Nonequilibrium Colloids: Temperature-Induced Bouquet Formation of Flower-like Micelles as a Time-Domain-Shifting Macromolecular Heat Alert.

Climate change requires enhanced autonomous temperature monitoring during logistics/transport. A cheap approach comprises the use of temperature-sensitive copolymers that undergo temperature-induced irreversible coagulation. The synthesis/characterization of pentablock copolymers (PBCP) starting from poloxamer PEO130-b-PPO44-b-PEO130 (poly(ethylene oxide)130-b-poly(propylene oxide)44-b-poly(ethylene oxide)130) and adding two terminal qPDMAEMA85 (quaternized poly[(2-dimethylamino)ethyl methacrylate]85) blocks is presented. Mixing of PBCP solutions with hexacyanoferrate(III)/ferricyanide solutions leads to a reduction of the decane/water interfacial tension accompanied by a co/self-assembly toward flower-like micelles in cold water because of the formation of an insoluble/hydrophobic qPDMAEMA/ferricyanide complex. In cold water, the PEO/PPO blocks provide colloidal stability over months. In hot water, the temperature-responsive PPO block is dehydrated, leading to a pronounced temperature dependence of the oil-water interfacial tension. In solution, the sticky PPO segments exposed at the micellar corona cause a colloidal clustering above a certain threshold temperature, which follows Smoluchowski-type kinetics. This coagulation remains for months even after cooling, indicating the presence of a kinetically trapped nonequilibrium state for at least one of the observed micellar structures. Therefore, the system memorizes a previous suffering of heat. This phenomenon is linked to an exchange of qPDMAEMA-blocks bridging the micellar cores after PPO-induced clustering. The addition of ferrous ions hampers the exchange, leading to the reversible coagulation of Prussian blue loaded micelles. Hence, the Fe2+ addition causes a shift from history monitoring to the sensing of the present temperature. Presumably, the system can be adapted for different temperatures in order to monitor transport and storage in a simple way. Hence, these polymeric "flowers" could contribute to preventing waste and sustaining the quality of goods (e.g., food) by temperature-induced bouquet formation, where an irreversible exchange of "tentacles" between the flowers stabilizes the bouquet at other temperatures as well.

Interfacial Rearrangements of Block Copolymer Micelles Toward Gelled Liquid-Liquid Interfaces with Adjustable Viscoelasticity.

Though amphiphiles are ubiquitously used for altering interfaces, interfacial reorganization processes are in many cases obscure. For example, adsorption of micelles to liquid-liquid interfaces is often accompanied by rapid reorganizations toward monolayers. Then, the involved time scales are too short to be followed accurately. A block copolymer system, which comprises poly(ethylene oxide)110 -b-poly{[2-(methacryloyloxy)ethyl]diisopropylmethylammonium chloride}170 (i.e., PEO110 -b-qPDPAEMA170 with quaternized poly(diisopropylaminoethyl methacrylate)) is presented. Its reorganization kinetics at the water/n-decane interface is slowed down by electrostatic interactions with ferricyanide ([Fe(CN)6 ]3- ). This deceleration allows an observation of the restructuring of the adsorbed micelles not only by tracing the interfacial pressure, but also by analyzing the interfacial rheology and structure with help of atomic force microscopy. The observed micellar flattening and subsequent merging toward a physically interconnected monolayer lead to a viscoelastic interface well detectable by interfacial shear rheology (ISR). Furthermore, the "gelled" interface is redox-active, enabling a return to purely viscous interfaces and hence a manipulation of the rheological properties by redox reactions. Additionally, interfacial Prussian blue formation stiffens the interface. Such manipulation and in-depth knowledge of the rheology of complex interfaces can be beneficial for the development of emulsion formulations in industry or medicine, where colloidal stability or adapted permeability is crucial.

Electrochemical Stimulation of Water-Oil Interfaces by Nonionic-Cationic Block Copolymer Systems.

