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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)Fe2O4 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.

To make photoelectrochemical water splitting with metal oxide absorbers an economically viable technology for the production of green hydrogen, further improvements of solar-to-hydrogen conversion efficiency as well as photoelectrode stability have to be accomplished. One step towards optimized photoelectrodes is nanostructuring of the metal oxide absorbers addressing the generally short minority charge carrier diffusion lengths. In this work, mesoporous CuFe2O4 (CFO) thin film photoanodes were prepared by a sol-gel chemistry-based dip-coating and soft-templating strategy. The mesoporous CFOs were fabricated with distinct pore morphologies in order to study the impact of pore ordering and surface structure on the photoelectrochemical properties. The degree of pore ordering and geometry was varied by using different structure-directing copolymer surfactants, which were poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic F-127), polyisobutylene-block-poly(ethyleneoxide) (PIB-PEO), and poly(ethylene-co-butylene)-block-poly(ethylene oxide) (Kraton liquid-PEO, KLE). The distinctly mesostructured CFO materials were characterised by means of scanning electron (SEM) and transmission electron microscopies (TEM), grazing-incidence X-ray diffraction (GIXRD), and X-ray photoelectron spectroscopy (XPS). The structural and electronic properties were correlated with the photoelectrochemical water and sulfite oxidation scans. The non-ordered, Pluronic F-127 templated 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 (1.5 µA/cm2) for water oxidation. This 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. These results are confirmed by intensity-modulated photocurrent spectroscopy (IMPS). These yield the lowest surface recombination rate for the ordered KLE-based mesoporous CFO thin films, which retain spherical pore shapes at the surface resulting in fewer surface defects and thus in the highest water oxidation activity. Vibrating Kelvin probe surface photovoltage spectroscopy (VKP-SPS) on CFO films in contact with aqueous NaIO4 solution confirms these results and further reveals the presence of a detrimental Schottky junction at the FTO-CFO interface. Lastly, the electronic band diagram of the CFO photoanodes was investigated via X-ray photoelectron spectroscopy providing electronic structure arguments about the photoelectrochemical reactions the material is capable of driving. Post-use XPS data suggest that the concentration of hydroxyl groups, oxygen vacancies and adsorbed water/oxygen has indeed changed during photoelectrochemical operation, however the chemical state of the surface metal cations remained unaffected.

Organic–inorganic composite materials with tailored properties can be designed in the lab through bio-inspired approaches. In this context, we exploited the particle-based crystallisation process of calcium sulfate, a technologically important mineral, to hybridise inorganic and organic matter. We identified and synthesised an organic polymer showing strong affinity to bind to the surfaces of mineral precursors as well as intrinsic tendency to self-organise. Subsequently, polymer-coated building units were allowed to self-assemble via oriented attachment, aggregation and phase transformation, which produced ordered superstructures where the organic polymer is intercalated between the subunits and surrounds the hybrid core as a shell. This specific architecture across multiple length scales leads to unique mechanical properties, comparable to those of natural biominerals. Thus, our results devise a straightforward pathway to prepare organic–inorganic hybrid structures via bottom-up self-assembly processes innate to the crystallisation of the inorganic phase. This approach can likely be transferred to other inorganic minerals, affording next-generation materials for applications in the construction sector, biomedicine and beyond. published

