Super-Nernstian Shifts of Interfacial Proton-Coupled Electron Transfers: Origin and Effect of Noncovalent Interactions

Peer reviewed

Investigation of the chemical origin and evidential value of differences in the SERS spectra of blue gel inks

Highly swellable polymer films doped with Ag nanoparticle aggregates (poly-SERS films) have been used to record very high signal:noise ratio, reproducible surface-enhanced (resonance) Raman (SER(R)S) spectra of in situ dried ink lines and their constituent dyes using both 633 and 785 nm excitation. These allowed the chemical origins of differences in the SERRS spectra of different inks to be determined. Initial investigation of pure samples of the 10 most common blue dyes showed that the dyes which had very similar chemical structures such as Patent Blue V and Patent Blue VF (which differ only by a single OH group) gave SERRS spectra in which the only indications that the dye structure had been changed were small differences in peak positions or relative intensities of the bands. SERRS studies of 13 gel pen inks were consistent with this observation. In some cases inks from different types of pens could be distinguished even though they were dominated by a single dye such as Victoria Blue B (Zebra Surari) or Victoria Blue BO (Pilot Acroball) because their predominant dye did not appear in other inks. Conversely, identical spectra were also recorded from different types of pens (Pilot G7, Zebra Z-grip) because they all had the same dominant Brilliant Blue G dye. Finally, some of the inks contained mixtures of dyes which could be separated by TLC and removed from the plate before being analysed with the same poly-SERS films. For example, the Pentel EnerGel ink pen was found to give TLC spots corresponding to Erioglaucine and Brilliant Blue G. Overall, this study has shown that the spectral differences between different inks which are based on chemically similar, but nonetheless distinct dyes, are extremely small, so very close matches between SERRS spectra are required for confident identification. Poly-SERS substrates can routinely provide the very stringent reproducibility and sensitivity levels required. This, coupled with the awareness of the reasons underlying the observed differences between similarly coloured inks allows a more confident assessment of the evidential value of inks SERS and should underpin adoption of this approach as a routine method for the forensic examination of inks.

Molecular characterization of immunoglobulin gene rearrangements in diffuse large B-cell lymphoma: antigen-driven origin and IGHV4-34 as a particular subgroup of the non-GCB subtype.

The pathogenesis of diffuse large B-cell lymphoma (DLBCL) remains partially unknown. The analysis of the B-cell receptor of the malignant cells could contribute to a better understanding of the DLBCL biology. We studied the molecular features of the immunoglobulin heavy chain (IGH) rearrangements in 165 patients diagnosed with DLBCL not otherwise specified. Clonal IGH rearrangements were amplified according to the BIOMED-2 protocol and PCR products were sequenced directly. We also analyzed the criteria for stereotyped patterns in all complete IGHV-IGHD-IGHJ (V-D-J) sequences. Complete V-D-J rearrangements were identified in 130 of 165 patients. Most cases (89%) were highly mutated, but 12 sequences were truly unmutated or minimally mutated. Three genes, IGHV4-34, IGHV3-23, and IGHV4-39, accounted for one third of the whole cohort, including an overrepresentation of IGHV4-34 (15.5% overall). Interestingly, all IGHV4-34 rearrangements and all unmutated sequences belonged to the nongerminal center B-cell-like (non-GCB) subtype. Overall, we found three cases following the current criteria for stereotyped heavy chain VH CDR3 sequences, two of them belonging to subsets previously described in CLL. IGHV gene repertoire is remarkably biased, implying an antigen-driven origin in DLBCL. The particular features in the sequence of the immunoglobulins suggest the existence of particular subgroups within the non-GCB subtype.

Origin and dispersal routes of foreign green and Kemp's ridley turtles in Spanish Atlantic and Mediterranean waters

[EN] The presence of the green and Kemp's ridley turtles is rare at Atlantic and Mediterranean Spanish waters, but the records have increased during the last decades. We reported a new set of records and reviewed all the historical observations of these species. The analysis of a mitochondrial DNA fragment of the newest records provided insights about the origin of the individuals. The Kemp's ridley turtles arrived from the western Atlantic nesting beaches, although the discovering of a new haplotype suggested the existence of an unknown or low sampled nesting area of origin.