Variable interfacial tension could be desirable for many applications. Beyond classical stimuli like temperature, we introduce an electrochemical approach employing polymers. Hence, aqueous solutions of the nonionic-cationic block copolymer poly(ethylene oxide)114-b-poly{[2-(methacryloyloxy)ethyl]diisopropylmethylammonium chloride}171 (i.e., PEO114-b-PDPAEMA171 with a quaternized poly(diisopropylaminoethyl methacrylate) block) were investigated by emerging drop measurements and dynamic light scattering, analyzing the PEO114-b-qPDPAEMA171 impact on the interfacial tension between water and n-decane and its micellar formation in the aqueous bulk phase. Potassium hexacyanoferrates (HCFs) were used as electroactive complexants for the charged block, which convert the bishydrophilic copolymer into amphiphilic species. Interestingly, ferricyanides ([Fe(CN)6]3-) act as stronger complexants than ferrocyanides ([Fe(CN)6]4-), leading to an insoluble qPDPAEMA block in the presence of ferricyanides. Hence, bulk micellization was demonstrated by light scattering. Due to their addressability, in situ redox experiments were performed to trace the interfacial tension under electrochemical control, directly utilizing a drop shape analyzer. Here, the open-circuit potential (OCP) was changed by electrolysis to vary the ratio between ferricyanides and ferrocyanides in the aqueous solution. While a chemical oxidation/reduction is feasible, also an electrochemical oxidation leads to a significant change in the interfacial tension properties. In contrast, a corresponding electrochemical reduction showed only a slight response after converting ferricyanides to ferrocyanides. Atomic force microscopy (AFM) images of the liquid/liquid interface transferred to a solid substrate showed particles that are in accordance with the diameter from light scattering experiments of the bulk phase. In conclusion, the present results could be an important step toward economic switching of interfaces suitable, e.g., for emulsion breakage.

Electroactive and degradable supramolecular microgels.

In this work, we synthesized electroactive and degradable microgels based on biomacromolecular building blocks, which enable the controlled release of therapeutic drugs. Functional chitosan-poly(hydroquinone) (Ch:PHQ) microgels exhibiting redox-active and pH-sensitive properties were synthesized by an oxidative polymerization in an inverse miniemulsion system. Physically crosslinked microgels were formed by polymerization of hydroquinone in the presence of chitosan through the formation of hydrogen bonds between PHQ and Ch. A series of microgel samples with variable Ch : PHQ ratios were synthesized. These obtained microgels exhibit pH-responsive properties due to the protonation/deprotonation of amino-groups of chitosan in the microgel system. Poly(hydroquinone) is a redox-active polymer exhibiting a two-electron/proton-transfer behavior and conveys this property to the microgels as confirmed by cyclic voltammetry. In addition, the microgels can be switched by electrochemical means: they swell in the oxidized state or shrink in the reduced state. In the presence of urea or lysozyme, the microgels undergo a fast degradation due to the disruption of hydrogen bonds acting as physical crosslinks in the microgel networks or due to the cleavage of glucosidic linkages of the incorporated chitosan scaffold, respectively. Doxorubicin (DOX), an anticancer drug, could be effectively encapsulated into the microgels and released in the presence of an enzyme, indicating that these biodegradable microgels could be used as drug delivery vehicles for tumor cells.

Cargo shuttling by electrochemical switching of core-shell microgels obtained by a facile one-shot polymerization.

Controlling and understanding the electrochemical properties of electroactive polymeric colloids is a highly topical but still a rather unexplored field of research. This is especially true when considering more complex particle architectures like stimuli-responsive microgels, which would entail different kinetic constraints for charge transport within one particle. We synthesize and electrochemically address dual stimuli responsive core-shell microgels, where the temperature-responsiveness modulates not only the internal structure, but also the microgel electroactivity both on an internal and on a global scale. In detail, a facile one-step precipitation polymerization results in architecturally advanced poly(N-isopropylacrylamide-co-vinylferrocene) P(NIPAM-co-VFc) microgels with a ferrocene (Fc)-enriched (collapsed/hard) core and a NIPAM-rich shell. While the remaining Fc units in the shell are electrochemically accessible, the electrochemical activity of Fc in the core is limited due to the restricted mobility of redox active sites and therefore restricted electron transfer in the compact core domain. Still, prolonged electrochemical action and/or chemical oxidation enable a reversible adjustment of the internal microgel structure from core-shell microgels with a dense core to completely oxidized microgels with a highly swollen core and a denser corona. The combination of thermo-sensitive and redox-responsive units being part of the network allows for efficient amplification of the redox response on the overall microgel dimension, which is mainly governed by the shell. Further, it allows for an electrochemical switching of polarity (hydrophilicity/hydrophobicity) of the microgel, enabling an electrochemically triggered uptake and release of active guest molecules. Hence, bactericidal drugs can be released to effectively kill bacteria. In addition, good biocompatibility of the microgels in cell tests suggests suitability of the new microgel system for future biomedical applications.

