Determination of glucosinolates and isothiocyanates in glucosinolate-rich vegetables and oilseeds using infrared spectroscopy: A systematic review.

Cruciferous vegetables and oilseeds are rich in glucosinolates that can transform into isothiocyanates upon enzymic hydrolysis during post-harvest handling, food preparation and/or digestion. Vegetables contain glucosinolates that have beneficial bioactivities, while glucosinolates in oilseeds might have anti-nutritional properties. It is therefore important to monitor and assess glucosinolates and isothiocyanates content through the food value chain as well as for optimized crop production. Vibrational spectroscopy methods, such as infrared (IR) spectroscopy, are used as a nondestructive, rapid and low-cost alternative to the current and common costly, destructive, and time-consuming techniques. This systematic review discusses and evaluates the recent literature available on the use of IR spectroscopy to determine glucosinolates and isothiocyanates in vegetables and oilseeds. NIR spectroscopy was used to predict glucosinolates in broccoli, kale, rocket, cabbage, Brussels sprouts, brown mustard, rapeseed, pennycress, and a combination of Brassicaceae family seeds. Only one study reported the use of NIR spectroscopy to predict broccoli isothiocyanates. The major limitations of these studies were the absence of the critical evaluation of errors associated with the reference method used to develop the calibration models and the lack of interpretation of loadings or regression coefficients used to predict glucosinolates.

Manipulation of the Phytochemical Profile of Tenderstem® Broccoli Florets by Short Duration, Pre-Harvest LED Lighting.

Light quality has been reported to influence the phytochemical profile of broccoli sprouts/microgreens; however, few studies have researched the influence on mature broccoli. This is the first study to investigate how exposing a mature glasshouse grown vegetable brassica, Tenderstem® broccoli, to different light wavelengths before harvest influences the phytochemical content. Sixty broccoli plants were grown in a controlled environment glasshouse under ambient light until axial meristems reached >1 cm diameter, whereupon a third were placed under either green/red/far-red LED, blue LED, or remained in the original compartment. Primary and secondary spears were harvested after one and three weeks, respectively. Plant morphology, glucosinolate, carotenoid, tocopherol, and total polyphenol content were determined for each sample. Exposure to green/red/far-red light increased the total polyphenol content by up to 13% and maintained a comparable total glucosinolate content to the control. Blue light increased three of the four indole glucosinolates studied. The effect of light treatments on carotenoid and tocopherol content was inconclusive due to inconsistencies between trials, indicating that they are more sensitive to other environmental factors. These results have shown that by carefully selecting the wavelength, the nutritional content of mature broccoli prior to harvest could be manipulated according to demand.

Design of practicable phase-change metadevices for near-infrared absorber and modulator applications.

Phase-change chalcogenide alloys, such as Ge2Sb2Te5 (GST), have very different optical properties in their amorphous and crystalline phases. The fact that such alloys can be switched, optically or electrically, between such phases rapidly and repeatedly means that they have much potential for applications as tunable photonic devices. Here we incorporate chalcogenide phase-change films into a metal-dielectric-metal metamaterial electromagnetic absorber structure and design absorbers and modulators for operation at technologically important near-infrared wavelengths, specifically 1550 nm. Our design not only exhibits excellent performance (e.g. a modulation depth of ~77% and an extinction ratio of ~20 dB) but also includes a suitable means for protecting the GST layer from environmental oxidation and is well-suited, as confirmed by electro-thermal and phase-transformation simulations, to in situ electrical switching. We also present a systematic study of design optimization, including the effects of expected manufacturing tolerances on device performance and, by means of a sensitivity analysis, identify the most critical design parameters.

Correction: Surface nanobubbles on the carbonate mineral dolomite.

[This corrects the article DOI: 10.1039/C8RA07952H.].

Vibrational Strong Coupling with Surface Plasmons and the Presence of Surface Plasmon Stop Bands.

We demonstrate strong coupling between surface plasmon resonances and molecular vibrational resonances of poly(methyl methacrylate) (PMMA) molecules in the mid-infrared range through the use of grating coupling, complimenting earlier work using microcavities and localized plasmon resonances. We choose the period of the grating so that we may observe strong coupling between the surface plasmon mode associated with a patterned gold film and the C=O vibrational resonance in an overlying polymer film. We present results from experiments and numerical simulations to show that surface plasmon modes provide convenient open cavities for vibrational strong coupling experiments. In addition to providing momentum matching between surface plasmon modes and incident light, gratings may also produce a modification of the surface plasmon properties, notably their dispersion. We further show that for the parameters used in our experiment surface plasmon stop bands are formed, and we find that both stop-band edges undergo strong coupling.

Surface nanobubbles on the rare earth fluorcarbonate mineral synchysite.

