Properties and Curing Kinetics of a Processable Binary Benzoxazine Blend.

A benzoxazine system is presented combining liquid cardanol-based benzoxazine (CA-a) and an effective initiator (3,3'-thiodipropionic acid, TDA) to bisphenol A-based benzoxazine (BA-a). The resultant mixture of monomeric precursors shows excellent fluidity and a relatively low peak polymerization temperature of around 200 °C. Moreover, the cured polybenzoxazine displays a high thermal decomposition temperature (Td,5% > 330 °C), a moderately high glass transition temperature (∼148 °C), and robust mechanical strength (storage modulus ∼ 2.8 GPa) comparable to those of the polybenzoxazine homopolymer obtained by curing BA-a. A comprehensive investigation into the microstructure and curing kinetics has also been conducted on the system, offering an extensive background for future studies.

A Photo-degradable Crosslinker for the Development of Light-responsive Protocell Membranes.

The achievement of light-responsive behaviours is an important target for protocell engineering to allow control of fundamental protocellular processes such as communication via diffusible chemical signals, shape changes or even motility at the flick of a switch. As a step towards this ambitious goal, here we describe the synthesis of a novel poly(ethylene glycol)-based crosslinker, reactive towards nucleophiles, that effectively degrades with UV light (405 nm). We demonstrate its utility for the fabrication of the first protocell membranes capable of light-induced disassembly, for the photo-generation of patterns of protocells, and for the modulation of protocell membrane permeability. Overall, our results not only open up new avenues towards the engineering of spatially organised, communicating networks of protocells, and of micro-compartmentalised systems for information storage and release, but also have important implications for other research fields such as drug delivery and soft materials chemistry.

Automated analysis of soft material microindentation.

An understanding of the mechanical properties of soft hydrogel materials over multiple length scales is important for their application in many fields. Typical measurement methods provide either bulk mechanical properties (compression, tensile, rheology) or probing of nano or microscale properties and heterogeneity (nanoindentation, AFM). In this work we demonstrate the complementarity of instrumented microindentation to these techniques, as it provides representative Young's moduli for soft materials with minimal influence of the experimental parameters chosen, and allows mechanical property mapping across macroscopic areas. To enable automated analysis of the large quantities of data required for these measurements, we develop a new fitting algorithm to process indentation data. This method allows for the determination of Young's moduli from imperfect data by automatic selection of a region of the indentation curve which does not display inelastic deformation or substrate effects. We demonstrate the applicability of our approach with a range of hydrogels, including materials with patterns and gradients in stiffness, and expect the techniques described here to be useful developments for the mechanical analysis of a wide range of soft and biological systems.

(Hydroxypropyl)methyl Cellulose-Chitosan Film as a Matrix for Lipase Immobilization-Part ΙΙ: Structural Studies.

The present work reports on the structural study of a film made of a hybrid blend of biopolymers used as an enzyme carrier. A cellulose derivative (HPMC) and chitosan (CS) were combined in order to formulate a film on which Mucor miehei lipase was immobilized. The film was successfully used as a biocatalyst; however, little is known about the structure of the system. Therefore, small-angle X-ray scattering, Fourier transform infrared spectroscopy (FTIR), optical microscopy, and scanning electron microscopy (SEM), as well as microindentation measurements, were used to shed light on the structure of the promising biocatalyst. Among the results, intermolecular hydrogen bonds were observed between the amide groups of the two polymers and the lipase. The presence of the enzyme does not seem to affect the mechanical properties of the matrix. The used film after 35 cycles of reaction seemed to be fatigued and had lost part of its humidity, explaining the reduction of the enzyme activity.

Quantification of Respirable Aerosol Particles from Speech and Language Therapy Exercises.

