Sulfur-Polymer Nanoparticles: Preparation and Antibacterial Activity.

High sulfur content polymers prepared by inverse vulcanization have many reported potential applications, including as novel antimicrobial materials. High sulfur content polymers usually have limited water-solubility and dispersibility due to their hydrophobic nature, which could limit the development of their applications. Herein, we report the formulation of high sulfur content polymeric nanoparticles by a nanoprecipitation and emulsion-based method. High sulfur content polymeric nanoparticles were found to have an inhibitory effect against important bacterial pathogens, including Gram-positive methicillin-resistant Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa. Salt-stable particles were formulated with the addition of a surfactant, which did not inhibit the antibacterial activity of the polymeric particles. Furthermore, the polymeric nanoparticles were found to inhibit S. aureus biofilm formation and exhibited low cytotoxicity against mammalian liver cells. Interaction of the polymeric particles with cellular thiols could be a potential mechanism of action against bacterial cells, as demonstrated by reaction with cysteine as a model thiol. The findings presented demonstrate methods of preparing aqueous dispersions of high sulfur content polymeric nanoparticles that could have useful biological applications.

Photoinduced inverse vulcanization.

The inverse vulcanization (IV) of elemental sulfur to generate sulfur-rich functional polymers has attracted much recent attention. However, the harsh reaction conditions required, even with metal catalysts, constrains the range of feasible crosslinkers. We report here a photoinduced IV that enables reaction at ambient temperatures, greatly broadening the scope for both substrates and products. These conditions enable volatile and gaseous alkenes and alkynes to be used in IV, leading to sustainable alternatives for environmentally harmful plastics that were hitherto inaccessible. Density functional theory calculations reveal different energy barriers for thermal, catalytic and photoinduced IV processes. This protocol circumvents the long curing times that are common in IV, generates no H2S by-products, and produces high-molecular-weight polymers (up to 460,000 g mol-1) with almost 100% atom economy. This photoinduced IV strategy advances both the fundamental chemistry of IV and its potential industrial application to generate materials from waste feedstocks.

Mechanochemical synthesis of inverse vulcanized polymers.

Inverse vulcanization, a sustainable platform, can transform sulfur, an industrial by-product, into polymers with broad promising applications such as heavy metal capture, electrochemistry and antimicrobials. However, the process usually requires high temperatures (≥159 °C), and the crosslinkers needed to stabilize the sulfur are therefore limited to high-boiling-point monomers only. Here, we report an alternative route for inverse vulcanization-mechanochemical synthesis, with advantages of mild conditions (room temperature), short reaction time (3 h), high atom economy, less H2S, and broader monomer range. Successful generation of polymers using crosslinkers ranging from aromatic, aliphatic to volatile, including renewable monomers, demonstrates this method is powerful and versatile. Compared with thermal synthesis, the mechanochemically synthesized products show enhanced mercury capture. The resulting polymers show thermal and light induced recycling. The speed, ease, versatility, safety, and green nature of this process offers a more potential future for inverse vulcanization, and enables further unexpected discoveries.

Investigating the viability of sulfur polymers for the fabrication of photoactive, antimicrobial, water repellent coatings.

Elemental sulfur (S8), a by-product of the petroleum refining industries, possesses many favourable properties including photocatalytic activity and antibacterial activity, in addition to being intrinsically hydrophobic. Despite this, there is a relative lack of research employing elemental sulfur and/or sulfur copolymers within superhydrophobic materials design. In this work, we present the use of sulfur copolymers to produce superhydrophobic materials with advanced functionalities. Using inverse vulcanization and the use of a natural organic crosslinker, perillyl alcohol (PER), stable S8-PER copolymers were synthesised and later combined with silica (SiO2) nanoparticles, to achieve highly water repellent composites that displayed both antimicrobial and photocatalytic properties, in the absence of carcinogenic and/or expensive materials. Here, we investigated the antibacterial performance of coatings against the Staphylococcus aureus bacterial strain, where coatings displayed great promise for use in antifouling applications, as they were found to limit surface adhesion by more than 99%, when compared to uncoated glass samples. Furthermore, UV dye degradation tests were performed, utilizing the commercially available dye resazurin, and it was shown that coatings had the potential to simultaneously exhibit surface hydrophobicity and photoactivity, demonstrating a great advancement in the field of superhydrophobic materials.