PEO-b-PPO star-shaped polymers enhance the structural stability of electrostatically coupled liposome/polyelectrolyte complexes.

We propose a strategy to counteract the salt-driven disassembly of multiliposomal complexes made by electrostatic co-assembly of anionic small unilamellar liposomes and cationic star-shaped polyelectrolytes (made of quaternized poly(dimethylaminoethyl methacrylate) (qPDMAEMA100)3.1). The combined action of (qPDMAEMA100)3.1 and a nonionic star-shaped polymer (PEO12-b-PPO45)4, which comprises diblock copolymer arms uniting a poly(ethylene oxide) PEO inner block and a poly(propylene oxide) PPO terminal block, leads to a stabilization of these complexes against disintegration in saline solutions. Hereby, the anchoring of the PPO terminal blocks to the lipid bilayer and the bridging between several liposomes are at the origin of the promoted structural stability. Two-focus fluorescence correlation spectroscopy verifies the formation of multiliposomal complexes with (PEO12-b-PPO45)4. The polyelectrolyte and the amphiphilic polymer work synergistically, as the joint action still assures some membrane integrity, which is not seen for the mere (PEO12-b-PPO45)4-liposome interaction alone.

Spacer Chains Prevent the Intramolecular Complexation in Miktoarm Star Polymers.

The influence of spacer chains on the intramolecular complexation in star-shaped heteroarm (miktoarm) polymers is investigated. To overcome the mutual attraction of different polymeric components present in a miktoarm star with different homopolymeric arms, spacer chains of different length are attached to the core of the star at three different positions. In most of the investigated cases, this leads to diblock copolymer arms within the miktoarm star. Hereby, the inner spacer separates the outer blocks from their attractively interacting homopolymeric arms. The effect on the intramolecular complexation and the structure of the star polymer is obtained by Monte Carlo simulations of a simple bead-spring model. Then, long spacers can completely prevent the complexation. Both, local shielding by the spacer chains and the increased distance between the complex-forming polymers due to the spacer chains inhibit the complex formation. For a range of spacer positions and lengths, an equilibrium between a system forming a complex and a complex free system is found. The spacer chains can be used as a tool to tune the intramolecular complexation.

Surface Functionalization by Stimuli-Sensitive Microgels for Effective Enzyme Uptake and Rational Design of Biosensor Setups.

We highlight microgel/enzyme thin films that were deposited onto solid interfaces via two sequential steps, the adsorption of temperature- and pH-sensitive microgels, followed by their complexation with the enzyme choline oxidase, ChO. Two kinds of functional (ionic) microgels were compared in this work in regard to their adsorptive behavior and interaction with ChO, that is, poly(N-isopropylacrylamide-co-N-(3-aminopropyl)methacrylamide), P(NIPAM-co-APMA), bearing primary amino groups, and poly(N-isopropylacrylamide-co-N-[3-(dimethylamino) propyl]methacrylamide), P(NIPAM-co-DMAPMA), bearing tertiary amino groups. The stimuli-sensitive properties of the microgels in the solution were characterized by potentiometric titration, dynamic light scattering (DLS), and laser microelectrophoresis. The peculiarities of the adsorptive behavior of both the microgels and the specific character of their interaction with ChO were revealed by a combination of surface characterization techniques. The surface charge was characterized by electrokinetic analysis (EKA) for the initial graphite surface and the same one after the subsequent deposition of the microgels and the enzyme under different adsorption regimes. The masses of wet microgel and microgel/enzyme films were determined by quartz crystal microbalance with dissipation monitoring (QCM-D) upon the subsequent deposition of the components under the same adsorption conditions, on a surface of gold-coated quartz crystals. Finally, the enzymatic responses of the microgel/enzyme films deposited on graphite electrodes to choline were tested amperometrically. The presence of functional primary amino groups in the P(NIPAM-co-APMA) microgel enables a covalent enzyme-to-microgel coupling via glutar aldehyde cross-linking, thereby resulting in a considerable improvement of the biosensor operational stability.

