The Use of Porous Silica Particles as Carriers for a Smart Delivery of Antimicrobial Essential Oils in Food Applications.

The objective of this study was to design, develop, and quantify the effectiveness of a simple method to facilitate the smart delivery of antimicrobial essential oils (EOs) via their absorption into a chemically bound high surface area support material. To this end, Santa Barbara Amorphous 15 (SBA-15) was functionalized by means of a post-synthetic reaction using (3-aminopropyl)triethoxysilane (APTES) to create an amine-terminated SBA-15 (SBA-APTES), and functionalization was confirmed by FTIR, TGA, and N2 isotherm analysis. Amine-modified SBA-15 was then grafted to a 3-glycidyloxypropyltrimethoxysilane (GPTS)-modified silicon (Si) surface (Si-GPTS), and subsequent attachment to the GPTS-modified surface was confirmed through XPS, dynamic contact angle, and SEM analysis. The smart delivery devices (SBA-15 and SBA-APTES) were then loaded with antimicrobial oregano essential oil (OEO) and the antimicrobial activity was assessed against common food spoilage microorganisms Escherichia coli, Bacillus cereus, Staphylococcus aureus, and Pseudomonas fluorescens. Antimicrobial activity results indicate that both SBA-OEO and SBA-APTES-OEO have good antimicrobial activity and that functionalization of bare SBA-15 with APTES has no effect on antimicrobial activity (P > 0.05) compared to SBA-OEO. Moreover, it appears that direct surface coating of the modified SBA to a surface substrate may not provide a significant quantity of oil needed to elicit an antimicrobial response. Nevertheless, given the strong absorption properties of SBA materials, good antimicrobial activity, and the GRAS nature of SBA-OEO and SBA-APTES-OEO, the results found in this study open potential applications of the functionalized carrier materials.

Precise Definition of a "Monolayer Point" in Polymer Brush Films for Fabricating Highly Coherent TiO2 Thin Films by Vapor-Phase Infiltration.

In this work, we show that in order to fabricate coherent titania (TiO2) films with precise thickness control, it is critical to generate a complete polymer brush monolayer. To date, demonstrations of such dense polymer monolayer formation that can be utilized for inorganic infiltration have been elusive. We describe a versatile bottom-up approach to covalently and rapidly (60 s processing) graft hydroxyl-terminated poly(2-vinyl pyridine) (P2VP-OH) polymers on silicon substrates. P2VP-OH monolayer films of varying thicknesses can subsequently be used to fabricate high-quality TiO2 films. Our innovative strategy is based upon room-temperature titanium vapor-phase infiltration of the grafted P2VP-OH polymer brushes that can produce TiO2 nanofilms of 2-4 nm thicknesses. Crucial parameters are explored, including molecular weight and solution concentration for grafting dense P2VP-OH monolayers from the liquid phase with high coverage and uniformity across wafer-scale areas (>2 cm2). Additionally, we compare the P2VP-OH polymer systems with another reactive polymer, poly(methyl methacrylate)-OH, and a relatively nonreactive polymer, poly(styrene)-OH. Furthermore, we prove the latter to be effective for surface blocking and deactivation. We show a simple process to graft monolayers for polymers that are weakly interacting with one another but more challenging for reactive systems. Our methodology provides new insight into the rapid grafting of polymer brushes and their ability to form TiO2 films. We believe that the results described herein are important for further expanding the use of reactive and unreactive polymers for fields including area-selective deposition, solar cell absorber layers, and antimicrobial surface coatings.

The use of hydrophobic amino acids in protecting spray dried trehalose formulations against moisture-induced changes.

Trehalose is commonly used as a protein stabilizer in spray dried protein formulations delivered via the pulmonary route. Spray dried trehalose formulations are highly hygroscopic, which makes them prone to deliquescence and recrystallization when exposed to moisture, leading to impairment in aerosolization performance. The main aim of this study was to investigate and compare the effect of hydrophobic amino acids (i.e. L-leucine and L-isoleucine) in enhancing aerosolization performance and in mitigating moisture-induced changes in spray dried trehalose formulations. Trehalose was spray dried with 20-60% w/w of amino acid (i.e. L-leucine or L-isoleucine). The spray dried formulations were stored at 25 °C/50% RH for 28 days. Solid state characterization and in vitro aerosolization performance studies were performed on the spray dried formulations before and after storage. The addition of 20-60% w/w of amino acid (i.e. L-leucine or L-isoleucine) improved the emitted fractions of spray dried trehalose formulations from a dry powder inhaler. However, ≥ 40% w/w of L-leucine/L-isoleucine was needed to prevent recrystallization of trehalose in the formulations when exposed to 25 °C/50% RH for 28 days. X-ray photoelectron spectroscopy (XPS) demonstrated that samples with 40-60% w/w L-isoleucine had more amino acid on the surfaces of the particles compared to their L-leucine counterparts. This may explain the greater ability of the L-isoleucine (40-60% w/w) samples to cope with elevated humidity compared to L-leucine samples of the same concentrations, as observed in the dynamic vapour sorption (DVS) studies. In conclusion, this study demonstrated that both L-leucine and L-isoleucine were effective in enhancing aerosolization performance and mitigating moisture-induced reduction in aerosolization performance in spray dried trehalose formulations. L-isoleucine proved to be superior to L-leucine in terms of its moisture protectant effect when incorporated at the same concentration in the formulations.