For driving the (photo-) electrocatalytic water splitting reaction both efficient and photostable absorber materials and electrocatalysts are needed in order to make the technology economically competitive. The novel material class of high entropy oxides with their unique and unexpected physicochemical properties is a potential candidate for energy applications. Herein, we report for the first time about the physico- and (photo-) electrochemical properties of ordered mesoporous (CoNiCuZnMg)Fe2O4 thin films synthesized by a soft-templating and dip-coating approach. The high entropy ferrites (HEF) are composed of 15 ‒ 18 nm sized and periodically ordered mesopores building a highly accessible inorganic nanoarchitecture with specific surface areas up to 170 m2/g. The mesoporous HEF thin films crystallize in the cubic spinel structure and were found to be crack-free on the meso- and macroscale. The formation of the spinel structure hosting six distinct cations was verified by means of gracing incidence X-ray diffraction, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and transmission electron microscopy accompanied with energy dispersive X-ray spectroscopy. Photoelectron spectroscopy gave insight into chemical state of the implemented transition metals supporting the structural characterization data. Analyzed as photoanode for photoelectrochemical water splitting, the HEFs showed only low photoconductivity owing to fast surface recombination as suggested by intensity-modulated photocurrent spectroscopy. When applied as oxygen evolution reaction electrocatalyst, the HEF thin films possess overpotentials of 420 mV vs. RHE at 10 mA/cm2 in 1 M KOH. The results imply that the increase of the configurational disorder within the spinel structure enhances the electronic transport properties. The evaluation of the energy band alignment by Mott-Schottky analysis allows for an estimation which redox reactions can be driven, showing that the materials are theoretically capable of promoting overall water splitting.

A series of biomass-derived levoglucosenyl alkyl ethers (alkyl = methyl, ethyl, n-propyl, isopropyl, and n-butyl) were synthesized and polymerized by ring-opening olefin metathesis polymerization using the Grubbs catalyst C793 at room temperature. Polymerizations were successfully performed in conventional solvents such as 1,4-dioxane and dichloromethane as well as in polar aprotic “green” solvents such as 2-methyltetrahydrofuran, dihydrolevoglucosenone (Cyrene), and ethyl acetate. The prepared polyacetals with degrees of polymerization of ∼100 exhibit Schulz–Flory-type molar mass distributions and are thermoplastic materials with rather low glass transition temperatures in the range of 43–0 °C depending on the length of the alkyl substituent. Kinetic studies revealed that the polymerization proceeded rapidly to a steady state with a certain minimum monomer concentration threshold. When the steady state was reached, just about half of the [Ru] catalyst had been effective to initiate the polymerization, indicating that the initiation step was a slow process. The remaining catalyst was still active and did no longer react with monomers but with in-chain double bonds, cutting the formed polymer chains into shorter fragments. In the long term, all catalyst was consumed and propagating [Ru] chain ends were deactivated by the elimination of [Ru] from the chain ends to form inactive chains with terminal aldehyde groups.

The acyclic monoterpene beta-myrcene is polymerized by anionic polymerization at room temperature using sec-butyllithium as the initiator and the cyclic monoterpene DL-limonene as an unsaturated hydrocarbon solvent. The polymerization is a living process and allows production of polymyrcenes with narrow molar mass distribution ((sic) similar to 1.06) and high content of 1,4 units (similar to 90%) as well as block copolymers.

A cationic polyelectrolyte based on the styrenic ionic liquid tributyl-4-vinylbenzylphosphonium pentanesulfonate was found to undergo a lower critical solution temperature (LCST)-type phase transition in aqueous solutions. This phase transition occurs in a wide temperature range in terms of polymer concentration as well as type and concentration of externally added salts. Anion exchange and salting out effects are responsible for the flexible phase transition temperature.

This study aims to explore the photoinitiated cationic ring-opening polymerization of levoglucosenyl methyl ether (LGME), a chemical obtained from the most abundant biomass – cellulose. Direct and sensitized photopolymerizations of LGME using photoinitiators acting at the near UV or visible range in conjunction with diphenyliodonium hexafluoroantimonate (DPI) yielded unsaturated polyacetals with varying molar masses and distributions.

A series of polystyrene- and poly(methyl methacrylate)-dithioesters was subjected to aminolysis under ambient atmospheric conditions, i.e., in the presence of oxygen. Polymer disulfide coupling by oxidation occurred within tens of minutes and the yield of disulfide-coupled polymer increased with decreasing polymer molar mass. Oxidation of thiolates is usually an unwanted side reaction, here it is employed to obtain exclusively polymeric mixed disulfides through in situ aminolysis/functionalization in the presence of a thiol. The in situ aminolysis/functionalization in the presence of a disulfide, Ellman's reagent or polymer disulfide, resulted in the exclusive formation of polymer-dithionitrobenzoic acid, which can be further reacted with a thiol to exchange the terminal functionality, or block copolymer with dynamic disulfide linker, respectively.

