Testing for Breaks Using Alternating Observations

This paper proposes several new tests for structural change in the multivariate linear regression model. One of the most popular alternatives are Sup-Wald type tests along the lines of Bai, Lumsdaine and Stock (1998), which Bernard,Idoudi, Khalaf and Yélou (2007) show to have very large size distortions, especially for high dimensional systems. They propose the use of Monte Carlo type tests to control for size in finite samples. In this paper we propose several procedures that find a balance between the two previous approaches. We first estimate the break point using alternating observations, and then use the estimated breakpoint to create a test statistic either with the whole sample or with the observations not used for the breakpoint estimation. For the latter approach, it is then possible to use Monte Carlo methods to control size. In contrast to the Sup-Wald type tests, which have non-standard asymptotic distributions, we show that our tests are asymptotically distributed Chisquare using methods similar to those in Andrews (2004). Additionally, our tests stay asymptotically valid even when the distributional assumption made for the Monte Carlo adjustments is incorrect. We illustrate the new test statistics in the univariate context of discount rates and changes in the interest rates, and also in the multivariate setting of the Capital Asset Pricing Model.structural stability; structural change; multivariage linear regression model; breaks; Monte Carlo test; CAPM; discount rate

Application of accelerated heteronuclear single quantum coherence experiments to the rapid quantification of monosaccharides and disaccharides in dairy products

Monosaccharides and disaccharides are important dietary components, but if insufficiently metabolized by some population subgroups, they are also linked to disease patterns. Thus, the correct analytical identification, quantification, and labeling of these food components are crucial to inform and potentially protect consumers. Enzymatic assays and high-performance anion-exchange chromatography with pulsed amperometric detection are established methods for the quantification of monosaccharides and disaccharides that, however, require long measuring times (60–180 min). Accelerated methods for the identification and quantification of the nutritionally relevant monosaccharides and disaccharides d-glucose, d-galactose, d-fructose, sucrose, lactose, and maltose were therefore developed. To realize this goal, the NMR experiments HSQC (heteronuclear single quantum coherence) and acceleration by sharing adjacent polarization (ASAP)-HSQC were applied. Measurement times were reduced to 27 and 6 min, respectively, by optimizing the interscan delay and applying non-uniform sampling. The optimized methods were used to quantify d-glucose, d-galactose, d-fructose, sucrose, and lactose in various dairy products. Results of the HSQC and ASAP-HSQC methods are equivalent to the results of the reference methods in terms of both precision and accuracy, demonstrating that these methods can be used to correctly analyze nutritionally relevant monosaccharides and disaccharides in short times

Zearalenone-malonyl-glucosides as phase II metabolites in plant cell suspension cultures

Background and objectives Conjugation of mycotoxins in the phase II metabolism of plants results in modified mycotoxins such as glucosides and malonyl‐glucosides. However, malonyl‐glucosides have not yet been completely elucidated for zearalenone (ZEN). Thus, the aim of this study was to produce and isolate malonyl‐glucosides of ZEN for an unambiguous identification by NMR spectroscopy. Findings Zearalenone was incubated in plant cell suspension cultures of wheat, soy, and tobacco, and phase II metabolites were analyzed by using LC‐DAD‐MS, ‐HRMS, and NMR spectroscopy. Four main metabolites of ZEN were detected in the cell extracts and identified as two glucosides (attached in positions 14 and 16) and their 6´‐malonyl derivatives. Conclusions Zearalenone‐malonyl‐glucosides should be incorporated in future analyses of modified mycotoxins because of their potential relevance for food and feed safety. Significance and novelty For the first time, the structures of the two malonyl‐glucosides of ZEN were unambiguously identified by NMR spectroscopy after preparative isolation as 14‐O‐(6’‐O‐malonyl‐β‐D‐glucopyranosyl)ZEN and 16‐O‐(6’‐O‐malonyl‐β‐D‐glucopyranosyl)ZEN

Mechanical properties and compositional characteristics of beet (Beta vulgaris L.) varieties and their response to nitrogen application

Mechanical properties of sugar beet are important during harvesting and processing. To potentially correlate mechanical properties with structural features of cell wall polymers, four different Beta varieties (Beta vulgaris L.) were characterized for their mechanical properties and cell wall composition. In addition, the influence of nitrogen fertilization was analyzed. Additional nitrogen fertilization only slightly influenced mechanical properties and cell wall composition. Hardly any structural differences of cell wall polysaccharides were observed for all Beta varieties. Slight differences in alcohol insoluble residue and protein contents, in amino acid profiles of proteins, and in esterification degree of pectins were found. The Beta varieties differed in their contents of cell wall bound phenolic components, and particularly in their dry matter contents. Analyses of mechanical properties of the Beta varieties demonstrated differences in tissue firmness and compressive strength. However, no evidence was found that the observed differences of cell wall composition are responsible for the divergent mechanical properties, with the exception of water contents that were higher in samples with less compressive strength

