Synthesis of PEG-Polycycloether Block Copolymers: Poloxamer Mimics Containing a Rigid Helical Block.

Poloxamers are amphiphilic block copolymers consisting of poly(ethylene glycol) (PEG) and poly(propylene glycol) segments. Their self-assembly and interfacial properties are tied to the relative hydrophilicity and hydrophobicity of each block and can therefore be adjusted by changing block lengths. Here, a series of PEG-polycycloether block copolymers is synthesized that have the same structure as a poloxamer, but they encompass a rigid polycyclic backbone as the hydrophobic block. A variety of polymer structures are synthesized, for example diblock or triblock architectures, with/without olefinic units, atactic or isotactic backbone, and different block lengths. Due to their amphiphilicity, self-assembly into spherical aggregates (diameters ranging from 64 to 132 nm) at low concentrations (critical aggregation concentration as low as 0.04 mg mL-1) is observed in water. Low surface tensions (as low as 26.7 mN m-1) are observed as well as the formation of stable high internal phase emulsions (HIPEs) irrespective of the oil/water ratio. This contrasts with the properties of the commonly used poloxamers P188 or P407 and illustrates the significance of the rigid polycycloether block. These new colloidal properties offer new prospects for applications in emulsion formulations for biomedicine, cosmetics, and the food industry.

Multicompartment Hydrogels.

Hydrogels belong to the most promising materials in polymer and materials science at the moment. As they feature soft and tissue-like character as well as high water-content, a broad range of applications are addressed with hydrogels, e.g., tissue engineering and wound dressings but also soft robotics, drug delivery, actuators, and catalysis. Ways to tailor hydrogel properties are crosslinking mechanisms, hydrogel shape, and reinforcement, but new features can be introduced by variation of hydrogel composition as well, e.g., via monomer choice, functionalization or compartmentalization. In particular, multicompartment hydrogels drive progress toward complex and highly functional soft materials. In the present review the latest developments in multicompartment hydrogels are highlighted with a focus on three types of compartments; micellar/vesicular, droplets, and multilayers including various subcategories. Furthermore, several morphologies of compartmentalized hydrogels and applications of multicompartment hydrogels will be discussed as well. Finally, an outlook toward future developments of the field will be given. The further development of multicompartment hydrogels is highly relevant for a broad range of applications and will have a significant impact on biomedicine and organic devices.

Stimuli-Responsive Aggregation of High Molar Mass Poly(N,N-Diethylacrylamide)-b-Poly(4-Acryloylmorpholine) in Tetrahydrofuran.

The self-assembly of block copolymers constitutes a timely research area in polymer science with implications for applications like sensing or drug-delivery. Here, the unprecedented aggregation behavior of high molar mass block copolymer poly(N,N-diethylacrylamide)-b-poly(4-acryloylmorpholine) (PDEA-b-PAM) (Mn >400 kg mol-1 ) in organic solvent tetrahydrofuran (THF) is investigated. To elucidate the aggregation, dynamic light scattering, cryo-transmission electron microscopy, and turbidimetry are employed. The aggregate formation is assigned to the unprecedented upper critical solution temperature behavior of PAM in THF at elevated concentrations (> 6 wt.%) and high molar masses. Various future directions for this new thermo-responsive block copolymer are envisioned, for example, in the areas of photonics or templating of inorganic structures.

Polysaccharide nanoparticles: from fabrication to applications.

Polysaccharides have attracted considerable attention in a broad range of applications in recent years, which is due to their remarkable features such as biocompatibility, biodegradability, renewable origin, and facile modification. Considerable research efforts have been focused on developing polysaccharide nanoparticles and to promote their applications in various areas and biomedicine in particular. The present review highlights the properties of common polysaccharides used in nanoparticle formation as well as strategies to fabricate polysaccharide nanoparticles. Furthermore, the combination of polysaccharide nanoparticles and polymers is presented and brought into the context of applications. Finally, applications of polysaccharide nanoparticles as nano-delivery system, Pickering emulsion stabilisers, and material reinforcing agent in the fields of nanomedicine, cosmetics, and food system are highlighted. Moreover, this review describes and critically discusses present limitations and drawbacks in the preparation and use of polysaccharide nanoparticles, revealing directions to develop polysaccharide nanoparticles for further utilisation in various applications in the future.

Molding and Encoding Carbon Nitride-Containing Edible Oil Liquid Objects via Interfacial Toughening in Waterborne Systems.

