Controlled Release of Volatile Antimicrobial Compounds from Mesoporous Silica Nanocarriers for Active Food Packaging Applications.

Essential oils and their active components have been extensively reported in the literature for their efficient antimicrobial, antioxidant and antifungal properties. However, the sensitivity of these volatile compounds towards heat, oxygen and light limits their usage in real food packaging applications. The encapsulation of these compounds into inorganic nanocarriers, such as nanoclays, has been shown to prolong the release and protect the compounds from harsh processing conditions. Nevertheless, these systems have limited shelf stability, and the release is of limited control. Thus, this study presents a mesoporous silica nanocarrier with a high surface area and well-ordered protective pore structure for loading large amounts of natural active compounds (up to 500 mg/g). The presented loaded nanocarriers are shelf-stable with a very slow initial release which levels out at 50% retention of the encapsulated compounds after 2 months. By the addition of simulated drip-loss from chicken, the release of the compounds is activated and gives an antimicrobial effect, which is demonstrated on the foodborne spoilage bacteria Brochothrixthermosphacta and the potentially pathogenic bacteria Escherichia coli. When the release of the active compounds is activated, a ≥4-log reduction in the growth of B. thermosphacta and a 2-log reduction of E. coli is obtained, after only one hour of incubation. During the same one-hour incubation period the dry nanocarriers gave a negligible inhibitory effect. By using the proposed nanocarrier system, which is activated by the food product itself, increased availability of the natural antimicrobial compounds is expected, with a subsequent controlled antimicrobial effect.

Destabilization of NaBH4 by Transition Metal Fluorides.

In order to improve the suitability of NaBH4 as a clean fuel, its decomposition temperature needs to be decreased to below 535 °C, while its hydrogen release must be as high as possible. In this work, the influence of a collection of first and second period transition metal fluorides on the destabilization of NaBH4 is studied on samples produced by ball milling NaBH4 with 2 mol% of a metal fluoride additive. The effects obtained by increasing additive amount and changing oxidation state are also evaluated for NbF5, CeF3, and CeF4. The as-milled products are characterized by in-house power X-ray diffraction, while the hydrogen release and decomposition are monitored by temperature programmed desorption with residual gas analysis, differential scanning calorimetry, and thermogravimetry. The screening of samples containing 2 mol% of additive shows that distinctive groups of transition metal fluorides affect the ball milling process differently depending on their enthalpy of formation, melting point, or their ability to react at the temperatures achieved during ball milling. This leads to the formation of NaBF4 in the case of TiF4, MnF3, VF4, CdF2, NbF5, AgF, and CeF3 and the presence of the metal in CrF3, CuF2, and AgF. There is no linear correlation between the position of the transition metal in the periodic table and the observed behavior. The thermal behavior of the products after milling is given by the remaining NaBH4, fluoride, and the formation of intermediate metastable compounds. A noticeable decrease of the decomposition temperature is seen for the majority of the products, with the exceptions of the samples containing YF3, AgF, and CeF3. The largest decrease of the decomposition temperature is observed for NbF5. When comparing increasing amounts of the same additive, the largest decrease of the decomposition temperature is observed for 10 mol% of NbF5. Higher amounts of additive result in the loss of the NaBH4 thermal signal and ultimately the loss of the crystalline borohydride. When comparing additives with the same transition metal and different oxidation states, the most efficient additive is found to be the one with a higher oxidation state. Furthermore, among all the samples studied, higher oxidation state metal fluorides are found to be the most destabilizing agents for NaBH4. Overall, the present study shows that there is no single parameter affecting the destabilization of NaBH4 by transition metal fluorides. Instead, parameters such as the transition metal electronegativity and oxidation state or the enthalpy of formation of the fluoride and its melting point are competing to influence the destabilization. In particular, it is found that the combination of a high metal oxidation state and a low fluoride melting point will enhance destabilization. This is observed for MnF3, NbF5, NiF2, and CuF2, which lead to high gas releases from the decomposition of NaBH4 at the lowest decomposition temperatures.

