Phenolic Extraction of Moringa oleifera Leaves in DES: Characterization of the Extracts and Their Application in Methylcellulose Films for Food Packaging.

In this work, a qualitative study of the phenolic content of Moringa oleifera leaves (MO), extracted with deep eutectic solvents (DES) based on choline chloride (ChCl) with lactic acid (LA) or glycerol (GLY), was performed by high-resolution mass spectrometry (HPLC-DAD-ESI-MSn). The two solvents (DES-LA and DES-GLY) extract similar classes of phenolics, and ten compounds were identified. The antioxidant profile was also studied (TPC, TFC, DPPH, FRAP, ORAC, and ABTS). Both solvents show an efficient extraction of phenolic compounds and high antioxidant capacity was verified for the extracts. However, the DES-Gly have a higher capacity for polyphenolic extraction (TPC led to 38.409 ± 0.095 mg GAE.g-1 and 2.259 ± 0.023 mg QE.g-1 for TFC). Films based on methylcellulose (MC) containing different amounts of DES or MO extracts, acting as plasticizers, were developed and characterized regarding their mechanical, optical, water vapor permeability, and microstructural properties. All films are uniform, clear, and transparent with smooth, homogeneous surfaces. It was found that the presence of more than 10% of MO extract and/or DES provided more flexible films (Eb for MC 2%_DES 20% achieved 4.330 ± 0.27 %, and 8.15 ± 0.39 % for MC 2%_MO 20%) with less mechanical and barrier resistance. The ultimate objective of this study was to provide information that could assist in the development of antimicrobial active methylcellulose films for sliced wheat bread packaging.

Real Time Water-In-Oil Emulsion Size Measurement in Optofluidic Channels.

In this work, we investigated a platform for real-time emulsion droplet detection and size measurement in optofluidic platforms. An 8.2 µm core diameter input optical fiber and a multi-mode Gradient Refractive Index (GRIN) output fiber were integrated into an acrylic microfluidic channel platform consisting of three layers. Water-in-oil emulsions were investigated, since relevant applications have emerged in the recent past for these types of emulsions, such as drug encapsulation as well as droplet-based Polymerase Chain Reaction (PCR) amplification of DNA, among others. The main contribution of this work is in understanding the main physical phenomena (i.e., total internal reflection, refraction, and interference) behind the complex transmittance pattern obtained for these droplets. For this purpose, a frequency domain electromagnetic wave propagation modelling of the structure using the Finite Element Method (FEM) was used along with experimental measurements.

A review on the fate of phenolic compounds during malting and brewing: Technological strategies and beer styles.

This review provides an overview on the influence of malting and brewing on the overall phenolic content of barley malt and beer. Beer phenolics are mainly originated from barley malt and can be found in free and bound forms, in concentrations up to 50% lower comparing to sweet wort. The use of roasted malts, in combination with proper milling and high mashing temperatures at low pH can lead to a release of bound phenolic forms and increased extraction. New technological strategies such as special yeasts, manipulation of enzymatic activity and dry-hopping may be relevant to improve the phenolic profile of beer and attain phenolic levels with benefits both for beer stability and consumer's health. As the content of free ferulic acid in beer only accounts up to approximately 15% of total content, further studies should put emphasis on its bound forms in different beer styles and non-alcoholic beers.

Gas-Diffusion Microextraction (GDME) Combined with Derivatization for Assessing Beer Staling Aldehydes: Validation and Application.

In this work, a gas-diffusion microextraction (GDME) methodology was optimized and validated for the analysis of selected staling aldehydes (furfural (FURF), 2-methylpropanal (2-MP), 2-methylbutanal (2-MB), 3-methylbutanal (3-MB), and acetaldehyde (ACET)) during natural and forced aging of beer. The methodology was optimized considering time, temperature of extraction, and derivatizing agent. Using 4-hydrazinobenzoic acid (HBA) as a derivatizing agent, the performance of the method was evaluated by assessing several parameters such as detection limits (ranging from 1.2 to 1857.7 µg/L for 2-MB and ACET, respectively), quantification limits (ranging from 3.9 to 6192.4 µg/L for 2-MB and ACET, respectively), recoveries (higher than 96%), intraday and interday precisions (lower than 3.4 and 9.2%, respectively), and linearity (r2 ≥ 0.995). During beer aging, higher content of Strecker aldehydes and FURF were found, while no significant variations in ACET levels were observed. In general, the aldehydes content assessed for beers stored at 37 ± 1 °C for 7 and 14 days mimics that observed for beers stored at 20 ± 2 °C for 3 and 6 months, respectively. Lower temperatures of storage (4 ± 1 °C) delayed the development of staling aldehydes. Based on PCA analysis, the content of staling aldehydes and beer color were responsible for 91.39% of the variance among the analyzed samples, and it was demonstrated that these are key parameters to discriminate fresh from aged beers. The results herein presented showed that the proposed analytic methodology is a valuable strategy for the characterization and quantification of important staling aldehydes in beer with a potential application in the quality control of beer during storage.

