Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

The reversible oxidation of methionine residues in proteins has emerged as a biologically important post-translational modification. However, detection and quantitation of methionine sulfoxide in proteins is difficult. Our aim is to develop a method for specifically derivatizing methionine sulfoxide residues. We report a Pummerer rearrangement of methionine sulfoxide treated sequentially with trimethylsilyl chloride and then 2-mercaptoimidazole or pyridine-2-thiol to produce a dithioacetal product. This derivative is stable to standard mass spectrometry conditions, and its formation identified oxidized methionine residues. The scope and requirements of dithioacetal formation are reported for methionine sulfoxide and model substrates. The reaction intermediates have been investigated by computational techniques and by ¹³C NMR spectroscopy. These provide evidence for an α-chlorinated intermediate. The derivatization allows for detection and quantitation of methionine sulfoxide in proteins by mass spectrometry and potentially by immunochemical methods.     

Gene Discovery in Gelsemium Highlights Conserved Gene Clusters in Monoterpene Indole Alkaloid Biosynthesis

Genome mining is a routine technique in microbes for discovering biosynthetic pathways. In plants, however, genomic information is not commonly used to identify novel biosynthesis genes. Here, we present the genome of the medicinal plant and oxindole monoterpene indole alkaloid (MIA) producer Gelsemium sempervirens (Gelsemiaceae). A gene cluster from Catharanthus roseus, which is utilized at least six enzymatic steps downstream from the last common intermediate shared between the two plant alkaloid types, is found in G. sempervirens, although the corresponding enzymes act on entirely different substrates. This study provides insights into the common genomic context of MIA pathways and is an important milestone in the further elucidation of the Gelsemium oxindole alkaloid pathway.     

Chemical Ecology and Sociality in Aphids: Opportunities and Directions

Aphids have long been recognized as good phytochemists. They are small sap-feeding plant herbivores with complex life cycles that can involve cyclical parthenogenesis and seasonal host plant alternation, and most are plant specialists. Aphids have distinctive traits for identifying and exploiting their host plants, including the expression of polyphenisms, a form of discrete phenotypic plasticity characteristic of insects, but taken to extreme in aphids. In a relatively small number of species, a social polyphenism occurs, involving sub-adult “soldiers” that are behaviorally or morphologically specialized to defend their nestmates from predators. Soldiers are sterile in many species, constituting a form of eusociality and reproductive division of labor that bears striking resemblances with other social insects. Despite a wealth of knowledge about the chemical ecology of non-social aphids and their phytophagous lifestyles, the molecular and chemoecological mechanisms involved in social polyphenisms in aphids are poorly understood. We provide a brief primer on aspects of aphid life cycles and chemical ecology for the non-specialists, and an overview of the social biology of aphids, with special attention to chemoecological perspectives. We discuss some of our own efforts to characterize how host plant chemistry may shape social traits in aphids. As good phytochemists, social aphids provide a bridge between the study of insect social evolution sociality, and the chemical ecology of plant-insect interactions. Aphids provide many promising opportunities for the study of sociality in insects, and to understand both the convergent and novel traits that characterize complex sociality on plants.     

Stability of microencapsulated lactic acid bacteria under acidic and bile juice conditions

The probiotic strains Lactobacillus brevis CCMA1284 and Lactobacillus plantarum CCMA0359 were microencapsulated by spray drying using different matrices – whey powder (W), whey powder with inulin (WI) and whey powder with maltodextrin (WM). Viability of the microencapsulated strains in acid and bile juices and during 90 days of storage (seven and 25 °C) was evaluated. The two strains exhibited high encapsulation efficiency (> 86%) by spray drying. The different matrices maintained L. plantarum viability above six log CFU g⁻¹ at 7 °C for 90 days, whereas similar results for L. brevis were observed only for W. The use of inulin as matrix of encapsulation did not enhance bacterial viability in the evaluated conditions. In general, the use of W and WM as matrices was effective for L. plantarum viability. However, only W was effective for L. brevis in the evaluated conditions. The spray drying technique was successfully adopted for the encapsulation of L. plantarum CCMA0359 and L. brevis CCMA1284 strains.     

Preliminary Developments of Miniplate-Type Fuel of U-2.5Zr-7.5Nb Alloy Dispersed and Cladded in Zircaloy

Nuclear fuel based on uranium metal alloys is utilized in research and test reactors. For the purpose of the reduction of fuel enrichment, high densities of uranium-235 in this kind of fuel are needed. This can be achieved when uranium alloys are used containing elements such as Zr, Mo and Nb. The construction of fuel element with high-uranium density requires materials with low cross sections for neutron absorption, stability under irradiation and absence of the chemical interactions between the fuel and cladding elements. In case of U-Zr-Nb alloys, Zry （zircaloy） cladding is a better option due to the fact that they have a higher chemical compatibility when compared with the use of aluminum alloys. This study aims to develop plate type nuclear fuel using the U-2.5Zr-7.5Nb alloy dispersed in Zry. Powders of this uranium based alloy and Zry were obtained by hydriding-dehydriding process. These powders were homogenized, compacted in pellet that was sandwiched in plates and frame of Zry. This assembly was hot rolled forming the dispersion fuel miniplate.     

