Clara Piccirillo

The antimicrobial properties of light-activated polymers containing methylene blue and gold nanoparticles

We report the formation of polysiloxane polymers containing embedded methylene blue and gold nanoparticles incorporated by a swell-encapsulation-shrink method. These polymers show significant antimicrobial activity against methicillin-resistant Staphylococcus aureus and Escherichia coli with up to a 3.5 log(10) reduction in the viable count when exposed for 5 min to light from a low power 660 nm laser. The bacterial kill is due to the light-induced production of singlet oxygen and other reactive oxygen species by the methylene blue. Interestingly, the presence of 2 nm gold nanoparticles significantly enhanced the ability of the methylene blue to kill bacteria.

Doped and un-doped vanadium dioxide thin films prepared by atmospheric pressure chemical vapour deposition from vanadyl acetylacetonate and tungsten hexachloride: the effects of thickness and crystallographic orientation on thermochromic properties

The atmospheric pressure chemical vapour deposition reaction of vanadyl acetylacetonate and tungsten hexachloride with oxygen led to the production of thin films of tungsten doped monoclinic vanadium dioxide on glass substrates. Scanning electron microscopy and X-ray diffraction indicated that the films had different morphologies and crystallinities depending on the deposition conditions used. Transmission and reflectance measurements showed a significant change in properties in the near infra-red either side of the metal to semiconductor transition. Variable temperature transmission studies show that the metal to semiconductor transition was lowered by tungsten doping. The effect of film thickness was studied with un-doped and doped films. It was found that film thickness limited the intensity of light passing through the film and the extent of the thermochromic transition but was found not to influence the hysteresis width or temperature of transition. Different film growth conditions led to a range of film morphologies which profoundly affected the resulting optical properties of the films. It was found that film morphology and preferred crystallographic orientation had a marked influence on the width and switching temperature of the thermochromic transition.

Extraction and characterisation of apatite- and tricalcium phosphate-based materials from cod fish bones

Apatite- and tricalcium phosphate-based materials were produced from codfish bones, thus converting a waste by-product from the food industry into high added-valued compounds. The bones were annealed at temperatures between 900 and 1200 °C, giving a biphasic material of hydroxyapatite and tricalcium phosphate (Ca10(PO4)6(OH)2 and β-Ca(PO4)3) with a molar proportion of 75:25, a material widely used in biomedical implants. The treatment of the bones in solution prior to their annealing changed the composition of the material. Single phase hydroxyapatite, chlorapatite (Ca10(PO4)6Cl2) and fluorapatite (Ca10(PO4)6F2) were obtained using CaCl2 and NaF solutions, respectively. The samples were analysed by several techniques (X-ray diffraction, infrared spectroscopy, scanning electron microscopy and differential thermal/thermogravimetric analysis) and by elemental analyses, to have a more complete understanding of the conversion process. Such compositional modifications have never been performed before for these materials of natural origin to tailor the relative concentrations of elements. This paper shows the great potential for the conversion of this by-product into highly valuable compounds for biomedical applications, using a simple and effective valorisation process.

Toluidine blue-containing polymers exhibit potent bactericidal activity when irradiated with red laser light

Toluidine blue and toluidine blue-nanogold mixtures were incorporated into polyurethane and silicone polymers by a swell-encapsulation-shrink method using acetone-water mixtures. The surface and mechanical properties of the polymers were changed by the swell-shrink process especially the Youngs modulus, but not by the introduction of toluidine blue or nanogold. The antibacterial properties of the various polymers were assessed under laser irradiation at 634 nm against Escherichia coli and methicillin-resistant Staphylococcus aureus (MRSA). The toluidine blue-incorporated polymers showed kills of (>105 cfu/ml) for MRSA after just one minute of exposure. This is, to our knowledge, the most potent light-activated antimicrobial polymer combination reported to date.

Antimicrobial activity of methylene blue and toluidine blue O covalently bound to a modified silicone polymer surface

Methylene Blue or Toluidine Blue O were covalently bound to an activated silicone polymer by means of an amide condensation reaction. UV-visible absorption spectra confirmed that the dye was surface bound. The new polymers with covalently attached dye display significant bactericidal activity against Escherichia coli and Staphylococcus epidermidis with a 99.999% reduction in viable bacteria after four minutes exposure to a low power laser.

Thermochromic Coatings for Intelligent Architectural Glazing

Thermochromic glazing is a type of intelligent glazing; one where the properties of the glazing change according to some external stimulus. More particularly a thermochromic window is a device that changes its transmission and reflectance properties at a critical temperature (Tc). Atthis specific temperature the material undergoes a semi-conductor to metal transition. At temperatures lower than Tc the window lets all of the solar energy that hits it through. At emperatures above Tc the window reflects the infra-red portion of solar energy. In such a way thermochromic windows may help reduce air conditioning and heating costs leading to more energy efficient buildings. This review details the nature of the semi-conductor to metal transition and indicates how substitutional doping within a crystal lattice can be used to manipulate and fine tune the critical temperature. Also detailed is the underlying science and methodologies so far employed in the production of thermochromic thin films.