Charge interaction-driven jamming of nanoparticle monolayers at the oil-water interface can be employed as a method to mold liquids into tailored stable 3D liquid objects. Here, 3D liquid objects are fabricated via a combination of biocompatible aqueous poly(vinyl sulfonic acid, sodium salt) solution and a colloidal dispersion of highly fluorescent organo-modified graphitic carbon nitride (g-C3N4) in edible sunflower oil. The as-formed liquid object shows stability in a broad pH range, as well as flexible pathways for efficient exchange of molecules at the liquid-liquid interphase, which allows for photodegradation of rhodamine B at the interface via visible light irradiation that also enables an encoding concept. The g-C3N4-based liquid objects point toward various applications, for example, all-liquid biphasic photocatalysis, artificial compartmentalized systems, liquid-liquid printing, or bioprinting.

Graphitic Carbon Nitride Stabilized Water-in-Water Emulsions.

Aqueous multiphase systems have attracted a lot of interest recently espeically due to target applications in the biomedical field, cosmetics, and food. In turn, water-in-water Pickering emulsions are investigated frequently. In here, graphitic carbon nitride (g-CN) stabilized water-in-water Pickering emulsions are fabricated via the dextran and poly(ethylene glycol)-based aqueous two-phase system. Five different derivatives of g-CN as the Pickering stabilizer are described and the effect of g-CN concentration on droplet sizes is investigated. Stable emulsions (up to 16 weeks) are obtained that can be broken on purpose via various approaches, including dilution, surfactant addition, and most notably light irradiation. The novel approach of water-in-water emulsion stabilization via g-CN opens up considerable advances in aqueous multiphase systems and may also introduce photocatalytic properties.

Responsive Janus and Cerberus emulsions via temperature-induced phase separation in aqueous polymer mixtures.

Complex aqueous emulsions represent a promising material platform for the encapsulation of cells, pharmaceuticals, or nutrients, for the fabrication of structured particles, as well as for mimicking the barrier-free compartmentalization of biomolecules found in living cells. Herein, we report a novel, simple, and scalable method of creating multicomponent aqueous droplets with highly uniform internal droplet morphologies that can be controllably altered after emulsification by making use of a thermal phase separation approach. Specifically, temperature-induced phase separation inside as-formed emulsion droplets comprising aqueous mixtures of two or more hydrophilic polymers allows for the generation of Janus and Cerberus emulsion droplets with adjustable internal morphologies that are solely controlled by a balance of interfacial tensions. We demonstrate our approach by applying both, microfluidic and scalable batch production, and present a detailed model study with predictive capabilities that enables fine-tuning and dynamically altering the droplet morphology as a function of types, molecular weights, and hydrophilicities of the polymers as well as the surfactant hydrophilic-lipophilic balance. The ability to rationally design complex aqueous emulsion droplets with previously unattainable dynamic control over their morphologies after emulsification entails the potential to design new responsive soft materials with implications for a variety of applications beyond encapsulation, including the design of complex adaptive and self-regulating materials, e.g. for chemical and biological sensing applications.

Temperature sensitive water-in-water emulsions.

A novel approach for a temperature-sensitive stabilization of water-in-water (W/W) emulsions is described. Specifically, we leveraged the thermal induced conformation change of tailored thermoresponsive block copolymers to reversibly stabilize and destabilize water-water interfaces. In addition, we investigated our approach to reversibly tune the reaction kinetics of enzymes compartmentalized within aqueous two-phase systems.

Controlling the morphology of metal-organic frameworks and porous carbon materials: metal oxides as primary architecture-directing agents.

Owing to their large ratio of surface area to mass and volume, metal-organic frameworks and porous carbons have revolutionized many applications that rely on chemical and physical interactions at surfaces. However, a major challenge today is to shape these porous materials to translate their enhanced performance from the laboratory into macroscopic real-world applications. In this review, we give a comprehensive overview of how the precise morphology control of metal oxides can be transferred to metal-organic frameworks and porous carbon materials. As such, tailored material structures can be designed in 0D, 1D, 2D, and 3D with considerable implications for applications such as in energy storage, catalysis and nanomedicine. Therefore, we predict that major research advances in morphology control of metal-organic frameworks and porous carbons will facilitate the use of these materials in addressing major needs of the society, especially the grand challenges of energy, health, and environment.

Polymer Brushes on Graphitic Carbon Nitride for Patterning and as a SERS Active Sensing Layer via Incorporated Nanoparticles.

