Imaging with a twist: Three-dimensional insights of the chiral nematic phase of cellulose nanocrystals via SHG microscopy.

Cellulose nanocrystals (CNCs) are bio-based nanoparticles that, under the right conditions, self-align into chiral nematic liquid crystals with a helical pitch. In this work, we exploit the inherent confocal effect of second-harmonic generation (SHG) microscopy to acquire highly resolved three-dimensional (3D) images of the chiral nematic phase of CNCs in a label-free manner. An in-depth analysis revealed a direct link between the observed variations in SHG intensity and the pitch. The highly contrasted 3D images provided unprecedented detail into liquid crystal's native structure. Local alignment, morphology, as well as the presence of defects are readily revealed, and a provisional framework relating the SHG response to the orientational distribution of CNC nanorods within the liquid crystal structure is presented. This paper illustrates the numerous benefits of using SHG microscopy for visualizing CNC chiral nematic systems directly in the suspension-liquid phase and paves the road for using SHG microscopy to characterize other types of aligned CNC structures, in wet and dry states.

Optically Active, Paper-Based Scaffolds for 3D Cardiac Pacing.

In this work, we report the design and fabrication of a light-addressable, paper-based nanocomposite scaffold for optical pacing and read-out of in vitro grown cardiac tissue. The scaffold consists of paper cellulose microfibers functionalized with gold nanorods (GNRs) and semiconductor quantum dots (QDs), embedded in a cell-permissive collagen matrix. The GNRs enable cardiomyocyte activity modulation through local temperature gradients induced by modulated near-infrared (NIR) laser illumination, with the local temperature changes reported by temperature-dependent QD photoluminescence (PL). The micrometer-sized paper fibers promote the tubular organization of HL-1 cardiac muscle cells, while the NIR plasmonic stimulation modulates reversibly their activity. Given the nanoscale spatial resolution and facile fabrication, paper-based nanocomposite scaffolds with NIR modulation offer excellent alternatives to electrode-based or optogenetic methods for cell activity modulation, at the single cell level, and are compatible with 3D tissue constructs. Such paper-based optical platforms can provide new possibilities for the development of in vitro drug screening assays and heart disease modeling.

Advancing plant cell wall modelling: Atomistic insights into cellulose, disordered cellulose, and hemicelluloses - A review.

The complexity of plant cell walls on different hierarchical levels still impedes the detailed understanding of biosynthetic pathways, interferes with processing in industry and finally limits applicability of cellulose materials. While there exist many challenges to readily accessing these hierarchies at (sub-) angström resolution, the development of advanced computational methods has the potential to unravel important questions in this field. Here, we summarize the contributions of molecular dynamics simulations in advancing the understanding of the physico-chemical properties of natural fibres. We aim to present a comprehensive view of the advancements and insights gained from molecular dynamics simulations in the field of carbohydrate polymers research. The review holds immense value as a vital reference for researchers seeking to undertake atomistic simulations of plant cell wall constituents. Its significance extends beyond the realm of molecular modeling and chemistry, as it offers a pathway to develop a more profound comprehension of plant cell wall chemistry, interactions, and behavior. By delving into these fundamental aspects, the review provides invaluable insights into future perspectives for exploration. Researchers within the molecular modeling and carbohydrates community can greatly benefit from this resource, enabling them to make significant strides in unraveling the intricacies of plant cell wall dynamics.

The comparative toxicity of biobased, modified biobased, biodegradable, and petrochemical-based microplastics on the brackish water flea Diaphanosoma celebensis.

