Microgels with controlled network topologies by photocrosslinking-assisted continuous precipitation polymerization.

In this study, we present a new synthesis methodology based on photo-crosslinking-assisted continuous precipitation polymerization which allows controlling the distribution of crosslinks in microgels. In our approach we substituted conventional crosslinking agent by a comonomer carrying photo-crosslinkable 4-oxocyclopent-2-en-1-yl group. Microgel size, morphology, distribution of crosslinks and packing density of the polymer chains are studied as a function of retention time (Rt) in the flow reactor.

Multiresponsive Core-Shell Microgels Functionalized by Nitrilotriacetic Acid.

Stimuli-responsive microgels with ionizable functional groups offer versatile applications, e.g., by the uptake of oppositely charged metal ions or guest molecules such as drugs, dyes, or proteins.

Fibrin-Dextran Hydrogels with Tunable Porosity and Mechanical Properties.

Hydrogels as scaffolds in tissue engineering have gained increasing attention in recent years. Natural hydrogels, e.g.

Mechanochemical Synthesis of Stimuli Responsive Microgels.

Mechanochemical approaches are widely used for the efficient, solvent-free synthesis of organic molecules, however their applicability to the synthesis of functional polymers has remained underexplored. Herein, we demonstrate for the first time that mechanochemically triggered free-radical polymerization allows solvent- and initiator-free syntheses of structurally and morphologically well-defined complex functional macromolecular architectures, namely stimuliresponsive microgels. The developed mechanochemical polymerization approach is applicable to a variety of monomers and allows synthesizing microgels with tunable chemical structure, variable size, controlled number of crosslinks and reactive functional end-groups.

Anisotropic Microgels by Supramolecular Assembly and Precipitation Polymerization of Pyrazole-Modified Monomers.

Soft colloidal macromolecular structures with programmable chemical functionalities, size, and shape are important building blocks for the fabrication of catalyst systems and adaptive biomaterials for tissue engineering. However, the development of the easy upscalable and template-free synthesis methods to obtain such colloids lack in understanding of molecular interactions that occur in the formation mechanisms of polymer colloids. Herein, a computer simulation-driven experimental synthesis approach based on the supramolecular self-assembly followed by polymerization of tailored pyrazole-modified monomers is developed.

Stimuli-responsive microgels with cationic moieties: characterization and interaction with cells.

Stimuli-responsive microgel copolymer networks with ionizable functional groups have important applications for encapsulation of drugs, peptides, enzymes, proteins, or cells. Rational design of such networks can be based on characterization of stimuli-induced volume phase transition and spatial distribution of neutral and charged monomer units in crosslinked polymer chains. In this work we successfully synthesized poly(-vinylcaprolactam--1-vinyl-3-methylimidazolium) (poly(VCL-VIM)) microgels carrying permanent positive charges and demonstrate that H high-resolution NMR spectroscopy in combination with transverse () magnetization relaxometry allows investigating separately the behavior of each functional group in the microgel network.

Poly(vinylamine-co-N-isopropylacrylamide) linear polymer and hydrogels with tuned thermoresponsivity.

The fabrication of functional hydrogels with tuned thermoresponsivity is a major challenge. To meet this challenge we copolymerize N-isopropylacrylamide (NIPAm) with N-vinylformamide (NVF) in different ratios with the formamide group being subsequently selectively hydrolyzed to the corresponding amine (VAm). The copolymers are crosslinked with phenylcarbonate telechelic glycol.

Selenium-Modified Microgels as Bio-Inspired Oxidation Catalysts.

Active colloidal catalysts inspired by glutathione peroxidase (GPx) were synthesized by integration of catalytically active selenium (Se) moieties into aqueous microgels. A diselenide crosslinker (Se X-linker) was successfully synthesized and incorporated into microgels through precipitation polymerization, along with the conventional crosslinker N,N'-methylenebis(acrylamide) (BIS). Diselenide bonds within the microgels were cleaved through oxidation by H O and converted to seleninic acid whilst maintaining the intact microgel microstructure.

Functional selenium modified microgels: temperature-induced phase transitions and network morphology.

