Characterising the mechanical properties of soft solids through acoustics and rheology, exemplified by anhydrous milk fat.

Foods vary in their elastic properties over a wide range of behaviours. In the case of mastication, textures vary from hard solid through brittle (chocolate bar) and crispy/crunchy (biscuits) to viscous and extensional flow (syrup) and finally very low viscosity fluid (water). Here we deploy an elastic description of soft solids which embraces all these behaviours to quantify the elastic behaviour of food, in particular through the use of sound. We illustrate the use of this mathematical description in the quantitative characterisation of the elastic and flow properties of food through orthodox measurement techniques and novel ultrasound methods. Measurement is complicated by human sensory capabilities that span the entire range from solid to fluid to gas in an integrated manner, during the appreciation of food. We use acoustic and rheological measurement techniques for the determination of the mechanical properties of soft solids, comparing oscillatory rheometry with acoustic parameters as exemplified by acoustic and oscillatory rheometry measurements in crystallising anhydrous milk fat (AMF). We conclude that acoustic and rheological measurements complement each other with acoustic techniques offering the possibility of inline, in process determination of mechanical and flow properties such as viscosity, rigidity, compressibility and bulk modulus.

"Sounding" out crystal nuclei-A mathematical-physical and experimental investigation.

We outline techniques for the control and measurement of the nucleation of crystalline materials. Small angle x-ray scattering/wide angle x-ray scattering x-ray diffraction measurements are presented that demonstrate the impact of low power, continuous, non-cavitational ultrasound on the nucleation and crystallization of a wax-n-eicosane dissolved in a heptane/toluene solvent. A mathematical-physical approach based on the rectification of heat and mass transport by such a low power oscillating pressure field is outlined, and it is suggested that this approach be combined with dissipative particle dynamics computational modeling to develop a predictive method capable of modeling the impact of low power oscillating pressure fields (acoustics and ultrasonics) on a wide range of nucleating systems. Combining the ultrasound pitch and catch speed of sound measurements with low power harmonically oscillating pressure fields to monitor and control nucleation presents the prospect of entirely new industrially significant methods of process control in crystallization. It also offers new insights into nucleation processes in general. However, for the acoustic control technique to be widely applied , further theoretical and modeling work will be necessary since, at present, we are unable to predict the precise effect of low power ultrasound in any given situation.

Early stages of fat crystallisation evaluated by low-field NMR and small-angle X-ray scattering.

Low-field time-domain nuclear magnetic resonance (NMR; 20 MHz) is commonly used in the studies of fats in the form of solid fat content (SFC) measurements. However, it has the disadvantage of low sensitivity to small amounts of crystalline material (0.5%), thus often incorrectly determining crystallisation induction times. From spin-lattice relaxation rate measurements (R1 ) during the isothermal crystallisation measurements of cocoa butter between 0.01 and 10 MHz using fast field cycling NMR, we learnt previously that the most sensitive frequency region is below 1 MHz. Thus, we focused on analysing our 10-kHz data in detail, by observing the time dependence of R1 and comparing it with standard SFCNMR and SFC determinations from small-angle X-ray scattering (SFCSAXS ). Although not reflecting directly the SFC, the R1 at this low frequency is very sensitive to changes in molecular aggregation and hence potentially serving as an alternative for determination of crystallisation induction times. Alongside R1 , we also show that SFCSAXS is more sensitive to early stages of crystallisation, that is, standard SFCNMR determinations become more relevant when crystal growth starts to dominate the crystallisation process but fail to pick up earlier crystallisation steps. This paper thus demonstrates the potential of studying triacylglycerols at frequencies below 1 MHz for obtaining further understanding of the early crystallisation stages of fats and presents an alternative and complementary method to estimate SFC by SAXS.

High-Stability Bi-Layer Films Incorporated with Liposomes @Anthocyanin/Carrageenan/Agar for Shrimp Freshness Monitoring.

High-stability bi-layer films were prepared by incorporating anthocyanin-loaded liposomes into carrageenan and agar (A-CBAL) for non-destructive shrimp freshness monitoring. The encapsulation efficiency of the anthocyanin-loaded liposomes increased from 36.06% to 46.99% with an increasing ratio of lecithin. The water vapor transmission (WVP) of the A-CBAL films, with a value of 2.32 × 10-7 g · m-1 · h-1 · pa-1, was lower than that of the film with free anthocyanins (A-CBA). The exudation rate of the A-CBA film reached 100% at pH 7 and pH 9 after 50 min, while the A-CBAL films slowed down to a value lower than 45%. The encapsulation of anthocyanins slightly decreased the ammonia sensitivity. Finally, the bi-layer films with liposomes successfully monitored shrimp freshness with visible color changes to the naked eye. These results indicated that films with anthocyanin-loaded liposomes have potential applications in high-humidity environments.

