Synthesis, characterization and chemical modification of a cationic polyelectrolyte poly(methylene amine)

Polyamine polymers have attracted attention due to their ability to demonstrate pH dependent cationic nature and presence of highly reactive pendant amino groups. These amino groups make them suitable for a host of applications through cross-linking and derivatization. As a result the end use application of a polyamine is largely driven by the number of amino groups and the way they are attached to the polymer backbone. Thus, this piece of work describes the synthesis and investigation of properties of a novel aliphatic polyamine, poly(methylene amine); that carries maximum number of amino group on its backbone. The target polymer, poly(methylene amine); was synthesized via two major steps viz.1.synthesis of precursor polymers of poly(methylene amine) and 2. Hydrolysis of the precursor polymers to obtain poly(methylene amine). The precursor polymers poly (1,3-diacetylimidazole-2-one)(6) and poly(1,3-diformyldihydroimidazol-2-one)(7) were synthesized via radical polymerization of their respective monomers. The monomers were polymerized in bulk as well as in solution at different reaction conditions. The maximum molecular weights were achieved by polymerizing the monomers in bulk (Mn = 6.5 x 104 g/mol and Mw = 2.13 x 105 g/mol) of 6. The precursor polymers were hydrolyzed under strong reaction conditions in ethanol in presence of NaOH, LiCl at 170°C to yield poly(methylene amine). The process of hydrolysis was monitored by IR spectroscopy. The solution properties of poly(methylene amine) and its hydrochloride were investigated by viscosimetry and light scattering. The reduced viscosity of poly (methylene amine) hydrochloride as a function of polymer concentration demonstrated a behavior typical of cationic polyelectrolyte. With decrease in polymer concentration the reduced viscosity of poly(methylene amine) hydrochloride increased gradually. The dynamic light scattering studies also revealed behaviors of a polyelectrolyte. Poly(methylene amine) was reacted with electrophiles to yield novel materials. While the attachment of alkyl group onto the nitrogen would increase nucleophilicity, it would also impose steric hindrance. As a result the degree of substitution on poly(methylene amine) would be governed by both the factors. Therefore, few model reactions with electrophiles were performed on polvinylamine under similar reaction conditions in order to make a comparative evaluation. It was found that under similar reaction conditions the degree of substitution was higher in case of polyvinylamine in comparison with poly (methylene amine).This shows that the steric hindrance outweighs nucleophilicity while deciding degree of substitution of electrophiles on poly(methylene amine). The modification was further extended to its use as an initiator for ring opening polymerization of benzyloxy protected N-carboxyanhydride of z-Lysine. The resulting polymer had an interesting brush like architecture. The solid state morphology of this polymer was investigated by SAXS. The 2D-WAXS diffractograms revealed hexagonal morphology of peptide segments without formation of alpha helices.

Chemical and kinematical properties of Blue Straggler stars in Galactic globular clusters

Blue straggler stars (BSSs) are brighter and bluer (hotter) than the main-sequence (MS) turnoff and they are known to be more massive than MS stars.Two main scenarios for their formation have been proposed:collision-induced stellar mergers (COL-BSSs),or mass-transfer in binary systems (MT-BSSs).Depleted surface abundances of C and O are expected for MT-BSSs,whereas no chemical anomalies are predicted for COL-BSSs.Both MT- and COL-BSSs should rotate fast, but braking mechanisms may intervene with efficiencies and time-scales not well known yet,thus preventing a clear prediction of the expected rotational velocities.Within this context,an extensive survey is ongoing by using the multi-object spectrograph FLAMES@VLT,with the aim to obtain abundance patterns and rotational velocities for representative samples of BSSs in several Galactic GCs.A sub-population of CO-depleted BSSs has been identified in 47 Tuc,with only one fast rotating star detected.For this PhD Thesis work I analyzed FLAMES spectra of more than 130 BSSs in four GCs:M4,NGC 6397,M30 and ω Centauri.This is the largest sample of BSSs spectroscopically investigated so far.Hints of CO depletion have been observed in only 4-5 cases (in M30 and ω Centauri),suggesting either that the majority of BSSs have a collisional origin,or that the CO-depletion is a transient phenomenon.Unfortunately,no conclusions in terms of formation mechanism could be drawn in a large number of cases,because of the effects of radiative levitation. Remarkably,however,this is the first time that evidence of radiative levitation is found in BSSs hotter than 8200 K.Finally, we also discovered the largest fractions of fast rotating BSSs ever observed in any GCs:40% in M4 and 30% in ω Centauri.While not solving the problem of BSS formation,these results provide invaluable information about the BSS physical properties,which is crucial to build realistic models of their evolution.