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., From crops to CROP: Cationic ring‐opening polymerization (CROP) of biomass‐derived levoglucosenyl methyl ether yields a semicrystalline thermoplastic unsaturated polyacetal. The double bonds can undergo hydrogenation and thiol–ene reactions as well as crosslinking, thus making this polyacetal potentially interesting as a reactive functional material.

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.

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.

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., Polyoxazoline block copolymers offer a wide range of possibilities for application depending on their molecular structure and properties. This study introduces the huge potential of this polyoxazoline toolkit and demonstrates how tailor‐made toolkit polymers can be applied in representative systems.

Isoprene and beta-myrcene were polymerized by anionic polymerization in bulk and in the 'green' ether solvents cyclopentyl methyl ether and 2-methyltetrahydrofuran and, for comparison, in cyclohexane and tetrahydrofuran. The polydienes produced in bulk and in cyclohexane contained high amounts of 1,4 units (>90%) whereas those produced in ether solvents were rich in 1,2 and 3,4 units (36%-86%). Comparison of the microstructures and glass transition temperatures of the polydienes obtained in the various solvents suggests that conventionally used solvents can be substituted by environmentally more friendly alternatives.

We present an experimental study of structure formation in a polypeptide hetero-arm star block copolymer solution, obtained by swelling thin films in chloroform solvent vapor to variable poly(γ-benzyl-L-glutamate) (PBLGlu) concentrations (cp). Direct observation by optical microscopy allowed us to follow in real time nucleation and growth of ordered three-dimensional structures of ellipsoidal shape. At low cp, growth stopped when cp decreased below the solubility limit (ccritical) but additional structures were formed when cp was rapidly increased to a higher value. Although water is not a solvent for this polymer, we demonstrate that water, even in trace amounts, is nonetheless considerably affecting solubility and consequently the process of structure formation. We have varied systematically the amount of water present in the environment. ccritical changed from about 0.53 (dry, i.e. desiccated surrounding vapour phase) viaccritical ≈ 0.16–0.25 for 30–50% humidity of the vapour phase to ccritical ≈ 0.03 for a vapour phase at 100% humidity. We attribute this change in solubility to complexation of water molecules with PBLGlu α-helix, which increases the interfacial tension between the polymer and the solvent. We have tested our hypothesis by replacing water with other non-solvents for the polymer. Only protic non-solvents changed the solubility of PBLGlu in chloroform.

Annealing of dilute aqueous solutions of poly(2-isopropyl-2-oxazoline) at above the cloud point leads to the irreversible formation of coagulate particles with hierarchical ordering on two length-scales: micron-sized assemblies of fibrils that measure tens of nanometres across.

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.

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 II 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 Pi 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 Pi 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.

Cystine was used as a platform chemical to prepare cyclic and acyclic monomers for entropy-driven ringopening polymerization (ED-ROMP) via olefin or disulfide metathesis and for step-growth polymerization. The olefin ED-ROMP of an olefin/disulfide containing 16-atom macrocycle using the 3rd generation Grubbs catalyst was examined in greater detail. Kinetic studies revealed that the catalyst turned inactive during the polymerization, which limited the achievable (apparent) polymer molar mass to similar to 70 kg mol(-1). Such limitation could be overcome with the disulfide ED-ROMP of the same macrocycle to yield polymers with molar masses of up to 180 kg mol(-1). The step-growth polymerizations of acyclic diene and dithiol monomers via olefin metathesis or oxidation were far less effective and yielded just low molar mass polymers or oligomers; photopolymerization of a thiol-ene monomer produced a polyester with a molar mass of 35 kg mol(-1).