Study on cinnamon essential oil release performance based on pH-triggered dynamic mechanism of active packaging for meat preservation.

The regular release kinetics of active ingredients is inconsistent with the demand of meat preservation. Herein, the pH-triggered dynamic mechanism of packaging film was developed based on L100 polymer incorporated with Cinnamon essential oil (CEO) by coaxial electrospinning. The acquired results revealed that UV-vis and fluorescence spectra confirmed the pH release behavior. The fabricated film was quickly dissolved and transformed from solid to liquid phase, resulting in a faster release rate of CEO from 68.9 % to 98.2 % with the pH increasing. The morphological structure verified the core-shell structure formation with a specific surface area value of 7.22 m2/g. The live/dead results of bacteria indicated good antibacterial efficacy against E. coli and S. aureus. The pH-sensitive film successfully extends the shelf-life of griskin by 3 days. In conclusion, this work will aid in optimizing durability of active ingredients in packaging.

Novel gellan gum-based probiotic film with enhanced biological activity and probiotic viability: Application for fresh-cut apples and potatoes.

A novel probiotic film based on gellan gum (GN), cranberry extract (CE), and Lactococcus lactis (LA) was developed in the present study. The fluorescence and SEM image results showed that GN/CE film containing LA was successfully fabricated. The incorporation of LA significantly enhanced the antibacterial activity of the film. The presence of CE strengthened the antioxidant activity and LA survivability in the film. The combination of LA (0-1.0 %) and CE (0.5-1.0 %) improved the mechanical property of the film through the formation of density structure. The best comprehensive properties were obtained with the film containing 2.0 %LA and 0.5 %CE. The GN/2.0 %LA/0.5 %CE film also showed the optimal preservation effect on fresh-cut potatoes and apples. Hence, GN/2.0 %LA/0.5 %CE probiotic film has proved to be suitable for fruit and vegetable preservation.

A visual bi-layer sensor based on Agar/TiO2/butterfly bean flower anthocyanin/κ-carrageenan with photostability for monitoring Penaeus chinensis freshness.

Visual indicator bi-layer films were manufactured incorporating κ-carrageenan, butterfly pea flower anthocyanin, varying Nano­titanium dioxide (TiO2) content and agar for Penaeus chinensis (Chinese white shrimp) freshness detection. The κ-carrageenan-anthocyanin (CA) layer served as indicator, while the TiO2-agar (TA) layer functioned as the protective layer to improve the photostability of film. The bi-layer structure was characterized by scanning electron microscopy (SEM). The TA2-CA film had the best tensile strength with a value of 17.8 MPa and the lowest water vapor permeability (WVP) value of bi-layer films was 2.98 × 10-7 g.m-1.h-1.pa-1. The bi-layer film protected anthocyanin against exudation when immersed in aqueous solution of varying pH. The TiO2 particles filled the pores of the protective layer, increasing the opacity from 1.61 up to 4.49 significantly improving the photostability with a consequent slight color change under illumination of UV/visible light. Under UV irradiation, the TA2-CA film had no significant color change with a ΔE value of 4.23. Finally, the TA2-CA films showed an obvious color change from blue to yellow green in the early stages of Penaeus chinensis putrefaction (≤48 h) then the color change and Penaeus chinensis freshness were well correlated (R2 = 0.8739).

Entrapment of probiotic (Bifidobacterium longum) in bilayer emulsion film with enhanced barrier property for improving viability.

The gelatin/gellan gum based-bilayer emulsion film was developed in this work to improve the survivability of Bifidobacterium longum during the storage process. The baobab seed oil (BO) was added to the gelatin (GE) matrix to develop emulsion film as the barrier outer layer. The blueberry anthocyanin extract (BE) was incorporated into the gellan gum (GG)-based inner layer to enhance the viability of B. longum. The SEM and FTIR results revealed that the probiotics were successfully entrapped in BO/BE-loaded bilayer film. The greatest survivability and viable cell numbers of the B. longum during the storage period were observed in the BO/BE loaded bilayer film. Furthermore, the stability of the colorful patterns by electrochemical writing was also evaluated in this work. Finally, the GE/BO-GG/BE/BM maintain satisfactory probiotic viability in steamed bread coating application. Hence, the GE/BO-GG/BE/BM bilayer film could be considered a novel material to deliver and protect the probiotics in food applications.