Seasonality and diel variation in blue whale D calls recorded in the Southern California Bight

Passive acoustic data have been collected using HARPs (High-frequency Acoustic Recording Packages) and were used to assess (1) the seasonality of blue whale D calls in the Southern California Bight, (2) their interannual abundance during 2007-2012 and (3) their diel variation. This goal has been achieved running the GPL (Generalized Power-Law) automated detector. (1) Blue whale D calls were detected in the Southern California Bight from May through November with a peak in July, even though few detections were from December to April as well. A key predictor for blue whale distribution and movement in the California Current region has been identified with zooplankton aggregations, paying a particular attention to those euphausiid species, such as E. pacifica and T. spinifera, which are blue whale favorite krill. The Southern California Bight experiences seasonal upwelling, resulting in an increase of productivity and prey availability. The summer and early fall have been marked as the most favorable periods. This supports the presence of blue whales in the area at that time, supposing these marine mammals exploit the region as a feeding ground. (2) As to the interannual abundance during 2007-2012, I found a large variability. I observed a great increase of vocalizations in 2007 and 2010, whereas a decrease was shown in the other years, which is well marked in 2009. It is my belief that these fluctuations in abundance of D calls detections through the deployed period are due to the alternation of El Nino and La Nina events, which occurred in those years. (3) The assessment of the daily timing of D calls production shows that D calls are more abundant during the day than during the night with a peak at 12:00 and 13:00. Assuming that D calling is associated with feeding, the daily pattern of D calls may be linked to the prey availability. E. pacifica and T. spinifera are among those species of krill which undertake daily vertical migrations, remaining at depth during the day and slowly coming up towards the surface at night. Because of some anatomical arrangements, these euphausiids are very sensitive to the light. Given that we believe D calls have a social function, I hypothesize that blue whales may recognize the hours at the highest solar incidence as the best moment of the day in terms of prey availability, exploiting this time window to advert their conspecifics.

La popolazione di Blue Straggler Stars in due ammassi globulari della Grande Nube di Magellano

Le Blue Straggler Stars (BSS) sono la popolazione di oggetti esotici piu' comune e numerosa negli ammassi globulari. Nel diagramma colore-magnitudine le BSS definiscono una sequenza più brillante e blu del punto di turn-off della Sequenza Principale, simulando una popolazione più giovane delle stelle dell'ammasso.  Osservazioni hanno dimostrato che le BSS hanno una massa significativamente più grande (1.2-1.7 Msun) di quella delle stelle di un ammasso globulare. Per questa proprietà, la distribuzione radiale delle BSS e' un utile strumento per tracciare empiricamente lo stato di evoluzione dinamica degli ammassi stellari. Il lavoro di tesi si è concentrato sullo studio della popolazione di BSS di due ammassi globulari della Grande Nube di Magellano: NGC2257 e NGC1754. Applicando metodi di indagine già usati per sistemi stellari della Via Lattea, abbiamo derivato le eta' dinamiche di questi due sistemi e le abbiamo confrontate con stime teoriche.

First assessment on genetic structure and phylogeography of Mediterranean blue shark (prionace glauca, L. 1758) population using mitochondrial gene variation: a comparison with the Atlantic.