INTRODUCTION: Voice assessment and treatment involve the manipulation of all the subsystems of voice production, and may lead to production of respirable aerosol particles that pose a greater risk of potential viral transmission via inhalation of respirable pathogens (eg, SARS-CoV-2) than quiet breathing or conversational speech. OBJECTIVE: To characterise the production of respirable aerosol particles during a selection of voice assessment therapy tasks. METHODS: We recruited 23 healthy adult participants (12 males, 11 females), 11 of whom were speech-language pathologists specialising in voice disorders. We used an aerodynamic and an optical particle sizer to measure the number concentration and particle size distributions of respirable aerosols generated during a variety of voice assessment and therapy tasks. The measurements were carried out in a laminar flow operating theatre, with a near-zero background aerosol concentration, allowing us to quantify the number concentration and size distributions of respirable aerosol particles produced from assessment/therapy tasks studied. RESULTS: Aerosol number concentrations generated while performing assessment/therapy tasks were log-normally distributed among individuals with no significant differences between professionals (speech-language pathologists) and non-professionals or between males and females. Activities produced up to 32 times the aerosol number concentration of breathing and 24 times that of speech at 70-80 dBA. In terms of aerosol mass, activities produced up to 163 times the mass concentration of breathing and up to 36 times the mass concentration of speech. Voicing was a significant factor in aerosol production; aerosol number/mass concentrations generated during the voiced activities were 1.1-5 times higher than their unvoiced counterpart activities. Additionally, voiced activities produced bigger respirable aerosol particles than their unvoiced variants except the trills. Humming generated higher aerosol concentrations than sustained /a/, fricatives, speaking (70-80 dBA), and breathing. Oscillatory semi-occluded vocal tract exercises (SOVTEs) generated higher aerosol number/mass concentrations than the activities without oscillation. Water resistance therapy (WRT) generated the most aerosol of all activities, ∼10 times higher than speaking at 70-80 dBA and >30 times higher than breathing. CONCLUSIONS: All activities generated more aerosol than breathing, although a sizeable minority were no different to speaking. Larger number concentrations and larger particle sizes appear to be generated by activities with higher suspected airflows, with the greatest involving intraoral pressure oscillation and/or an oscillating oral articulation (WRT or trilling).

A comparison of respiratory particle emission rates at rest and while speaking or exercising.

Background: The coronavirus disease-19 (COVID-19) pandemic led to the prohibition of group-based exercise and the cancellation of sporting events. Evaluation of respiratory aerosol emissions is necessary to quantify exercise-related transmission risk and inform mitigation strategies. Methods: Aerosol mass emission rates are calculated from concurrent aerosol and ventilation data, enabling absolute comparison. An aerodynamic particle sizer (0.54-20 µm diameter) samples exhalate from within a cardiopulmonary exercise testing mask, at rest, while speaking and during cycle ergometer-based exercise. Exercise challenge testing is performed to replicate typical gym-based exercise and very vigorous exercise, as determined by a preceding maximally exhaustive exercise test. Results: We present data from 25 healthy participants (13 males, 12 females; 36.4 years). The size of aerosol particles generated at rest and during exercise is similar (unimodal ~0.57-0.71 µm), whereas vocalization also generated aerosol particles of larger size (i.e. was bimodal ~0.69 and ~1.74 µm). The aerosol mass emission rate during speaking (0.092 ng s-1; minute ventilation (VE) 15.1 L min-1) and vigorous exercise (0.207 ng s-1, p = 0.726; VE 62.6 L min-1) is similar, but lower than during very vigorous exercise (0.682 ng s-1, p < 0.001; VE 113.6 L min-1). Conclusions: Vocalisation drives greater aerosol mass emission rates, compared to breathing at rest. Aerosol mass emission rates in exercise rise with intensity. Aerosol mass emission rates during vigorous exercise are no different from speaking at a conversational level. Mitigation strategies for airborne pathogens for non-exercise-based social interactions incorporating vocalisation, may be suitable for the majority of exercise settings. However, the use of facemasks when exercising may be less effective, given the smaller size of particles produced.

Comparing aerosol number and mass exhalation rates from children and adults during breathing, speaking and singing.