Self-Templated Generation of Triggerable and Restorable Nonequilibrium Micelles.

Conditional variations can lead to micellar transformations resulting in various (equilibrium) morphologies. However, creating differently shaped assemblies under the same final conditions (same ingredients, composition, temperature, etc.) is challenging. We present a thermoresponsive polyelectrolyte system allowing a pathway-dependent preparation of kinetically stable spherical star-like or cylindrical micelles. In more detail, a temperature-induced structure switch is used to generate equilibrated interpolyelectrolyte complex (IPEC) micelles of different morphologies (templates) below and above the lower critical solution temperature in the presence of plasticizer (salt). Then, lowering the salt concentration at a specific temperature kinetically freezes the formed IPECs, keeping the respective microstructural information encoded in the frozen IPEC also at other temperatures. Hence, different nonequilibrium morphologies at the same final conditions are provided. The salt-triggered transition from nonequilibrium to equilibrium micelles can be repeated for the same sample, highlighting a system with an on-demand changeable and restorable structure.

Stimulated Transitions of Directed Nonequilibrium Self-Assemblies.

Near-equilibrium stimulus-responsive polymers have been used extensively to introduce morphological variations in dependence of adaptable conditions. Far-less-well studied are triggered transformations at constant conditions. These require the involvement of metastable states, which are either able to approach the equilibrium state after deviation from metastability or can be frozen on returning from nonequilibrium to equilibrium. Such functional nonequilibrium macromolecular systems hold great promise for on-demand transformations, which result in substantial changes in their material properties, as seen for triggered gelations. Herein, a diblock copolymer system consisting of a hydrophilic block and a block that is responsive to both pressure and temperature, is introduced. This species demonstrates various micellar transformations upon leaving equilibrium/nonequilibrium states, which are triggered by a temperature deflection or a temporary application of hydrostatic pressure.

Thermoresponsive Segments Retard the Formation of Equilibrium Micellar Interpolyelectrolyte Complexes by Detouring to Various Intermediate Structures.

The kinetics of interpolyelectrolyte complexation involving architecturally complex (star-like) polymeric components is addressed. Specifically, the spontaneous coupling of branched cationic star-shaped miktoarm polymers, i.e., quaternized poly(ethylene oxide)114-(poly(2-(dimethylamino)ethyl methacrylate)17)4 (PEO114-(qPDMAEMA17)4), and temperature-sensitive linear anionic diblock copolymers poly(vinyl sulfonate)31-b-poly(N-isopropylacrylamide)27 (PVS31-b-PNIPAM27) and further rearrangements of the formed complexes were investigated by means of stopped-flow small-angle X-ray scattering (SAXS). Colloidally stable micelles were obtained upon mixing both polymers at a 1:1 charge molar ratio in saline solutions. The description of the time-resolved SAXS data with appropriate form factor models yielded dimensions for each micellar domain and detailed the picture of the time-dependent size changes and restructuring processes. A fast interpolyelectrolyte coupling and structural equilibration were observed when mixing occurs below the lower critical solution temperature (LCST) of PNIPAM, resulting in small spherical-like assemblies with hydrated PNIPAM coronal blocks. Above the LCST, the collapsed PNIPAM decelerates equilibration, though temperature as such is expected to boost the kinetics of complex formation: after a fast initial interpolyelectrolyte coupling, different nonequilibrium structures of spherical and worm-like shape are observed on different time scales. This study illustrates how a thermoresponsive component can modulate the influence of temperature on kinetics, particularly for rearrangement processes toward equilibrium structures during interpolyelectrolyte complexation.

Easy-Preparable Butyrylcholinesterase/Microgel Construct for Facilitated Organophosphate Biosensing.

