) Films through Variation of the Rate of Compression.

We studied morphological changes in a quasi-two-dimensional Langmuir film of low molar mass poly(l-lactide) upon increasing the surface density, starting from randomly distributed molecules to a homogeneous monolayer of closely packed molecules, followed by nucleation and growth of mesoscopic, three-dimensional clusters from an overcompressed monolayer. The corresponding nucleation density of mesoscopic clusters within the monolayer can be tailored through variation of the rate of compression. For a given surface density and temperature, the nucleation probability was found to increase linearly with the rate of compression, allowing to adjust the density of mesoscopic clusters over nearly 2 orders of magnitude.

Polylactide-Based Amphiphilic Block Copolymers: Crystallization-Induced Self-Assembly and Stereocomplexation.

The aqueous self-assembly behavior of a series of poly(ethylene glycol)-poly(l-/d-lactide) block copolymers and corresponding stereocomplexes is examined by differential scanning calorimetry, dynamic light scattering, and transmission electron microscopy. Block copolymers assemble into spherical micelles and worm-like aggregates at room temperature, whereby the fraction of the latter seemingly increases with decreasing lactide weight fraction or hydrophobicity. The formation of the worm-like aggregates arises from the crystallization of the polylactide by which the spherical micelles become colloidally unstable and fuse epitaxically with other micelles. The self-assembly behavior of the stereocomplex aggregates is found to be different from that of the block copolymers, resulting in rather irregular-shaped clusters of spherical micelles and pearl-necklace-like structures.

Cellulose-Derived Functional Polyacetal by Cationic Ring-Opening Polymerization of Levoglucosenyl Methyl Ether.

The unsaturated bicyclic acetal levoglucosenyl methyl ether was readily obtained from sustainable feedstock (cellulose) and polymerized by cationic ring-opening polymerization to produce a semicrystalline thermoplastic unsaturated polyacetal with relatively high apparent molar mass (up to ca. 36 kg mol-1 ) and decent dispersity (ca. 1.4). The double bonds along the chain can undergo hydrogenation and thiol-ene reactions as well as crosslinking, thus making this polyacetal potentially interesting as a reactive functional material.

Ring-Opening Metathesis Polymerization of Biomass-Derived Levoglucosenol.

The readily available cellulose-derived bicyclic compound levoglucosenol was polymerized through ring-opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass-derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High-molar-mass polyacetals with apparent weight-average molar masses of up to 100 kg mol-1 and dispersities of approximately 2 were produced despite the non-living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 °C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment.

Self-Assembly of α-Helical Polypeptides into Microscopic and Enantiomorphic Spirals.

Helical structures are ubiquitous in biological materials and often serve a structural purpose. Bioinspired helical materials can be challenging to synthesize and rarely reach the degree of hierarchy of their natural counterparts. Here we report the first example of particles synthesized by direct emulsification of polypeptides found to display spiral morphologies in the dry state. The polypeptides were α-helical homo- and copolypeptides of γ-benzyl glutamate and allylglycine. The chirality of the spirals was controlled by the chirality of the α-helices. Notably, right-handed α-helical polypeptides (rich in l residues) produced clockwise spirals, whereas left-handed α-helical polypeptides (rich in d residues) produced the enantiomorphs, i.e., counterclockwise spirals. The disruption of the α-helical conformation by the introduction of chiral defects led to less regular spirals and in some cases their suppression. A hypothesis for the transmission of helicity and chirality from a molecular to a higher hierarchical level, involving fibril bundling of coiled α-helices, is proposed.

Identifying the Hydrolysis of Carbonyl Sulfide as a Side Reaction Impeding the Polymerization of N-Substituted Glycine N-Thiocarboxyanhydride.

Polypeptoids are noticeable biological materials due to their versatile properties and various applications in drug delivery, surface modification, self-assembly, etc. N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are more stable monomers than the corresponding N-carboxyanhydrides (NNCAs) and enable one to prepare polypeptoids via ring-opening polymerization even in the presence of water. However, larger amounts of water (>10,000 ppm) cause inhibition of the polymerization. Herein, we discover that during polymerization hydrogen sulfide evolves from the hydrolysis of carbonyl sulfide, which is the byproduct of ring-opening reaction, and reacts with NNTA to produce cyclic oligopeptoids. The capture of N-ethylethanethioic acid as an intermediate product confirms the reaction mechanism together with density functional theory quantum computational results. By bubbling the polymerization solution with argon, the side reaction can be suppressed to allow the synthesis of polysarcosine with high molar mass ( Mn = 11,200 g/mol, D = 1.25) even in the presence of ∼10,000 ppm of water.