Antibacterial Activity of Inverse Vulcanized Polymers.

Inverse vulcanization is a bulk polymerization method for synthesizing high sulfur content polymers from elemental sulfur, a byproduct of the petrochemical industry, with vinylic comonomers. There is growing interest in polysulfides as novel antimicrobial agents due to the antimicrobial activity of natural polysulfides found in garlic and onions (Tsao et al. J. Antimicrob. Chemother. 2001, 47, 665-670). Herein, we report the antibacterial properties of several inverse vulcanized polymers against Gram-positive Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa, two common causes of nosocomial infection and pathogens identified by the World Health Organization as priorities for antimicrobial development. High sulfur content polymers were synthesized with different divinyl comonomers and at different sulfur/comonomer ratios, to determine the effect of such variables on the antibacterial properties of the resulting materials. Furthermore, polymers were tested for their potential as antibacterial materials at different temperatures. It was found that the test temperature influenced the antibacterial efficacy of the polymers and could be related to the glass transition temperature of the polymer. These findings provide further understanding of the antibacterial properties of inverse vulcanized polymers and show that such polymers have the potential to be used as antibacterial surfaces.

Magnetic sulfur-doped carbons for mercury adsorption.

Mercury pollution is a significant threat to the environment and health worldwide. Therefore, effective and low-cost absorbents that are easily scalable are needed for real-world applications. Enlarging the surface area of the materials and doping with heteroatoms are two of the most common strategies to cope with this problem. Sulfur-doped activated carbon synthesized from the carbonization of inverse vulcanized thiopolymers makes it possible to combine both large specific surface area and doping of heteroatoms, resulting in outperformance in mercury uptake against commercial activated carbons. Convenient recovery of mercury absorbents after treatment should be beneficial in mercury collecting and recycling. Therefore, magnetic sulfur-doped carbons (MSCs) were prepared by functionalizing sulfur doped carbons through chemical precipitation with magnetic iron oxides. Besides the characterisations of materials, mercury uptake experiments, such as stactic test, capacity test, impact of solution pH, and mixed ions interferences were performed. These MSCs exhibit high specific surface area (1,329 m2/g), high sulfur content (up to 14.8 wt%), porous structure, low cost, and are convenient for retrieval. MSCs are demonstrated high uptake capacity (187 mg g-1) and efficiency in mercury solution and multifunctional absorption in mixed ions solution, showing their potential to be applied in water purification and environmental remediation.

Carbonisation of a polymer made from sulfur and canola oil.

A polymer made from equal masses of sulfur and canola oil was carbonised at 600 °C for 30 minutes. The resulting material exhibited improved uptake of mercury from water compared to the polymer. The carbonisation could also be done after using the polymer to clean up oil spills, which suprisingly improved mercury uptake to levels rivaling commercial carbons.

Mesoporous knitted inverse vulcanised polymers.

Elemental sulfur is generated in large quantities when crude oil is refined. This elemental sulfur has limited use other than the production of sulfuric acid. Recently, the development of 'inverse vulcanised' polymers has attracted the attention of researchers. These polymers are formed from elemental sulfur and a small molecule alkene. The affinity of sulfur for heavy metals gives these polymers potential for specific adsorption; however, there is a lack of incorporation of high specific surface areas in pure polymers. Herein, we report the first mesoporous polymer generated using inverse vulcanised polymers, with a BET surface area of 236.04 m2 g-1. We explore the properties of polymers as an absorption medium for potent neurotoxin Hg(ii).

Insulating Composites Made from Sulfur, Canola Oil, and Wool*.