In Situ Flow MAS NMR Spectroscopy and Synchrotron PDF Analyses of the Local Response of the Brønsted Acidic Site in SAPO-34 during Hydration at Elevated Temperatures.

In situ flow magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and synchrotron-based pair distribution function (PDF) analyses were applied to study water's interactions with the Brønsted acidic site and the surrounding framework in the SAPO-34 catalyst at temperatures up to 300 °C for NMR spectroscopy and 700 °C for PDF. 29 Si enrichment of the sample enabled detailed NMR spectroscopy investigations of the T-atom generating the Brønsted site. By NMR spectroscopy, we observed dehydration above 100 °C and a coalescence of Si peaks due to local framework adjustments. Towards 300 °C, the NMR spectroscopy data indicated highly mobile acidic protons. In situ total X-ray scattering measurements analyzed by PDF showed clear changes in the Al local environment in the 250-300 °C region, as the Al-O bond lengths showed a sudden change. This fell within the same temperature range as the increased Brønsted proton mobility. We suggest that the active site in this catalyst under industrial conditions comprises not only the Brønsted proton but also SiO4 . To the best of our knowledge, this is the first work proposing a structural model of a SAPO catalyst by atomic PDF analysis. The combination of synchrotron PDF analysis with in situ NMR spectroscopy is promising in revealing the dynamic features of a working catalyst.

Destabilization effect of transition metal fluorides on sodium borohydride.

The effect of transition metal fluorides on the decomposition of NaBH4 has been investigated for NaBH4 ball milled with TiF3, MnF3 or FeF3. The compounds were examined by thermal programmed desorption with residual gas analysis, thermo gravimetric analysis and volumetric measurements using a Sieverts-type apparatus. The phase formation process during thermal decomposition was studied by in situ synchrotron radiation powder X-ray diffraction on the as-milled powders. NaBF4 was among the products in all mechano-chemical reactions. (11)B-NMR spectra analysis gave NaBF4 : NaBH4 ratios of 1 : 150 for Na-Ti, 1 : 40 for Na-Mn, and 1 : 10 for Na-Fe. Pure NaBH4 possessed a hydrogen release onset temperature of 430 °C. The hydrogen release in the NaBH4-MnF3 system began as low as 130 °C. FeF3 decreased the onset temperature to 161 °C and TiF3 to 200 °C. TiF3 reacted completely with NaBH4 below 320 °C. All the examined systems have negligible emissions of diborane species. H-sorption studies performed at selected temperatures above 300 °C exhibited relatively fast desorption kinetics. Partial hydrogen re-absorption was observed for the Na-Mn and Na-Fe samples.

Real-time regeneration of a working zeolite monitored via operando X-ray diffraction and crystallographic imaging: how coke flees the MFI framework.

We have monitored the regeneration of H-ZSM-5 via operando time-resolved powder X-Ray diffraction (PXRD) coupled with mass spectroscopy (MS). Parametric Rietveld refinements and calculation of the extra-framework electronic density by differential Fourier maps analysis provide details on the mode of coke removal combined with the corresponding sub-unit cell changes of the zeolite structure. It is clear that the coke removal is a complex process that occurs in at least two steps; a thermal decomposition followed by oxidation. In a coked zeolite, the straight 10-ring channel circumference is warped to an oval shape due to structural distortion induced by rigid aromatic coke species. The data presented explain why the difference in length between the a-vector and the b-vector of the MFI unit cell is a robust descriptor for bulky coke, as opposed to the unit cell volume, which is affected also by adsorbed species and thermal effects. Our approach holds the promise to quantify and identify coke removal (and formation) in structurally distinct locations within the zeolite framework.

Inorganic Nanocarriers for Encapsulation of Natural Antimicrobial Compounds for Potential Food Packaging Application: A Comparative Study.