In virtue of the rising demand for metal-free polymeric materials, organocatalytic polymerization has emerged and blossomed unprecedentedly in the past 15 years into an appealing research area and a powerful arsenal for polymer synthesis. In addition to the inherent merits as being metal-free, small-molecule organocatalysts have also provided opportunities to develop alternative and, in many cases, more expedient synthetic approaches toward macromolecular architectures, that play a crucial role in shaping the properties of the obtained polymers. A majority of preliminary studies exploring for new catalysts, catalytic mechanisms and optimized polymerization conditions are extended to application of the catalytic systems on rational design and controlled synthesis of various macromolecular architectures. Such endeavors are described in this review, categorized by the architectural elements including chain structure (types, sequence and composition of monomeric units constituting the polymer chains), topological structure (the fashion different polymer chains are covalently attached to each other within the macromolecule) and functionality (position and amount of functional groups that endow the entire macromolecule with specific chemical, physico-chemical or biological properties).

The mechanism of the primary ammonium/tertiary amine-mediated ring-opening polymerization of γ-benzyl- l -glutamate N-carboxyanhydride (B l G-NCA) was investigated. Kinetic analyses revealed that the normal amine mechanism (NAM) together with a dormant-active chain end equilibrium were responsible for the controlled nature of this polymerization pathway, but that the polymerization also proceeded via the activated monomer mechanism (AMM). Mixtures of primary amines (1 equiv) and tertiary amines (0–1.5 equiv) were therefore tested to confirm the co-existence of the NAM and AMM and determine the limits for a controlled polymerization. For tertiary amine molar fractions smaller than 0.8 equiv, the reaction times were greatly reduced (compared to primary amine-initiated polymerization) without compromising the control of the reaction. Hence, the polymerization of NCA can proceed in a controlled manner even when the AMM contributes to the overall chain growth mechanism.

Molecular dynamics simulations in conjunction with the Martini coarse-grained model have been used to investigate the (nonequilibrium) behavior of helical 22-residue poly(gamma-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 alpha-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.

Near-ambient pressure XPS (NAP-XPS) is a less traditional form of XPS that allows samples to be analyzed at relatively high pressures, i.e., at 2500 Pa or greater. With NAP-XPS, one can analyze moderately volatile liquids, biological samples, porous materials, and/or polymeric materials that outgas significantly. In this submission, the authors show C 1s, O 1s, and survey NAP-XPS spectra from 1,4-polymyrcene. The C 1s and O 1s envelopes are fit with Gaussian–Lorentzian product, asymmetric Lorentzian, and Gaussian–Lorentzian sum functions. Water vapor and argon are used to control sample charging, and the corresponding signals from the gases are present in the survey spectra. The effect of background gas pressure on photoelectron attenuation is illustrated with a sample of polytetrafluoroethylene.

Near ambient pressure - x-ray photoelectron spectroscopy (NAP-XPS) is a less traditional form of XPS that allows samples to be analyzed at relatively high pressures, i.e., at 2500 Pa or higher. With NAP-XPS, one can analyze moderately volatile liquids, biological samples, porous materials, and/or polymeric materials that outgas significantly. In this submission we show C 1s, O 1s, and survey NAP-XPS spectra from poly(l-lactic acid). The C 1s and O 1s envelopes were fit with three and two Gaussian-Lorentzian sum functions, respectively. Water vapor (800 Pa) was used as the residual gas for charge compensation, which was confirmed by the sharp peak at 535.0 eV in the O 1s narrow scan. The uniqueness plot corresponding to the C 1s fit shows that the fit parameters had statistical significance. C 1s and O 1s spectra of PLLA damaged by exposure to x-rays for ca. 1 hour are also included.Near ambient pressure - x-ray photoelectron spectroscopy (NAP-XPS) is a less traditional form of XPS that allows samples to be analyzed at relatively high pressures, i.e., at 2500 Pa or higher. With NAP-XPS, one can analyze moderately volatile liquids, biological samples, porous materials, and/or polymeric materials that outgas significantly. In this submission we show C 1s, O 1s, and survey NAP-XPS spectra from poly(l-lactic acid). The C 1s and O 1s envelopes were fit with three and two Gaussian-Lorentzian sum functions, respectively. Water vapor (800 Pa) was used as the residual gas for charge compensation, which was confirmed by the sharp peak at 535.0 eV in the O 1s narrow scan. The uniqueness plot corresponding to the C 1s fit shows that the fit parameters had statistical significance. C 1s and O 1s spectra of PLLA damaged by exposure to x-rays for ca. 1 hour are also included.