Antiangiogenic and Antioxidant In Vitro Properties of Hydroethanolic Extract from açaí (Euterpe oleracea) Dietary Powder Supplement.

The Euterpe oleracea fruit (açaí) is a promising source of polyphenols with health-promoting properties. To our knowledge, few studies have focused on the influence of açaí phytochemicals on angiogenesis, with a significant impact on cancer. This study aimed at investigating the phytochemical profile of a purple açaí hydroethanolic extract (AHE) obtained from a commercial dietary powder supplement by high-performance liquid chromatography coupled to diode array detection and electrospray ionization mass spectrometry, and evaluate its in vitro effects on distinct angiogenic steps during vessel growth and on oxidative markers in human microvascular endothelial cells (HMEC-1). The phenolic profile of AHE revealed the presence of significant levels of anthocyanins, mainly cyanidin-3-O-rutinoside, and other flavonoids with promising health effects. The in vitro studies demonstrated that AHE exerts antiangiogenic activity with no cytotoxic effect. The AHE was able to decrease HMEC-1 migration and invasion potential, as well as to inhibit the formation of capillary-like structures. Additionally, AHE increased antioxidant defenses by upregulating superoxide dismutase and catalase enzymatic activities, accompanied by a reduction in the production of reactive oxygen species. These data bring new insights into the potential application of angiogenic inhibitors present in AHE on the development of novel therapeutic approaches for angiogenesis-dependent diseases.

Low-loss pedestal Ta2O5 nonlinear optical waveguides.

In this work, we investigate a pedestal tantalum oxide (Ta2O5) material platform for integrated nonlinear optics (NLO). In order to achieve low propagation losses with this material, pedestal waveguides with Ta2O5 cores were designed. The nonlinear refractive index n2 of this new platform was obtained by measuring the amount of spectral broadening due to self-phase modulation (SPM) of 23 fs optical pulses at 785 nm propagating through the waveguides. In this manner, a nonlinear index of (5.8 ± 2.0) × 10-19 m2W-1 was found for this material, which is in good agreement with values reported in related works where strip waveguides were used for a similar purpose. Furthermore, due to the pedestal configuration, propagation losses as low as 1.6 dB·cm-1 for narrow waveguides and 0.1 dB·cm-1 for large waveguides were obtained. Finite element method (FEM) mode analysis was performed to calculate the mode characteristics, as well as the effective areas of the waveguides. The high nonlinear and linear refractive indices, wide bandgap and low propagation losses make this platform ideal for applications extending from the visible into the mid-IR regions of the optical spectrum. Due the large gap, Ta2O5 should have low two photon absorption at the near-IR as well.

Determination of Acrylamide in Biscuits by High-Resolution Orbitrap Mass Spectrometry: A Novel Application.

Acrylamide (AA), a molecule which potentially increases the risk of developing cancer, is easily formed in food rich in carbohydrates, such as biscuits, wafers, and breakfast cereals, at temperatures above 120 °C. Thus, the need to detect and quantify the AA content in processed foodstuffs is eminent, in order to delineate the limits and mitigation strategies. This work reports the development and validation of a high-resolution mass spectrometry-based methodology for identification and quantification of AA in specific food matrices of biscuits, by using LC-MS with electrospray ionization and Orbitrap as the mass analyser. The developed analytical method showed good repeatability (RSDr 11.1%) and 3.55 and 11.8 µg kg-1 as limit of detection (LOD) and limit of quantification (LOQ), respectively. The choice of multiplexed targeted-SIM mode (t-SIM) for AA and AA-d3 isolated ions provided enhanced detection sensitivity, as demonstrated in this work. Statistical processing of data was performed in order to compare the AA levels with several production parameters, such as time/cooking temperature, placement on the cooking conveyor belt, color, and moisture for different biscuits. The composition of the raw materials was statistically the most correlated factor with the AA content when all samples are considered. The statistical treatment presented herein enables an important prediction of factors influencing AA formation in biscuits contributing to putting in place effective mitigation strategies.

Xanthohumol inhibits cell proliferation and induces apoptosis in human thyroid cells.

