An infrared spectroscopic study of C7 intramolecular hydrogen bonds in peptides

The ir-spectra in the N-H stretching region of Piv-Pro-NHMe and Boc-Pro-NHMe have been studied in carbon tetrachloride and chloroform solutions over a wide range of concentrations. Based on the concentration dependence of the N-H stretching bands, it has been shown that the characteristic N-H stretching band due to the C7 intramolecular hydrogen bond is around 3335 cm-'. Intermolecular hydrogen bonding also occurs to a small extent in these peptides, giving rise to a slight concentration dependence of the N-H stretching bands. The band around 3335 cm-* need not necessarily be due to C7 hydrogen bonds alone as proposed by Tsuboi et al. or to intermolecular hydrogen bonding alone as proposed by Maxfield et al.; this conclusion is supported by studies on Boc-Leu-NHMe, which undergoes only intermolecular hydrogen bonding We have shown that 2-Aib-Aib-OMe and Z-Aib- Ala-OMe form C7 intramolecular hydrogen bonds in addition to C5 intramolecular hydrogen bonds. The present studies also show that all the peptides studied exist in more than one conformation in solution.

The upper Bay of Bengal salinity structure in a high-resolution model

Salinity in the Bay of Bengal is highly heterogeneous, with extremely fresh waters found at the surface in the Northern part of the basin, and saltier waters at subsurface as well as to the south. This paper investigates the seasonal structure of sea surface salinity of the Bay in a regional high-resolution model forced by ERA-Interim reanalysis and various precipitation products. Surface circulation is believed to drive the spreading of northern Bay of Bengal fresh waters to the rest of the Indian Ocean. We first present a series of experiments to infer the sensitivity of modeled circulation to various numerical choices. Surface circulation is found to be sensitive to the horizontal resolution of the model, with the 1/12 degrees version appearing much more realistic than the 1/4 degrees version. The sidewall boundary condition is also drastically influencing the characteristics of the western boundary current simulated. We then investigate the sensitivity of the salinity response to the various precipitation products. We observe that ERA-Interim excess precipitation induces a fresh bias in the surface salinity response. Spaceborne precipitation products are more satisfactory. We then identify the pathways of the northern Bay freshwater mass, based on passive tracers experiments. Our model suggests that over timescales of a few months, vertical exchanges between the upper fresh layer and the underlying saltier layer appear to be the main export pathway for the freshwater. The horizontal circulation within the mixed layer also acts to convey fresh waters out of the Bay at these timescales, but in a lesser quantity compared to the vertical export. Beyond its intrinsic interest for the understanding of Bay of Bengal physics, this study highlights the need for a careful design of any realistic numerical model, in three key aspects: the choice of the resolution of the model, the choice of the sub-grid scale parameterizations, and the choice of the forcing fluxes. (C) 2013 Elsevier Ltd. All rights reserved.

A modeling study of the processes of surface salinity seasonal cycle in the Bay of Bengal

In response to the Indian Monsoon freshwater forcing, the Bay of Bengal exhibits a very strong seasonal cycle in sea surface salinity (SSS), especially near the mouths of the Ganges-Brahmaputra and along the east coast of India. In this paper, we use an eddy-permitting (similar to 25 km resolution) regional ocean general circulation model simulation to quantify the processes responsible for this SSS seasonal cycle. Despite the absence of relaxation toward observations, the model reproduces the main features of the observed SSS seasonal cycle, with freshest water in the northeastern Bay, particularly during and after the monsoon. The model also displays an intense and shallow freshening signal in a narrow (similar to 100 km wide) strip that hugs the east coast of India, from September to January, in good agreement with high-resolution measurements along two ships of opportunity lines. The mixed layer salt budget confirms that the strong freshening in the northern Bay during the monsoon results from the Ganges-Brahmaputra river discharge and from precipitation over the ocean. From September onward, the East India Coastal Current transports this freshwater southward along the east coast of India, reaching the southern tip of India in November. The surface freshening results in an enhanced vertical salinity gradient that increases salinity of the surface layer by vertical processes. Our results reveal that the erosion of the freshwater tongue along the east coast of India is not driven by northward horizontal advection, but by vertical processes that eventually overcome the freshening by southward advection and restore SSS to its premonsoon values. The salinity-stratified barrier layer hence only acts as a ``barrier'' for vertical heat fluxes, but is associated with intense vertical salt fluxes in the Bay of Bengal.

