Phosphonium-Functionalized Polymer Micelles with Intrinsic Antibacterial Activity

New approaches to treat bacterial infections are badly needed to address the increasing problem of antibiotic resistance. This study explores phosphonium-functionalized block copolymer micelles as intrinsically antibacterial polymer assemblies. Phosphonium cations with varying alkyl lengths were conjugated to the terminus of a poly(ethylene oxide)− polycaprolactone block copolymer, and the phosphonium-functionalized block copolymers were self-assembled to form micelles in aqueous solution. The size, morphology, and ζ -potential of the assemblies were studied, and their abilities to kill Escherichia coli and Staphylococcus aureus were evaluated. It was found that the minimum bactericidal concentration depended on the phosphonium alkyl chain length, and different trends were observed for Gram-negative and Gram-positive bacteria. The most active assemblies exhibited no hemolysis of red blood cells above the bactericidal concentrations, indicating that they can selectively disrupt the membranes of bacteria. Furthermore, it was possible to encapsulate and release the antibiotic tetracycline using the assemblies, providing a potential multimechanistic approach to bacterial killing

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

Effect of counter ions on the self-assembly of polystyrene-polyphosphonium block copolymers

The ability to manipulate block copolymers on the nanoscale has led to many scientific and technological advances. These include nano-scale ordered bulk and thin films and also solution phase components, these are promising materials for making smaller ordered electronics, selective membranes, and also biomedical applications. The ability to manipulate block copolymer material architectures on such small scales has risen from thorough investigations into the properties that affect the architectures. Polyelectrolytes are an important class of polymers that are used to make amphiphilic block copolymers. In this context the authors synthesized polystyrene-b-polyphosphonium block copolymers with different anions coordinated to the polyphosphonium block in order to study the effect of the anion on the aqueous self-assembly of the polymers. The anions play an important role in the solubility of the monomeric materials which results in differences in the self-assembly observed through dynamic light scattering and transmission electron microscopy

Group 6 Metal Pentacarbonyl Complexes of Air-Stable Primary, Secondary, and Tertiary Ferrocenylethylphosphines

The synthesis and characterization of a series of Group 6 metal pentacarbonyl complexes of air stable primary, secondary, and tertiary phosphines containing ferrocenylethyl substituents are reported [M(CO)5L: M = Cr, Mo, W; L = PH2(CH2CH2Fc), PH(CH2CH2Fc)2, P(CH2CH2Fc)3]. The structure and composition of the complexes were confirmed by multinuclear NMR spectroscopy, IR and UV-Vis absorption spectroscopy, mass spectrometry, X-ray crystallography, and elemental analysis. The solid-state structural data reported revealed trends in M-C and M-P bond lengths that mirrored those of the atomic radii of the Group 6 metals involved. UV-Vis absorption spectroscopy and cyclic voltammetry highlighted characteristics consistent with electronically isolated ferrocene units including wavelengths of maximum absorption between 435 and 441 nm and reversible one-electron (per ferrocene unit) oxidation waves between 10 and -5 mV relative to the ferrocene/ferrocenium redox couple. IR spectroscopy confirmed that the σ donating ability of the phosphines increased as ferrocenylethyl substituents were introduced and that the tertiary phosphine ligand described is a stronger σ donor than PPh3 and a weaker σ donor than PEt3, respectively

Antibacterial Activity of Polymers: Discussions on the Nature of Amphiphilic Balance

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The purpose of this Viewpoint is to discuss the molecular design principles that guide development of synthetic antimicrobial polymers, especially those intended to mimic the structure of host defense peptides (HDPs). In particular, we focus on the principle of “amphiphilic balance” as it relates to some recently developed polyphosphoniums with somewhat atypical structure. We find that the fundamental concept of amphiphilic balance is still applicable to these new polymers, but that the method to achieve such balance is somewhat unique. We then briefly outline the future challenges and opportunities in this field

Análisis filogenético y revisión sistemática de la subfamilia Allidiostomatinae (Coleoptera: Scarabaeidae)

Tesis presentada para optar al Grado de Doctor en Ciencias NaturalesFil: Neita Moreno, Jhon César. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo; Argentin

Self-Healing Polyphosphonium Ionic Networks

Self healing, ionically crosslinked networks were prepared from poly(acrylic acid) (PAA) and poly(triethyl(4-vinylbenzyl)phosphonium chloride (P-Et-P) and their properties were studied. Three different ratios of PAA/P-Et-P were incorporated into the networks by varying the addition orders of the components. Swelling of the networks increased with increasing NaCl concentration when they were immersed in aqueous solution. All networks retained their structural integrity in 0.1 M NaCl. Studies of the rheological and tensile properties of the networks swelled in 0.1 M NaCl showed that PAA\u3eP-Et-Pexhibited high elongation and viscoelastic properties suitable for self-healing with a relaxation time of ~30 s, whereas the other networks exhibited predominantly elastic behavior. The moduli were similar to those of soft tissues. Self-healing of PAA\u3eP-Et-Pin 0.1 M NaCl was demonstrated through repair of a 0.5 mm diameter puncture in the material whereas healing was incomplete for the other networks and also for PAA\u3eP-Et-Pin the absence of NaCl. Healing after completely severing a tensile testing sample showed significant recovery of the modulus, strength, and elongation. The properties of these materials and their ability to self-heal in low and physiologically relevant salt concentrations make them promising candidates for a variety of applications, particularly in the biomedical area

Synthesis and Characterization of a Family of Air-Stable Ferrocene- and Ruthenocene-Containing Primary, Secondary, and Tertiary Phosphines

The synthesis and characterization of a family of air-stable primary, secondary, and tertiary phosphines containing all possible combinations of ethylferrocene and ethylruthenocene substituents are reported. Each phosphine was characterized by 1H, 13C, and 31P NMR spectroscopy, IR and UV-vis absorption spectroscopy, mass spectrometry, and elemental analysis. With the exception of primary ethylruthenocene phosphine 8a, all of the title compounds have been studied by single crystal X-ray crystallography. Ferrocene-containing phosphines showed maximum absorption at wavelengths of ca. 440 nm and qualitatively reversible oxidation waves in their cyclic voltammograms with intensities scaling to the number of ferrocene units present. The average metal-cyclopentadienyl centroid distances observed for ferrocene-containing phosphines were shorter than those of ruthenocene-containing phosphines, which also had maximum absorption wavelengths of ca. 320 nm and underwent irreversible electrochemical oxidation. Phosphines containing both ethylferrocene and ethylruthenocene substituents displayed properties consistent with the presence of both metallocene types

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

© 2019 American Chemical Society. 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