The escalating production and improper disposal of petrochemical-based plastics have led to a global pollution issue with microplastics (MPs), which pose a significant ecological threat. Biobased and biodegradable plastics are believed to mitigate plastic pollution. However, their environmental fate and toxicity remain poorly understood. This study compares the in vivo effects of different types of MPs, poly(butylene adipate-co-terephthalate) as a biodegradable plastic, polylactic acid (PLA) as a biobased plastic, ß-cyclodextrin-grafted PLA as a modified biobased plastic, and low density polyethylene as the reference petrochemical-based plastic, on the key aquatic primary consumer Diaphanosoma celebensis. Exposure to MPs resulted in significant reproductive decline, with comparable effects observed irrespective of MP type or concentration. Exposure to MPs induced distinct responses in redox stress, with transcriptional profiling revealing differential gene expression patterns that indicate varied cellular responses to different types of MPs. ATP-binding cassette transporter activity assays demonstrated altered efflux activity, mainly in response to modified biobased and biodegradable MPs. Overall, this study highlights the comparable in vivo and in vitro effects of biobased, biodegradable, and petrochemical-based MPs on aquatic primary consumers, highlighting their potential ecological implications.

Peptide Sequence Variations Govern Hydrogel Stiffness: Insights from a Multi-Scale Structural Analysis of H-FQFQFK-NH2 Peptide Derivatives.

Throughout the past decades, amphipathic peptide-based hydrogels have proven to be promising materials for biomedical applications. Amphipathic peptides are known to adopt ß-sheet configurations that self-assemble into fibers that then interact to form a hydrogel network. A fundamental understanding of how the peptide sequence alters the structural properties of the hydrogels would allow for a more rational design of novel peptides for a variety of biomedical applications in the future. Therefore, the current work investigates how changing the type of amino acid, the amphipathic pattern, and the peptide length affects the secondary structure, fiber characteristics, and stiffness of peptide-based hydrogels. Hereto, seven amphipathic peptides of different sequence and length, four of which have not been previously reported, based on and including the hexapeptide H-Phe-Gln-Phe-Gln-Phe-Lys-NH2, are synthesized and thoroughly characterized by circular dichroism (CD), Fourier Transform Infrared (FTIR) spectroscopy, Wide Angle X-ray Scattering (WAXS), Small Angle X-ray Scattering (SAXS), Transmission Electron Microscopy (TEM), and Thioflavin T (ThT) fibrillization assays. The results show that a high amount of regularly spaced ß-sheets, a high amount of fibers, and fiber bundling contribute to the stiffness of the hydrogel. Furthermore, a study of the time-dependent fibril formation process reveals complex transient dynamics. The peptide strands structure through an intermediate helical state prior to ß-sheet formation, which is found to be concentration- and time-dependent.

Dimensions of Cellulose Nanocrystals from Cotton and Bacterial Cellulose: Comparison of Microscopy and Scattering Techniques.

Different microscopy and scattering methods used in the literature to determine the dimensions of cellulose nanocrystals derived from cotton and bacterial cellulose were compared to investigate potential bias and discrepancies. Atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), depolarized dynamic light scattering (DDLS), and static light scattering (SLS) were compared. The lengths, widths, and heights of the particles and their respective distributions were determined by AFM. In agreement with previous work, the CNCs were found to have a ribbon-like shape, regardless of the source of cellulose or the surface functional groups. Tip broadening and agglomeration of the particles during deposition cause AFM-derived lateral dimensions to be systematically larger those obtained from SAXS measurements. The radius of gyration determined by SLS showed a good correlation with the dimensions obtained by AFM. The hydrodynamic lateral dimensions determined by DDLS were found to have the same magnitude as either the width or height obtained from the other techniques; however, the precision of DDLS was limited due to the mismatch between the cylindrical model and the actual shape of the CNCs, and to constraints in the fitting procedure. Therefore, the combination of AFM and SAXS, or microscopy and small-angle scattering, is recommended for the most accurate determination of CNC dimensions.

Thermodynamics of interactions between cellulose nanocrystals and monovalent counterions.

Alkali and quaternary ammonium cations interact with negatively charged cellulose nanocrystals (CNCs) bearing sulfated or carboxylated functional groups. As these are some of the most commonly occurring cations CNC encounter in applications, the thermodynamic parameters of these CNC-counterion interactions were evaluated with isothermal titration calorimetry (ITC). Whereas the adsorption of monovalent counterions onto CNCs was thermodynamically favourable at all evaluated conditions as indicated by a negative Gibbs free energy, the enthalpic and entropic contributions to the CNC-ion interactions were found to be strongly dependent on the hydration characteristics of the counterion and could be correlated with the potential barrier to water exchange of the respective ions. The adsorption of chaotropic cations onto the surface was exothermic, while the interactions with kosmotropic cations were endothermic and completely entropy-driven. The interactions of CNCs with more bulky quaternary ammonium counterions were more complex, and the mechanism of interaction shifted from electrostatic interactions with surface charged groups of CNCs towards adsorption of alkyl chains onto the CNC hydrophobic planes when the alkyl chain length increased.