The blue shark, Prionace glauca, is one of the most vagile shark species worldwide distributed. The particular body shape allows blue sharks make transoceanic movements, leading to a circumglobal distribution. Due to its reproductive cycle, an extraordinarily high number of specimens is globally registered but, even if it is still a major bycatch of longline fishery rather than a commercial target, it is characterized by a high vulnerability. In this perspective it is important to increase the amount of informations regarding its population extent in the different worldwide areas, evaluating the possible phylogeographic patterns between different locations. This study, included in the "MedBlueSGen" European project, aims exactly at filling a gap in knowledges regarding the genetic population structure of the Mediterranean blue sharks, which has never been investigated before, with a comparison with the North-Eastern Atlantic blue shark population. To reach this objective, we used a dataset of samples from different Mediterranean areas implementing it with some samples from North-Eastern Atlantic. Analyzing the variability of the two mitochondrial markers control region and cytochrome b, with the design of new species-specific primer pairs, we assessed the mitochondrial genetic structure of Mediterranean and North-Eastern Atlantic samples, focusing on the analysis of their possible connectivity, and we tried to reconstruct their demographic history and population size. Data analyses highlighted the absence of a genetic structuring within the Mediterranean and among it and North-Eastern Atlantic, suggesting that the Strait of Gibraltar doesn't represent a phylogeographic barrier. These results are coherent to what has been found in similar investigations on other worldwide blue shark populations. Analysis of the historical demographic trend revealed a general stable pattern for the cytochrome-b and a slightly population expansion for the control region marker.

Un nuovo indicatore di segregazione radiale delle blue stragglers

Le blue straggler stars (BSS) sono un importante strumento osservativo per gli studi mirati alla determinazione dell'evoluzione dinamica degli ammassi globulari. La loro distribuzione radiale, influenzata dal fenomeno di segregazione di massa, costituisce un efficace strumento per la determinazione dello stato di rilassamento del sistema. In questo lavoro di tesi sono esplorate le potenzialità di un nuovo indicatore di segregazione centrale delle BSS: la cosiddetta "Area Positiva (A+)", definita come la differenza tra l'area sottesa dalla distribuzione radiale cumulativa delle BSS e quella di una popolazione di riferimento. Per costruzione, questo parametro e` indicatore sensibile del livello di segregazione delle BSS. Il campione di ammassi e` costituito da 18 oggetti di bassa densità e concentrazione recentemente osservati nell'ambito di una survey ultravioletta con la camera WFC3/UVIS (Piotto et al. 2015) e 8 sistemi di densità più elevata, analizzati in lavori precedenti. Per ciascun ammasso sono state selezionate le popolazioni di BSS e di stelle di riferimento lungo la sequenza principale o il ramo delle giganti e sono state costruite le rispettive distribuzioni radiali cumulative, da cui e` stata poi determinata l'Area Positiva. Sono state infine individuate forti correlazioni tra A+ e alcuni parametri strutturali/dinamici degli ammassi, in particolare col tempo di rilassamento e la densita` centrali. Questi risultati dimostrano che il parametro A+ e` un buon misuratore del grado di evoluzione dinamica degli ammassi globulari.

Blue Light versus Green Light Autofluorescence: Lesion Size of Areas with Geographic Atrophy

Blue-light fundus autofluorescence (FAF) imaging is currently widely used for assessing dry age-related macular degeneration (ARMD). However, at this wavelength, the fovea appears as circular zone of marked hypofluorescence, due to the absorption of macular pigment (MP). This dark spot could be misinterpreted as an atrophic area and could lead to difficulties in identifying small, central changes. The purpose of the study was to analyze differences in image quality, FAF patterns, and lesion size, when using conventional blue-light (Λ(1) = 488 nm) and green-light (Λ(2) = 514 nm) FAF.

"Brienzi" - The blue Vivianite man of Switzerland: Time since death estimation of an adipocere body

In 1996, a cadaver in adipocere condition was discovered in a bay of the Brienzer See in Switzerland. The torso was named "Brienzi" following the "Iceman" Ötzi. Several outer parts of the body were incrusted; the incrustation was in blue color. Further investigations showed that the bluish covering of parts of the adipocere torso were a mineral known as Vivianite. Vivianite (Fe(3)(PO(4))(2-)(H(2)O)(8)) is an iron phosphate mineral with needle lengths between 100 and 150μm. It is normally associated in a context with organic archaeological and geological materials (some hundreds to millions of years old). Hitherto, it is only described in three cases of human remains. We were able to reconstruct the following facts about 'Brienzi': The man drowned in Lake Brienz or in one of its tributaries during the 1700s. The body was subsequently covered with sedimentation and thus buried under water. An earthquake produced an underwater landslide which eventually exposed the corpse.