A versatile guest matrix was fabricated from a temperature- and pH-sensitive poly(N-isopropylacrylamide)-co-(3-(N,N-dimethylamino)propylmethacrylamide) microgel (poly(NIPAM-co-DMAPMA), MG) for the gentle incorporation of butyrylcholinesterase (BChE). The microgel/BChE films were built up on a surface of graphite-based screen-printed electrodes (SPEs) premodified with MnO2 nanoparticles via a two-step sequential adsorption under careful temperature and pH control. On this basis, a rather simple amperometric biosensor construct was formed, which uses butyrylthiocholine as BChE substrate with subsequent MnO2-mediated thiocholine oxidation at a graphite-based SPE. The complexation of BChE with the microgel was found to be safe and effective, as confirmed by a high operational and rather good long-term storage stability of the resultant SPE-MnO2/MG/BChE biosensors. The small mesh size of the microgel with respect to the size of BChE results in a predominant outer complexation of BChE within the dangling chains of the microgel rather than a deep penetration of the enzyme into the microgels. Given such surface localization, BChE is easily accessible both for the substrate and for cholinesterase inhibitors. This was supported by the analytical characteristics of the SPE-MnO2/MG/BChE biosensor that were examined and optimized both for the substrate and for the enzyme detection. The SPE-MnO2/MG/BChE biosensor enabled precision detection of organophosphorus pesticides (diazinon(oxon), chlorpyrifos(oxon)) in aqueous samples with minimized interference from extraneous (nonanalyte) substances (e.g., ions of heavy metals). The detection limits for diazinon(oxon) and chlorpyrifos(oxon) were estimated to be as low as 6 × 10-12 M and 8 × 10-12 M, respectively, after 20 min of preincubation with these irreversible inhibitors of BChE.

Balancing Segregation and Complexation in Amphiphilic Copolymers by Architecture and Confinement.

Segregation is a well-known principle for micellization, as solvophobic components try to minimize interactions with other entities (such as solvent) by self-assembly. An opposite principle is based on complexation (or coacervation), leading to the coassembly/association of different components. Most cases in the literature rely on only one of these modes, though the classical micellization scheme (such as spherical micelles, wormlike micelles, and vesicles) can be enriched by a subtle balance of segregation and complexation. Because of their counteraction, micellar constructs with unprecedented structure and behavior could be obtained. In this feature, systems are highlighted, which are between both mechanisms, and we study concentration, architecture, and confinement effects. Systems with inter- and intramolecular interactions are presented, and the effects of polymer topology and monomer sequence on the resulting structures are discussed. It is shown that complexation can lead to altered micellization behavior as the complex of one hydrophobic and one hydrophilic component can have a very low surface tension toward the solvent. Then, the more soluble component is enriched at the surface of the complex and acts as a microsurfactant. Although segregation dominates for amphiphilic copolymers in solution, the effect of the complexation can be enhanced by branching (change of architecture). Another possibility to enhance the complexation is by confining copolymers in a (pseudo-) 2D environment (like the one available at liquid-liquid interfaces). These observations show how new structural features can be achieved by tuning the subtle balance between segregation and complexation/solubilization.

Functional Microgels and Microgel Systems.

Microgels are macromolecular networks swollen by the solvent in which they are dissolved. They are unique systems that are distinctly different from common colloids, such as, e.g., rigid nanoparticles, flexible macromolecules, micelles, or vesicles. The size of the microgel networks is in the range of several micrometers down to nanometers (then sometimes called "nanogels"). In a collapsed state, they might resemble hard colloids but they can still contain significant amounts of solvent. When swollen, they are soft and have a fuzzy surface with dangling chains. The presence of cross-links provides structural integrity, in contrast to linear and (hyper)branched polymers. Obviously, the cross-linker content will allow control of whether microgels behave more "colloidal" or "macromolecular". The combination of being soft and porous while still having a stable structure through the cross-linked network allows for designing microgels that have the same total chemical composition, but different properties due to a different architecture. Microgels based, e.g., on two monomers but have either statistical spatial distribution, or a core-shell or hollow-two-shell morphology will display very different properties. Microgels provide the possibility to introduce chemical functionality at different positions. Combining architectural diversity and compartmentalization of reactive groups enables thus short-range coexistence of otherwise instable combinations of chemical reactivity. The open microgel structure is beneficial for uptake-release purposes of active substances. In addition, the openness allows site-selective integration of active functionalities like reactive groups, charges, or markers by postmodification processes. The unique ability of microgels to retain their colloidal stability and swelling degree both in water and in many organic solvents allows use of different chemistries for the modification of microgel structure. The capability of microgels to adjust both their shape and volume in response to external stimuli (e.g., temperature, ionic strength and composition, pH, electrochemical stimulus, pressure, light) provides the opportunity to reversibly tune their physicochemical properties. From a physics point of view, microgels are particularly intriguing and challenging, since their intraparticle properties are intimately linked to their interparticle behavior. Microgels, which reveal interface activity without necessarily being amphiphilic, develop even more complex behavior when located at fluid or solid interfaces: the sensitivity of microgels to various stimuli allows, e.g., the modulation of emulsion stability, adhesion, sensing, and filtration. Hence, we envision an ever-increasing relevance of microgels in these fields including biomedicine and process technology. In sum, microgels unite properties of very different classes of materials. Microgels can be based on very different (bio)macromolecules such as, e.g., polysaccharides, peptides, or DNA, as well as on synthetic polymers. This Account focuses on synthetic microgels (mainly based on acrylamides); however, the general, fundamental features of microgels are independent of the chemical nature of the building moieties. Microgels allow combining features of chemical functionality, structural integrity, macromolecular architecture, adaptivity, permeability, and deformability in a unique way to include the "best" of the colloidal, polymeric, and surfactant worlds. This will open the door for novel applications in very different fields such as, e.g., in sensors, catalysis, and separation technology.