Graphitic carbon nitride (gCN) has a broad range of promising applications, from energy harvesting and storage to sensing. However, most of the applications are still restricted due to gCN poor dispersibility and limited functional groups. Herein, a direct photografting of gCN using various polymer brushes with tailorable functionalities via UV photopolymerization at ambient conditions is demonstrated. The systematic study of polymer brush-functionalized gCN reveals that the polymerization did not alter the inherent structure of gCN. Compared to the pristine gCN, the gCN-polymer composites show good dispersibility in various solvents such as water, ethanol, and tetrahydrofuran (THF). Patterned polymer brushes on gCN can be realized by employing photomask and microcontact printing technology. The polymer brushes with incorporated silver nanoparticles (AgNPs) on gCN can act as a multifunctional recyclable active sensing layer for surface-enhanced Raman spectroscopy (SERS) detection and photocatalysis. This multifunctionality is shown in consecutive cycles of SERS and photocatalytic degradation processes that can be applied to in situ monitor pollutants, such as dyes or pharmaceutical waste, with high chemical sensitivity as well as to water remediation. This dual functionality provides a significant advantage to our AgNPs/polymer-gCN with regard to state-of-the-art systems reported so far that only allow SERS pollutant detection but not their decomposition. These results may provide a new methodology for the covalent functionalization of gCN and may enable new applications in the field of catalysis, biosensors, and, most interestingly, environmental remediation.

Cascade Kinetics in an Enzyme-Loaded Aqueous Two-Phase System.

Macromolecular crowding plays a critical role in the kinetics of enzymatic reactions. Dynamic compartmentalization of biological components in living cells due to liquid-liquid phase separation represents an important cell regulatory mechanism that can increase enzyme concentration locally and influence the diffusion of substrates. In the present study, we probed partitioning of two enzymes (horseradish-peroxidase and urate-oxidase) in a poly(ethylene glycol)-dextran aqueous two-phase system (ATPS) as a function of salt concentration and ion position in the Hofmeister series. Moreover, we investigated enzymatic cascade reactions and their kinetics within the ATPS, which revealed a strong influence of the ion hydration stemming from the background electrolyte on the partitioning coefficients of proteins following the Hofmeister series. As a result, we were able to realize cross-partitioning of two enzymes because of different protein net charges at a chosen pH. Our study reveals a strong dependency of the enzyme activity on the substrate type and crowding agent interaction on the final kinetics of enzymatic reactions in the ATPS and therefore provides substantial implications en route toward dynamic regulation of reactivity in synthetic protocells.

Metal-Organic Frameworks in Polymer Science: Polymerization Catalysis, Polymerization Environment, and Hybrid Materials.

The development of metal-organic frameworks (MOFs) has had a significant impact on various fields of chemistry and materials science. Naturally, polymer science also exploited this novel type of material for various purposes, which is due to the defined porosity, high surface area, and catalytic activity of MOFs. The present review covers various topics of MOF/polymer research beginning with MOF-based polymerization catalysis. Furthermore, polymerization inside MOF pores as well as polymerization of MOF ligands is described, which have a significant effect on polymer structures. Finally, MOF/polymer hybrid and composite materials are highlighted, encompassing a range of material classes, like bulk materials, membranes, and dispersed materials. In the course of the review, various applications of MOF/polymer combinations are discussed (e.g., adsorption, gas separation, drug delivery, catalysis, organic electronics, and stimuli-responsive materials). Finally, past research is concluded and an outlook toward future development is provided.

Trends in Polymers 2017/2018: Polymer Synthesis.

Polymer synthesis is a substantial area in polymer science and marks the starting point for all sorts of polymer materials that have a plethora of applications in everyday life but also in academic research [...].

Grafting Polymers onto Carbon Nitride via Visible-Light-Induced Photofunctionalization.

Metal-free graphitic carbon nitride (g-CN) has attracted significant attention recently due to its multiple applications, such as photocatalysis, energy storage and conversion, and biomaterials, albeit formation of g-CN films is challenging. Herein, a "grafting to" route to graft polymer brushes onto g-CN via visible-light irradiation is described. Afterward, g-CN/polymer films can be obtained through spin coating on glass substrates. As such, the present material provides an improved process toward further application of g-CN in thin films. Moreover, an improved dispersibility in organic solvent was realized after grafting and functional groups (such as epoxides) were introduced to g-CN. Subsequently, the epoxy groups were utilized for further functionalization to adjust the surface polarity.

Supramolecular Compartmentalized Hydrogels via Polydopamine Particle-Stabilized Water-in-Water Emulsions.