An insulating composite was made from the sustainable building blocks wool, sulfur, and canola oil. In the first stage of the synthesis, inverse vulcanization was used to make a polysulfide polymer from the canola oil triglyceride and sulfur. This polymerization benefits from complete atom economy. In the second stage, the powdered polymer was mixed with wool, coating the fibers through electrostatic attraction. The polymer and wool mixture were then compressed with mild heating to provoke S-S metathesis in the polymer, which locks the wool in the polymer matrix. The wool fibers imparted tensile strength, insulating properties, and reduced the flammability of the composite. All building blocks are sustainable or derived from waste and the composite is a promising lead on next-generation insulation for energy conservation.

Chemically induced repair, adhesion, and recycling of polymers made by inverse vulcanization.

Inverse vulcanization is a copolymerization of elemental sulfur and alkenes that provides unique materials with high sulfur content (typically ≥50% sulfur by mass). These polymers contain a dynamic and reactive polysulfide network that creates many opportunities for processing, assembly, and repair that are not possible with traditional plastics, rubbers and thermosets. In this study, we demonstrate that two surfaces of these sulfur polymers can be chemically joined at room temperature through a phosphine or amine-catalyzed exchange of the S-S bonds in the polymer. When the nucleophile is pyridine or triethylamine, we show that S-S metathesis only occurs at room temperature for a sulfur rank > 2-an important discovery for the design of polymers made by inverse vulcanization. This mechanistic understanding of the S-S metathesis was further supported with small molecule crossover experiments in addition to computational studies. Applications of this chemistry in latent adhesives, additive manufacturing, polymer repair, and recycling are also presented.

Inverse Vulcanized Polymers with Shape Memory, Enhanced Mechanical Properties, and Vitrimer Behavior.

The invention of inverse vulcanization provides great opportunities for generating functional polymers directly from elemental sulfur, an industrial by-product. However, unsatisfactory mechanical properties have limited the scope for wider applications of these exciting materials. Here, we report an effective synthesis method that significantly improves mechanical properties of sulfur-polymers and allows control of performance. A linear pre-polymer containing hydroxyl functional group was produced, which could be stored at room temperature for long periods of time. This pre-polymer was then further crosslinked by difunctional isocyanate secondary crosslinker. By adjusting the molar ratio of crosslinking functional groups, the tensile strength was controlled, ranging from 0.14±0.01 MPa to 20.17±2.18 MPa, and strain was varied from 11.85±0.88 % to 51.20±5.75 %. Control of hardness, flexibility, solubility and function of the material were also demonstrated. We were able to produce materials with suitable combination of flexibility and strength, with excellent shape memory function. Combined with the unique dynamic property of S-S bonds, these polymer networks have an attractive, vitrimer-like ability for being reshaped and recycled, despite their crosslinked structures. This new synthesis method could open the door for wider applications of sustainable sulfur-polymers.

Investigating the Antibacterial Properties of Inverse Vulcanized Sulfur Polymers.

More than 60 million tons of sulfur are produced as a byproduct of the petrochemical industry annually. Recently, the inverse vulcanization process has transformed this excess sulfur into functional polymers by stabilization with organic cross-linkers. These interesting new polymers have many potential applications covering diverse areas. However, there has been very little focus on the potential of these high-sulfur polymers for their antibacterial properties. These properties are examined here by exposing two common bacteria species, Escherichia coli (E. Coli) and Staphylococcus aureus (S. aureus), to two structurally different, inverse vulcanized sulfur polymers: sulfur-co-diisopropenyl benzene (S-DIB) and sulfur dicyclopentadiene (S-DCPD). We report the highest bacteria log reduction (>log 4.3) of adhered bacterial cells (S. aureus) to an inverse vulcanized sulfur polymer to date and investigate the potential pathways in which antibacterial activity may occur.

NMR relaxation and modelling study of the dynamics of SF6 and Xe in porous organic cages.

