Nonlinear Transient Permeability in pH-Responsive Bicontinuous Nanospheres.

We demonstrate the construction of pH-responsive bicontinuous nanospheres (BCNs) with nonlinear transient permeability and catalytic activity. The BCNs were assembled from amphiphilic block copolymers comprising pH-responsive groups and were loaded with the enzymes urease and horseradish peroxidase (HRP). A transient membrane permeability switch was introduced by employing the well-known pH-increasing effect of urease upon conversion of urea to ammonia. As expected, the coencapsulated HRP displayed a transiently regulated catalytic output profile upon addition of urea, with no significant product formation after the pH increase. This transient process displayed a nonlinear "dampening" behavior, induced by a decrease in membrane permeability as a result of significant local ammonia production. Furthermore, the catalytic output of HRP could be modulated by addition of different amounts of urea or by altering the buffer capacity of the system. Finally, this nonlinear dampening effect was not observed in spherical polymersomes, even though the membrane permeability could also be inhibited by addition of urea. The specific BCN morphology therefore allows to optimally control catalytic processes by pH changes in the nanoreactor microenvironment compared to bulk conditions due to its unique permeability profile.

t-Butyl-Oxycarbonylated Diamines as Building Blocks for Isocyanate-Free Polyurethane/Urea Dispersions and Coatings.

t-Butyl-oxycarbonylated diamines ("di-Boc-carbamates") are investigated as dicarbamate monomers for diamine/dicarbamate polymerizations. Polyureas (PUs) and polyurethanes (PURs) with high molecular weights are prepared from stoichiometric polymerizations of diamines or diols with N-N'-di-t-butyl-oxycarbonyl isophorone diamine (DiBoc-IPDC) using KOt-Bu as a catalyst, while gelation is observed when an excess of DiBoc-IPDC is used with respect to the diamines or diols. Stable dispersions are obtained from PUs and PURs with 3,3'-diamino-N-methyldipropylamine (DMDPA) as internal dispersing agent. The corresponding PU-based coatings exhibit superior mechanical properties and solvent resistances compared to the polyurethane urea coatings synthesized from diols, DiBoc-IPDC, and DMDPA.

Graphene oxide single sheets as substrates for high resolution cryoTEM.

CryoTEM is an important tool in the analysis of soft matter, where generally defocus conditions are used to enhance the contrast in the images, but this is at the expense of the maximum resolution that can be obtained. Here, we demonstrate the use of graphene oxide single sheets as support for the formation of 10 nm thin films for high resolution cryoTEM imaging, using DNA as an example. With this procedure, the overlap of objects in the vitrified film is avoided. Moreover, in these thin films less background scattering occurs and as a direct result, an increased contrast can be observed in the images. Hence, imaging closer to focus as compared with conventional cryoTEM procedures is achieved, without losing contrast. In addition, we demonstrate an ~1.8 fold increase in resolution, which is crucial for accurate size analysis of nanostructures.

Kinetic Monte Carlo simulation of the photodegradation process of polyester-urethane coatings.

A numerical method to simulate reactions in a cross-linked polymer is developed and applied to the photodegradation process of polyester-urethane clearcoats during artificial exposure in a Weather-Ometer. This coarse-grained simulation method, which is based on a kinetic Monte Carlo scheme, is verified with experimental data on the depth-resolved changes in optical properties and chemical composition that have been previously determined. By modelling the depth-dependency of physical processes that occur in the coating, such as the absorption of photons and the diffusion of oxygen, the experimentally observed evolution of depth gradients in chemical composition can be well described by the simulation. A sensitivity analysis of individual simulation input parameters with respect to a set of resulting observables is performed and the results provide insight into the influence of specific reaction mechanisms on the overall degradation process and help to distinguish essential from less important processes. The values of input parameters that result in the most accurate simulation of the experimental data are determined with an optimisation procedure. In this way, the numerical values of several kinetic and physical parameters that are difficult to determine directly in an experimental way, such as various reaction rate constants, can be obtained from the simulations.