ENSO hindcast skill in the DWD - MPI-M - UHH seasonal prediction system

KlimawandelWe present an assessment of the El Niño Southern Oscillation (ENSO) hindcast skill in the DWD - MPI-M - UHH seasonal prediction system based on the earth system model MPI-ESM. The system is initialised from re-analysis in the atmospheric, oceanic and sea-ice component of the model. We use a hindcast ensemble with semi-annual start dates between 1981 and 2014 (10 member ensembles started every May and November for 6 months each). We find hindcast skill for Niño 3.4 sea surface temperatures up to 6 months ahead. Hindcast skill is higher for November start dates than for May start dates. In addition to the Niño 3.4 Index, we also assess hindcast skill for Niño3, the West Pacific Warm Water Volume and the zonal wind variability. In particular we focus on the difference in the hindcast skill in the May start dates for the 1997/98 and the 2014 November conditions - though for these two periods overall similar conditions were observed, the subsequent development with a strong El Niño in 1997/98 and a very weak El Niño in 2014 differed considerably

Toward bioeconomy of a multipurpose cereal: Cell wall chemistry of Sorghum is largely buffered against stem sugar content

Background and Objectives Sorghum (Sorghum bicolor L. Moench) is a multipurpose crop with high potential for the bioeconomy. Ten sweet, grain and dual-purpose sorghum genotypes were compared with respect to sugar-related traits and cell wall composition. Findings The dual-purpose hybrids Ganymed, Zerberus, and Tarzan performed better with respect to plant height, cane weight, and juice volume, but the sweet genotype KIT1 produced the highest sugar concentration (°Brix) in the stem. Analytical sugar data demonstrate genotypic differences in terms of sugar composition and concentrations, with sucrose being dominant. The monosaccharide composition of the stem cell wall polysaccharides showed surprisingly little genotypic variability. Variations in contents of lignin and cell wall-bound hydroxycinnamate monomers were moderate. Conclusions Sweet, grain and dual-purpose sorghum genotypes differ widely in terms of sugar-related morphological parameters but are comparable with respect to their cell wall chemistry. Significance and Novelty The use of sorghum as a bioeconomy crop has mainly focused on the extraction of sugar for bioethanol production. However, besides cell wall polymers, the potential usage of hydroxycinnamates as platform molecules for the chemical industry may improve the valorization of the residues after sugar extraction. This application appears to be fairly independent of genotype, further increasing the potential of sorghum for the bioeconomy

Chemical composition and technofunctional properties of carrot (Daucus carota L.) pomace and potato (Solanum tuberosum L.) pulp as affected by thermomechanical treatment

Fiber rich by-products derived from primary agri-food production such as carrot pomace and potato pulp are available in large quantities, but their functional properties do not necessarily meet the requirements for use in specific food applications. Thermomechanical treatment (extrusion) of carrot pomace and potato pulp changes both dietary fiber polysaccharide structures and technofunctionality of the materials. Solubility of dietary fiber constituents changes, resulting in higher levels of water- and ethanol-soluble poly-/oligosaccharides. On a structural level, particularly arabinans and galactans as neutral side chains of type I rhamnogalacturonan were degraded under thermomechanical stress. Galacturonic acid portions (preferably from homogalacturonan or rhamnogalacturonan I) and their degree of methylation were also negatively affected. On a functional level, water absorption of potato pulp increased up to three times following extrusion, whereas water absorption of carrot pomace decreased with extrusion processing. The observed, enhanced swelling behavior for extruded carrot pomace was accompanied by higher complex viscosity of the dispersions. Swelling of potato pulp particles increased largely (up to 25 times) following extrusion, resulting in highly viscous pastes. Phytochemicals were retained up to 50%, heat-induced contaminants were formed only to a small extent (up to 8.1 mg 5-hydroxymethylfurfural·kg− 1 dry matter for carrot pomace; up to 71 µg acrylamide·kg$^{− 1}$ dry matter for potato pulp)

Molecular Characterization of Thymus capitellatus Extracts and Their Antioxidant, Neuroprotective and Anti-Proliferative Activities