Facile Screening of Various Micellar Morphologies by Blending Miktoarm Stars and Diblock Copolymers.

A time-saving phase-diagram screening is introduced for the self-assembly of miktoarm star polymers with different arm numbers for the insoluble part. Agreeing with theory, all conventional micellar morphologies (spherical star-like micelles, cylindrical micelles and vesicles) can be accessed by adjusting the average arm number when blending miktoarm stars with diblock copolymers (at constant arm/block lengths). Additionally, a rare clustered vesicle phase is detected. Hence, this approach permits an easy tuning of the equilibrium morphology and the size of the solvophobic domain. Such screening by scattering, ultracentrifugation, and electron microscopy techniques assists the targeted synthesis of miktoarm stars with a well-defined arm number, aimed at the morphology control of the nanostructures without blending. Specifically, we demonstrate a systematic variation of all classical micellar morphologies based on interpolyelectrolyte complexes (IPECs), consisting of a water-insoluble part formed by electrostatically coupled poly(styrenesulfonate) chains/quaternized poly(2-(dimethylamino)ethyl methacrylate) blocks, being stabilized by hydrophilic poly(ethylene oxide) blocks.

Poly(iminoborane)s: An Elusive Class of Main-Group Polymers?

The significance of inorganic main-group polymers is demonstrated most clearly by the commercial relevance of polysiloxanes (silicones). Organoboron-based materials such as π-conjugated organoborane polymers and BN-doped polycyclic aromatic hydrocarbons are currently attracting considerable attention. Surprisingly, poly(iminoborane)s (PIBs; [BRNR']n ), that is, the parent unsaturated BN polymers, which are formally isoelectronic to polyacetylene, have not been convincingly characterized thus far. Herein, we present the synthesis and comprehensive characterization of a linear oligo(iminoborane), which comprises a chain of 12-14 BN units on average. With our synthetic approach, unwanted side reactions that result in borazine formation are effectively suppressed. Supporting DFT and TD-DFT calculations provide deeper insight into the microstructure and the electronic structure of the oligomer.

Microstructured Hydrogel Templates for the Formation of Conductive Gold Nanowire Arrays.

Microstructured hydrogel allows for a new template-guided method to obtain conductive nanowire arrays on a large scale. To generate the template, an imprinting process is used in order to synthesize the hydrogel directly into the grooves of wrinkled polydimethylsiloxane (PDMS). The resulting poly(N-vinylimidazole)-based hydrogel is defined by the PDMS stamp in pattern and size. Subsequently, tetrachloroaurate(III) ions from aqueous solution are coordinated within the humps of the N-vinylimidazole-containing polymer template and reduced by air plasma. After reduction and development of the gold, to achieve conductive wires, the extension perpendicular to the long axis (width) of the gold strings is considerably reduced compared to the dimension of the parental hydrogel wrinkles (from ≈1 µm down to 200-300 nm). At the same time, the wire-to-wire distance and the overall length of the wires is preserved. The PDMS templates and hydrogel structures are analyzed with scanning force microscopy (SFM) and the gold structures via scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy. The conductivity measurements of the gold nanowires are performed in situ in the SEM, showing highly conductive gold leads. Hence, this method can be regarded as a facile nonlithographic top-down approach from micrometer-sized structures to nanometer-sized features.