Nucleation and growth of monodisperse silica nanoparticles.

Although monodisperse amorphous silica nanoparticles have been widely investigated, their formation mechanism is still a topic of debate. Here, we demonstrate the formation of monodisperse nanoparticles from colloidally stabilized primary particles, which at a critical concentration undergo a concerted association process, concomitant with a morphological and structural collapse. The formed assemblies grow further by addition of primary particles onto their surface. The presented mechanism, consistent with previously reported observations, reconciles the different theories proposed to date.

Dampened Transient Actuation of Hydrogels Autonomously Controlled by pH-Responsive Bicontinuous Nanospheres.

The fabrication of a soft actuator with a dampened actuation response is presented. This was achieved via the incorporation into an actuating hydrogel of urease-loaded pH-responsive bicontinuous nanospheres (BCNs), whose membrane was able to regulate the permeability and thus conversion of fuel urea into ammonia. The dampened response of these nanoreactors to the enzymatically induced pH change was translated to a pH-responsive soft actuator. In hydrogels composed of a pH-responsive and nonresponsive layer, the transient pH gradient yielded an asymmetric swelling behavior, which induced a bending response. The transient actuation profile could be controlled by varying the external fuel concentrations. Furthermore, we showed that the spatial organization of the BCNs within the actuator had a great influence on the actuation response. Embedding the urease-loaded nanoreactors within the active, pH-responsive layer resulted in a reduced response due to local substrate conversion in comparison to embedding them within the passive layer of the bilayer hydrogel. Finally, we were able to induce transient actuation in a hydrogel comprising two identical active layers by the immobilization of the BCNs within one specific layer. Upon addition of urea, a local pH gradient was generated, which caused accelerated swelling in the BCN layer and transient bending of the device before the pH gradient was attenuated over time.

Benzene Tetraamide: A Covalent Supramolecular Dual Motif in Dynamic Covalent Polymer Networks.

In dynamic polyamide networks, 1,2,4,5-benzene tetraamide (B4A) units act simultaneously as a dynamic covalent cross-linker and as supramolecular stacking motif. This results in materials with a rubbery plateau modulus that is about 20 times higher than that of a corresponding reference network in which the supramolecular interaction is suppressed. In branched polyamides with the same B4A dynamic motif, hydrogen bonding and stacking lead to strong and reversible supramolecular networks, whereas a branched polyamide with the nonstacking reference linker is a viscous liquid under the same conditions. Wide-angle X-ray scattering and variable-temperature infrared experiments confirm that covalent cross-linking and stacking cooperatively contribute to the dynamics of the network. Stress relaxation in the reference network is dominated by a single mode related to the dynamic covalent chemistry, whereas relaxation in the B4A network has additional modes assigned to the stacking dynamics.

RNA-inspired phosphate diester dynamic covalent networks.

Neighboring group assisted rearrangement substantially increases relaxation rates in dynamic covalent networks, allowing easier (re)processing of these materials. In this work, we introduce a dynamic covalent network with anionic phosphate diesters as the sole dynamic group, incorporating ß-hydroxy groups as a neighboring group, mimicking the self-cleaving backbone structure of RNA. The diester-based networks have slightly slower dynamics, but significantly better hydrolytic (and thermal) stability than analogous phosphate triester-based networks. Catalysis by the ß-hydroxy group is vital for fast network rearrangement to occur, while the nature of the counterion has a negligible effect on the relaxation rate. Variable temperature 31P solid-state NMR demonstrated a dissociative bond rearrangement mechanism to be operative.

Investigating the Morphology and Mechanics of Biogenic Hierarchical Materials at and below Micrometer Scale.