Microgels that host selenium and mimic the structure of the enzyme glutathione peroxidase are of great interest for biotechnological and catalytic applications. For this purpose selenium-functionalized thermoresponsive poly(N-vinylcaprolactam) (PVCL) microgels with cleavable diselenide crosslinks have been investigated. Thermodynamic and morphological parameters characterizing the temperature-induced phase transitions of dual crosslinked PVCL microgels were obtained using dynamic light scattering (DLS), 1H high-resolution magic-angle sample-spinning (MAS) NMR spectroscopy, and transverse magnetization (T2) NMR relaxometry.

Diffusion of Gold Nanorods Functionalized with Thermoresponsive Polymer Brushes.

Understanding the diffusion of gold nanorods (AuNRs) and their composites in dispersion is important at fundamental level and in fields as diverse as material science, nanobiotechnology to drug delivery. The translational and rotational diffusion of AuNRs decorated with thermoresponsive poly( N-isopropylacrylamide) brushes having hydrophilic and hydrophobic end groups was investigated in the dilute regime by dynamic light scattering. The same series of functionalized AuNRs were studied in the isotropic concentrated dispersions by high-resolution NMR diffusometry.

Thermodynamic Parameters of Temperature-Induced Phase Transition for Brushes onto Nanoparticles: Hydrophilic versus Hydrophobic End-Groups Functionalization.

Quantification of the stimuli-responsive phase transition in polymers is topical and important for the understanding and development of novel stimuli-responsive materials. The temperature-induced phase transition of poly(N-isopropylacrylamide) (PNIPAm) with one thiol end group depends on the confinement-free polymer or polymer brush-on the molecular weight and on the nature of the second end. This paper describes the synthesis of heterotelechelic PNIPAm of different molecular weights with a thiol end group-that specifically binds to gold nanorods and a hydrophilic NIPAm end group by reversible addition-fragmentation chain-transfer polymerization.

Peptizing Mechanism at the Molecular Level of Laponite Nanoclay Gels.

In the presence of additives such as etidronic acid (1-hydroxyethane-1,1-diphosphonic acid, HEDP), a process of peptizing of Laponite clay gels takes place. The peptizing process at the molecular level was directly revealed by P and H high-resolution magic-angle sample spinning (HRMAS) NMR spectroscopy. Two NMR spectral components were detected and assigned to free etidronic acid and bound to the Laponite disk edges.

Aggregation behaviour of biohybrid microgels from elastin-like recombinamers.

Investigation of the aggregation behavior of biohybrid microgels, which can potentially be used as drug carriers, is an important topic, because aggregation not only causes loss of activity, but also toxicity and immunogenicity. To study this effect we synthesized microgels from elastin-like recombinamers (ELRs) using the miniemulsion technique. The existence of aggregation for such biohybrid microgels at different concentrations and temperatures was studied by different methods which include dynamic light scattering (DLS), (1)H high-resolution magic angle sample spinning (HRMAS) NMR spectroscopy, relaxometry and diffusometry.

Keratin made micro-tubes: The paradoxical thermal behavior of cortex and cuticle.

Keratin micro-tubes were obtained by heating medullated keratin fibres to temperatures above 230°C under nitrogen atmosphere, when, as documented by microscopy, the cortex (the core of the fibre) melts from the medulla outwards, followed by pyrolysis of the material through the remaining solid cuticle (shell) layer. The resulted hollow tubes from fibres void of cortical material keep the external cuticle structure, as shown by AFM investigation, and the moisture sorption properties of the initial keratin fibre. Despite similar amino-acid compositions of cuticle and cortex the two morphological components differ significantly in their thermal behaviour, which appears to be a "cortex-cuticle thermal stability paradox".

Coacervation of Elastin-Like Recombinamer Microgels.

The investigation of the coacervation (self-aggregation) behavior of biomicrogels which can potentially be used as drug carriers is an important topic, because self-aggregation can not only cause loss of activity, but also toxicity and immunogenicity. To study this effect microgels from elastin-like recombinamer are synthesized using miniemulsion technique. The existence of coacervation for such microgels, at different concentrations and temperatures, is studied and proved by cryo-field emission scanning clectron microscopy (cryo-FESEM), cryo-transmission electron microscopy (cryo-TEM), and by a novel (1) H high-resolution magic angle sample spinning (HRMAS), nuclear magnetic resonance (NMR) spectroscopy, and relaxometry methods.