Temperature-induced structure switch in thermo-responsive micellar interpolyelectrolyte complexes: toward core-shell-corona and worm-like morphologies.

The spontaneous formation and thermo-responsiveness of a colloidally-stable interpolyelectrolyte complex (IPEC) based on a linear temperature-sensitive diblock copolymer poly(vinyl sulfonate)31-b-poly(N-isopropyl acrylamide)27 (PVS31-b-PNIPAM27) and a star-shaped quaternized miktoarm polymer poly(ethylene oxide)114-(poly(2-(dimethylamino)ethyl methacrylate)17)4 (PEO114-(qPDMAEMA17)4) was investigated in aqueous media at 0.3 M NaCl by means of dynamic light scattering (DLS), small angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryo-TEM). The micellar macromolecular co-assemblies show a temperature-dependent size and morphology, which result from the lower critical solution temperature (LCST) behavior of the PNIPAM-blocks. Hence, the micellar co-assemblies grow upon heating. At 60 °C, spherical core-shell-corona co-assemblies are proposed with a hydrophobic PNIPAM core, a water-insoluble IPEC shell, and a hydrophilic PEO corona. These constructs develop into a rod-like structure upon extended equilibration. In turn, PEO-arms and PNIPAM-blocks within a hydrophilic mixed two-component corona surround the water-insoluble IPEC domain at 20 °C, thereby forming spherical core-corona co-assemblies. Reversibility of the structural changes is suggested by the scattering data. This contribution addresses the use of a combination of oppositely charged thermo-responsive and bis-hydrophilic star-shaped polymeric components toward IPECs of diverse morphological types.

Dehydrocoupling and Silazane Cleavage Routes to Organic-Inorganic Hybrid Polymers with NBN Units in the Main Chain.

Despite the great potential of both π-conjugated organoboron polymers and BN-doped polycyclic aromatic hydrocarbons in organic optoelectronics, our knowledge of conjugated polymers with B-N bonds in their main chain is currently scarce. Herein, the first examples of a new class of organic-inorganic hybrid polymers are presented, which consist of alternating NBN and para-phenylene units. Polycondensation with B-N bond formation provides facile access to soluble materials under mild conditions. The photophysical data for the polymer and molecular model systems of different chain lengths reveal a low extent of π-conjugation across the NBN units, which is supported by DFT calculations. The applicability of the new polymers as macromolecular polyligands is demonstrated by a cross-linking reaction with Zr(IV) .

Engineering Systems with Spatially Separated Enzymes via Dual-Stimuli-Sensitive Properties of Microgels.

This work examines the adsorption regime and the properties of microgel/enzyme thin films deposited onto conductive graphite-based substrates. The films were formed via two-step sequential adsorption. A temperature- and pH-sensitive poly(N-isopropylacrylamide)-co-(3-(N,N-dimethylamino)propylmethacrylamide) microgel (poly(NIPAM-co-DMAPMA microgel) was adsorbed first, followed by its interaction with the enzymes, choline oxidase (ChO), butyrylcholinesterase (BChE), or mixtures thereof. By temperature-induced stimulating both (i) poly(NIPAM-co-DMAPMA) microgel adsorption at T > VPTT followed by short washing and drying and then (ii) enzyme loading at T < VPTT, we can effectively control the amount of the microgel adsorbed on a hydrophobic interface as well as the amount and the spatial localization of the enzyme interacted with the microgel film. Depending on the biomolecule size, enzyme molecules can (in the case for ChO) or cannot (in the case for BChE) penetrate into the microgel interior and be localized inside/outside the microgel particles. Different spatial localization, however, does not affect the specific enzymatic responses of ChO or BChE and does not prevent cascade enzymatic reaction involving both BChE and ChO as well. This was shown by the methods of electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM), and amperometric analysis of enzymatic responses of immobilized enzymes. Thus, a novel simple and fast strategy for physical entrapment of biomolecules by the polymeric matrix was proposed, which can be used for engineering systems with spatially separated enzymes of different types.