Covalent immobilization of N-heterocyclic carbenes on pristine carbon substrates: from nanoscale characterization to bulk catalysis.

To control the synthesis of designer catalysts on graphitic materials up to the nanometer scale, methods should be provided that combine both nanoscale characterization and bulk scale experiments. This work reports the grafting of N-heterocyclic carbene (NHC)-type catalysts on graphite, both at nanometer and bulk scale, as it allows increased insights into the nature of the immobilized catalysts.

Heterogeneous Pt-catalyzed transfer dehydrogenation of long-chain alkanes with ethylene.

The dehydrogenation of long-chain alkanes to olefins and alkylaromatics is a challenging endothermic reaction, typically requiring harsh conditions which can lead to low selectivity and coking. More favorable thermodynamics can be achieved by using a hydrogen acceptor, such as ethylene. In this work, the potential of heterogeneous platinum catalysts for the transfer dehydrogenation of long-chain alkanes is investigated, using ethylene as a convenient hydrogen acceptor. Pt/C and Pt-Sn/C catalysts were prepared via a simple polyol method and characterized with CO pulse chemisorption, HAADF-STEM, and EDX measurements. Conversion of ethylene was monitored via gas-phase FTIR, and distribution of liquid products was analyzed via GC-FID, GC-MS, and 1H-NMR. Compared to unpromoted Pt/C, Sn-promoted catalysts show lower initial reaction rates, but better resistance to catalyst deactivation, while increasing selectivity towards alkylaromatics. Both reaction products and ethylene were found to inhibit the reaction significantly. At 250 °C for 22 h, TON up to 28 and 86 mol per mol Pt were obtained for Pt/C and PtSn2/C, respectively, with olefin selectivities of 94% and 53%. The remaining products were mainly unbranched alkylaromatics. These findings show the potential of simple heterogeneous catalysts in alkane transfer dehydrogenation, for the preparation of valuable olefins and alkylaromatics, or as an essential step in various tandem reactions.

Gamma radiation effects on AG MP-50 cation exchange resin and sulfonated activated carbon for bismuth-213 separation.

Medical 225Ac/213Bi radionuclide generators are designed to provide a local supply of the short-lived 213Bi for cancer treatment. However, radiation-induced damage to the sorbents commonly used in such radionuclide generators remains a major concern. In this study, the effects of gamma radiation on AG MP-50 cation exchange resin and sulfonated activated carbon (SAC) were studied by analyzing the changes in the morphological characteristics, functional groups, and the La3+/Bi3+ sorption performance, with La3+ being a suitable non-radioactive substitute for Ac3+. The surface sulfonic acid groups of AG MP-50 resin suffered from severe radiation-induced degradation, while the particle morphology was changed markedly after being exposed to absorbed doses of approximately 11 MGy. As a result, the sorption performance of irradiated AG MP-50 for La3+ and Bi3+ was significantly decreased with increasing absorbed doses. In contrast, no apparent changes in acquired morphological characteristics were observed for pristine and irradiated SAC based on SEM and XRD characterization. The surface oxygen content (e.g., O-C[double bond, length as m-dash]O) of irradiated SAC increased for an absorbed dose of 11 MGy due to free radical-induced oxidation. The sorption performance of pristine and irradiated SAC materials for La3+ and Bi3+ remained generally the same at pH values of 1 and 2. Furthermore, the applicability of AG MP-50 and SAC in the 225Ac/213Bi generators was illustrated in terms of their radiolytic stability. This study provides further evidence for the practical implementation of both AG MP-50 and SAC in 225Ac/213Bi radionuclide generators.