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.

The nucleophilic thiol-ene (thia-Michael) reaction between molecular rods bearing terminal thiols and bis-maleimides was investigated. The molecular rods have oligospiroketal (OSK) and oligospirothioketal (OSTK) backbones. Contrary to the expectations, cyclic oligomers were always obtained instead of linear rigid-rod polymers. Replacing the OS(T)K rods with a flexible chain yielded polymeric products, suggesting that the OS(T) K structure is responsible for the formation of cyclic products. The reason for the preferred formation of cyclic products is due to the presence of folded conformations, which have already been described for articulated rods.

Macrocycles based on L-cystine were synthesized by ring-closing metathesis (RCM) and subsequently polymerized by entropy-driven ring-opening metathesis polymerization (ED-ROMP). Monomer conversion reached similar to 80% in equilibrium and the produced poly (ester-amine-disulfide-alkene)s exhibited apparent molar masses (M-w(app)) of up to 80 kDa and dispersities (D) of similar to 2. The polymers can be further functionalized with acid anhydrides and degraded by reductive cleavage of the main-chain disulfide.

This report describes the aggregation behavior of an ABC-type ampholytic block copolypeptide, poly(ethylene oxide)-block-poly(l-lysine)-block-poly(l-glutamate), in aqueous media in dependence of pH. Polypeptide secondary structures and self-assemblies are investigated by circular dichroism (CD), Fourier transform infrared (FT-IR) and NMR spectroscopy, zeta potential measurements, analytical ultracentrifugation (AUC), dynamic/static light scattering (DLS/SLS), and cryogenic transmission electron microscopy (cryo-TEM). The polymer chains tend to form vesicles when the hydrophobic polypeptide helix is located at the chain end (acidic pH) and are existing as single chains when it is located in the center and flanked by the two hydrophilic segments (basic pH). Precipitation occurs in the intermediate pH range due to polyion complexation of the charged polypeptide segments.

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 (M-n = 11,200 g/mol, D = 1.25) even in the presence of similar to 10,000 ppm of water.

Silk protein–based materials show promise for application as biomaterials for tissue engineering. The simple and rapid photochemical modification of silk protein–based materials composed of either Bombyx mori silkworm silk or engineered spider silk proteins (eADF4(C16)) is reported. Radicals formed on the silk‐based materials initiate the polymerization of monomers (acrylic acid, methacrylic acid, or allylamine) which functionalize the surface of the silk materials with poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), or poly(allylamine) (PAAm). To demonstrate potential applications of this type of modification, the polymer‐modified silks are mineralized. The PAA‐ and PMAA‐functionalized silks are mineralized with calcium carbonate, whereas the PAAm‐functionalized silks are mineralized with silica, both of which provide a coating on the materials that may be useful for bone tissue engineering, which will be the subject of future investigations. published

In this study, we present a novel and facile method for the synthesis of multiresponsive plasmonic nanoparticles with an interesting interfacial behavior. We used thiol-initiated photopolymerization technique to graft poly(N-isopropylacrylamide) onto the surface of protein-coated gold nanoparticles. The combination of the protein bovine serum albumin with the thermoresponsive polymer leads to smart hybrid nanoparticles, which show a stimuli-responsive behavior of their aggregation and a precisely controllable phase transfer behavior. Three interconnected stimuli, namely, temperature, ionic strength, and pH, were identified as property tuning switches. The aggregation was completely reversible and was quantified by determining Smoluchowski’s instability ratios with time-resolved dynamic light scattering. The tunable hydrophobicity via the three stimuli was used to study interfacial activity and phase transfer behavior of the nanoparticles at an octanol/water interface. Depending on the type of coating (i.e., protein or protein/polymer) as well as the three external stimuli, the nanoparticles either remained in the aqueous phase (aggregated or nonaggregated), accumulated at the oil/water interface, wet the glass wall between the glass vial and the octanol phase, or even crossed the oil/water interface. Such smart and interfacially active nanoparticles with external triggers that are capable of crossing oil/water interfaces under physiological conditions open up new avenues for a variety of applications ranging from the development of drug-delivery nanosystems across biological barriers to the preparation of new catalytic materials.