Calcium phosphate-based materials of natural origin showing photocatalytic activity

Calcium phosphate based materials of natural origin with photocatalytic properties were produced. Bones of Atlantic cod fish were treated in appropriate solutions (either Ca- or Ti-containing salts) and successively annealed. Results showed multiphasic materials (hydroxyapatite, β-tricalcium phosphate and anatase titania) with excellent photocatalytic performance under both UV and visible light, with an anatase concentration of only about 2 mol%. Results with such a low amount of anatase have never been reported before for a calcium phosphate-based material; this is attributed to the presence of anatase being mainly on the surface. Single-phase hydroxyapatite (Ca10(PO4)6(OH)2 or HAp) also showed some photocatalytic properties and antibacterial activity.

Extraction of high added value biological compounds from sardine, sardine-type fish and mackerel canning residues--a review.

Different valuable compounds, which can be employed in medicine or in other industries (i.e. food, agrochemical, pharmaceutical) can be recovered from by-products and waste from the fish canning industries. They include lipids, proteins, bio-polymers, minerals, amino acids and enzymes; they can be extracted from wastewaters and/or from solid residues (head, viscera, skin, tails and flesh) generated along the canning process, through the filleting, cooking, salting or smoking stages. In this review, the opportunities for the extraction and the valorisation of bioactive compounds from sardine, sardine-type fish and mackerel canning residues are examined and discussed. These are amongst the most consumed fishes in the Mediterranean area; moreover, canning is one of the most important and common methods of preservation. The large quantities of by-products generated have great potentials for the extraction of biologically desirable high added value compounds.

Antimicrobial Properties of Light-activated Polyurethane Containing Indocyanine Green:

The aim of this study was to produce novel antimicrobial polymers containing the light-activated antimicrobial agent indocyanine green (ICG). The novel materials were prepared by swelling polyurethane in acetone containing water and ICG, followed by solvent evaporation. The uptake of ICG was dependent upon the ratio of acetone to water. Only at a ratio of 99 parts acetone to 1 part water was there any substantial colouration of the samples. When exposed to laser light from the near infrared spectrum (808 nm), polyurethane-containing ICG exhibited antimicrobial activity against Gram-positive bacteria; a 2 log10 reduction was achieved against methicillin-resistant Staphylococcus aureus (MRSA) and Staphylococcus epidermidis after 15 min exposure, corresponding to an energy dose of 31.83 J delivered at an energy density of 31.83 J/cm2. Under the same conditions, Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) appeared to be less susceptible, the viable count being reduced by 0.5 log10. Some of the physical properties of the resulting material were also investigated and it was found that the elasticity (Young’s modulus) was reduced by approximately 60%. Furthermore, when the ICG-containing polymer was stretched, the breaking point occurred when the elongation was 6.7 times the initial value, while ICG-free polyurethane samples did not break following a 7-fold elongation. The contact angles for water droplets revealed that the ICG-containing polymer was more hydrophobic than untreated polyurethane. The results of this study show that ICG can be embedded in polyurethane to produce materials which when irradiated with near-infrared light can exert a bactericidal effect particularly against MRSA and S. epidermidis. Such materials may be useful for preparing intravenous catheters, which are often colonized by such organisms.

A hydroxyapatite–Fe2O3 based material of natural origin as an active sunscreen filter

The use of sunscreens as protective barriers against skin damage and cancer, by absorbing harmful UVA and UVB rays, is becoming an increasingly important issue. Such products are usually based on TiO2 or ZnO, although both Fe2O3 and hydroxyapatite (Ca10(PO4)6(OH)2, HAp) doped with metal ions have been reported as being ultraviolet (UV) absorbing materials. HAp is the main component of bone; it is, therefore, highly biocompatible. In the present work, an iron-doped HAp-based material, containing both Fe ions substituted into the HAp structure and iron oxide in hematite (α-Fe2O3) form, was successfully developed from waste cod fish bones. This was achieved through a simple process of treating the bones in a Fe(ii) containing solution, followed by heating at 700 °C. The material showed good absorption in the whole UV range and did not form radicals when irradiated. The sunscreen cream formulated with this material could be used as a broad sunscreen protector (λcrit > 370 nm), showing high absorption both in the UVA and UVB ranges. Because of its absorption properties it would be classified as 5 star protection according to the Boots UVA star rating system. The cream is also photostable, and does not cause irritation or erythema formation when in contact with the human skin. These results show that a food by-product such as fish bones could be converted into a valuable product, with potential applications in health care and cosmetics. This is the first time a HAp-based sunscreen cream has been developed and validated as a proof of concept.