Emma-Rose Janeček

Hybrid Supramolecular and Colloidal Hydrogels that Bridge Multiple Length Scales

Hybrid nanocomposites were constructed based on colloidal nanofibrillar hydrogels with interpenetrating supramolecular hydrogels, displaying enhanced rheological yield strain and a synergistic improvement in storage modulus. The supramolecular hydrogel consists of naphthyl-functionalized hydroxyethyl cellulose and a cationic polystyrene derivative decorated with methylviologen moieties, physically cross-linked with cucurbit[8]uril macrocyclic hosts. Fast exchange kinetics within the supramolecular system are enabled by reversible cross-linking through the binding of the naphthyl and viologen guests. The colloidal hydrogel consists of nanofibrillated cellulose that combines a mechanically strong nanofiber skeleton with a lateral fibrillar diameter of a few nanometers. The two networks interact through hydroxyethyl cellulose adsorption to the nanofibrillated cellulose surfaces. This work shows methods to bridge the length scales of molecular and colloidal hybrid hydrogels, resulting in synergy between reinforcement and dynamics.

Multifunctional supramolecular polymer networks as next-generation consolidants for archaeological wood conservation

Significance The preservation of cultural heritage is of widespread importance all over the world. Yet the lack of development in the field of conservation treatments means the fate of some of the most culturally important artifacts in the world remain in jeopardy. In the preservation of waterlogged wooden artifacts, conservators rely almost exclusively on poly(ethylene glycol) doped with a broad-spectrum biocide. The concept of a chemotactic consolidant, one that can adapt to the artifact it is treating, as described here has never before been described for an archaeological/conservation treatment. Additionally, the cross-links holding the consolidant together are entirely reversible, resulting in a material that is a greener, safer, and sustainable alternative to current conservation strategies. The preservation of our cultural heritage is of great importance to future generations. Despite this, significant problems have arisen with the conservation of waterlogged wooden artifacts. Three major issues facing conservators are structural instability on drying, biological degradation, and chemical degradation on account of Fe3+-catalyzed production of sulfuric and oxalic acid in the waterlogged timbers. Currently, no conservation treatment exists that effectively addresses all three issues simultaneously. A new conservation treatment is reported here based on a supramolecular polymer network constructed from natural polymers with dynamic cross-linking formed by a combination of both host-guest complexation and a strong siderophore pendant from a polymer backbone. Consequently, the proposed consolidant has the ability to chelate and trap iron while enhancing structural stability. The incorporation of antibacterial moieties through a dynamic covalent linkage into the network provides the material with improved biological resistance. Exploiting an environmentally compatible natural material with completely reversible chemistries is a safer, greener alternative to current strategies and may extend the lifetime of many culturally relevant waterlogged artifacts around the world.

Nondestructive optical detection of monomer uptake in wood polymer composites

A noninvasive method to assess the local monomer concentration within a wooden matrix, post monomer impregnation, by time-resolved diffuse optical spectroscopy is demonstrated. A data analysis technique for improving accuracy, which takes account of changes in the refractive index during the monomer uptake, has been employed. This technique can be potentially applied in the wood industry for the study of polymer composites as well as in cultural heritage science for noninvasively monitoring the penetration of chemical compounds used for consolidation or conservation purposes.

Natural polymers as alternative consolidants for the preservation of waterlogged archaeological wood

In recent years, there has been increased interest in examining alternative polymers for the conservation of archaeological artefacts, particularly waterlogged timbers, providing better, renewable, greener alternatives to poly(ethylene glycol) (PEG). The degradation of PEG consolidants in the timbers of the sixteenth century warship Mary Rose has been examined and the rheological and thermal properties of PEG have been compared with its monomethyl and dimethyl ethers and several polysaccharide consolidants (chitosan, guar, and 2-hydroxyethyl cellulose) in order to evaluate their potential as alternative consolidants for the conservation of waterlogged wooden artefacts. Additionally, the effect of the polymers on the archaeological wood was characterised by thermogravimetric analysis and solid-state nuclear magnetic resonance spectroscopy. The results suggest that the future of conservation technologies lies with polysaccharide consolidant materials, which show enhanced compatibility with wooden artefacts with no detectable side effects while also being cheap, with extremely low toxicity, renewable, and sustainably resourced.

Single-molecule force spectroscopy quantification of adhesive forces in cucurbit[8]uril host-guest ternary complexes.

Cucurbit[8]uril (CB[8]) heteroternary complexes display certain characteristics making them well-suited for molecular level adhesives. In particular, careful choice of host-guest binding pairs enables specific, fully reversible adhesion. Understanding the effect of the environment is also critical when developing new molecular level adhesives. Here we explore the binding forces involved in the methyl viologen·CB[8]·naphthol heteroternary complex using single-molecule force spectroscopy (SMFS) under a variety of conditions. From SMFS, the interaction of a single ternary complex was found to be in the region of 140 pN. Additionally, a number of surface interactions could be readily differentiated using the SMFS technique allowing for a deeper understanding of the dynamic heteroternary CB[8] system on the single-molecule scale.