Mealtime Behaviors and Food Consumption of Perceived Picky and Nonpicky Eaters through Home Use Test

Picky eating has been investigated through numerous surveys and food recalls, but few studies have applied in‐home meal evaluations as a method to investigate behaviors and food preferences of children perceived by their parent to be a picky eater (PE) or nonpicky eater (NPE). A 2‐wk in‐home meal study was completed to investigate differences in PE and NPE mealtime behaviors and food selections using real‐time parental observations. Parents (n = 170) and their 2‐ to 4‐y‐old children (83 PE and 87 NPE) evaluated 5 standardized meals in‐home. Parents recorded their child's and their own hedonic liking of the products and completed an assessment of their child's behavior and consumption at each meal. Significant differences were found between perceived PE and NPE children for all 16 behaviors assessed. On average, perceived NPE were assessed to consume a higher percentage of the meal served and to have higher acceptance scores for most of the foods evaluated. Some foods, though, like breaded chicken and plain pasta, were liked equally by PE and NPE. Several significant differences in hedonic liking were revealed when PE children were compared to their parents. Yet, few differences in liking occurred between NPE children and their parents or between the 2 parental groups. Because study participants evaluated meals real‐time rather than memory recall, the differences and similarities found between perceived PE and NPE may be considered direct experiential evidence with reduced subjective bias as created when subjects recall past experiences. Thus, findings from this study can provide the foundation to establish an objective definition and classification of PE and NPE.     

Dynamic affinity-based classification of multi-class imbalanced data with one-versus-one decomposition: a fuzzy rough set approach

Although the relevance problem in recommender systems, which typically refers to the similarity between the preference of the user and the items the system recommends, has been well studied, the issue of making recommendations in right orders has barely been mentioned before. The order defines the way in which items should be better consumed in relation to each other. The analysis of real-world data sets demonstrates strong item consumption patterns in the degree of order. In this paper, we propose a novel method to tackle the right-order recommendation problem based on a graph structure that incorporates the item consumption orders. The proposed method can combine relevance and order effects in recommendations. We attempt to recommend the relevant items in the consecutive steps within a user session so that the user’s selected items in the consecutive steps can be stringed together in a right order. The experimental evaluation conducted on three real-world data sets shows that the recommendation accuracy is improved by considering item consumption orders compared with the baseline recommendation methods. In addition, the study on right-order recommendation contributes to the exploration on recommendation appropriateness besides relevance.     

Sugarcane Serine Peptidase Inhibitors,Serine Peptidases,and Clp Protease System Subunits Associated with Sugarcane Borer (Diatraea saccharalis) Herbivory and Wounding

Sugarcane’s (Saccharum spp.) response to Diatraea saccharalis (F.) (Lepidoptera: (Crambidae) herbivory was investigated using a macroarray spotted with 248 sugarcane Expressed Sequence Tags (ESTs) encoding serine peptidase inhibitors, serine peptidases. and Clp protease system subunits. Our results showed that after nine hours of herbivory, 13 sugarcane genes were upregulated and nine were downregulated. Among the upregulated genes, nine were similar to serine peptidase inhibitors and four were similar to Bowman-Birk Inhibitors (BBIs). Phylogenetic analysis revealed that these sequences belong to a phylogenetic group of sugarcane BBIs that are potentially involved in plant defense against insect predation. The remaining four upregulated genes included serine peptidases and one homolog to the Arabidopsis AAA+ chaperone subunit ClpD, which is a member of the Clp protease system. Among the downregulated genes, five were homologous to serine peptidases and four were homologous to Arabidopsis Clp subunits (three homologous to Clp AAA+ chaperones and one to a ClpP-related ClpR subunit). Although the roles of serine peptidase inhibitors in plant defenses against herbivory have been extensively investigated, the roles of plant serine peptidases and the Clp protease system represent a new and underexplored field of study. The up- and downregulated D. saccharalis genes presented in this study may be candidate genes for the further investigation of the sugarcane response to herbivory.     

Social Exclusion in Later Life: A Systematic Review of the Literature

In the last decade, there has been a growing awareness regarding social exclusion. Considering the ageing population and the likelihood of older people being socially excluded, the aims of this article are to: (1) review existing studies concerning social exclusion in later life; and (2) identify how environmental and life-course perspectives are presented in studies focusing on social exclusion in later life. A systematic review in seven scientific databases was conducted to explore the peer-reviewed evidence. In total, 26 articles were included and analysed. Findings describe the variety of methods, conceptualisation, dimensions and measures used in this recent area of research. Determinants of social exclusion in later life are discussed and life-course and environmental perspectives are examined. The discussion highlights the complex character of the concept and measurement of social exclusion, and the presence of general and age-specific dimensions of social exclusion in later life. The time and context relativity and the need for life-course and environmental perspectives on social exclusion in later life are discussed. Finally, future directions of research are discussed.