Exposición y crítica de la ética de Clemente de Alejandría

Resumen: En este artículo, el autor expone la ética de san Clemente de Alejandría recurriendo principalmente a El Pedagogo y al Protréptico. Da especial importancia a conceptos como salvación, libre albedrío, consejo, imitación, entre otros. Después, el autor realiza una crítica buscando retomar algunas tesis que pueden mantener cierta vigencia para el planteamiento de una ética hodierna, buscando que esta última sea filosófica. Pero es importante tener presente que la ética por naturaleza recurre a la tradición, de la cual se alimenta para elaborar su reflexión filosófica. En otras palabras, la ética no parte desde el vacío, sino en el seno de una tradición, uno de cuyos representantes y constructores, en el contexto del mundo occidental, es Clemente de Alejandría.

O riso e suas metáforas : um estudo bem-humorado sobre subjetividade, linguagem e psicanálise

o presente trabalho propõe discutir o papel ocupado pelo riso na teoria e na clínica psicanalíticas através de uma abordagem multidisciplinar. Para fundamentar tal proposta, foi elaborada uma investigação de algumas das diferentes formas pelas quais o riso foi tomado como objeto do pensamento ao longo da história da cultura ocidental, assim como alguns dos lugares sociais que já foram por estes ocupados nesta mesma cultura. Tal abordagem teve como intuito a demonstração do caráter cultural e contingencial do riso, visando, deste modo, romper com uma interpretação do mesmo como fenômeno essencial, intrínseco e universal da experiência humana e afirmando-o como fenômeno de linguagem, no sentido dos jogos de linguagem propostos por Wittgenstein. O primeiro capítulo apresenta um mosaico composto por aproximações do fenômemo do riso elaboradas desde a Antiguidade até o final do século XVIII, contemplando pensadores com Platão, Aristóteles, Cicero, Quintiliano, Laurent Joubert e Imannuel Kant, dentre outros. No segundo capítulo são expostas algumas das principais concepções modernas do riso e assinalados. Os efeitos do advento do pensamento racionalista sobre tais concepções, ora pelo viés da apropriação do riso como objeto do discurso fisicalista, como em Spencer e Darwin, ora por uma interpretação deste como ultrapassando as dimensões da ordem e da razão, como em Nietzsche, Bataille, Foucault, Clement Rosset e Deleuze. No terceiro capítulo, o trabalho volta-se para o campo específico da Psicanálise, desenvolvendo as idéias freudianas acerca dos chistes, do cômico e do humor, aprofundando-os e estabelecendo as diferenças entre estes. O quarto capítulo da continuidade a discussão no âmbito psicanalítico desenvolvendo uma leitura crítica de algumas formulações pós-freudianas sobre o papel do riso na clínica (strictu sensu e ampliada), na teoria e nas instituições de transmissão da Psicanálise, enfatizando a relevância deste, especialmente por meio do humor, para o estabelecimento de uma direção ética na produção de saber em Psicanálise. O capítulo final parte do conceito de ironia para aprofundar a proposta de uma perspectiva do riso como postura ética em psicanálise, tomando como método possível de flexibilização e de crítica em oposição a uma postura determinista e dogmática, através, especialmente, das metáforas do ironista de Rorty e do cyborg de Donna Haraway.

The food habits of hatchery-produced pond-cultured shad (Alosa sapidissima) reared to a length of two inches

The present study was aimed at determining the food habits of hatchery-produced, pond-cultured shad (Alosa sapidissima) reared to a total length of approximately two inches. More specifically, the objectives were to determine: (1) That point in life at which young shad start to consume food; (2) What type or types of food the young shad consume at the onset of feeding; (3) Food changes, if any, which occur with age and growth in size up to the arbitrarily designated total length of two inches. The plan was that the shad larvae be introduced into an outdoor rearing pond previously fertilized, and that the larvae be dependent upon the plankton for food as they would be under natural conditions.

Small-boat surveys for coastal dolphins: line-transect surveys of Hector’s dolphins (Cephalorhynchus hectori)

Management of coastal species of small cetaceans is often impeded by a lack of robust estimates of their abundance. In the Austral summers of 1997−98, 1998−99, and 1999−2000 we conducted line-transect surveys of Hector’s dolphin (Cephalorhynchus hectori) abundance off the north, east, and south coasts of the South Island of New Zealand. Survey methods were modified for the use of a 15-m sailing catamaran, which was equipped with a collapsible sighting platform giving observers an eye-height of 6 m. Eighty-six percent of 2061 km of survey effort was allocated to inshore waters (4 nautical miles [nmi] or 7.4 km from shore), and the remainder to offshore waters (4−10 nmi or 7.4–18.5 km from shore). Transects were placed at 45° to the shore and spaced apart by 1, 2, 4, or 8 nmi according to pre-existing data on dolphin density. Survey effort within strata was uniform. Detection functions for sheltered waters and open coasts were fitted separately for each survey. The effect of attraction of dolphins to the survey vessel and the fraction of dolphins missed on the trackline were assessed with simultaneous boat and helicopter surveys in January 1999. Hector’s dolphin abundance in the coastal zone to 4 nmi offshore was calculated at 1880 individuals (CV=15.7%, log-normal 95% CI=1384−2554). These surveys are the first line-transect surveys for cetaceans in New Zealand’s coastal waters.