The Blue Of

When I first started my thesis, I intended for my finished project to be a compilation of poems that aims to reflect and reveal several repeating themes of our society's collective unconscious, such as the relationship between the physical and spiritual aspects of being and the representation of women's lives, organized religion,adolescence, and mental illness. I proposed writing a chapbook of poetry that reflects an exploration of, and sensitivity to, the human unconscious mind, fears, and desires. Consulting other works of surreal, lyric, and confessional poetry, I sought to personallydevelop as both a poet and a psychology student. I made a conscious effort to avoid trying to attach a specific 'meaning' to each poem. I understand that, in poetry, the reader is never entirely aware of exactly what the poet is trying to convey. All the reader knows is what he or she sees in a given poem and how he or she responds to that poem. However, through working on my thesis I discovered that, while meaning may not be intentional in the drafting process, developing what the poem meant to me was central to the process of revision. Furthermore, I realized that I unconsciously returned to specific themes across various poems, something that was not apparent to me until I re-read my entire collection ...

The Blue Dog Coalition: Impact of a Single-Issue Caucus from the 104th to the 110th Congress

The Blue Dog Coalition is an informal organization of legislators within the House of Representatives that strives to influence policy on fiscal responsibility, attract the attention of the electorate, They are a group that elicits wide range of reactions covering the length of the political spectrum, but despite this, their claims of special defense of fiscal conservatism within the Democratic Party have gone relatively undocumented by the academic community.This project has integrated a party literature with a caucus literature, in the attempt of building a novel framework for research. Work on polarization, the significance of parties, the purpose and history of caucuses all have been fused in such away that the Blue Dogs have created an opportunity to test broad congressional questions on a caucus-microcosm scale. Three important questions have emerged from the many possible avenues of exploration on the topic: How does admission into the Blue Dog Coalition effect voting behavior - measured by interest, ideology, and party unityscores? How does party leadership delegate prestigious committee assignments, a traditional indicator of partisan favor and influence, towards Blue Dogs? Can we use the Blue Dog Coalition as an indicator of fiscal conservatism? To each of these questions, a number of interesting results emerged. Blue Dogs, in the 104th scored higher in conservative interest group scores, more towards the center in ideological methods, and lower in party unity Dogs began to behave closer to their Democratic counterparts. In addition, membership on these select committees rose from a very small number to greater proportional parity within the Democratic Party. Perhaps most interesting, the Blue Dog Coalition does behave as a significant, independent predictor effect on NTU scores, a variable used to demonstrate fiscal conservatism. This research has shown, first and foremost, that it is useful and practical to applyold arguments within the party literature to a smaller, caucus level of analysis that is relatively untouched by the political science field. For the Blue Dogs, specifically, we have tested the validity of their claims in an attempt to reach broader questions ofdemocratic responsibility and electoral clarity. This work, and other work I have drawn upon, has barely scratched the surface on Blue Dog Democrats and other caucuses of comparable influence and popularity, and there remains a wealth of research material onthis caucus alone to be explored by scholars in the field of congressional politics.

Does a pleiotropic gene explain deafness and blue irises in white cats?

The prevalence of deafness is high in cat populations in which the dominant white gene is segregating. The objective of this study was to investigate whether there is a gene that is responsible for deafness as well as for blue eyes and to establish a plausible mode of inheritance. For this purpose, data from an experimental colony with deaf cats were analyzed. The hearing status was determined by acoustically evoked brain stem responses (BAER). Complex segregation analyses were conducted to find out the most probable mode of inheritance using maximum likelihood procedures. The prevalence of deafness and partial hearing in the experimental colony was 67% and 29%, respectively. The results of the bivariate segregation analysis support the hypothesis of a pleiotropic major gene segregating for deafness and blue iris colour. The high heritability coefficients for both traits, 0.55 and 0.75 respectively, indicate that beside the major gene there is an important influence of polygenic effects.

Blue-footed Boobie

Oil/P