Aerosol particles of respirable size are exhaled when individuals breathe, speak and sing and can transmit respiratory pathogens between infected and susceptible individuals. The COVID-19 pandemic has brought into focus the need to improve the quantification of the particle number and mass exhalation rates as one route to provide estimates of viral shedding and the potential risk of transmission of viruses. Most previous studies have reported the number and mass concentrations of aerosol particles in an exhaled plume. We provide a robust assessment of the absolute particle number and mass exhalation rates from measurements of minute ventilation using a non-invasive Vyntus Hans Rudolf mask kit with straps housing a rotating vane spirometer along with measurements of the exhaled particle number concentrations and size distributions. Specifically, we report comparisons of the number and mass exhalation rates for children (12-14 years old) and adults (19-72 years old) when breathing, speaking and singing, which indicate that child and adult cohorts generate similar amounts of aerosol when performing the same activity. Mass exhalation rates are typically 0.002-0.02 ng s-1 from breathing, 0.07-0.2 ng s-1 from speaking (at 70-80 dBA) and 0.1-0.7 ng s-1 from singing (at 70-80 dBA). The aerosol exhalation rate increases with increasing sound volume for both children and adults when both speaking and singing.

Design and Control of Perylene Supramolecular Polymers through Imide Substitutions.

The number and type of new supramolecular polymer (SMP) systems have increased rapidly in recent years. Some of the key challenges faced for these novel systems include gaining full control over the mode of self-assembly, the creation of novel architectures and exploring functionality. Here, we provide a critical overview of approaches related to perylene-based SMPs and discuss progress to exert control over these potentially important SMPs through chemical modification of the imide substituents. Imide substitutions affect self-assembly behaviour orthogonally to the intrinsic optoelectronic properties of the perylene core, making for a valuable approach to tune SMP properties. Several recent approaches are therefore highlighted, with a focus on controlling 1) morphology, 2) H- or J- aggregation, and 3) mechanism of growth and degree of aggregation using thermodynamic and kinetic control. Areas of potential future exploration and application of these functional SMPs are also explored.

Molecular engineering of polymeric supra-amphiphiles.

Polymeric supra-amphiphiles are amphiphiles that are fabricated by linking polymeric segments, or small molecules and polymeric segments, by noncovalent interactions or dynamic covalent bonds. Compared with conventional amphiphilic polymers, polymeric supra-amphiphiles are advantageous in that they possess dynamic features and their preparation may be to some extent more facile. Moreover, polymeric supra-amphiphiles are endowed with richer structure and higher stability compared with small-molecule supra-amphiphiles. Owing to these properties, polymeric supra-amphiphiles have so far shown great promise as surfactants, nanocarriers and in therapies. In this tutorial review, recent work on polymeric supra-amphiphiles, from molecular architectures to functional assemblies, is presented and summarized. Different polymeric supra-amphiphile topologies and related applications are highlighted. By combining polymer chemistry with supramolecular chemistry and colloid science, we anticipate that the study of polymeric supra-amphiphiles will promote the continued development of the molecular engineering of functional supramolecular systems, and lead to practical applications, especially in drug delivery.

Living Supramolecular Polymerisation of Perylene Diimide Amphiphiles by Seeded Growth under Kinetic Control.

The controlled solution self-assembly of an amphiphilic perylene diimide (PDI), with a hydrophobic perylene core and hydrophilic imide substituents with polydisperse oligo(ethylene glycol) (OEG) tethers is presented. It was possible, by a seeded-growth mechanism, to form colloidally stable, one-dimensional fibres with controllable lengths (from 400 to 1700 nm) and low dispersities (1.19-1.29) via a living supramolecular polymerisation process. Under the solvent conditions used, it was found that molecularly dissolved material (unimer) was present in samples of the fibre-like supramolecular assemblies. The free unimer may be present in a conformationally derived kinetically trapped state and/or may represent a more soluble PDI fraction with longer hydrophilic tethers. Significantly, it was also possible to form segmented supramolecular block copolymers by the addition of PDI unimer to chemically distinct PDI seeds, yielding fibres with controlled lengths. These results represent a significant advance in the ability to form PDI-based supramolecular polymers with precisely controlled lengths and architectures.