Distinguishing relaxation dynamics in transiently crosslinked polymeric networks

Polymeric materials based on reversible non-covalent associations possess diverse mechanical behaviour, responsiveness to external stimuli and self-healing properties. Unlike covalently-bonded polymeric materials, whose properties are conventionally engineered through the polymer structure alone, the mechanical performance of a supramolecular material can be designed via two motifs: the polymer architecture (e.g., polymer molecular weight or structure) and the physical crosslinks (e.g., thermodynamics or kinetics of binding) between polymers. Here, we demonstrate the preparation of aqueous-based supramolecular polymeric materials utilising cucurbit[8]uril (CB[8]) crosslinking of multivalent polymers of varying molecular weights. By exploiting three kinetically distinct supramolecular motifs, we show that it is possible to relate the contributions of polymer architecture and dynamic crosslinking to the ultimate mechanical properties of the materials. These studies improve our understanding of the challenging relationships between design of supramolecular polymeric materials and their complex viscoelastic behaviour as well as relaxation dynamics.

A Facile Route to Viologen Functional Macromolecules through Azide–Alkyne [3+2] Cycloaddition

Viologen end and side-chain functional macromolecules are synthesized through a high-yielding, copper-mediated azide-alkyne [3+2] cycloaddition reaction. Specifically, poly(ethylene glycol) (PEG) and the C-terminus of a model oligopeptide are quantitatively end-coupled to a viologen moiety as confirmed by (1) H NMR, gel permeation chromatography (GPC), and mass spectrometry (MS). Side-chain functionalization of a styrene backbone is also readily achieved forming a polyelectrolyte species and demonstrating the applicability of this method across a range of macromolecular species. It is found that viologen itself slows the reaction and that careful choice of counter ions, the specific chelating ligand for the copper-mediated reaction, solvent, as well as the amount of copper also play major roles in the time to completion of the reaction and hence the yield. Macromolecules formed through this route bind effectively with supramolecular host molecule cucurbit[8]uril allowing for controlled solution-phase self-assembly, for example of a supramolecular star polymer.

Chemical composition of processed bamboo for structural applications

Natural materials are a focus for development of low carbon products for a variety of applications. To utilise these materials, processing is required to meet acceptable industry standards. Laminated bamboo is a commercial product that is currently being explored for structural applications, however there is a gap in knowledge about the effects of commercial processing on the chemical composition. The present study utilised interdisciplinary methods of analysis to investigate the effects of processing on the composition of bamboo. Two common commercial processing methods were investigated: bleaching (chemical treatment) and caramelisation (hygrothermal treatment). The study indicated that the bleaching process results in a more pronounced degradation of the lignin in comparison to the caramelised bamboo. This augments previous research, which has shown that the processing method (strip size) and treatment may affect the mechanical properties of the material in the form of overall strength, failure modes and crack propagation. The study provides additional understanding of the effects of processing on the properties of bamboo.

Predicting the pore-filling ratio in lumen-impregnated wood

Lumen impregnation, unlike most other wood modification methods, is typically assessed by the pore-filling ratio (PFR) (i.e. the fraction of luminal porosity filled) rather than by weight percentage gain (WPG). During lumen impregnation, the impregnants act on the voids in the wood rather than on the solid mass (e.g. cell walls), but the PFR cannot be measured as conveniently as the WPG during processing. Here, it is demonstrated how the PFR can be calculated directly from the WPG if the bulk density of the untreated wood is known. The relationship between the WPG and bulk density was examined experimentally by applying a pressured impregnation on knot-free specimens from Sitka spruce with a liquid mixture of methacrylate monomers. Based on the validated model, it was possible to further study the effect of different process-related parameters, such as hydraulic pressure, on lumen impregnation. Skeletal density is another key parameter in this model, which directly reflects the amount of inaccessible pores and closed lumens, and can be independently determined by helium pycnometry. The permeability can be qualitatively evaluated by PFR as well as skeletal density. For instance, poor permeability of knotty wood, due to the large extractives content around knots, was reflected by a lower skeletal density and inefficient lumen impregnation (low PFR). Although this model was examined on a laboratory scale, it provides guidance on the precise effect of different parameters on lumen impregnation, thereby improving the fundamental understanding of and enabling better control over the modification of wood by impregnation.

Time-resolved laser spectroscopy for the in situ characterization of methacrylate monomer flow within spruce

Time-resolved diffuse optical spectroscopy (TRS) was investigated as a nondestructive method to characterize the post-impregnation distribution of methacrylate monomers within spruce (Picea abies). TRS was also used to monitor the flow of methacrylate monomers in situ, within spruce, during impregnation with both spatial and temporal resolution. The data were compared to fluid flow models developed by Darcy and Bramhall demonstrating that neither of these models were able to accurately describe the experimental results, highlighting the need for development of new models. Nondestructive characterization by TRS did not require staining of the monomer treatment solution, multivariate analysis or complex sample pre-treatment, thus highlighting the facile applicability of this technique.