Origin and ecological selection of core and food-specific bacterial communities associated with meat and seafood spoilage

The microbial spoilage of meat and seafood products with short shelf lives is responsible for a significant amount of food waste. Food spoilage is a very heterogeneous process, involving the growth of various, poorly characterized bacterial communities. In this study, we conducted 16S ribosomal RNA gene pyrosequencing on 160 samples of fresh and spoiled foods to comparatively explore the bacterial communities associated with four meat products and four seafood products that are among the most consumed food items in Europe. We show that fresh products are contaminated in part by a microbiota similar to that found on the skin and in the gut of animals. However, this animal-derived microbiota was less prevalent and less abundant than a core microbiota, psychrotrophic in nature, mainly originated from the environment (water reservoirs). We clearly show that this core community found on meat and seafood products is the main reservoir of spoilage bacteria. We also show that storage conditions exert strong selective pressure on the initial microbiota: alpha diversity in fresh samples was 189 +/- 58 operational taxonomic units (OTUs) but dropped to 27 +/- 12 OTUs in spoiled samples. The OTU assemblage associated with spoilage was shaped by low storage temperatures, packaging and the nutritional value of the food matrix itself. These factors presumably act in tandem without any hierarchical pattern. Most notably, we were also able to identify putative new clades of dominant, previously undescribed bacteria occurring on spoiled seafood, a finding that emphasizes the importance of using culture-independent methods when studying food microbiota.

Origin and fate of surface drift in the oceanic convergence zones of the eastern Pacific

This study investigates the structure and intensity of the surface pathways connecting to and from the central areas of the large-scale convergence regions of the eastern Pacific Ocean. Surface waters are traced with numerical Lagrangian particles transported in the velocity field of three different ocean models with horizontal resolutions that range from ¼° to 1/32°. The connections resulting from the large-scale convergent Ekman dynamics agree qualitatively but are strongly modulated by eddy variability that introduces meridional asymmetry in the amplitude of transport. Lagrangian forward-in-time integrations are used to analyze the fate of particles originating from the central regions of the convergence zones and highlight specific outflows not yet reported for the southeastern Pacific when using the currents at the highest resolutions (1/12° and 1/32°). The meridional scales of these outflows are comparable to the characteristic width of the fine-scale striation of mean currents.

Ionic composition of endolymph in teleosts: Origin and importance of endolymph alkalinity

Ionic (Na+, K+, Cl-, PO43-, pH), total CO2, total calcium and protein concentrations in the plasma and endolymph of the inner ear were compared in trout Oncorhynchus mykiss and turbot Scophthalmus maximus. In both species, saccular endolymph was characterized by high levels of K+ and total CO2 and in trout by an alkaline pH, The kinetic characteristics of proton secretion across the saccular epithelium of trout were investigated using a titration technique in which isolated saccules were mounted as closed sacs. The rate of proton secretion depends strongly on the pH of the Ringer's solution and secretion stops at a pH below 7.2, Proton secretion is driven by an energy-dependent mechanism involving basolateral ouabain-sensitive Na+/K+ exchangers. Proton secretion was partially inhibited by acetazolamide and completely inhibited in Na+-free Ringer or in the presence of 1 mmol l(-1) amiloride. A cellular model stressing the importance of proton exchange through the saccular epithelium is proposed to explain the regulation of endolymph pH, a crucial factor for the deposition of otolith calcium.

A Ride-Sharing System with High Capacity Vehicles and Flexible Meeting Points

In many major cities, fixed route transit systems such as bus and rail serve millions of trips per day. These systems have people collect at common locations (the station or stop), and board at common times (for example according to a predetermined schedule or headway). By using common service locations and times, these modes can consolidate many trips that have similar origins and destinations or overlapping routes. However, the routes are not sensitive to changing travel patterns, and have no way of identifying which trips are going unserved, or are poorly served, by the existing routes. On the opposite end of the spectrum, personal modes of transportation, such as a private vehicle or taxi, offer service to and from the exact origin and destination of a rider, at close to exactly the time they desire to travel. Despite the apparent increased convenience to users, the presence of a large number of small vehicles results in a disorganized, and potentially congested road network during high demand periods. The focus of the research presented in this paper is to develop a system that possesses both the on-demand nature of a personal mode, with the efficiency of shared modes. In this system, users submit their request for travel, but are asked to make small compromises in their origin and destination location by walking to a nearby meeting point, as well as slightly modifying their time of travel, in order to accommodate other passengers. Because the origin and destination location of the request can be adjusted, this is a more general case of the Dial-a-Ride problem with time windows. The solution methodology uses a graph clustering algorithm coupled with a greedy insertion technique. A case study is presented using actual requests for taxi trips in Washington DC, and shows a significant decrease in the number of vehicles required to serve the demand.

