Phosphonium versus Ammonium Compact Polyelectrolyte Complex Networks with Alginate-Comparing Their Properties and Cargo Encapsulation.

Phosphonium and ammonium polymers can be combined with polyanions to form polyelectrolyte complex (PEC) networks, with potential application in self-healing materials and drug delivery vehicles. While various structures and compositions have been explored, to the best of our knowledge, analogous ammonium and phosphonium networks have not been directly compared to evaluate the effects of phosphorus versus nitrogen cations on the network properties. In this study, we prepared PECs from sodium alginate and poly[triethyl(4-vinylbenzyl)phosphonium chloride], poly[triethyl(4-vinylbenzyl)ammonium chloride], poly[tri(n-butyl)(4-vinylbenzyl)phosphonium chloride], poly[tri(n-butyl)(4-vinylbenzyl)ammonium chloride], and poly[tris(hydroxypropyl)(4-vinylbenzyl)phosphonium chloride]. These networks were ultracentrifuged to form compact PECs (CoPECs), and their physical properties, chemical composition, and self-healing abilities were studied. In phosphate-buffered saline, the phosphonium polymer networks swelled to a higher degree than their ammonium salt-containing counterparts. However, the viscous and elastic moduli, along with their relaxation times, were quite similar for analogous phosphoniums and ammoniums. The CoPEC networks were loaded with anions including fluorescein, etodolac, and methotrexate, resulting in loading capacities ranging from 5 to 14 w/w % and encapsulation efficiencies from 29 to 93%. Anion release occurred over a period of several days to weeks, with the rate depending largely on the anion structure and polycation substituent groups. Whether the cation was an ammonium or a phosphonium had a smaller effect on the release rates. The cytotoxicities of the networks and polycations were investigated and found to depend on both the network and polycation structure.

Phosphonium Polyelectrolyte Complexes for the Encapsulation and Slow Release of Ionic Cargo.

Polyelectrolyte complexation, the combination of anionically and cationically charged polymers through ionic interactions, can be used to form hydrogel networks. These networks can be used to encapsulate and release cargo, but the release of cargo is typically rapid, occurring over a period of hours to a few days and they often exhibit weak, fluid-like mechanical properties. Here we report the preparation and study of polyelectrolyte complexes (PECs) from sodium hyaluronate (HA) and poly[tris(hydroxypropyl)(4-vinylbenzyl)phosphonium chloride], poly[triphenyl(4-vinylbenzyl)phosphonium chloride], poly[tri(n-butyl)(4-vinylbenzyl)phosphonium chloride], or poly[triethyl(4-vinylbenzyl)phosphonium chloride]. The networks were compacted by ultracentrifugation, then their composition, swelling, rheological, and self-healing properties were studied. Their properties depended on the structure of the phosphonium polymer and the salt concentration, but in general, they exhibited predominantly gel-like behavior with relaxation times greater than 40 s and self-healing over 2-18 h. Anionic molecules, including fluorescein, diclofenac, and adenosine-5'-triphosphate, were encapsulated into the PECs with high loading capacities of up to 16 wt %. Fluorescein and diclofenac were slowly released over 60 days, which was attributed to a combination of hydrophobic and ionic interactions with the dense PEC network. The cytotoxicities of the polymers and their corresponding networks with HA to C2C12 mouse myoblast cells was investigated and found to depend on the structure of the polymer and the properties of the network. Overall, this work demonstrates the utility of polyphosphonium-HA networks for the loading and slow release of ionic drugs and that their physical and biological properties can be readily tuned according to the structure of the phosphonium polymer.

Sleep characteristics, sources of perceived stress and coping strategies in adolescent athletes.

The aim of the study was to examine sleep characteristics, scheduling of activities, perceived stress and coping strategies between periods of perceived high and low scheduling commitments in adolescent athletes. Twenty adolescents (10 male and 10 female) wore an Actiwatch during two 14-day testing periods, one in in January (JAN), which was deemed to be a period of low school and sport commitments, and one in March (MAR), during which there was a high volume of school and sport commitments. Actiwatches and sleep diaries assessed sleep quantity and quality, a daily schedule of all activities in 30-min increments was recorded and questionnaires related to perceived stress and coping strategies were administered. Time in bed and asleep, latency, efficiency and number of awakenings were not different between JAN and MAR (p > 0.05). Sleep durations were lower than their age-related recommendations (JAN 449 ± 47 min versus MAR 437 ± 31 min). Examination of differences between sexes showed shorter latency and higher sleep efficiency in female participants compared with male participants. Participants spent more time at school, completing homework, and travelling to and competing in sport, with reduced time spent on resting, social activities, physical activity and meal times during MAR compared with JAN (p < 0.05). Finally, stress levels were significantly increased during MAR compared with JAN, with no difference between sexes (p < 0.05). Adolescent athletes not attaining sufficient sleep quantity or quality during periods of low and high school and sport commitments, are experiencing increased perceived stress during these busy times but are using a wider range of coping strategies during this time.

Phosphonium hydrogels for controlled release of ionic cargo.

We describe the synthesis of three different phosphonium salts and their reaction with poly(ethylene glycol) dimethacrylate to create cationic hydrogels. The hydrogels were loaded with an anionic dye and an anionic anti-inflammatory drug through ionic interactions and compared with an analogous ammonium gel. The release rates of these anions depended on their structure and pKa values, as well as the pH and ionic strength of the release medium.

Surprising Antibacterial Activity and Selectivity of Hydrophilic Polyphosphoniums Featuring Sugar and Hydroxy Substituents.

There is currently an urgent need for the development of new antibacterial agents to combat the spread of antibiotic-resistant bacteria. We explored the synthesis and antibacterial activities of novel, sugar-functionalized phosphonium polymers. While these compounds exhibited antibacterial activity, we unexpectedly found that the control polymer poly(tris(hydroxypropyl)vinylbenzylphosphonium chloride) showed very high activity against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus and very low haemolytic activity against red blood cells. These results challenge the conventional wisdom in the field that lipophilic alkyl substituents are required for high antibacterial activity and opens prospects for new classes of antibacterial polymers.

Synthesis, properties, and antibacterial activity of polyphosphonium semi-interpenetrating networks.

The development of new approaches to antibacterial surfaces is of growing interest to combat the spread of harmful bacterial infections. Relative to polyammoniums, polyphosphoniums can exhibit enhanced chemical and thermal stability, but have not yet been widely explored for the preparation of antibacterial surfaces. In this work, polyphosphoniums of varying chain lengths were synthesized by reversible addition-fragmentation chain-transfer polymerization of 4-vinylbenzyl derivatives of triethyl, tributyl, and trioctylphosphonium. These polyphosphoniums were then incorporated into semi-interpenetrating networks (SIPNs) based on tetra(ethylene glycol) diacrylate (TEGDA) via a UV light-initiated curing process. Measurements of cure percentage, gel content, water contact angle, and surface charge density suggested that all polyphosphoniums were well integrated into the network with the exception of one formulation. The results also suggested that the triethylphosphonium system tended to undergo surface reversion. Even at relatively low loadings of 0.1 to 10 wt% of polyphosphonium, the surfaces exhibited high accessible surface charge. Antibacterial testing revealed high activity against S. aureus for the triethyl and tributylphosphonium SIPNs and lower activity for the trioctyl systems. On the other hand, antibacterial activity against E. coli increased with increasing alkyl chain length. This can likely be attributed to differences in the compositions of the membranes of Gram-positive versus Gram-negative bacteria. The results also indicated that while killed bacteria tended to adsorb to the surface of the triethylphosphonium system, the more hydrophobic surfaces were more effective at preventing bacterial adsorption.