The cell growth inhibitory potential of xanthohumol (XN), a natural prenylflavonoid present in hops and beer, on human papillary thyroid cancer cells is reported. We demonstrate that XN decreases the proliferation of TPC-1 cancer cells in a dose and time dependent manners. At low concentration (10 µM) XN was shown to significantly inhibit carcinogenesis by a mechanism that stops or slows down cell division, preserving the viability of the cells. At higher concentration (100 µM) a decrease of cell viability was observed by induction of apoptosis. As evidenced, XN induced DNA fragmentation in TPC-1 cells and promoted cell cycle arrest, which decreased the percentage of cells in G1 phase and increased in S phase after 72 h of treatment. Furthermore, XN exposure triggered an increase in caspase-3 and caspase-7 activity, supporting its role in the activation of apoptosis. Cell-free studies demonstrated that high concentrations of XN are responsible for an increase of free radicals generated in a Fenton system which may mediate apoptosis through a pro-oxidant pathway. Altogether, our data show that XN induces the apoptosis of TPC-1 cancer cells in a concentration-dependent manner, suggesting XN to be a promising candidate for thyroid cancer therapy.

Study of the pedestal process for reducing sidewall scattering in photonic waveguides.

In this work we investigate the principles of an alternative method for defining sidewall in optical waveguides fabricated using planar technology. The efficiency of this method is demonstrated through simulations and experimental results regarding propagation losses of a solid core ARROW waveguide fabricated on silicon substrate. It is well known that waveguides fabricated using sidewalls etched via Reactive Ion Etching (RIE) can present high sidewall roughness, especially if metallic hard-masks are used. This is largely responsible for the undesirable losses observed in these waveguides. The basic strategy of the proposed method is to do the etching step, in the fabrication of the waveguides, before the deposition of the core, so as to have the lower cladding layer and part of the silicon substrate etched away. Only after this, is the core of the waveguide deposited. This results in a waveguide sustained by a silicon pedestal. With this process, losses as low as 0.45 dB cm-1 for multimode and 0.84 dB cm-1 for single mode waveguides are obtained. The numerical simulations demonstrate that roughness in sidewalls implicates in propagation losses which are at least five times larger that those in the bulk of the material, thus corroborating the idea behind the proposed method.

Dose-Dependent Protective and Inductive Effectsof Xanthohumol on Oxidative DNA Damage inSaccharomyces cerevisiae.

The effect of xanthohumol, a prenylflavonoid isolated from the hop plant (Humulus lupulus L.), on Saccharomyces cerevisiae DNA oxidative damage and viability was evaluated. Yeast cultures under oxidative stress, induced by H2O2, displayed stronger growth in the presence of 5 mg/L of xanthohumol than cultures with only H2O2. Likewise, DNA damage assessed by the comet assay was significantly lower in cells co-incubated with xanthohumol and H2O2. Accordingly, fluorescence of dichlorofluorescein in cells treated with H2O2 and xanthohumol was considerably lower than in cells exclusively treated with H2O2, indicative of a reactive oxygen species scavenging mechanism and consequent formation of oxidation products, as detected by mass spectrometry. However, at concentrations above 5 mg/L, xanthohumol elicited an opposite effect, leading to a slower growth rate and significant increase in DNA damage. A yeast yap1 deletion mutant strain sensitive to oxidative stress grew more slowly in the presence of at least 5 mg/L of xanthohumol than cultures of the wild type, suggesting that xanthohumol toxicity is mediated by oxidative stress. This evidence provides further insight into the impact of xanthohumol on yeast cells, supporting dose-dependent antioxidant/antigenotoxic and prooxidant/genotoxic effects.

Quantum random number generator using a microresonator-based Kerr oscillator.

We demonstrate an all-optical quantum random number generator using a dual-pumped degenerate optical parametric oscillator in a silicon nitride microresonator. The frequency-degenerate bi-phase state output is realized using parametric four-wave mixing in the normal group-velocity dispersion regime with two nondegenerate pumps. We achieve a random number generation rate of 2 MHz and verify the randomness of our output using the National Institute of Standards and Technology Statistical Test Suite. The scheme offers potential for a chip-scale random number generator with gigahertz generation rates and no postprocessing.

Overall Antioxidant Properties of Malt and How They Are Influenced by the Individual Constituents of Barley and the Malting Process.

In the past several years researchers have focused on the study of the antioxidant properties of barley and barley malt as well as their influence on beer quality. Some malt constituents have been reported as potent antioxidants due to their radical-scavenging and reducing properties, with a positive effect on beer oxidative stability. However, barley and malt can suffer some serious modifications during malting and roasting, namely on the levels of phenolic compounds and the development of Maillard reaction products, which may have a great impact on the overall antioxidant properties of malt. Although some studies have reported an increase of the antioxidant capacity during malting, others have mentioned an opposite effect. Recently, researchers have shown that compounds developed in malt during heat treatment at high temperature and long periods of time, as result of the Maillard reaction, can also exhibit pro-oxidant properties involving the metal-catalyzed Fenton reaction due to its reductive properties. This paper reviews important information and recent data regarding the chemical changes malting and roasting undergo along with their influence on the different anti- and pro-oxidant properties described for barley and malt. The contribution of individual components to the overall antioxidant capacity of malt is also discussed.