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 alpha-helical homo- and copolypeptides of gamma-benzyl glutamate and allylglycine. The chirality of the spirals was controlled by the chirality of the alpha-helices. Notably, right-handed alpha-helical polypeptides (rich in 1, residues) produced clockwise spirals, whereas left-handed alpha-helical polypeptides (rich in D residues) produced the enantiomorphs, i.e., counterclockwise spirals. The disruption of the alpha-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 alpha-helices, is proposed.

Block copolypeptoids comprising a thermosensitive, crystallizable poly(N-(n-propyl)glycine) block and a water-soluble poly(N-methylglycine) block, P70My (y = 23, 42, 76, 153, and 290), were synthesized by ring-opening polymerization of the corresponding N-alkylglycine N-carboxyanhydrides (NCAs) and examined according to their thermo-induced aggregation and crystallization in water by turbidimetry, micro-differential scanning calorimetry (micro-DSC), cryogenic scanning electron microscopy (cryo-SEM), analytical ultracentrifugation (AUC), and static light scattering (SLS). At a temperature above the cloud point temperature, the initially formed micellar aggregates started to crystallize and grow into larger complex assemblies of about 100–500 nm, exhibiting flower-like (P70M23), ellipsoidal (P70M42 and P70M72), or irregular shapes (P70M153 and P70M290).

Poly(2-alkyl-2-oxazoline)s (PAOx) exhibit different crystallization behavior depending on the length of the alkyl side chain. PAOx having methyl, ethyl, or propyl side chains do not show any bulk crystallization. Crystallization in the heating cycle, that is, cold crystallization, is observed for PAOx with butyl and pentyl side chains. For PAOx with longer alkyl side chains crystallization occurs in the cooling cycle. The different crystallization behavior is attributed to the different polymer chain mobility in line with the glass transition temperature (Tg) dependency on alkyl side chain length. The decrease in chain mobility with decreasing alkyl side chain length hinders the relaxation of the polymer backbone to the thermodynamic equilibrium crystalline structure. Double melting behavior is observed for PButOx and PiPropOx which is explained by the melt-recrystallization mechanism. Isothermal crystallization experiments of PButOx between 60 and 90 °C and PiPropOx between 90 and 150 °C show that PAOx can crystallize in bulk when enough time is given. The decrease of Tg and the corresponding increase in chain mobility at T > Tg with increasing alkyl side chain length can be attributed to an increasing distance between the polymer backbones and thus decreasing average strength of amide dipole interactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 721–729

As polypeptoids become increasingly popular, they present a more soluble and processable alternative to natural and synthetic polypeptides; the breadth of their potential functionality slowly comes into focus. This report analyzes the ability of an alkyne-functionalized polypeptoid, poly(N-propargyl glycine), to crosslink upon heating. The crosslinking process is analyzed by thermal analysis (differential scanning calorimetry and thermogravimetric analysis), Fourier-transform infrared, electron paramagnetic resonance, and solid-state NMR spectroscopy. While a precise mechanism cannot be confidently assigned, it is clear that the reaction proceeds by a radical mechanism that exclusively involves the alkyne functionality, which, upon crosslinking, yields alkene and aromatic products.

Item does not contain fulltext The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle's physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 mum. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanoparticles and proteins and the accumulation of nanoparticles in a targeted body region.

Die Selbststrukturierung von Makromolekulen ist ein grundlegender Prozess des Lebens; historisch wurden diese Vorbilder durch die Entwicklung amphiphiler Polymere nachgebildet, deren Strukturbildung durch den hydrophoben Effekt getrieben wird. Hier zeigen wir, dass auch rein hydrophile Systeme leicht zur Selbstorganisation gebracht werden konnen. Dazu synthetisierten wir doppelt hydrophile Blockcopolymere aus Polysacchariden und Poly(ethylenoxid) oder Poly(sarcosin) mit hoher Molmasse durch Oximchemie. Diese hydrophilen Stoffe konnen sich einfach zu polymeren Vesikeln im Nanometer- ( 5 μm) organisieren, in Abhangigkeit von der Polymerkonzentration und der relativen Zusammensetzung. Wegen der rein hydrophilen Natur dieser Polymere erwarten wir auserst wasserdurchlassige Mikrokompartimente, die sich gut als Modelle fur Zellen eignen sollten.