Compartmentalized hydrogels constitute a significant research area, for example, for catalytic and biomedical applications. As presented here, a generic method is used for compartmentalization of supramolecular hydrogels by using water-in-water emulsions based on aqueous two-phase systems. By forming the supramolecular hydrogel throughout the continuous phase of all-aqueous emulsions, distinct, microcompartmentalized materials were created. The basis for the presented compartmentalized water-in-water hydrogels is polydopamine particle-stabilized water-in-water emulsions from dextran and poly(ethylene glycol) (PEG). Addition of α-cyclodextrin (α-CD) led to supramolecular complexation with PEG and subsequent hydrogel formation showing no signs of creaming. Due to the supramolecular nature of the compartmentalized hydrogels, selective network cleavage could be induced via competing guest addition, while keeping the emulsion substructure intact.

Three-Phase Photocatalysis for the Enhanced Selectivity and Activity of CO2 Reduction on a Hydrophobic Surface.

The photocatalytic CO2 reduction reaction (CRR) represents a promising route for the clean utilization of stranded renewable resources, but poor selectivity resulting from the competing hydrogen evolution reaction (HER) in aqueous solution limits its practical applicability. In the present contribution a photocatalyst with hydrophobic surfaces was fabricated. It facilitates an efficient three-phase contact of CO2 (gas), H2 O (liquid), and catalyst (solid). Thus, concentrated CO2 molecules in the gas phase contact the catalyst surface directly, and can overcome the mass-transfer limitations of CO2 , inhibit the HER because of lowering proton contacts, and overall enhance the CRR. Even when loaded with platinum nanoparticles, one of the most efficient HER promotion cocatalysts, the three-phase photocatalyst maintains a selectivity of 87.9 %. Overall, three-phase photocatalysis provides a general and reliable method to enhance the competitiveness of the CRR.

A biomimetic nanofluidic diode based on surface-modified polymeric carbon nitride nanotubes.

A controllable ion transport including ion selectivity and ion rectification across nanochannels or porous membranes is of great importance because of potential applications ranging from biosensing to energy conversion. Here, a nanofluidic ion diode was realized by modifying carbon nitride nanotubes with different molecules yielding an asymmetric surface charge that allows for ion rectification. With the advantages of low-cost, thermal and mechanical robustness, and simple fabrication process, carbon nitride nanotubes with ion rectification have the potential to be used in salinity-gradient energy conversion and ion sensor systems.

Influence of Thiazole-Modified Carbon Nitride Nanosheets with Feasible Electronic Properties on Inverted Perovskite Solar Cells.

Effective, solution-processable designs of interfacial electron-transporting layers (ETLs) or hole-blocking layers are promising tools in modern electronic devices, e.g., to improve the performance, cost, and stability of perovskite-based solar cells. Herein, we introduce a facile synthetic route of thiazole-modified carbon nitride with 1.5 nm thick nanosheets which can be processed to a homogeneous, metal-free ETL for inverted perovskite solar cells. We show that thiazole-modified carbon nitride enables electronic interface enhancement via suppression of charge recombination, achieving 1.09 V in Voc and a rise to 20.17 mA/cm2 in Jsc. Hence, this report presents the successful implementation of a carbon-nitride-based structure to boost charge extraction from the perovskite absorber toward the electron transport layer in p-i-n devices.

Micro-Blooming: Hierarchically Porous Nitrogen-Doped Carbon Flowers Derived from Metal-Organic Mesocrystals.

Synthesis of 3D flower-like zinc-nitrilotriacetic acid (ZnNTA) mesocrystals and their conformal transformation to hierarchically porous N-doped carbon superstructures is reported. During the solvothermal reaction, 2D nanosheet primary building blocks undergo oriented attachment and mesoscale assembly forming stacked layers. The secondary nucleation and growth preferentially occurs at the edges and defects of the layers, leading to formation of 3D flower-like mesocrystals comprised of interconnected 2D micropetals. By simply varying the pyrolysis temperature (550-1000 °C) and the removal method of in the situ-generated Zn species, nonporous parent mesocrystals are transformed to hierarchically porous carbon flowers with controllable surface area (970-1605 m2 g-1 ), nitrogen content (3.4-14.1 at%), pore volume (0.95-2.19 cm3 g-1 ), as well as pore diameter and structures. The carbon flowers prepared at 550 °C show high CO2 /N2 selectivity due to the high nitrogen content and the large fraction of (ultra)micropores, which can greatly increase the CO2 affinity. The results show that the physicochemical properties of carbons are highly dependent on the thermal transformation and associated pore formation process, rather than directly inherited from parent precursors. The present strategy demonstrates metal-organic mesocrystals as a facile and versatile means toward 3D hierarchical carbon superstructures that are attractive for a number of potential applications.