On the nucleation and fast reaction kinetics of 2D polymerisation with a 2-in-1 monomer.

We report on the fast reaction kinetics of an imine based 2D polymer (2DP) formed from a single monomer carrying both aldehyde and amine groups. Our results point towards a direct monomer-to-crystalline polymer transition without an amorphous intermediate.

Review on the Degradation of Poly(lactic acid) during Melt Processing.

This review paper presents an overview of the state of the art on process-induced degradation of poly(lactic acid) (PLA) and the relative importance of different processing variables. The sensitivity of PLA to degradation, especially during melt processing, is considered a significant challenge as it may result in deterioration of its properties. The focus of this review is on degradation during melt processing techniques such as injection molding and extrusion, and therefore it does not deal with biodegradation. Firstly, the general processing and fundamental variables that determine the degradation are discussed. Secondly, the material properties (for example rheological, thermal, and mechanical) are presented that can be used to monitor and quantify the degradation. Thirdly, the effects of different processing variables on the extent of degradation are reviewed. Fourthly, additives are discussed for melt stabilization of PLA. Although current literature reports the degradation reactions and clearly indicates the effect of degradation on PLA's properties, there are still knowledge gaps in how to select and predict the processing conditions that minimize process-induced degradation to save raw materials and time during production.

Phase behavior of medium-length hydrophobically associating PEO-PPO multiblock copolymers in aqueous media.

HYPOTHESIS: The micellization of block copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) is driven by the dehydration of PPO at elevated temperatures. At low concentrations, a viscous solution of isolated micelles is obtained, whereas at higher concentrations, crowding of micelles results in an elastic gel. Alternating PEO-PPO multiblock copolymers are expected to exhibit different phase behavior, with altered phase boundaries and thermodynamics, as compared to PEO-PPO-PEO triblock copolymers (Pluronics®) with equal hydrophobicity, thereby proving the pivotal role of copolymer architecture and molecular weight. EXPERIMENTS: Multiple characterization techniques were used to map the phase behavior as a function of temperature and concentration of PEO-PPO multiblock copolymers (ExpertGel®) in aqueous solution. These techniques include shear rheology, differential and adiabatic scanning calorimetry, isothermal titration calorimetry and light transmittance. The micellar size and topology were studied by dynamic light scattering. FINDINGS: Multiblocks have lower transition temperatures and higher thermodynamic driving forces for micellization as compared to triblocks due to the presence of more than one PPO block per chain. With increasing concentration, the multiblock copolymers in solution gradually evolve into a viscoelastic network formed by soluble bridges in between micellar nodes, whereas hairy triblock micelles jam into liquid crystalline phases resembling an elastic colloidal crystal.

Sulfobetaine-based ultrathin coatings as effective antifouling layers for implantable neuroprosthetic devices.

Foreign body response (FBR), inflammation, and fibrotic encapsulation of neural implants remain major problems affecting the impedance of the electrode-tissue interface and altering the device performance. Adhesion of proteins and cells (e.g., pro-inflammatory macrophages, and fibroblasts) triggers the FBR cascade and can be diminished by applying antifouling coatings onto the implanted devices. In this paper, we report the deposition and characterization of a thin (±6 nm) sulfobetaine-based coating onto microfabricated platinum electrodes and cochlear implant (CI) electrode arrays. We found that this coating has stable cell and protein-repellent properties, for at least 31 days in vitro, not affected by electrical stimulation protocols. Additionally, its effect on the electrochemical properties relevant to stimulation (i.e., impedance, charge injection capacity) was negligible. When applied to clinical CI electrode arrays, the film was successful at inhibiting fibroblast adhesion on both the silicone packaging and the platinum/iridium electrodes. In vitro, in fibroblast cultures, coated CI electrode arrays maintained impedance values up to five times lower compared to non-coated devices. Our studies demonstrate that such thin sulfobetaine containing layers are stable and prevent protein and cell adhesion in vitro and are compatible for use on CI electrode arrays. Future in vivo studies should be conducted to investigate its ability to mitigate biofouling, fibrosis, and the resulting impedance changes upon long-term implantation in vivo.