Thymus capitellatus Hoffmanns & Link is an endemic species of the Iberian Peninsula listed as near-threatened, due to its restricted geographical distribution, occurring mainly in Portugal’s mainland. In this work, we detail for the first time T. capitellatus extracts’ phytochemical composition, as well as an evaluation of bioactivities to point out potential health benefits. Aqueous decoction (AD) and hydroethanolic (HE) extracts were obtained, both rich in flavonoids. However, quercetin-(?)-O-hexoside was identified as the main compound in T. capitellatus HE extract, while the phenolic acid rosmarinic acid was the main component of AD extracts. In addition, HE extract presents significant amounts of salvianolic acids and of the terpenoids oleanolic and ursolic acid. Both extracts showed antioxidant activity, evaluated by their capacity to scavenge ABTS and superoxide radicals, as well as an ability to prevent lipid peroxidation. AD extracts were also effective in scavenging hydroxyl and nitric oxide radicals. As potential functional foods, T. capitellatus extracts presented neuroprotective and anti-diabetic activity, in addition to time- and dose-dependent anti-proliferative activity against Caco-2 (colorectal adenocarcinoma) and HepG2 (hepatic carcinoma) cells. HE extract presented higher cytotoxicity than AD extract, and HepG2 cells were more resistant than Caco-2 cells. After 24 h exposure to HE extract, the IC$_{50}$ values were 330 μg/mL and 447 μg/mL for Caco-2 and HepG2 cells, respectively. T. capitellatus has potential as a functional food or as a source of bioactive molecules. These results also highlight the need to preserve species with as yet unknown molecular compositions and potential medicinal applications

Quantitative profiling of feruloylated arabinoxylan side-chains from graminaceous cell walls

Graminaceous arabinoxylans are distinguished by decoration with feruloylated monosaccharidic and oligosaccharidic side-chains. Although it is hypothesized that structural complexity and abundance of these feruloylated arabinoxylan side-chains may contribute, among other factors, to resistance of plant cell walls to enzymatic degradation, quantitative profiling approaches for these structural units in plant cell wall materials have not been described yet. Here we report the development and application of a rapid and robust method enabling the quantitative comparison of feruloylated side-chain profiles in cell wall materials following mildly acidic hydrolysis, C18-solid phase extraction (SPE), reduction under aprotic conditions, and liquid chromatography with diode array detection/mass spectrometry (LC-DAD/MS) separation and detection. The method was applied to the insoluble fiber/cell wall materials isolated from 12 whole grains: wild rice (Zizania aquatica L.), long-grain brown rice (Oryza sativa L.), rye (Secale cereale L.), kamut (Triticum turanicum Jakubz.), wheat (Triticum aestivum L.), spelt (Triticum spelta L.), intermediate wheatgrass (Thinopyrum intermedium), maize (Zea mays L.), popcorn (Zea mays L. var. everta), oat (Avena sativa L.) (dehulled), barley (Hordeum vulgare L.) (dehulled), and proso millet (Panicum miliaceum L.). Between 51 and 96% of the total esterified monomeric ferulates were represented in the quantified compounds captured in the feruloylated side-chain profiles, which confirms the significance of these structures to the global arabinoxylan structure in terms of quantity. The method provided new structural insights into cereal grain arabinoxylans, in particular, that the structural moiety α-L-galactopyranosyl (1→2)-β-D-xylopyranosyl-(1→2)-5-O-trans-feruloyl-L-arabinofuranose (FAXG), which had previously only been described in maize, is ubiquitous to cereal grains. © 2016 Schendel, Meyer and Bunzel

Defined shear and heat treatment of apple pomace: impact on dietary fiber structures and functional properties

Food by-products can be modified by extrusion processing. However, the impact of thermal and mechanical stress, respectively, on the structure and thus functional properties of dietary fiber-rich food by-products is still unknown. In the extrusion process, thermal and mechanical stress are coupled, not constant, and difficult to measure or calculate. Thus, their influence on structural changes and functional properties cannot be evaluated separately. In this work, a specific shear cell, denoted by closed cavity rheometer, was used to treat apple pomace with defined thermal and/or mechanical stress. Dietary fiber composition and fiber polysaccharide structures appeared to be more susceptible to high temperatures than mechanical stress. With increasing temperature (and mechanical stress) soluble and low-molecular-weight soluble dietary fiber contents increased, whereas insoluble fiber contents decreased. Arabinans as rhamnogalacturonan type I polysaccharides and galacturonic acid containing pectic polysaccharides were identified as being most susceptible to degradation under these conditions. Furthermore, the defined treatment affected the functional properties. Although changes in the water solubility index (WSI) and/or the water absorption index (WAI) were not detected up to 90 °C, WSI and WAI decreased significantly at a treatment temperature of 120 °C. However, at very high temperatures (160 °C), WSI and WAI increased. The application of shear and longer treatment times resulted in higher WSI values and complex viscosities as compared to low shear stress