Investigating and understanding the intrinsic material properties of biogenic materials, which have evolved over millions of years into admirable structures with difficult to mimic hierarchical levels, holds the potential of replacing trial-and-error-based materials optimization in our efforts to make synthetic materials of similarly advanced complexity and properties. An excellent example is biogenic silica which is found in the exoskeleton of unicellular photosynthetic algae termed diatoms. Because of the complex micro- and nanostructures found in their exoskeleton, determining the intrinsic mechanical properties of biosilica in diatoms has only partly been accomplished. Here, a general method is presented in which a combination of in situ deformation tests inside an SEM with a realistic 3D model of the frustule of diatom Craspedostauros sp. (C. sp.) obtained by electron tomography, alongside finite element method (FEM) simulations, enables quantification of the Young's modulus (E = 2.3 ± 0.1 GPa) of this biogenic hierarchical silica. The workflow presented can be readily extended to other diatom species, biominerals, or even synthetic hierarchical materials.

Dynamic Polyamide Networks via Amide-Imide Exchange.

The diamide-imide equilibrium was successfully exploited for the synthesis of dynamic covalent polymer networks in which a dissociative bond exchange mechanism leads to high processibility at temperatures above ≈110 °C. Dynamic covalent networks bridge the gap between thermosets and thermoplastic polymers. At the operating temperature, when the network is fixed, dynamic covalent networks are elastic solids, while at high temperatures, chemical exchange reactions turn the network into a processible viscoelastic material. Upon heating a dissociative network, the viscosity may also decrease due to a shift of the chemical equilibrium; in such materials, the balance between processibility and excessive flow is important. In this study, a network is prepared that upon heating to above ≈110 °C dissociates to a significant extent due to a shift in the amide-imide equilibrium of a bisimide, pyromellitic diimide, in combination with poly(tetrahydrofuran) diamines. At room temperature, the resulting materials are elastic rubbers with a tensile modulus of 2-10 MPa, and they become predominantly viscous above a temperature of approximately 110 °C, which is dependent on the stoichiometry of the components. The diamide-imide equilibrium was studied in model reactions with NMR, and variable temperature infrared (IR) spectroscopy was used to investigate the temperature dependence of the equilibrium in the network. The temperature-dependent mechanical properties of the networks were found to be fully reversible, and the material could be reprocessed several times without loss of properties such as modulus or strain at break. The high processibility of these networks at elevated temperatures creates opportunities in additive manufacturing applications such as selective laser sintering.

Efficient Exchange in a Bioinspired Dynamic Covalent Polymer Network via a Cyclic Phosphate Triester Intermediate.

Bond exchange via neighboring group-assisted reactions in dynamic covalent networks results in efficient mechanical relaxation. In Nature, the high reactivity of RNA toward nucleophilic substitution is largely attributed to the formation of a cyclic phosphate ester intermediate via neighboring group participation. We took inspiration from RNA to develop a dynamic covalent network based on ß-hydroxyl-mediated transesterifications of hydroxyethyl phosphate triesters. A simple one-step synthetic strategy provided a network containing phosphate triesters with a pendant hydroxyethyl group. 31P solid-state NMR demonstrated that a cyclic phosphate triester is an intermediate in transesterification, leading to dissociative network rearrangement. Significant viscous flow at 60-100 °C makes the material suitable for fast processing via extrusion and compression molding.

Chain length of bioinspired polyamines affects size and condensation of monodisperse silica particles.

Polyamines play a major role in biosilicification reactions in diatoms and sponges. While the effects of polyamines on silicic acid oligomerization and precipitation are well known, the impact of polyamines chain length on silica particle growth is unclear. We studied the effects of polyamine chain length on silica particle growth and condensation in a known, simple, and salt-free biphasic reaction system; with tetraethyl orthosilicate as organic phase and polyamine dissolved in the aqueous phase. The particles at various growth stages were characterized by Cryo- Transmission Electron Microscopy, Scanning Electron Microscopy, Thermogravimetric Analysis, Zeta Potential, and solid-state NMR analysis. Polyamines were found co-localized within silica particles and the particle diameter increased with an increase in polyamine chain length, whereas silica condensation showed the opposite trend. Particle growth is proposed to progress via a coacervate intermediate while the final particles have a core shell structure with an amine-rich core and silica-rich shell. The results presented in this paper would of interest for researchers working in the field of bioinspired materials.