Metal Ion and Guest-Mediated Spontaneous Resolution and Solvent-Induced Chiral Symmetry Breaking in Guanine-Based Metallosupramolecular Networks.

Two-dimensional (2D) chirality has been actively studied in view of numerous applications of chiral surfaces such as in chiral resolutions and enantioselective catalysis. Here, we report on the expression and amplification of chirality in hybrid 2D metallosupramolecular networks formed by a nucleobase derivative. Self-assembly of a guanine derivative appended with a pyridyl node was studied at the solution-graphite interface in the presence and absence of coordinating metal ions. In the absence of coordinating metal ions, a monolayer that is representative of a racemic compound was obtained. This system underwent spontaneous resolution upon addition of a coordinating ion and led to the formation of a racemic conglomerate. The spontaneous resolution could also be achieved upon addition of a suitable guest molecule. The mirror symmetry observed in the formation of the metallosupramolecular networks could be broken via the use of an enantiopure solvent, which led to the formation of a globally homochiral surface.

Efficient Depolymerization of Glass Fiber Reinforced PET Composites.

The transition to an eco-friendly circular materials system for garbage collected after use from end-users is a serious matter of concern for current society. One important tool in this challenge to achieve a truly circular economy is the chemical recycling of polymers. It has previously been demonstrated that chemical recycling is a feasible alternative to reach carbon circularity, which promotes the maximization of carbon recovery through all possible means. Among the advantages of chemical recycling, one must highlight its ability to selectively attack one or several target functionalities inside a complex mixed stream of polymers to obtain pure monomers, which can then be used to prepare virgin-like polymers as a final product. In previous works from our group, we used a microwave-heated potassium hydroxide in methanol (KMH) system to instantaneously depolymerize PET bottles. The KMH system was also effective for polycarbonate (PC), and intimately mixed PET/PC blends. In the present study, glass fiber reinforced (GFR) PET composites were submitted to depolymerization using the KMH system, and it was verified that more strict conditions were required for full depolymerization of GFR pellets than for pure PET pellets. Evidence of the reorganization of PET chains leading to increased crystallinity were obtained through DSC and WAXD. Surface adhesion of PET and crystallization onto glass fibers led to a different crystalline phase that seems to be more protected against the depolymerization solution, thus increasing the time required for full depolymerization when compared to unreinforced PET. An activation energy of 123 kJ/mol was estimated, in the same range of pristine PET pellets and PET bottles. The optimization of depolymerization conditions permitted 100% depolymerization within 5 min of reaction at 120 °C using 30 mL of KMH solution per g of composite. The green chemistry metrics reflect that our system is more efficient than most of the depolymerization systems found in the literature. The optimal depolymerization conditions here reported for GFR PET composites represent another step towards a total recycling system that includes not only pure polymers but also composites, commonly present in daily life.

Adsorptive separation using self-assembly on graphite: from nanoscale to bulk processes.

Adsorptive separation is a promising lower-energy alternative for traditional industrial separation processes. While carbon-based materials have a long history in adsorptive removal of organic contaminants from solution or gas mixtures, separation using an adsorption/desorption protocol is rarely considered. The main drawbacks are the limited control in bulk adsorption experiments, as often all organic molecules are adsorbed, and lack of desorption methods to retrieve the adsorbed molecules. Using high-resolution on-surface characterization with scanning tunneling microscopy (STM), an increased understanding of the on-surface adsorption behavior under different conditions was obtained. The insight obtained from the nanoscale experiments was used to develop a highly selective separation method using adsorption and desorption on graphite, which was tested for the separation of quinonoid zwitterions. These experiments on adsorptive separation using self-assembly on graphite show its potential and demonstrate the advantage of combining surface characterization techniques with bulk experiments to exploit different possible applications of carbon-based materials.

Highly regioselective surface acetylation of cellulose and shaped cellulose constructs in the gas-phase.