Design and development of novel inorganic nanocarriers for encapsulation of natural antimicrobial substances for food packaging applications have received great interest during the last years. Natural nanoclays are the most investigated nanocarriers and recently interest has also grown in the synthetically produced porous silica particles. However, these different carrier matrices have not been compared in terms of their loading capability and subsequent release. In this study, the feasibility of porous silica particles (with different pore structures and/or surface functionalities) and commercially available nanoclays were evaluated as encapsulation matrices. Two well-studied antimicrobial substances, thymol and curcumin, were chosen as volatile and non-volatile model compounds, respectively. The encapsulation efficiency, and the subsequent dispersibility and release, of these substances differed significantly among the nanocarriers. Encapsulation of the volatile compound highly depends on the inner surface area, i.e., the protective pore environment, and an optimal nanocarrier can protect the encapsulated thymol from volatilization. For the non-volatile compound, only the release rate and dispersibility are affected by the pore structure. Further, water-activated release of the volatile compound was demonstrated and exhibited good antimicrobial efficacy in the vapor phase against Staphylococcus aureus. This comparative study can provide a base for selecting the right nanocarrier aimed at a specific food packaging application. No nanocarrier can be considered as a universally applicable one.

A nano-silicate material with exceptional capacity for CO2 capture and storage at room temperature.

In order to mitigate climate change driven by the observed high levels of carbon dioxide (CO2) in the atmosphere, many micro and nano-porous materials are being investigated for CO2 selectivity, capture and storage (CCS) purposes, including zeolites, metal organic frameworks (MOFs), functionalized polymers, activated carbons and nano-silicate clay minerals. Key properties include availability, non-toxicity, low cost, stability, energy of adsorption/desorption, sorbent regeneration, sorption kinetics and CO2 storage capacity. Here, we address the crucial point of the volumetric capture and storage capacity for CO2 in a low cost material which is natural, non-toxic, and stable. We show that the nano-silicate Nickel Fluorohectorite is able to capture 0.79 metric tons of CO2 per m3 of host material - one of the highest capacities ever achieved - and we compare volumetric and gravimetric capacity of the best CO2 sorbent materials reported to date. Our results suggest that the high capture capacity of this fluorohectorite clay is strongly coupled to the type and valence of the interlayer cation (here Ni2+) and the high charge density, which is almost twice that of montmorillonite, resulting in the highest reported CO2 uptake among clay minerals.

Deactivation of Zeolite Catalyst H-ZSM-5 during Conversion of Methanol to Gasoline: Operando Time- and Space-Resolved X-ray Diffraction.

The deactivation of zeolite catalyst H-ZSM-5 by coking during the conversion of methanol to hydrocarbons was monitored by high-energy space- and time-resolved operando X-ray diffraction (XRD) . Space resolution was achieved by continuous scanning along the axial length of a capillary fixed bed reactor with a time resolution of 10 s per scan. Using real structural parameters obtained from XRD, we can track the development of coke at different points in the reactor and link this to a kinetic model to correlate catalyst deactivation with structural changes occurring in the material. The "burning cigar" model of catalyst bed deactivation is directly observed in real time.

Volumetric apparatus for hydrogen adsorption and diffusion measurements: sources of systematic error and impact of their experimental resolutions.

The development of a volumetric apparatus (also known as a Sieverts' apparatus) for accurate and reliable hydrogen adsorption measurement is shown. The instrument minimizes the sources of systematic errors which are mainly due to inner volume calibration, stability and uniformity of the temperatures, precise evaluation of the skeletal volume of the measured samples, and thermodynamical properties of the gas species. A series of hardware and software solutions were designed and introduced in the apparatus, which we will indicate as f-PcT, in order to deal with these aspects. The results are represented in terms of an accurate evaluation of the equilibrium and dynamical characteristics of the molecular hydrogen adsorption on two well-known porous media. The contribution of each experimental solution to the error propagation of the adsorbed moles is assessed. The developed volumetric apparatus for gas storage capacity measurements allows an accurate evaluation over a 4 order-of-magnitude pressure range (from 1 kPa to 8 MPa) and in temperatures ranging between 77 K and 470 K. The acquired results are in good agreement with the values reported in the literature.