Saccharomyces cerevisiae-incorporated and sucrose-rich sodium alginate film: An effective antioxidant packaging film for longan preservation.

A sodium alginate (SA) film incorporated with Saccharomyces cerevisiae (SE) and sucrose (SU) was fabricated to control the quality and pericarp browning of longan. The SE with satisfactory glutathione production was selected as the antioxidant agent. The scanning electron microscopy (SEM) results revealed that the SU-rich SA film could be used as an effective carrier to protect the cell integrity of SE. The FTIR and mechanical property results indicated that the SA-SE film with the incorporation of SU has good flexibility due to the existence of hydrogen bonds. Notably, the cell viability of the SE was significantly improved with the addition of SU, which positively affects the antioxidant property of the film during the storage period. Finally, the SA-SE-3.0%SU films obviously improved the quality and pericarp browning of longan. The SA-based film incorporated with SU and SE may be established as a novel antioxidant fruit packaging material.

Bilayer pH-sensitive colorimetric films with light-blocking ability and electrochemical writing property: Application in monitoring crucian spoilage in smart packaging.

Bilayer colorimetric films were developed for monitoring fish spoilage by using gelatin (GN) incorporated with ZnO nanoparticles as the upper layer (GN-ZnO), and gellan gum (GG) incorporated with mulberry anthocyanins (MBA) as the lower layer (GG-MBA). The color stability of the bilayer colorimetric films under visible and ultraviolet light was improved with the increase of ZnO nanoparticles content. Meanwhile, the bilayer films had good NH3 sensitivity. The limit of detection of the GG-MBA/GN-2.0% ZnO film to NH3 was 0.01 mM. The electrochemical writing ability of the bilayer films was also identified, indicating the feasibility of inks-free printing on biopolymer films. Finally, the GG-MBA/GN-2.0% ZnO film with an electrochemical writing pattern was used to monitor crucian spoilage. The GG-MBA/GN-2.0% ZnO film with electrochemical writing pattern showed visible color changes with the crucian spoilage. In conclusion, the bilayer colorimetric film was expected to be a good fish spoilage indicator in smart packaging.

Estimating the asphaltene critical nanoaggregation concentration region using ultrasonic measurements and Bayesian inference.

Bayesian inference and ultrasonic velocity have been used to estimate the self-association concentration of the asphaltenes in toluene using a changepoint regression model. The estimated values agree with the literature information and indicate that a lower abundance of the longer side-chains can cause an earlier onset of asphaltene self-association. Asphaltenes constitute the heaviest and most complicated fraction of crude petroleum and include a surface-active sub-fraction. When present above a critical concentration in pure solvent, asphaltene "monomers" self-associate and form nanoaggregates. Asphaltene nanoaggregates are thought to play a significant role during the remediation of petroleum spills and seeps. When mixed with water, petroleum becomes expensive to remove from the water column by conventional methods. The main reason of this difficulty is the presence of highly surface-active asphaltenes in petroleum. The nanoaggregates are thought to surround the water droplets, making the water-in-oil emulsions extremely stable. Due to their molecular complexity, modelling the self-association of the asphaltenes can be a very computationally-intensive task and has mostly been approached by molecular dynamic simulations. Our approach allows the use of literature and experimental data to estimate the nanoaggregation and its credible intervals. It has a low computational cost and can also be used for other analytical/experimental methods probing a changepoint in the molecular association behaviour.

Latest advances in imaging techniques for characterizing soft, multiphasic food materials.

Over the last two decades, the development and production of innovative, customer-tailored food products with enhanced health benefits have seen major advances. However, the manufacture of edible materials with tuned physical and organoleptic properties requires a good knowledge of food microstructure and its relationship to the macroscopic properties of the final food product. Food products are complex materials, often consisting of multiple phases. Furthermore, each phase usually contains a variety of biological macromolecules, such as carbohydrates, proteins and lipids, as well as water droplets and gas bubbles. Micronutrients, such as vitamins and minerals, might also play an important role in determining and engineering food microstructure. Considering this complexity, highly advanced physio-chemical techniques are required for characterizing the microstructure of food systems prior to, during and after processing. Fast, in situ techniques are also essential for industrial applications. Due to the wide variety of instruments and methods, the scope of this paper is focused only on the latest advances of selected food characterization techniques, with emphasis on soft, multi-phasic food materials.