The porous solid formed from organic CC3 cage molecules has exceptional performance for rare gas separation. NMR spectroscopy provides a way to reveal the dynamical details by using experimental relaxation and diffusion measurements. Here, we investigated T1 and T2 relaxation as well as diffusion of 129Xe and SF6 gases in the CC3-R molecular crystal at various temperatures and magnetic field strengths. Advanced relaxation modelling made it possible to extract various important dynamical parameters for gases in CC3-R, such as exchange rates, activation energies and mobility rates of xenon, occupancies of the cavities, rotational correlational times, effective relaxation rates, and diffusion coefficients of SF6.

A ternary system for delayed curing inverse vulcanisation.

Completion of inverse vulcanisation reactions leads to a crosslinked insoluble polymer, but insufficient reaction allows phase separation of the sulfur and organic corsslinkers. A ternary co-polymer system allows delayed curing to be used, keeping the pre-polymer stable, homogeneous, and ready to be set into its final form when and where needed, allowing greater opportunities for practical production.

Synthesis of a Large, Shape-Flexible, Solvatomorphic Porous Organic Cage.

Porous organic cages have emerged over the last 10 years as a subclass of functional microporous materials. However, among all of the organic cages reported, large multicomponent organic cages with 20 components or more are still rare. Here, we present an [8 + 12] porous organic imine cage, CC20, which has an apparent surface area up to 1752 m2 g-1, depending on the crystallization and activation conditions. The cage is solvatomorphic and displays distinct geometrical cage structures, caused by crystal-packing effects, in its crystal structures. This indicates that larger cages can display a certain range of shape flexibility in the solid state, while remaining shape persistent and porous.

Crosslinker Copolymerization for Property Control in Inverse Vulcanization.

Sulfur is an underused by-product of the petrochemicals industry. Recent research into inverse vulcanization has shown how this excess sulfur can be transformed into functional polymers, by stabilization with organic crosslinkers. For these interesting new materials to realize their potential for applications, more understanding and control of their physical properties is needed. Here we report four new terpolymers prepared from sulfur and two distinct alkene monomers that can be predictively tuned in glass transition, molecular weight, solubility, mechanical properties, and color.

Catalytic inverse vulcanization.

The discovery of inverse vulcanization has allowed stable polymers to be made from elemental sulfur, an unwanted by-product of the petrochemicals industry. However, further development of both the chemistry and applications is handicapped by the restricted choice of cross-linkers and the elevated temperatures required for polymerisation. Here we report the catalysis of inverse vulcanization reactions. This catalytic method is effective for a wide range of crosslinkers reduces the required reaction temperature and reaction time, prevents harmful H2S production, increases yield, improves properties, and allows crosslinkers that would be otherwise unreactive to be used. Thus, inverse vulcanization becomes more widely applicable, efficient, eco-friendly and productive than the previous routes, not only broadening the fundamental chemistry itself, but also opening the door for the industrialization and broad application of these fascinating materials.

Sulfur polymer composites as controlled-release fertilisers.

Sulfur polymer composites were prepared by the reaction of canola oil and elemental sulfur in the presence of the NPK fertiliser components ammonium sulfate, calcium hydrogen phosphate, and potassium chloride. These composites released nutrients in a controlled fashion, resulting in less wasted fertiliser and better health for potted tomato plants when compared to free NPK.

High sulfur content polymers: The effect of crosslinker structure on inverse vulcanization.

The discovery of inverse vulcanization has allowed polymers to be made using elemental sulfur as the major component. However, until now, there has been little discussion of why seemingly similar crosslinkers result in polymers with radically different properties. Combining synthesis, spectroscopy, and modeling, this study reveals the structure-property relationships of sulfur polymers and reports a new system using 5-ethylidene-2-norbornene as a crosslinker that can stabilize up to 90 wt % of elemental sulfur.

Core-Shell Crystals of Porous Organic Cages.

The first examples of core-shell porous molecular crystals are described. The physical properties of the core-shell crystals, such as surface hydrophobicity, CO2 /CH4 selectivity, are controlled by the chemical composition of the shell. This shows that porous core-shell molecular crystals can exhibit synergistic properties that out-perform materials built from the individual, constituent molecules.