Nacre-mimetics with synthetic nanoclays up to ultrahigh aspect ratios.

Nacre-mimetics hold great promise as mechanical high-performance and functional materials. Here we demonstrate large progress of mechanical and functional properties of self-assembled polymer/nanoclay nacre-mimetics by using synthetic nanoclays with aspect ratios covering three orders in magnitude (25-3,500). We establish comprehensive relationships among structure formation, nanostructuration, deformation mechanisms and mechanical properties as a function of nanoclay aspect ratio, and by tuning the viscoelastic properties of the soft phase via hydration.

Microencapsulation of hydrophobic liquids in closed all-silica colloidosomes.

A facile approach for the microencapsulation of hydrophobic liquids in closed solid all-silica colloidosomes is reported. The method is based on the formation of oil-in-water emulsions stabilized by silica nanoparticles and subsequent gluing of the particles at the water/oil interface by a silica precursor polymer-hyperbranched polyethoxysiloxane. By this means different oils are successfully enclosed in hence formed all-silica colloidosomes with almost 100% efficiency.

Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone.

Molecular dynamics parameter maps by 1H Hahn echo and mixed-echo phase-encoding MRI.

Residual dipolar couplings and averaged correlation time maps in soft matter were obtained by mixed echo phase-encoding solid imaging (MIPSI). Use of the mixed echo in soft matter NMR imaging experiments has two crucial advantages: the signal intensity is recovered with a weak incoherence losses, and second, the intervals during which the phase-encoding evolution due to the magnetic field gradients takes place can be chosen to be much larger than with all other spin echo experiments and hence, a higher special resolution can be achieved. The parameter maps are compared to those obtained by the Hahn-echo phase-frequency encoding method.

Tough and catalytically active hybrid biofibers wet-spun from nanochitin hydrogels.

Sustainable alternatives for high-performance and functional materials based on renewable resources are intensely needed as future alternatives for present-day, fossil-based materials. Nanochitin represents an emerging class of highly crystalline bionanoparticles with high intrinsic mechanical properties and the ability for conjugation into functional materials owing to reactive amine and hydroxyl groups. Herein we demonstrate that hydrogels containing surface-deacetylated chitin nanofibrils of micrometer length and average diameters of 9 nm, as imaged by cryogenic transmission electron microscopy, can be wet-spun into macrofibers via extrusion in a coagulation bath, a simple low energy and large-scale processing route.

Morphology and molecular mobility of fibrous hard alpha-keratins by 1H, 13C, and 129Xe NMR.

The morphology and molecular mobility changes of the side chains for hard alpha-keratin due to oxidative and reductive/oxidative treatments for temperatures around the DSC denaturation peak were investigated by (1)H, (13)C, and (129)Xe NMR spectroscopy and (1)H spin diffusion. Proton wide-line spectra were used to obtain the phase composition (rigid, interface, and amorphous fractions) and molecular dynamics of each phase. Proton spin diffusion experiments using a double-quantum filter and initial rate approximation were employed to obtain the dependence of the rigid domain sizes on chemical treatments and denaturation temperatures.

Thermal denaturation of hydrated wool keratin by 1H solid-state NMR.

Thermal denaturation of hydrated keratin in wool was investigated by NMR using 1H wide-line spectra to obtain the phase composition and 1H spin-diffusion experiments using a double-quantum filter to obtain the domain sizes for the wool fibers. The denaturation process detected by DSC takes place for wool fibers in deuterated water in the temperature range 140-144 degreeC. The phase composition measured by 1H wide line NMR spectra reveals a rigid, semirigid and an amorphous phase for temperatures in the range 25-160 degreeC.

Segmental mobility in short-chain grafted-PDMS by homo- and heteronuclear residual dipolar couplings.

Different homo- ((1)H-(1)H) and heteronuclear ((1)H-(13)C) multiple quantum solid-state NMR experiments were applied to a series of short poly (dimethylsiloxane) (PDMS) chains grafted onto hydrophilic silica. The existence and clear separation of a strongly dipolar coupled region which is attributed to the silica-PDMS interface and a weakly dipolar coupled region attributed to the mobile chain portions outside the interface is evident in all experiments. In a sample series with different average chain lengths the residual dipolar couplings and with that the average order parameters are constant for the interface part and correlate for the mobile part linearly with the average chain length.