West versus East Mediterranean Sea: origin and genetic differentiation of the sea cucumber Holothuria polii

We studied the genetic structure of the sea cucumber Holothuria (Roweothuria) polii (Delle Chiaje 1823) by analysing the mitochondrial DNA variation in two fragments of cytochrome oxidase I (COI) and 16S genes. Individuals were collected in seven locations along the Mediterranean Sea, which cover a wide range of the species distribution. We found high haplotype diversity for COI and moderate diversity for 16S, and low nucleotide diversity for both genes. Our results for the COI gene showed many recent and exclusive haplotypes with few mutational changes, suggesting recent or ongoing population expansion. The Western and Eastern Mediterranean populations exhibited slight but significant genetic differentiation (COI gene) with higher genetic diversity in the East. The most ancient haplotype was not present in the westernmost sampling location (SE Spain). The oldest expansion time was observed in Turkey, corresponding to mid-Pleistocene. Turkey had also the highest genetic diversity (number of total and exclusive haplotypes, polymorphisms, haplotype and nucleotide diversity). This suggests that this region could be the origin of the subsequent colonizations through the Mediterranean Sea, a hypothesis that should be assessed with nuclear markers in future research.

Social Mobility and Demand for Redistribution. A Comparative Analysis

The literature on preferences for redistribution has paid little attention to the effect of social mobility on the demand for redistribution, which is in contrast with the literature on class-voting, where studies on the effect of social mobility has been very common. Some works have addressed this issue but no systematic test of the hypotheses connecting social mobility and preferences has been done. In this paper we use the diagonal reference models to estimate the effect of origin and destination class on preferences for redistribution in a sample of European countries using data from the European Social Survey. Our findings indicate that social origin matters to a little extent to explain preferences, as newcomers tend to adopt the preferences of the destination class. Moreover, we have found only limited evidence supporting the acculturation hypothesis and not support for the status maximization hypothesis. Furthermore, the effect of social origin varies largely between countries. In a second step of the analysis we investigate what are the national factors explaining this variation. The empirical evidence we present leads to conclude that high rates of upward social mobility sharply reduce the effect of social origin on preferences for redistribution

Association mapping provides insights into the origin and the fine structure of the sorghum aluminum tolerance locus, AltSB.

2014

Investigation of un-American propaganda activities in the United States : Hearings before a Special Committee on Un-American Activities, House of Representatives, Seventy-fifth Congress, third session-Seventy-eighth Congress, second session, on H. Res. 282, to investigate (1) the extent, character, and objects of un-American propaganda activities in the United States, (2) the diffusion within the United States of subversive and un-American propaganda that is instigated from foreign countries or of a domestic origin and attacks the principle of the form of government as guaranteed by our Constitution, and (3) all other questions in relation thereto that would aid Congress in any necessary remedial legislation.

Martin Dies, chairman.

Revisiting the origin and development of pleonastic that in English

The origin of pleonastic that can be traced back to Old English where it could appear in syntactic constructions consisting of a preposition + demonstrative pronoun (i.e. for þy þat, for þæm þe) or a subordinator (i.e. oþ þat). Its diffusion with other subordinators is considered an early Middle English development as a result of the standardization of this item as the general subordinator in the period, which motivated its use as a pleonastic word in combination with all kinds of conjunctions (i.e. now that, gif that, when that, etc.) and prepositions (i.e. before that, save that, in that). Its use considerably increased in late Middle English, declining throughout the 17th century. The list of subordinating elements includes relativizers (i.e. this that), adverbial relatives (i.e. there that) and a number of subordinators (i.e. after, as, because, before, beside, for, if, since, sith, though, until, when, while, etc.). The present paper pursues the following objectives: a) to analyse the use and distribution of pleonastic that in a corpus of early English medical writing (in the period 1375-1700); b) to classify the construction in terms of the two different varieties of medical texts, i.e. treatises and recipes; and c) to assess the decline of the construction with the different conjunctive words. The data used as sources of evidence come from The Corpus of Early English Medical Writing, i.e. Middle English Medical Texts (MEMT for the period 1375-1500) and Early Modern English Medical Texts (EMEMT for the period 1500-1700).

Mobilidade geográfica de trabalhadores qualificados : principais evidências para o Brasil e o Espírito Santo

O objetivo desta dissertação, de forma geral, foi estimar empiricamente a probabilidade de imigração interestadual de trabalhadores qualificados para o Brasil. Consideraram-se tanto as variáveis relativas ao indivíduo quanto as variáveis relacionadas aos fatores regionais de origem e destino do imigrante e as análises foram feitas para os anos de 2001, 2006 e 2011. Para estimar os coeficientes das variáveis explicativas foram utilizados os modelos probit e logit. Os bancos de dados utilizados foram os microdados da PNAD e os principais resultados mostram que o principal polo de atração de trabalhadores qualificados é o estado de São Paulo. Em geral a probabilidade de migração de trabalhadores qualificados é maior para os indivíduos do sexo masculino, brancos e solteiros. Pessoas mais jovens e com maiores salários também são mais propensas a serem imigrantes qualificados.

Inferência de percursos dos utentes de um transporte coletivo

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Redes de Comunicações e Multimédia