In Situ Manipulation and Micromechanical Characterization of Diatom Frustule Constituents Using Focused Ion Beam Scanning Electron Microscopy.

Biocomposite structures are difficult to characterize by bulk approaches due to their morphological complexity and compositional heterogeneity. Therefore, a versatile method is required to assess, for example, the mechanical properties of geometrically simple parts of biocomposites at the relevant length scales. Here, it is demonstrated how a combination of Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) and micromanipulators can be used to isolate, transfer, and determine the mechanical properties of frustule constituents of diatom Thalassiosira pseudonana (T.p.). Specifically, two parts of the diatom frustule, girdle bands and valves, are separated by FIB milling and manipulated using a sharp tungsten tip without compromising their physical or chemical integrity. In situ mechanical studies on isolated girdle bands combined with Finite Element Method (FEM) simulations, enables the quantitative assessment of the Young's modulus of this biosilica; E = 40.0 GPa. In addition, the mechanical strength of isolated valves could be measured by transferring and mounting them on top of premilled holes in the sample support. This approach may be extended to any hierarchical biocomposite material, regardless of its chemical composition, to isolate, transfer, and investigate the mechanical properties of selected constituents or specific regions.

Intramolecularly Catalyzed Dynamic Polyester Networks Using Neighboring Carboxylic and Sulfonic Acid Groups.

Dynamic covalent bonds in a polymer network lead to plasticity, reshapability, and potential recyclability at elevated temperatures in combination with solvent-resistance and better dimensional stability at lower temperatures. Here we report a simple one-step procedure for the catalyst-free preparation and intramolecularly catalyzed stress-relaxation of dynamic polyester networks. The procedure is based on the coupling of branched OH-end functional polyesters (functionality ≥ 3) by pyromellitic dianhydride (PMDA) or 2,5-bis(methoxy-carbonyl) benzenesulfonic acid resulting in ester linkages with, respectively, a COOH or a SO3H group in a position ortho to the ester bond. This approach leads to an efficient external catalyst-free dynamic polyester network, in which the topology rearrangements occur via a dissociative mechanism involving anhydrides. The SO3H-containing network is particularly interesting, as it shows the fastest stress relaxation and does not suffer from unwanted additional transesterification reactions, as was observed in the COOH-containing network.

Phosphate Triester Dynamic Covalent Networks.

Dynamic covalent networks are a class of polymeric materials that combine the merits of classical thermosets and thermoplastics, in terms of mechanical properties and reprocessability, in one material. Various dynamic covalent chemistries have thus been implemented in polymeric materials with recent interests shifting toward chemistries that would allow rearrangements in network topology without the aid of external catalysts. Here we introduce transesterification in phosphate triesters as a new dynamic covalent chemistry in polymeric networks. A simple one-step synthetic strategy has been utilized to synthesize polytetrahydrofuran networks with phosphate triester cross-links. The materials showed finite viscous flow at elevated temperatures via transesterification at the cross-links without externally added catalyst. This approach provides an easy method for cross-linking OH-end-functionalized polyethers and has the potential for general use with other OH-functionalized polymers.

Modifying the thickness, pore size, and composition of diatom frustule in Pinnularia sp. with Al3+ ions.

Diatoms are unicellular photosynthetic algae that produce a silica exoskeleton (frustule) which exposes a highly ordered nano to micro scale morphology. In recent years there has been a growing interest in modifying diatom frustules for technological applications. This is achieved by adding non-essential metals to the growth medium of diatoms which in turn modifies morphology, composition, and resulting properties of the frustule. Here, we investigate the frustule formation in diatom Pinnularia sp., including changes to overall morphology, silica thickness, and composition, in the presence of Al3+ ions at different concentrations. Our results show that in the presence of Al3+ the total silica uptake from the growth medium increases, although a decrease in the growth rate is observed. This leads to a higher inorganic content per diatom resulting in a decreased pore diameter and a thicker frustule as evidenced by electron microscopy. Furthermore, 27Al solid-state NMR, FIB-SEM, and EDS results confirm that Al3+ becomes incorporated into the frustule during the silicification process, thus, improving hydrolysis resistance. This approach may be extended to a broad range of elements and diatom species towards the scalable production of silica materials with tunable hierarchical morphology and chemical composition.