Surface nanobubbles have been identified to play an important role in a range of industries from mineral processing to food science. The formation of surface nanobubbles is of importance for mineral processing in the extraction of complex ores, such as those containing rare earth elements. This is due to the way minerals are extracted utilising froth flotation. In this study, surface nanobubbles were imaged using non-contact atomic force microscopy on a polished cross section containing rare earth minerals. Nanobubbles were found on synchysite under reagent conditions expected to induce hydrophobicity in rare earth minerals, which is required for efficient processing. Synchysite -(Ce) is a rare earth fluorcarbonate mineral containing over 30% rare earth elements. Relatively little research has been conducted on synchysite, with only a few papers on its surface behaviour and flotation. The resulting nanobubbles were analysed and showed an average contact angle of 24°â€¯±â€¯8. These are in line with contact angles found on dolomite and galena by previous studies.

Apatite enrichment by rare earth elements: A review of the effects of surface properties.

Apatite subspecies depend on their halogen and hydroxyl content; chlorapatite, hydroxylapatite and fluorapatite, with additional substitution of other elements within the lattice such as rare earth elements (REE), sodium, strontium and manganese also possible. Rare earth elements are vital to green and emerging technologies, with demand set to outstrip supply. Apatite provides a possible future source of REE. Processing rare earth deposits is often complex, with surface behaviour having a significant effect on the optimization of a process flow sheet. The effect of enrichment of natural apatite and the doping of synthetic apatite on surface behaviour can be determined by measuring the zeta potential and the isoelectric point of the mineral. In this paper, we review zeta potential studies of natural and synthetic apatite to determine the effect of elemental enrichment on surface behaviour. Fifty three studies of natural apatite and forty four studies of synthetic apatite were reviewed. The isoelectric point of apatite varied from pH 1 to pH 8.7, with studies of apatite specified to be >90% pure reducing the variation to pH 3 to pH 6.5. Of the four studies of rare earth enriched apatite found, three had IEP values between pH 3 and pH 4. A study of synthetic apatite showing enrichment of between 1 and 10% by the REE europium does not affect surface behaviour. However, no studies were found that investigated the effect of common REE processing reagents on REE enriched apatite zeta potentials. Therefore, in addition to comparing previous studies we also therefore present new zeta potential measurements of apatite from a REE enriched deposit under water and common flotation collector conditions. The IEP value of this apatite under water conditions was at pH 3.6, shifting to <3.5 under both hydroxamic acid and betacol conditions. When compared to previous studies, the behaviour of REE enriched apatite under collector conditions is similar to non-REE apatite. This result could be important for future processing of apatite enriched with REE, and therefore global apatite and rare earth supply.

Metamaterial-enhanced infrared attenuated total reflection spectroscopy.

The use of Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR) allows solid or liquid samples to be characterised directly without specific sample preparation. In such a system, the evanescent waves generated through total internal reflection within a crystal interact with the sample under test. In this work we explore the use of a mid-infrared metasurface to enhance the interaction between molecular vibrations and the evanescent waves. A complementary ring-resonator structure was patterned onto both silicon and SiO2/Si substrates, and the spectral properties of both devices were characterised using a FTIR-ATR system. Minima in reflectance were observed corresponding to the resonance of the metasurface on the silicon substrate, and to the hybrid resonance of phonon modes and metasurface resonances on the SiO2/Si substrate, in good agreement with simulations. Preliminary experiments were undertaken using mixtures containing trace amounts of butyl acetate diluted with oleic acid. Without the use of a metasurface, the minimum concentration of butyl acetate that could be clearly detected was 10%, whereas the use of the metasurface on the SiO2/Si substrate allowed the detection of 1% butyl acetate. This demonstrates the potential of using metasurfaces to enhance trace chemical detection in FTIR-ATR systems.

Surface nanobubbles on the carbonate mineral dolomite.

Surface nanobubbles are of wide interest to a number of research fields, ranging from mineral processing to metamaterials. Their formation on hydrophobic surfaces has long been confirmed but the factors controlling their size and location are less well understood. In this work we investigate, using non-contact atomic force microscopy, the properties of surface nanobubbles on the mineral dolomite under three aqueous solutions; water, depressant and collector. Nanobubbles were observed under all three conditions, but with the highest density observed under collector conditions. Analysis of the critical angle of the bubbles suggests that the collector does not affect the surface tension of the bubbles, but instead does affect their pinning, consistent with the observed increased density.

Highly tunable hybrid metamaterials employing split-ring resonators strongly coupled to graphene surface plasmons.

Metamaterials and plasmonics are powerful tools for unconventional manipulation and harnessing of light. Metamaterials can be engineered to possess intriguing properties lacking in natural materials, such as negative refractive index. Plasmonics offers capabilities of confining light in subwavelength dimensions and enhancing light-matter interactions. Recently, the technological potential of graphene-based plasmonics has been recognized as the latter features large tunability, higher field-confinement and lower loss compared with metal-based plasmonics. Here, we introduce hybrid structures comprising graphene plasmonic resonators coupled to conventional split-ring resonators, thus demonstrating a type of highly tunable metamaterial, where the interaction between the two resonances reaches the strong-coupling regime. Such hybrid metamaterials are employed as high-speed THz modulators, exhibiting ∼60% transmission modulation and operating speed in excess of 40 MHz. This device concept also provides a platform for exploring cavity-enhanced light-matter interactions and optical processes in graphene plasmonic structures for applications including sensing, photo-detection and nonlinear frequency generation.