Listeria monocytogenes in the Irish dairy farm environment.

Listeria monocytogenes is a potentially lethal foodborne pathogen commonly found in the environment. European Union hygiene legislation places responsibility for safety on primary production facilities, including farms, as part of a policy to introduce traceability throughout the food chain. This study aimed to determine the occurrence of L. monocytogenes in the Irish dairy farm environment and in particular the milking facility. Two hundred ninety-eight environmental samples were collected from 16 farms in the southern region of Ireland. A number of farms within the group supply raw milk to the unpasteurized milk cheese industry. The samples taken included cow feces, milk, silage, soil, water, etc. Samples were enriched in Listeria enrichment broth and incubated for 48 h, followed by plating on chromogenic agar Listeria Ottavani & Agosti and further incubation of the plates for 24 to 48 h. Presumptive L. monocytogenes isolates were purified and confirmed by PCR targeting the hly gene. Overall, 19% of the samples (57 of 298) were positive for L. monocytogenes. These were serotyped using conventional and PCR methods; serotypes 1/2a, 1/2b, and 4b made up 78% of the typeable isolates. A correlation was found between the level of hygiene standards on the farm and the occurrence of L. monocytogenes. There was little difference in the occurrence of L. monocytogenes between farms supplying milk to the unpasteurized milk cheese industry and those supplying milk for processing. This study demonstrates the prevalence of L. monocytogenes in the dairy farm environment and the need for good hygiene practices to prevent its entry into the food chain.

Effect of silane reagent functionality for fluorinated alkyl and phenyl silica bonded stationary phases prepared in supercritical carbon dioxide.

This research examines the effect of silane reagent functionality for the preparation of fluorinated alkyl silica-bonded stationary phases prepared using supercritical carbon dioxide (sc-CO(2)) as a bonding medium. We present results that demonstrate that alkyl (C(8) and C(10)) and phenyl (pentafluorophenylpropyl, PFPP) silica bonded stationary phases can be prepared under sc-CO(2) conditions of 100 degrees C, 414bar and 3h, with surface coverages comparable to those obtained using organic solvent based methods. Fluorinated alkyl silica bonded phase preparation with a trichloro silane generates high ligand densities and more chemically uniform silica surface species compared to phases prepared using a monochloro or alkoxy silanes, as evidenced by thermogravimetric analysis (TGA) and (29)Si cross polarisation magic angle spinning (CP-MAS) NMR spectroscopy. In addition, the sc-trichloro prepared fluorinated C(8) bonded phases have demonstrated the ability to separate solutes on the basis of their molecular shape with the separation of the LC column shape selectivity test mixture, SRM 869a in the elution order of PhPh

Supercritical fluid generated stationary phases for liquid chromatography and capillary electrochromatography.

Chromatographic silica-bonded stationary phases have been prepared using supercritical CO(2) as the reaction medium. (29)Si solid-state NMR spectra of the generated bonded silica phases show unreacted silica species Q(3) and Q(4), alongside important resonances for surface-bound ligands, T(1), T(2), and T(3). Initially, a fluorinated octyl silica (C(8)) phase was produced, by reacting (1)H,(1)H,(2)H,(2)H-perfluorooctyltriethoxysilane with silica particles (3 microm) in sc-CO(2) at 60 degrees C and 450 atm for 3 h. In-house-packed LC columns of this fluorinated sc-C(8) silica phase yielded typical reversed-phase behavior when a standard test mix of benzamide (k' = 1.03), benzophenone (k' = 8.11), and biphenyl (k' = 14.92) was eluted. When packed into fused-silica capillaries for CEC, this fluorinated sc-C(8) silica phase gave linear plots of log k' versus percentage MeOH for benzophenone and biphenyl and, in contrast to octyl or octadecyl silica phases, displayed selectivity for aromatic thioureas when chromatographed among a series of synthetic organic thiourea test solutes. Similarily, an octadecyl silica phase (sc-C(18) silica) was prepared by reaction of n-octadecyltriethoxysilane in sc-CO(2), packed at 9500 psi and examined by LC. The sc-C(18) silica LC column yielded high column efficiency (up to 141 000 N/m (fluorene)) and excellent asymmetry factors (1.06, fluorene) without resource to end-capping. Following a second silylating or end-capping step using hexamethyldisilazane in sc-CO(2), sc-end-capped sc-C(18) silica phases elute N,N-DMA before toluene and the toluidine isomers as a single peak, indicating lowered silanol activity according to the Engelhardt test. A rapid separation of the important pharmaceutical substances, ketoprofen, naproxen, fentoprofen, and ibuprofen, on an sc-end-capped sc-C(18) silica phase is also shown.