Evolutionary implications of multiple SINE insertions in an intronic region from diverse mammals

An analysis of the nuclear beta-fibrinogen intron 7 locus from 30 taxa representing 12 placental orders of mammals reveals the enriched occurrences of short interspersed clement (SINE) insertion events. Mammalian-wide interspersed repeats (MIRs) are present at orthologous sites of all examined species except those in the order Rodentia. The higher substitution rate in mouse and a rare MIR deletion from rat account for the absence of MIR in the rodents. A minimum of five lineage-specific SINE sequences are also found to have independently inserted into this intron in Carnivora, Artiodactyla and Lagomorpha. In the case of Carnivora, the unique amplification pattern of order-specific CAN SINE provides important evidence for the "pan-carnivore" hypothesis of this repeat element and reveals that the CAN SINE family may still be active today. Particularly interesting is the finding that all identified lineage-specific SINE elements show a strong tendency to insert within or in very close proximity to the preexisting MIRs for their efficient integrations, suggesting that the MIR clement is a hot spot for successive insertions of other SINEs. The unexpected MIR excision as a result of a random deletion in the rat intron locus and the non-random site targeting detected by this study indicate that SINEs actually have a greater insertional flexibility and regional specificity than had previously been recognized. Implications for SINE sequence evolution upon and following integration, as well as the fascinating interactions between retroposons and the host genomes are discussed.

AlN-based BAW resonators with CNT electrodes for gravimetric biosensing

Solidly mounted resonators (SMRs) with a top carbon nanotubes (CNTs) surface coating that doubles as an electrode and as a sensing layer have been fabricated. The influence of the CNTs on the frequency response of the resonators was studied by direct comparison to identical devices with a top metallic electrode. It was found that the CNTs introduced significantly less mass load on the resonators and these devices exhibited a greater quality factor, Q (>2000, compared to ∼1000 for devices with metal electrodes), which increases the gravimetric sensitivity of the devices by allowing the tracking of smaller frequency shifts. Protein solutions with different concentrations were loaded on the top of the resonators and their responses to mass-load from physically adsorbed coatings were investigated. Results show that resonators using CNTs as the top electrode exhibited a higher frequency change for a given load (∼0.25 MHz cm2 ng-1) compared to that of a metal thin film electrode (∼0.14 MHz cm2 ng-1), due to the lower mass of the CNT electrodes and their higher active surface area compared to that of a thin film metal electrode. It is therefore concluded that the use of CNT electrodes on resonators for their use as gravimetric biosensors is a significant improvement over metallic electrodes that are normally employed. © 2011 Elsevier B.V. All rights reserved.

Direct comparison of the gravimetric responsivities of ZnO-based FBARs and SMRs

Film bulk acoustic resonators (FBARs) and solidly mounted resonators (SMRs) have the potential to significantly improve upon the sensitivity and minimum detection limit of traditional gravimetric sensors based on quartz crystal microbalances (QCMs) and surface acoustic wave resonators (SAWs). To date, neither FBAR nor SMR devices have been demonstrated to be superior to the other; hence the choice between them depends primarily on the users' ability to design/fabricate membranes and/or Bragg reflectors. In this work, it is shown that identically designed FBAR and SMR devices resonating at the same frequency exhibit different responsivities to mass loadings, Rm, and that the SMRs are less responsive than the FBARs. For the specific device design and resonant frequency (~2 GHz) of the resonators presented here, the FBARs' mass responsivity is ~20% greater than that of the SMRs', and although this value is not universal for all possible device designs, it clearly shows that FBAR devices should be favoured over SMRs in gravimetric sensing applications where the FBARs' fragility is not an issue. Numerical calculations based on Mason's model offer an insight into the physical mechanisms behind the greater FBARs responsivity, and it was shown that the Bragg reflector has an effect on the acoustic load at one of the facets of the piezoelectric films which is in turn responsible for the SMRs' lower responsivity to mass loadings. © 2013 Elsevier B.V.