Water Swelling Behavior of Poly(ethylene glycol)-Based Polyurethane Networks.

Defects in a polymer network complicate an accurate calculation of structural parameters such as the molar mass between cross-links M c, typically obtained from experimental swelling data. In this paper the formation and structure of poly(ethylene glycol) (PEG)-based polyurethane networks containing PEG-mono methyl ether dangling chains are studied. The phantom network model can describe the swelling behavior of these networks only when a composition-dependent interaction parameter is used and the formation of allophanates is accounted for. A clear transition in the network formation is found at the PEG network precursor molar mass at which entanglements are formed in the melt. Correction factors based on structure calculations using the Miller-Macosko-Vallés probability approach are proposed and validated for an accurate calculation of the M c of these defect-containing networks. This provides a new approach for studies that requires an accurate estimate of the M c, only based on experimentally straightforward swelling experiments.

Isocyanate-Free Approach to Water-Borne Polyurea Dispersions and Coatings.

Here, an isocyanate-free approach to produce polyureas from diamines and dicarbamates as monomers is reported. A side reaction limiting the molecular weight during the diamine/ dicarbamate polymerization, that is, N-alkylation of amine end groups, is investigated. Mitigation of the N-alkylation, either by enhancing the carbamate aminolysis rate or by substitution of dimethylcarbamates with more sterically hindered diethylcarbamates, affords polyureas with sufficiently high molecular weights to assure satisfactory mechanical properties. Stable polyurea dispersions with polyamines as internal dispersing agents are prepared, and the properties of the corresponding coatings are evaluated.

Enhancing the functionality of biobased polyester coating resins through modification with citric acid.

Citric acid (CA) was evaluated as a functionality-enhancing monomer in biobased polyesters suitable for coating applications. Model reactions of CA with several primary and secondary alcohols and diols, including the 1,4:3,6-dianhydrohexitols, revealed that titanium(IV) n-butoxide catalyzed esterification reactions involving these compounds proceed at relatively low temperatures, often via anhydride intermediates. Interestingly, the facile anhydride formation from CA at temperatures around CA's melting temperature ( T m = 153 degrees C) proved to be crucial in modifying sterically hindered secondary hydroxyl end groups. OH-functional polyesters were reacted with CA in the melt between 150 and 165 degrees C, yielding slightly branched carboxylic acid functional materials with strongly enhanced functionality. The acid/epoxy curing reaction of the acid-functional polymers was simulated with a monofunctional glycidyl ether. Finally, the CA-modified polyesters were applied as coatings, using conventional cross-linking agents. The formulations showed rapid curing, resulting in chemically and mechanically stable coatings. These results demonstrate that citric acid can be applied in a new way, making use of its anhydride formation to functionalize OH-functional polyesters, which is an important new step toward fully biobased coating systems.

Unique Base-Initiated Depolymerization of Limonene-Derived Polycarbonates.

The depolymerization of poly(limonene carbonate) (PLC) initiated by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was investigated. The strong organic base TBD was capable of deprotonating the OH-terminated PLC, leading to fast degradation via backbiting reactions at high temperature. An interesting feature of the base-initiated breakdown of PLC lies in the quantitative depolymerization into the corresponding initial limonene oxide monomer. This result implies the complete back-to-monomer recyclability of the fully biobased PLC, which accordingly can be considered as a really sustainable material. Additionally, the stability of PLC when exposed to TBD was enhanced by an end-capping reaction, which further supported the proposed degradation pathway.