A colorimetric hydrogen sulfide sensor based on gellan gum-silver nanoparticles bionanocomposite for monitoring of meat spoilage in intelligent packaging.

A colorimetric hydrogen sulfide (H2S) sensor based on gellan gum capped silver nanoparticles was developed to real-time monitor meat spoilage. The colorimetric sensor strategy was attributed to the ultrastrong binding ability of Ag with H2S to form Ag2S. The sensor enables the analysis of H2S with a limit of detection (LOD) of 0.81 µM, and it exhibited excellent selectivity toward H2S against other volatile components generated from chicken breast and silver carp during spoilage. By these virtues, the sensor presented visible color changes from yellow to colorless by in situ and nondestructively sensing H2S generated from chicken breast and silver carp in a packaging system. This strategy provided a simple but useful, non-destructive, robust, cost-effective, and user-friendly platform to real time monitor meat spoilage for intelligent food packaging.

Global Small-Angle X-ray Scattering Data Analysis of Triacylglycerols in the α-Phase (Part II).

The early-stage crystallization behavior in a triacylglycerol mixture has been investigated on the nanoscale with a novel global small-angle X-ray scattering analysis technique. This method has been tailored for the determination of the electron density profiles (EDPs) replicating both (i) the nanostructural texture of molten triacylglycerols (TAGs) (refer to "Global Small-Angle X-ray Scattering Data Analysis of Triacylglycerols in the Molten State (Part I)" of this publication series) and (ii) the lamellar structure of the metastable α-polymorph. In a first stage, the α-phase scattering contribution alone was examined by classical Fourier analysis as well as by globally fitting the data, leading to practically identical EDPs. On the basis of these findings, we extended our analysis to the entire X-ray scattering contribution arising from molten TAGs and the solid α-phase fraction. Remarkably, the experimental and theoretical data agree very well, providing for the first time a detailed nanostructural understanding about the coexisting molecular assemblies. This, in turn, also allowed us to quantitatively determine the solid fat content (SFC) with X-ray scattering data. Our new theoretical approach for measurement of SFC is based on the global analysis of small-angle scattering/diffraction patterns, and the SFC results are in good agreement with values obtained from other techniques such as NMR spectroscopy.

Global Small-Angle X-ray Scattering Data Analysis of Triacylglycerols in the Molten State (Part I).

The study of triacylglycerols (TAGs) in their molten state is of fundamental importance for a deeper understanding of the TAG crystallization processes, being highly relevant for both manufacturing and medical applications. Although different models have been proposed to explain the nanostructured nature of the fluid state of TAGs, none of them are fully satisfactory. In this paper, we propose a new model consisting of positionally uncorrelated lamellar TAG assemblies embedded in an isotropic medium that assist as prenucleating structures. This model was validated by applying a novel global fitting method, resulting in an excellent agreement with the small-angle X-ray scattering data. A deeper analysis of the scattering patterns at different temperatures, both in cooling and heating directions, allowed us further to detect the crystalline traces of TAGs even after heating to 40 °C and record, on cooling, the onset of crystallization at 30-25 °C. The application of the presented novel model not only explains the outstandingly structured fluid of molten TAGs, but also lays the basis for analyzing first the crystallization steps in greater detail, which is outlined in our follow-up paper "Global Small-Angle X-ray Scattering Data Analysis of Triacylglycerols in the α-Phase (Part II)".

Natural Biomaterial-Based Edible and pH-Sensitive Films Combined with Electrochemical Writing for Intelligent Food Packaging.

An edible and pH-sensitive film combined with electrochemical writing was developed by using gelatin, gellan gum, and red radish anthocyanins extract for intelligent food packaging. The composite film showed an orange red-to-yellow color change in the pH range of 2-12. The tensile strength, ductility, and barrier abilities to ultraviolet (UV) light and oxygen of the films were improved as the concentration of red radish anthocyanins increased. Multicolor patterns were successfully drawn on the films by using the electrochemical writing method. The composite films, which acted as gas sensors, presented visible color changes in the presence of milk and fish spoilage, while the written patterns were well-preserved. Accordingly, this composite film with written patterns could be an easy-to-use indicator with great potential for monitoring food spoilage as a part of an intelligent packaging system.