Dual-pumped degenerate Kerr oscillator in a silicon nitride microresonator.

We demonstrate a degenerate parametric oscillator in a silicon nitride microresonator. We use two frequency-detuned pump waves to perform parametric four-wave mixing and operate in the normal group-velocity dispersion regime to produce signal and idler fields that are frequency degenerate. Our theoretical modeling shows that this regime enables generation of bimodal phase states, analogous to the χ(2)-based degenerate OPO. Our system offers potential for realization of CMOS-chip-based coherent optical computing and an all-optical quantum random number generator.

Determination of Phenolic Content in Different Barley Varieties and Corresponding Malts by Liquid Chromatography-diode Array Detection-Electrospray Ionization Tandem Mass Spectrometry.

A simple and reliable method for the simultaneous determination of nine phenolic compounds in barley and malted barley was established, using liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS/MS). The phenolic compounds can be easily detected with both systems, despite significant differences in sensitivity. Concentrations approximately 180-fold lower could be achieved by mass spectrometry analysis compared to diode array detection, especially for the flavan-3-ols (+)-catechin and (-)-epicatechin, which have poor absorptivity in the UV region. Malt samples were characterized by higher phenolic content comparing to corresponding barley varieties, revealing a significant increase of the levels of (+)-catechin and (-)-epicatechin during the malting process. Moreover, the industrial malting is responsible for modification on the phenolic profile from barley to malt, namely on the synthesis or release of sinapinic acid and epicatechin. Accordingly, the selection of the malting parameters, as well as the barley variety plays an important role when considering the quality and antioxidant stability of beer.

Bandwidth shaping of microresonator-based frequency combs via dispersion engineering.

We investigate experimentally and theoretically the role of group-velocity dispersion and higher-order dispersion on the bandwidth of microresonator-based parametric frequency combs. We show that the comb bandwidth and the power contained in the comb can be tailored for a particular application. Additionally, our results demonstrate that fourth-order dispersion plays a critical role in determining the spectral bandwidth for comb bandwidths on the order of an octave.

Further insights into the role of melanoidins on the antioxidant potential of barley malt.

The role of Maillard reaction products isolated from barley malt by gel permeation chromatography and ultrafiltration on the antioxidant potential of pale, melano80 and black malts was evaluated. The roasting process is responsible for the polymerisation of early formed lower molecular weight compounds (<10 kDa) into high molecular weight melanoidins (>300 kDa). Melanoidins showed 3-fold higher capacity to scavenge radicals than the lower molecular weight colorants by the metmyoglobin assay. However, a significant decrease of the capacity of black malt and high molecular weight melanoidins to inhibit Fenton induced hydroxyl degradation of deoxyribose was observed. As the high molecular weight fraction, isolated from the black malt extract, exhibited 4-fold higher reducing power than the lower molecular weight fraction, our results support a pro-oxidant effect due to the catalytic formation of hydroxyl radicals in the presence of ferric ions.

Fundamentals and health benefits of xanthohumol, a natural product derived from hops and beer.

In recent years, there has been a growing interest in phenolic compounds and their presumed role in the prevention of various degenerative diseases, such as cancer and cardiovascular diseases. Xanthohumol, a prenylated chalcone from hops and beer, is among the phenolic compounds which have received the most attention in recent years. This compound has a range of interesting biological properties that may have therapeutic utility. Based on the health-promoting properties of xanthohumol, the production of a beer enriched in this substance would be of huge interest to the brewing industry, for the benefits this could bring to consumer's health. This paper reviews recent and important data with respect to the health benefits or biological activities of xanthohumol and beer. In addition, an overview of the chemistry and biotechnological aspects of xanthohumol is presented.

Detection and quantification of provitamin D2 and vitamin D2 in hop (Humulus lupulus L.) by liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry.

In this work, ergosterol and ergocalciferol were identified for the first time in hop. In addition, in this article, a simple and reliable analytical methodology for analysis of these compounds in different commercial forms of hop is presented. The performance of the method was assessed by the evaluation of parameters such as absolute recovery (higher than 70%), repeatability (lower than 3 %), linearity ( r(2) > 0.9988) and limits of detection (ranging from 0.034 for ergocalciferol to 0.058 mg/L for ergosterol) and quantification (ranging from 0.113 for ergocalciferol to 0.195 mg/L for ergosterol). On the basis of standard additions applied with the optimized procedure and high-performance liquid chromatography with diode array detection, it appears that the Nugget hop plant (crop 2006) contains 1.84 +/- 0.09 microg/g of ergosterol and 1.95 +/- 0.05 microg/g of ergocalciferol. The identity of the compounds was confirmed by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry in the positive ion mode. The presence of ergosterol here reported should have great potential for the assessment of hop as related to the fungal contamination proportion and hence the quality of this raw material.