Polypeptoids have been of great interest in the polymer science community since the early half of the last century; however, they had been basically forgotten materials until the last decades in which they have enjoyed an exciting revival. In this mini-review, we focus on the recent developments in polypeptoid chemistry, with particular focus on polymers synthesized by the ring-opening polymerization (ROP) of amino acid N-carboxyanhydrides (NCAs). Specifically, we will review traditional monomer synthesis (such as Leuchs, Katchalski, and Kricheldorf) and recent advances in polymerization methods to yield both linear, cyclic, and functional polymers, solution and bulk thermal properties, and preliminary results on the use of polypeptoids as biomaterials (i.e immunogenicity, biodistribution, degradability, and drug delivery).

Multiblock-like amphiphilic polyurethanes constituted by poly(ethylene oxide) and biosourced betulin are designed for antifouling and synthesized by a convenient organocatalytic route comprising tandem chain-growth and step-growth polymerizations. The doping density of betulin (D-B) in the polymer chain structure is readily varied by a mixed-initiator strategy. The spin-coated polymer films exhibit unique nanophase separation and protein resistance behaviors. Higher D-B leads to enhanced surface hydrophobicity and, unexpectedly, improved protein resistance. It is found that the surface holds molecular-level heterogeneity when D-B is substantially high due to restricted phase separation; therefore, broad-spectrum protein resistance is achieved despite considerable surface hydrophobicity. As D-B decreases, the distance between adjacent betulin units increases so that hydrophobic nanodomains are formed, which provide enough landing areas for relatively small-sized proteins to adsorb on the surface.

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); M-w(app) = 44-60 kDa, (sic) > 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 y-valerolactone. Thiol-terminated polymers are stable in bulk or when dissolved in weakly polar solvents, but rapidly depolymerize in dilute polar solution.

Bio-inspired V2O5–polymer hybrid films were prepared following a one-step self-organization procedure based on liquid crystal formation of organic and inorganic components. These materials were previously reported to exhibit advantageous mechanical properties, comparable to biomaterials, such as human bone and dentin. Here, we show that these hybrid films prepared via a fast and simple synthesis procedure have an additional function as an electrochromic material, exhibiting a long-term cycle stability under alternating potentials. The structures were found to remain intact without visible changes after more than hundred switching cycles and storing the devices for several weeks. Consequently, this multifunctional V2O5–polymer hybrid system shows great promise for various technical applications.

High fractions of gold nanorods were locally aligned by means of a polymeric liquid crystalline phase. The gold nanorods constituting >80 wt % of the thin organic–inorganic composite films form a network with side-by-side and end-to-end combinations. Organization into these network structures was induced by shearing gold nanorod–LC polymer dispersions via spin-coating. The LC polymer is a polyoxazoline functionalized with pendent cholesteryl and carboxyl side groups enabling the polymer to bind to the CTAB stabilizer layer of the gold nanorods via electrostatic interactions, thus forming the glue between organic and inorganic components, and to form a chiral nematic lyotropic phase. The self-assembled locally oriented gold nanorod structuring enables control over collective optical properties due to plasmon resonance coupling, reminiscent of enhanced optical properties of natural biomaterials.

This paper presents a low-cost method to coat polymer particles with silica nanoparticles from inexpensive sodium silicate solution, which is a less-common precursor compared with tetraethyl orthosilicate for coating of polymer particles. The method is based on deposition of active silicic acid in the presence of polymer particles, prepared by emulsion polymerization of styrene involving poly(N-vinyl-2-pyrrolidone), under conditions that a dilute silica sol can be formed from this active silicic acid. The whole process was conducted in aqueous media. The effects of different reaction parameters, such as reaction temperature, amount of active silicic acid and solution pH, on the morphology and size of composite particles were investigated.