Gas-phase acylation is an attractive and sustainable method for modifying the surface properties of cellulosics. However, little is known concerning the regioselectivity of the chemistry, i.e., which cellulose hydroxyls are preferentially acylated and if acylation can be restricted to the surface, preserving crystallinities/morphologies. Consequently, we reexplore simple gas-phase acetylation of modern-day cellulosic building blocks - cellulose nanocrystals, pulps, dry-jet wet spun (regenerated cellulose) fibres and a nanocellulose-based aerogel. Using advanced analytics, we show that the gas-phase acetylation is highly regioselective for the C6-OH, a finding also supported by DFT-based transition-state modelling on a crystalloid surface. This contrasts with acid- and base-catalysed liquid-phase acetylation methods, highlighting that gas-phase chemistry is much more controllable, yet with similar kinetics, to the uncatalyzed liquid-phase reactions. Furthermore, this method preserves both the native (or regenerated) crystalline structure of the cellulose and the supramolecular morphology of even delicate cellulosic constructs (nanocellulose aerogel exhibiting chiral cholesteric liquid crystalline phases). Due to the soft nature of this chemistry and an ability to finely control the kinetics, yielding highly regioselective low degree of substitution products, we are convinced this method will facilitate the rapid adoption of precisely tailored and biodegradable cellulosic materials.

Cellulose nanocrystals modification by grafting from ring opening polymerization of a cyclic carbonate.

Surface modification of cellulose nanocrystals (CNC) by organocatalysed grafting from ring-opening polymerization (ROP) of trimethylene carbonate was investigated. Organocatalysts including an amidine (DBU), a guanidine (TBD), an amino-pyridine (DMAP) and a phosphazene (BEMP) were successfully assessed for this purpose, with performances in the order TBD > BEMP > DMAP, DBU. The grafting ratio can be tuned by varying the experimental parameters, with the highest grafting of 74 % by weight obtained under mild conditions, i.e at room temperature in tetrahydrofuran with a low amount of catalyst. This value is much higher than that of typical ring opening polymerizations of cyclic esters initiated from the surface of cellulose nanoparticles. Additionally, DSC analysis of the modified material revealed the presence of a glass transition temperature, indicative of a sufficient graft length to display polymeric behaviour. This is, to our knowledge, the first example of cellulose nanocrystals grafted with polycarbonate chains.

Stress-controlled shear flow alignment of collagen type I hydrogel systems.

Disease research and drug screening platforms require in vitro model systems with cellular cues resembling those of natural tissues. Fibrillar alignment, occurring naturally in extracellular matrices, is one of the crucial attributes in tissue development. Obtaining fiber alignment in 3D, in vitro remains an important challenge due to non-linear material characteristics. Here, we report a cell-compatible, shear stress-based method allowing to obtain 3D homogeneously aligned fibrillar collagen hydrogels. Controlling the shear-stress during gelation results in low strain rates, with negligible effects on the viability of embedded SH-SY5Y cells. Our approach offers reproducibility and tunability through a paradigm shift: The shear-stress initiation moment, being the critical optimization parameter in the process, is related to the modulus of the developing gel, whereas state of the art methods often rely on a predefined time to initiate the alignment procedure. After curing, the induced 3D alignment is maintained after the release of stress, with a linear relation between the total acquired strain and the fiber alignment. This method is generally applicable to 3D fibrillar materials and stress/pressure-controlled setups, making it a valuable addition to the fast-growing field of tissue engineering. STATEMENT OF SIGNIFICANCE: Controlling fiber alignment in vitro 3D hydrogels is crucial for developing physiologically relevant model systems. However, it remains challenging due to the non-linear material characteristics of fibrillar hydrogels, limiting the scalability and repeatability. Our approach tackles these challenges by utilizing a stress-controlled rheometer allowing us to monitor structural changes in situ and determine the optimal moment for applying a shear-stress inducing alignment. By careful parameter control, we infer the relationship between time, induced strain, alignment and biocompatibility. This tunable and reproducible method is both scalable and generally applicable to any fibrillar hydrogel, therefore, we believe it is useful for research investigating the link between matrix anisotropy and cell behavior in 3D systems, organ-on-chip technologies and drug research.