Entropy-Driven Ring-Opening Disulfide Metathesis Polymerization for the Synthesis of Functional Poly(disulfide)s.

Metal-free entropy-driven disulfide metathesis polymerization of unsaturated l-cystine based macrocycles produces high-molar-mass heterofunctional poly(disulfide)s, i.e., poly(ester-disulfide-alkene) and poly(amide-disulfide-alkene); Mwapp = 44-60 kDa, Р> 1.7. The polymerization is fast and reaches equilibrium within 1-5 minutes (monomer conversion 70-90%) in polar aprotic solvents such as N,N-dimethylacetamide, dimethylsulfoxide, or γ-valerolactone. Thiol-terminated polymers are stable in bulk or when dissolved in weakly polar solvents, but rapidly depolymerize in dilute polar solution.

Structure Formation in Langmuir Peptide Films As Revealed from Coarse-Grained Molecular Dynamics Simulations.

Molecular dynamics simulations in conjunction with the Martini coarse-grained model have been used to investigate the (nonequilibrium) behavior of helical 22-residue poly(γ-benzyl-l-glutamate) (PBLG) peptides at the water/vapor interface. Preformed PBLG mono- or bilayers homogeneously covering the water surface laterally collapse in tens of nanoseconds, exposing significant proportions of empty water surface. This behavior was also observed in recent AFM experiments at similar areas per monomer, where a complete coverage had been assumed in earlier work. In the simulations, depending on the area per monomer, either elongated clusters or fibrils form, whose heights (together with the portion of empty water surface) increase over time. Peptides tend to align with respect to the fiber axis or with the major principal axis of the cluster, respectively. The aspect ratio of the cluster observed is 1.7 and, hence, comparable to though somewhat smaller than the aspect ratio of the peptides in α-helical conformation, which is 2.2. The heights of the fibrils is 3 nm after 20 ns and increases to 4.5 nm if the relaxation time is increased by 2 orders of magnitude, in agreement with the experiment. Aggregates with heights of about 3 or 4.5 nm are found to correspond to local bi- or trilayer structures, respectively.

Stable Covalently Photo-Crosslinked Poly(Ionic Liquid) Membrane with Gradient Pore Size.

Porous polyelectrolyte membranes stable in a highly ionic environment are obtained by covalent crosslinking of an imidazolium-based poly(ionic liquid). The crosslinking reaction involves the UV light-induced thiol-ene (click) chemistry, and the phase separation, occurring during the crosslinking step, generates a fully interconnected porous structure in the membrane. The porosity is on the order of the micrometer scale and the membrane shows a gradient of pore size across the membrane cross-section. The membrane can separate polystyrene latex particles of different size and undergoes actuation in contact with acetone due to the asymmetric porous structure.

Physical Gelation of α-Helical Copolypeptides.

Owing to its rod-like α-helical secondary structure, the synthetic polypeptide poly(γ-benzyl-l-glutamate) (PBlG) can form physical and thermoreversible gels in helicogenic solvents such as toluene. The versatility of PBlG can be increased by introducing functionalizable comonomers, such as allylglycine (AG). In this work we examined the secondary structure of PBlG and a series of statistical poly(γ-benzyl-l-glutamate-co-allylglycine) copolypeptides, varying in composition and chain length, by circular dichroism (CD), Fourier-transform infrared (FTIR) and Raman spectroscopy, and wide-angle X-ray scattering (WAXS). The secondary structure of PBlG and the copolypeptides presented dissimilarities that increased with increasing AG molar fraction, especially when racemic AG units were incorporated. The physical gelation behavior of these copolypeptides was analyzed by temperature-sweep (1)H NMR and rheological measurements. The study revealed that both copolypeptide composition and chain length affected secondary structure, gelation temperature, and gel stiffness.